TITLE ANTIFUNGAL CARBINOLS

Cross-Reference This application is a continuation-in-part of co- pending application Serial No. 042,541, filed April 29, 1987, which in turn is a continuation-in-part of application Serial No. 877,525, filed June 23, 1986.

Field of the Invention

This invention relates to antifungal carbinols, particularly o-styryl carbinols, and the corresponding epoxy carbinols, pharmaceutical and agricultural compositions containing them, processes for preparing them and methods of using them as antifungal agents in mammals and plants.

Background Including Prior Art

Systemic fungal infections are of increasing importance because of continued and expanded use of immunosuppressive therapies, antimicrobial therapies and indwelling catheters. Currently there are limited therapies available to treat such fungal infections. Amphotericin B remains the drug of choice because it has the widest spectrum of antifungal activity of any systemic antifungal drug, however its utility is limited by its toxicity. Because of the potential seriousness of its toxic effects, intravenous use of amphotericin B is primarily for patients with progressive, potentially fatal infections in which the patient is hospitalized during the course of therapy.

Thus, there is a continuing need to develop safer and more effective drugs which are useful for the treatment of fungal infections.

Plant pathogenic fungi and other disease incitants 5 also cause extensive losses in crops annually. While there are commercially available materials used to control many plant diseases, further improvement in this art is needed if full food and fiber production is to be realized.

10 There are a large number of patent and literature references in the area of azole antifungal drugs and plant disease control agents, --lost pertinent to the a- styryl carbinol compounds of this invention are the following references:

15 B. Sugavanam in U.S. Patent 4,507,140 issued March

26, 1985 discloses fungicidal or plant growth regulating 7-styryl triazoles or imidazoles, amongst others of the formula:

where R ¹ is CH=CH-X; -C≡C-X or -CH ₂ -CH ₂ -X;

25 X is substituted aryl, aralkyl, or heterocycle; R2 is alkyl, cycloalkyl, or optionally substituted arylj Z is OR ³ ;

30 R ³ is H, acetyl; Y is -N- or -CH-.

35

German Patent 3,018,865, published May 16, 1980 discloses antimycotic agents of the formula:

where amongst others

R is alkyl, optionally substituted cycloalkyl or optionally substituted phenyl radical; X is N, or a CH group; Y is -OCH2-, -CH2CH2- or CH=CH; Z is halogen, alkyl, cycloalkyl, alkoxy, alkythio, etc. German Patent 3,314,548-A, published April 21, 1983 discloses substituted 1-hydroxy-ethyl-triazole derivatives of the formula:

where amongst others

R is alkyl, cycloalkyl or phenyl optionally substituted; X is -OCH2-, -SCH2-, -(CH ₂ ) _p or

-CH=CH-; Z is halogen, alkyl, alkoxy, alkylthio, haloalkyl, haloalkoxy, or haloalkylthio; m and p are 0, 1 and 2.

The compounds are antimycotics for treating dermatophytomycoses and systemic mycoses caused, e.g., by Candida sp., Aspergillus sp., Trichophyton sp.

The above three references, which pertain to β- styryl azoles, are believed to be the most relevant. The ?-styryl azole analog of one of the preferred compounds of the instant invention was prepared and found to be significantly less active.

European Patent Application 114,487 which published August 1, 1984 discloses azolylethanol derivatives of the formula:

Where amongst others R^ and R^ which may be the same or different are hydrogen, alkyl, cycloalkyl, al enyl, heterocyclyl aryl, or aralkyl optionally substituted; ¥ is N or CH; and X is C=0. The compounds have fungicidal activity and plant growth regulating activity.

European Patent 117,578-A, published February 23,

1984 discloses heterocyclic-hydroxy-alkyl alkyl ketone(s) and analogues of the formula:

where

A is CO amongst others;

is imidazoyl or 1H- or 4H-1,2,4- triazol-1-yl; R ¹ is H, 1-5C alkyl, or 1-8C acyl; R ² and R ³ are 1-5C alkyl, 3-6C cycloalkyl, 2-6C alkenyl, benzyl (optionally substituted by 1-3 halogen), pyridyl, furyl, thienyl, or phenyl optionally substituted by 1-3 halogen, 1-3 alkyl, or 1-3C alkoxy. Belgian Patent 900,594-A published September 22, 1983 discloses 1-phenyl-l-azolyl-hydroxyethyl cycloalkane derivatives of the formula:

where

R and R = H, halo, NO2, lower alkyl, alkenyl, alkynyl, alkoxy or alkylthio (all optionally substituted by 1 or more halo) , or optionally substituted phenyl or phenoxy; R3 = H or lower alkyl; R4 and R5 = H or halo; Y = CH or N; A = 2-7C alkylene; n = 0 or 1.

The compounds are useful as agricultural fungicides and antimycotics.

None of the cited references nor any known references suggest the novel antifungal compounds of this invention.

SUMMARY OF THE INVENTION

According to the present invention compounds are provided having the formula:

or a pharmaceutically or agriculturally suitable salt thereof wherein

E is a bond or an oxygen atom with the proviso that when E is oxygen; R, R are not halogen; A is perfluoroalkyl of 1-8 carbon atoms, N( ⁽ 313)2, OH, naphthyl optionally substituted with a total of 1-3 substituents each of which is indβDβndently selected from halogen and CF3, -N X optionally substituted with 1 or 2 methyl groups, phenyl optionally substituted with a total of 1-3 substituents each of which is independently selected from: halogen, alkyl of 1-4 carbon atoms, haloalkyl of 1-4 carbon atoms, alkoxy of 1-4 carbon atoms, and with no more than one group selected from:

haloalkoxy of 1-4 carbon atoms, CN, C0 ₂ Ri4, CH=N0Ri4, S(0) _m R5, R ₆ , 2-,3-, or 4-pyridyl or an N-oxide thereof, inidaaol-l-yl, 1,2,4- 5 triazol-l-yl, and -N X optionally substituted with 1 or 2 methyl groups, or a heterocycle selected from imidazol-1-yl, 1,2,4-triazol-l-yl, 2-or 3-thienyl, and 2-,3-, 10 or 4-pyridyl or an N-oxide thereof, optionally substituted with one or two substituents each of which is independently selected from: halogen, alkyl of 1-4 carbon atoms, CF3, alkoxy of 1-4 carbon atoms, haloalkoxy of 15 1-4 carbon atoms, and S(0),g ^

B is alkyl of 1-8 carbon atoms, naphthyl, biphenyl,

Cl ₂

R", perfluoroalkyl of 1-8 carbon atoms,

20 phenyl optionally substituted with 1-3 substituents each of which is independently selected from: halogen, alkyl of 1-4 carbon atoms, haloalkyl of 1- 4 carbon atoms, alkoxy of 1-4 carbon

25 atoms, and with no more than one group selected from haloalkoxy of 1-4 carbon atoms, CN, CO2R14, CH=N0Ri4, S(0) _o R ⁵ , 2-,3-,4-pyridyl or an N oxide thereof,

30 benzyl optionally substituted on the phenyl ring with halogen or alkyl of 1-4 carbon atoms, or optionally α-substituted with 1 or 2 methyl groups, or

35

a heterocycle selected from 2-or 3-thienyl, and 2-,3-,or 4-pyridyl, said heterocycles being optionally substituted with one or two substituents each of which is independently selected from: halogen, alkyl of 1-4 carbon atoms, haloalkoxy of 1-4 carbon atoms, CF3, or SCI NS.

¹⁰ ! !

Q is H, halogen, S(0) R ¹¹ , SCNHR ¹² , CHO, C-CH,,

13 12

COgR , SCN, SSR , or SH or its corresponding disulfide, provided however that when Q is other than H, then n is 0, R, R^, and R* are

15 independently H or CH3, R ³ is H, and A and B are each phenyl optionally substituted with from 1-3 substituents each of which is independently halogen, CH3, CF3, OCH3, or

S(0) _m R ⁵ ;

20

L is CH or N with the proviso that when L = CH then 04. ^ n is 0-4 with the proviso that when A is -N X

N(CH3)2, or OH, then n is other than 0;

25 m each occurrence is 0, 1 or 2; X is C, NR ¹⁰ , or 0;

R and R independently are H, alkyl of 1-4 carbon atoms, halogen, or phenyl, or taken together

30 form cycloalkyl of 3-7 carbon atoms;

35

R2 is H, allyl, propargyl, alkyl of 1-4 carbon atoms,

0 0 0

^■ 7 ^■ 8 9 * 7 -CR', -C-NR°R , -COR', or

5 haloalkyl of 1-4 carbon atoms;

R ³ and R^ independently are H, F, or alkyl of 1-4 carbon atoms;

10

R° is alkyl of 1-4 carbon atoms;

R6 is phenyl optionally substituted with a total of 1-3 substituents each of which is independently selected from halogen and CF3;

15

R' is alkyl of 1-4 carbon atoms, phenyl, or benzyl;

R8 and R^ independently are H, alkyl of 1-4

20 carbon atoms, phenyl or benzyl;

RlO _s H, alkyl of 1-4 carbon atoms, or acetyl;

R* ¹ is alkyl of 1-4 carbon atoms, haloalkyl of

25 1-2 carbon atoms, CH2CN, CH ₂ SCN, CH(CH ₃ )CN, CH ₂ C0 ₂ CH3, or.CH C0 ₂ CH ₂ CH3;

30

35

R!2 i _s alkyl of 1-4 carbon atoms, allyl, phenyl optionally substituted with 1-2 substituents each of which is independently halogen, CH3, or OCH3, or benzyl optionally substituted with 1-2 substituents each of which is independently halogen, CH3, or OCH3;

R 3 i _s H _j or alkyl of 1-4 carbon atoms; and Rl4 i _s alkyl of 1-4 carbon atoms.

Also provided are pharmaceutical compositions comprising a suitable pharmaceutical carrier and a therapeutically effective amount of a compound of Formula (I) or its pharmaceutically suitable salt and methods of using the compounds of Formula (I) as antifungal agents.

This invention further provides agricultural compositions comprising a compound of Formula (I) or its agriculturally suitable salt together with an agriculturally acceptable diluent or carrier and a method of controlling fungal diseases in plants.

Certain compounds of this invention are useful as herbicides and plant growth regulants. This invention, therefore, also relates to the herbicidal composition of these compounds and their method of use as herbicides.

The herbicidal compounds are those of Formula (I) wherein:

E is a bond; ■- ^is N;

A is perfluoroalkyl of 1-4 carbon atoms, naphthyl optionally substituted with a total of 1-2 substituents each of which is independently selected from halogen and CF3, -N X 5 optionally substituted with 1 or 2 methyl groups, phenyl optionally substituted with a total of 1-3 substituents each of which is independently selected from: halogen, alkyl of 1-3 carbon atoms, 10 haloalkyl of 1-3 carbon atoms, alkoxy of

1-3 carbon atoms, and with no more than one group selected from: haloalkoxy of 1-3 carbon atoms, CN, C0 ₂ R ¹⁴ , CH=N0R ¹⁴ , R ₆ , 2-,3-,or 4- 15 pyridyl, or an N-oxide thereof, imidazol-1-yl, 1,2,4-triazol-l-yl, and -N . optionally substituted with 1 or 2 methyl groups, or a heterocycle selected from imidazol-1-yl, 0 1,2,4-triazol-l-yl, 2-or 3-thienyl, and 2-,3-, or 4-pyridyl, said heterocycles being optionally substituted with one or two substituents each of which is independently selected from: 25 halogen, alkyl of 1-2 carbon atoms, and

CF3;

30

35

B is alkyl of 1-4 carbon atoms, naphthyl, perfluoroalkyl of 1-4 carbon atoms, phenyl optionally substituted with 1-2 substituents each of which is independently selected from: ° halogen, alkyl of 1-3 carbon atoms, haloalkyl of 1-3 carbon atoms, alkoxy of 1-3 carbon atoms, and with no more than one group selected from haloalkoxy of 1-3 carbon atoms, and CN,

10 benzyl optionally substituted on the phenyl ring with halogen or alkyl of 1-3 carbon atoms, or optionally -substituted with 1 or 2 methyl groups, or

15 a heterocycle selected from 2-or 3-thienyl, and 2-,3-,or 4-pyridyl, said heterocycles being optionally substituted with one or two substituents each of which is independently 20 selected from: halogen, alkyl of 1-3 carbon atoms, or CF3;

0 0

²⁵ Q. is H, halogen, S(0) R ¹¹ , SCNHR ¹² , CHO, C-CH,, ffl

13 12

COJt , SCN, SSR , or SH or its corresponding disulfide, provided however that when Q is other than H, then n is 0, R, R^, and R ⁴ are

30 independently H or CH3, R ³ is H, and A and B are each phenyl optionally substituted with from 1-3 substituents each of which is independently halogen, CH3, CF3, or OCH3;

35

n is 0-2 with the proviso that when A is -N X, then n is other than 0; m each occurrence is 0, 1 or 2; X is C, N lO, or 0;

R and R independently are H, alkyl of 1-2 carbon atoms, halogen, or phenyl, or taken together form cycloalkyl of 3-6 carbon atoms;

R ² is H, allyl, propargyl, alkyl of 1-2 carbon atoms, 0 0 0

■ 7 ■ R Q ■ 7

-CR', -C-NRV, -COR', or

haloalkyl of 1-4 carbon atoms;

R and R ⁴ independently are H, F, or alkyl of 1-2 carbon atoms;

Rδ is phenyl optionally substituted with a total of 1-3 substituents each of which is independently selected from halogen and CF3;

R ⁷ is alkyl of 1-2 carbon atoms, phenyl, or benzyl;

R8 and R^ independently are H, alkyl of 1-2 carbon atoms, phenyl or benzyl;

RlO i _s H, alkyl of 1-2 carbon atoms, or acetyl;

R 1 is alkyl of 1-2 carbon atoms, haloalkyl of 1-2 carbon atoms, CH ₂ C.N, CH SCN, CH(CH3)CN, CH ₂ C0 ₂ CH3, or CH2C0 CH ₂ CH3;

Rl ² is alkyl of 1-2 carbon atoms, allyl, phenyl optionally substituted with 1-2 substituents each of which is independently halogen, CH3, or OCH3, or benzyl optionally substituted with 1-2 substituents each of which is independently halogen, CH3, or OCH3; and

Rl3 is H, or alkyl of 1-2 carbon atoms.

Further provided are processes for the preparation of the aforesaid compounds, which processes are described hereinafter.

Additionally provided are novel intermediates having the formulas (II) and (Ha) shown below:

(II) (Ha; where X is Br, Cl, I) wherein A, B, R, R^, R ³ , R ⁴ and n are as defined above, except that R ³ , R ⁴ are not F and not both alkyl.

PREFERRED EMBODIMENTS

Preferred compounds are the α-styryl compounds of formula (I) (E is a bond) where:

1) n = 0, or 1; and/or

2) R ³ and R ⁴ independently are H, CH3, or F.

More preferred compounds are preferred compounds where:

1) A, and B independently are phenyl optionally substituted with from 1-3 substituents each of which is halogen, alkyl of 1-4 carbon atoms, haloalkyl of 1-4 carbon atoms, alkoxy of 1-4 carbon atoms, or S(0) _B R^; and/or

2) n = 0; and/or

3) R and R* independently are H, CH3 or halogen; and/or

4) R = H, alkyl of 1-4 carbon atoms, allyl, or propargyl; and/or

5) Q is H, I, SH.

Most preferred compounds are more preferred compounds where:

1) A and B independently are phenyl optionally substituted with from 1-3 halogen atoms, CH3, OCH3, CF3, or SCH3; and/or; 2) R, Rl, R2, 3, R4 ^ Q ^e all H.

Specifically preferred because of their biological activity are the following compounds or salts thereof:

(a) 2-(4-Fluoropheny1)-3-pheny1-1-(1H-1,2,4- triazol-l-yl)-3-buten-2-ol; and the (S) enantiomer thereof.

(b) 2,3-Bis(4-fluorophenyl)-l-(lH-l,2,4- triazol-l-yl)-3-buten-2-ol; and the (S) enantiomer thereof. (c) 2-(2,4-Dichlorophenyl)-3-(4-chlorophenyl)- l-(lH-l,2,4-triazol-l-yl)-3-buten-2-ol; and the (S) enantiomer thereof.

(d) 2-(4-Chloropheny1)-3-(2-chloropheny1)-1- (lH-l,2,4-triazol-l-yl)-3-buten-2-ol; and the (S) enantiomer thereof.

(e) 2-(2, -Dichlorophenyl)-3-(3-fluorophenyl)- l-(lH-l,2,4-tria»ol-l-yl)-3-buten-2-ol; and the (S) enantiomer thereof.

(f) 2-(2-Chlorophenyl)-3-(2-chloropheny1)-1- (lH-l,2,4-triazol-l-yl)-3-buten-2-ol; and the (S) enantiomer thereof. (g) 2-(2,4-Dichlorophenyl)-3-(3-chlorophenyl)- l-(lH-l,2,4-triazol-l-yl)-3-buten-2-ol; and the (S) enantiomer thereof.

(h) 2-(4-Fluorophenyl)-3-(4-trifluoromethyl- phenyl)-l-(lH-l,2,4-tria*ol-l-yl)-3-buten-2-ol; and the (S) enantiomer thereof.

(i) 2-(2,4-Dichlorophenyl)-3-pheny1-1-(1H- l,2,4-tria*ol-l-yl)-3-buten-2-ol; and the (S) enantiomer thereof.

(j) 2-(3,4-Dichlorophen l)-3-(4- luorophen l)- l-(lH-l,2-4-tria«ol-l-yl)-3-buten-2-ol; and the (S) enantiomer thereof.

(k) 2-(4-Chloropheny1)-3-(3-chlorophenyl)-1- (lH-l,2,4-triazol-l-yl)-3-buten-2-ol; and the (S) enantiomer thereof. (1) 2-(4-Fluorophenyl)-3-(2, -difluorophenyl)-

1-Q.H-l,2,4-triazol-l-yl)-3-buten-2-ol; and the (S) enantiomer thereof.

(m) 2-(2, -Difluorophenyl)-3-(2-chloropheny1)- (lH-l,2,4-triazol-l-yl)-3-buten-2-ol; and the (S) enantiomer thereof.

(n) 2-(2,4-Dichlorophenyl)-3-(2-chlorophenyl)- 1-(1H-1,2,4-triazol-l-yl)-3-buten-2-ol; and the (S) enantiomer thereof.

(o) 2-(2, -Difluorophenyl)-3-phenyl)-1-(1H- imidazol-l-yl)-3-buten-2-ol; and the (S) enantiomer thereof.

(p) 2-(2, -Difluorophenyl)-3-(4-fluorophenyl)- l-(lH-imidazol-l-yl)-3-buten-2-ol; and the (S) enantiomer thereof. (q) 2-(2, -Difluorophenyl)-3-(2-chlorophenyl)- l-(lH-imidazol-l-yl)-3-buten-2-ol; and the (S) enantiomer thereof.

(r) 2-(2, -Difluorophenyl)-3-phenyl-l-(1H- l,2,4-triazol-l-yl)-3-buten-2-ol; and the (S) enantiomer thereof.

(s) 2-(2,4-Difluorophenyl)-3-(4-fluorophenyl)- l-(lH-l,2,4-triazol-l-yl)-3-buten-2-ol; and the (S) enantiomer thereof.

(t) 2-(2-Fluorophenyl)-3-(4-fluorophenyl)-1- (lH-l,2,4-triazol-l-yl)-3-buten-2-ol; and the (S) enantiomer thereof.

(u) 2-(2-Fluorophenyl)-3-(4-chlorophenyl)- l-(lH-l,2,4-triazol-l-yl)-3-buten-2-ol; and the (S) enantiomer thereof. (v) 2-(2,4-Difluorophenyl)-3-(4-chlorophenyl)-

1-(1H-1,2,4-triazol-l-yl)-3-buten-2-ol; and the (S) enantiomer thereof.

(w) 2-(2-Chlorophenyl)-3-(4-fluorophenyl)- l-(lH-l,2,4-triazol-l-yl)-3-buten-2-ol; and the (S) enantiomer thereof.

(x) 2-(4-Chlorophenyl)-3-phenyl-l-(1H-1,2,4- triazol-l-yl)-3-buten-2-ol; and the (S) enantiomer thereof.

All of the compounds within the scope of this invention are active in either pharmaceutical or agricultural fungicidal assays. Thus, it should be recognized that there are compounds which are not always active in both assays as is shown with some compounds in the Examples. Of the above listed specifically preferred compounds, compounds (a)-(r) or their salts are preferred for pharmaceutical uses and compounds (r)-(x) or their salts are preferred for agricultural uses.

Detailed Description of the Invention Synthesis

The novel compounds of Formula (I) can be prepared using the reactions and techniques described in this section. The reactions are usually performed in a solvent appropriate to the reagents and materials employed, and suitable for the transformation being effected. In some cases functional groups on the starting materials may need to be protected by standard protecting groups reported in the chemical literature which are well known to one skilled in the art.

In some cases, substituents on the starting materials may be incompatible with some of the reaction conditions required in some of the methods described. Such restrictions to the substituents which are compatible with the reaction conditions will be readily apparent to one skilled in the art and alternative methods described must then be used. The compounds of the present invention can contain at least one chiral center and as such can exist as two individual isomers or as a racemic mixture of both. This invention relates to the (S) isomer, as well as to racemic mixtures containing both isomers. For the purposes of this invention, the (S)-isomer of compounds of Formula (I) is intended to mean compounds of the configuration depicted:

(la)

When a single chiral center is present the resolution can be performed by reacting the compound with a chiral strong acid (e.g. substituted camphor- sulfonic acids) in a suitable solvent (e.g. aceto- nitrile) or mixture of solvents (e.g. 3/1 ether- acetone) . This reaction is carried out at a temperature between 25 ^β C to 100°C, preferably at the reflux temperature of the solvent(s) employed. The reaction produces two diastereomeric adducts that can be separated by fractional crystallization. The adduct can then be cleaved in basic medium (e.g. sat. NaHCU3, sat. a ₂ Cθ3) to give the resolved product.

The compounds of Formula I, where E is a bond, R ² and are H and R ³ , R ⁴ are not F and not both alkyl, can be prepared by contacting an oxirane of Formula (H) or a halohydrin of Formula (Ha) , or a mixture of (H) or (Ha) with imidazole or triazole or a corresponding alkali metal salt (preferably the Na ⁺ or K ⁺ salt) in a suitable solvent (Scheme I).

Scheme 1

(ID

and/or N-e solvent

A(CH ₂ ,)) (CH ₂ ) _n f c c— > Λ

B X B (Ila) (I)

X = I, Br, Cl; M = H, alkali metal

When imidazole or triazole is used, an acid acceptor, such as potassium carbonate, sodium methoxide or sodium hydride, is added to the reaction mixture. Suitable inert solvents include polar, aprotic solvents such as dimethylformamide (DMF) , dimethylsulfoxide

(DMSO) and ethereal solvents such as tetrahydrofuran (THF) . Non-polar solvents, such as toluene, may be used if a phase transfer catalyst, such as tetrabutylammonium bromide, is added. The reaction is carried out at a temperature in the range of 10° to 150°C, preferably from 50° to 120°C, for a period of 0.25 to 24 hours. It is recognized that varying amounts of the 4H-l,2,4-triazol-4-yl isomers of Formula (I) may be formed when triazole is used in the above reaction. The isomers can be separated, if desired, using standard separation techniques, e.g., chromatography.

The 4H-l,2,4-triazol-4-yl isomers of Formula (I) can be converted to the compounds of Formula (I) by isomerization with base as described in EP 143384A2, or by heating with 2-100 mol % of oxiranes of Formula (II) , halohydrins of Formula (Ha) , reactive alkyl or benzyl bromides or iodides, such as benzyl bromide or methyl iodide, or commercial oxiranes such as styrene oxide, at temperatures of 100-200°C; preferably, in a polar aprotic solvent such as DMF, or a non-polar solvent such as one of the xylenes.

The oxiranes of Formula (II) can be prepared using one or both of the following methods; (Scheme 2) . In the first, vinyl organometallic reagents, e.g., vinyl Grignard reagents, of Formula (III) are allowed

to react with haloketones of Formula (IY) in the presence of ethereal solvents, such as THF or diethyl ether, at a temperature ranging from -90° to 60°C, preferably -10° to 50 ^β C, for 0.5 to 24 hours. Depending on the reaction conditions and the value of X in the haloketone starting material (IV) , the product may be an oxirane (II) , a halohydrin (Ha) or a mixture of (II) and (Ha) . If desired, the halohydrins (Ha) may be converted to oxiranes (II) by treatment with base, e.g., potassium hydride (KH) , in a solvent such as THF.

Scheme 2

(V)

In the second method, keto-oxiranes of formula (Y) are olefinated with, for example, Wittig reagents, which provide epoxy-olefins of Formula (II) .

Unsaturated ketones of Formula (VII) can be converted to expoxy-olefins (II) by treatment with dimethylsulfonium methylide. The enones (VII) can be prepared by treatment of ketones of Formula (VI) with carbonyl compounds and appropriate catalysts (Scheme 3).

Scheme 3

+ -

CRR

RR' C=0 (CH ₃ ) ₂ SCH,

ACCH > _n CH ₂ CB ^> A(CH ₂ ) _n 1C-CB > ⁽ ID o

(VII)

(VI)

Unsaturated ketones of Formula (VIII) can be converted to epoxyketones (V) using basic hydrogen peroxide. Olefination of (Y) , as described above, provides epoxyolefins (II) (Scheme 4) .

Scheme 4

O ^H 2°2 O

(VIII) (V)

The vinyl organometallics of Formula (HI) are prepared using standard procedures from the corresponding chlorides, bromides or iodides. The haloolefins, the haloketones of Formula (TV) , the keto- oxiranes of Formula (V) and the ketones of Formula (VI) are known, or can be prepared using methods known to ^one skilled in the art.

Compounds of Formula (I) can also be prepared by olefination of ketones (DC) with, for example, Wittig reagents (Scheme 5) . Ketones of Formula (DC) where R ² , R ³ and R ⁴ = H are known (EP 117578A) .

Scheme 5

A(

(ix) (i)

Compounds of general Formula (I) where R ³ and/or R ⁴ ≠ H can be made as shown in Scheme 6 by reacting ketones of general Formula (X) with the appropriate organometallic reagent (e.g. Grignard reagent, organolithium reagent). The ketones (X) are prepared by conventional methods from the corresponding a-haloketones (IV) (see e.g. EP 0044605, UK 2099818A, UK 146224, EP 1337718, and EP 0153803) .

Scheme 6

(IV) (X)

X«Br. Cl. I

CRR ^b > (X) + A-(CH _{2 Π} M > (I)

(III)

M»MgX. Li X*C1. Br. I

Compounds of Formula (I) where A=(heterocycle)-phenyl can be prepared from appropriately substituted precursors using the methods described above, or by using substitution reactions on (I) wherein A is halophenyl. For example, compounds of

Formula (I) where A is (pyridyl)phenyl can be prepared by treatment of (I) , wherein A is bromophenyl or iodophenyl, with the appropriate pyridylstannanes in the presence of palladium catalysts (see Tetrahedron Letters, 27, 4407, 1986). Copper assisted displacement of halogen (Tetrahedron, 40, 1433, 1984) with heterocyclic nucleophiles provides compounds of Formula (I) where A is for example 1-imidazolylphenyl.

In some cases, it may be desirable to begin with compounds of Formula I, wherein A is aminophenyl, and construct the heterocyclic ring using X(CH ₂ CH C1) ₂ (see ES 8603-473-A) .

The compounds of Formula (I) where ≠ H and L = N can be prepared as shown in Scheme 7. Metalation of (I), Q=H with strong base provides the 5-metalated triazoles (la) (See Heterocycles, 23, 1645-49, 1985). When R2 is H, 2 equivalents of base are required. Typical conditions involve treatment of a solution of (I) in THF at -70° with n-butyllithium for 15-30 minutes. Where the metalated triazole (la) is less soluble than (I), the addition of co-solvents, such as dimethylpropyleneurea (DMPU) may be beneficial.

Scheme 7

( I )

The treatment of (la) with electrophiles gives a wide variety of (I) where ≠ H. Electrophiles of relevance to the present invention include halogenating agents, sulfur, disulfides, carbon dioxide, di ethyl- amides and sulfur dioxide followed by alkyl halides. Subsequent functionalization, using methods known to one skilled in the art, provide other compounds of Formula (I) wherein ≠ H. For example, the treatment of (I) , where Q is SH with isocyanates or phthalimidosulfides provides thiocarbamates (I;

Q = SCNHR ¹² or disulfides (I; = SSR ¹² ) , respectively.

The compounds of general Formula (I) where E is oxygen can be prepared by oxidation of compounds of general Formula (I) where E is a bond provided that R, JL- ≠ halogen using methods described in the literature (Scheme 8):

Scheme 8

Suitable reagents which can effect this oxidation, depending on the nature of the substituents, include peracids such as m-chloroperbenzoic acid;

hydroperoxides such as tert-butyl hydroperoxide in the presence of an appropriate catalyst such as vanadium acetonylacetonate; or hydrogen peroxide. Alterna¬ tively, the transformation can be effected by first forming the halohydrin with a hypohalous acid such as hypobromous acid and then reacting the intermediate halohydrin with a proton acceptor such as potassium tert-butoxide.

It will be noted by those skilled in the art that, depending on the nature of the compound to be oxidized, a mixture of diastereomers can be obtained. This can be controlled through selection of appropriate oxidation methods or, alternatively, the resulting mixture of diastereomers can be separated in a conventional manner (e.g. chromatography, fractional crystallization) .

Compounds of Formula (I) where R is H can be alkylated, acylated and carbamoylated, using standard procedures, to prepare functional derivatives of the alcohol moiety.

The compounds of this invention and their preparation can be understood further by the following examples, but should not constitute a limitation thereof. In these examples, unless otherwise indicated, all temperatures are in degrees centigrade and parts and percentages are by weight.

Nuclear magnetic resonance (nmr) spectra were obtained in CDCI3 solution, unless otherwise noted. Abbreviations for nmr spectra are s=singlet, d=doublet, t=triplet, q=quartet, m=multiplet; peak positions are reported as parts per million downfield from tetramethylsilane.

Example 1 PART A: 2-(4-Fluorophenyl)-2-[I-(4-fluorophenyl)- ethenyl] oxirane PROCESS 1: Grignard Addition to an α-Haloketone

To a 25° solution of Grignard reagent prepared from 6.0 g (0.030 mol) of l-bromo-4'-fluorostyrene and 0.85 g (0.035 mol) of magnesium turnings in 60 mL of THF was added a solution of 5.2 g (0.030 mol) of 2- chloro^'-fluoroacetophenone in 10 mL of THF. The solution was stirred for 2 hours at 25°. Saturated aqueous NH4CI (10 mL) was added, the aqueous layer was extracted with 1:1 Et 0/hexane and the combined organic layers were washed with brine, dried over gS04 and evaporated to give 10.2 g of an amber oil. Analysis by NMR (CDCI3) indicated that the desired oxirane was the major product: δ 3.1, 3.3 (two d, epoxide protons; 5.5, 5.8 (two s, vinyl protons). The material was of sufficient purity to be used in the next step.

PROCESS 2: Olefination of 2-(4-Fluorophenyl)-2-(4- luorobenzoyl)oxirane

To a suspension of 4.3 g (0.012 mol) of methyltriphenylphosphonium bromide in 15 mL of THF cooled to -70° was added 8.4 mL (0.013 mol) of 1.55 M n-butyllithium over 3 min., keeping the temperature at less than -55° . The resulting yellow suspension was allowed to warm to 0° over 10 min, and was then treated with 2.6 g (0.010 mol) of 2-(4-fluorophenyl)-2-

(4-fluorobenzoyl)oxirane in 5 mL of THF. The light-

brown suspension was stirred for 6 hours at 25°. Standard workup gave 3.4 g of crude product which was flash chromatographed (Et ₂ 0) to give 1.7 g of the desired product, which was of sufficient purity to be used in the next step. NMR (CDCI3) δ 3.1 (d) : 3.3 (d) ; 5.5 (s); 5.8 (s) .

PART B: 2,3-Bis (4-Fluoropheny1)-1-(1H-1,2,4-triazol- l-yl)-3-buten-2-ol

A mixture of 10.2 g (0.040 mol) of crude 2-(4- fluorophenyl)-2-[1-(4-fluorophenyl)ethenyl]oxirane and

7.0 g (0.065 mol) of potassium triazole in 60 mL of DMF was heated at 60° overnight, then cooled and poured into 100 mL of 1:1 Et ₂ 0/hexanes. After washing the organic layer three times with H ₂ 0 and once with brine, a precipitate formed in the organic layer. Filtering gave 4.8 g of a brown solid which was recrystallized from 500 mL of cyclohexane to yield 2.5 g of a light- tan powder, mp 136-137°: NMR (CDCI3) 51.7 (br s, OH); 4.7 (q, 2H); 5.3 (s, IH) ; 5.5 (s, IH) ; 6.8-7.1 (m, 6H) ; 7.4 (m, 2H); 7.8 (s, IH) ; 7.9 (s, IH) ; IR (nujol) 3120 (br), 1900, 1600, 1505, 1220, 1139, 835 cm" ¹ .

The compounds shown in Table 1 were prepared or can be prepared by the method described hereinabove. In the tables, Ph means phenyl and substituted aryl groups are abbreviated, e.g., 4-F-Ph is 4- fluorophenyl, 2,4-Cl -Ph is 2,4-dichlorophenyl and 2- thienyl is thiophen-2-yl.

Table 1

Ex. No. B n R R ¹ R ² R ³ R ⁴ M.P.°C

4-F-Ph 4-F-Ph

2 4-F-Ph 2,4-Cl ₂ -Ph

3 4

5

6

7

8 9

10 11

12 13 14 15 16

17 18

19

20

Table 1 (Continued)

Ex.

No. B n R ¹ R ² R ³ R ⁴ R M.P.'C

21 3-F-Ph n-C ₄ F _g 0 H H H H H

223-F-Ph Ph 0 H H H H H

233-F-Ph 2-F-Ph 0 H H H H H 122-124

243-F-Ph 2-Cl-Ph 0 H H H H H

¹⁰ 254-Cl-Ph 4-F-Ph 0 H H H H H 110-115

264-Cl-Ph 2,4-Cl„-Ph 0 H H H H H 89-91

^Δ (HCl salt

184-190)

274-Cl-Ph 4-Cl-Ph 0 H H H H H 132-135 ₁₅ 284-Cl-Ph 2,4-F ₂ -Ph 0 H H H H H 124-125.5

294-Cl-Ph 4-CF ₃ -Ph 0 H H H H H

304-Cl-Ph n-C ₄ H _g 0 H H H H H

314-Cl-Ph n-C ₄ F _g 0 H H H H H

20322-Cl-Ph 4-F-Ph O H H H H H (oil) ^c

332-Cl-Ph 2,4-Cl ₂ -Ph 0 H H H H H 150-152 (HCl salt 124-127)

342-Cl-Ph 4-Cl-Ph 0 H H H H H 153-154 HN0 ₃ salt 138-141

(HCl salt H ₂ S0 salt 180-182 175-180) H3PO4 salt 158-160

₂₅ 352-Cl-Ph 2,4-F -Ph 0 H H H H H 128-129 H ₂ S0 ₄ salt 184-187

^Δ (HCl salt HNO3 salt 158-159

156-161) H3PO4 salt 141-143

362-Cl-Ph 4-CF ₃ -Ph 0 H H H H H

372-Cl-Ph n-C ₄ H _g 0 H H H H H 30382-Cl-Ph n-C ₄ F _g 0 H H H H H

393-Cl-Ph 4-F-Ph 0 H H H H H 95-96.5

403-Cl-Ph 2,4-Cl ₂ -Ph 0 H H H H H 144-146

41 3-Cl-Ph 4-Cl-Ph 0 H H H H H 112-115 35

Table 1 (Continued)

Table 1 (Continued)

Table 1 (Continued)

Table 1 (Continued)

Ex.

No! A B n R R ¹ R ² R ³ R ⁴ M.P.°C

1144-t-Bu-Ph 4-F-Ph 0 H H H H H 110-113

1154-t-Bu-Ph 2,4-F ₂ -Ph 0 H H H H H

1164-t-Bu-Ph 2-Cl-Ph 0 H H H H H

1174-t-Bu-Ph 4-Cl-Ph 0 H H H H H (oil) ^f

1184-t-Bu-Ph 2,4-Cl ₂ -Ph 0 H H H H H

1192-CH ₃ S-Ph Ph 0 H H H H H

1202-CH ₃ S-Ph 2-F-Ph 0 H H H H H

1212-CH,S-Ph 4-F-Ph 0 H H H H H <5

1222-CH ₃ S-Ph 2,4-F ₂ -Ph 0 H H H H H

1232-CH ₃ S-Ph 2-Cl-Ph 0 H H H H H

1242-CH ₃ S-Ph 4-Cl-Ph 0 H H H H H 1252-CH ₃ S-Ph 2,4-Cl ₂ -Ph 0 H H H H H

1262-CH ₃ S(0)-Ph Ph 0 H H H H H

1272-CH ₃ S(0)-Ph 2-F-Ph 0 H H H H H

1282-CH ₃ S(0)-Ph 4-F-Ph 0 H H H H H 1292-CH ₃ S(0)-Ph 2,4-F ₂ -Ph 0 H H H H H

1302-CH ₃ S(0)-Ph 2-Cl-Ph 0 H H H H H

1312-CH ₃ S(0)-Ph 4-Cl-Ph 0 H H H H H

1322-CH ₃ S(0)-Ph 2,4-Cl ₂ ~Ph 0 H H H H H

1332-CH ₃ S(0) ₂ -Ph Ph 0 H H H H H

1342-CH ₃ S(0) ₂ -Ph 2-F-Ph 0 H H H H H

1352-CH ₃ S(0) ₂ -Ph 4-F-Ph 0 H H H H H

1362-CH.S(0) -Ph 2,4-F _n -Ph 0 H H H H H ^{3 2} ' 2

Table 1 (Continued)

Ex. No. B n R R ¹ R ² R ³ R ⁴ M.P.°C

Table 1 (Continued)

1684-CH ₃ S(0)-Ph Ph 0 H H H H H

1694-CH ₃ S(0)-Ph 2-F-Ph 0 H H H H H

1704-CH ₃ S(0)-Ph 4-F-Ph

1714-CH ₃ S(0)-Ph 2,4-F ₂ ~Ph

1724-CH ₃ S(0)-Ph 2-Cl-Ph

1734-CH ₃ S(0)-Ph 4-Cl-Ph

1744-CH ₃ S(0)-Ph 2,4-Cl ₂ -Ph

1754-CH ₃ S(0) ₂ -Ph Ph

1764-CH ₃ S(0) ₂ -Ph 2-F-Ph

1774-CH ₃ S(0) ₂ -Ph 4-F-Ph

1784-CH ₃ S(0) ₂ -Ph 2,4-F ₂ ~Ph 0 H H H H H

1794-CH ₃ S(0) ₂ -Ph 2-Cl-Ph 0 H H H H H

1804-CH ₃ S(0) ₂ -Ph 4-Cl-Ph 0 H H H H H

1814-CH ₃ S(0) ₂ -Ph 2,4-Cl ₂ -Ph 0 H H H H H

Table 1 (Continued)

Ex. No. B n R R ¹ R ² R ³ R ⁴ M.P.'C

1823- -n-BuS(O)- ^■ Ph 4-F-Ph 0 H H H H H

1833--n-BuS(O)- ^• Ph 2,4-F ₂ -Ph 0 H H H H H

1843- -n-BuS(O)- -Ph 4-Cl-Ph 0 H H H H H

1853--n-BuS(O)- •Ph 2-4-Cl ₂ -Ph 0 H H H H H

1862- -CF ₃ 0-Ph Ph 0 H H H H H

1872- -CF ₃ 0-Ph 2-F-Ph 0 H H H H H

1882- -CF ₃ 0-Ph 4-F-Ph 0 H H H H H

1892- -CF ₃ 0-Ph 2,4-F ₂ -Ph 0 H H H H H

1902- -CF ₃ 0-Ph 2-Cl-Ph 0 H H H H H

1912- -CF ₃ 0-Ph 4-Cl-Ph 0 H H H H H

1922- -CF ₃ 0-Ph 2,4-Cl ₂ -Ph 0 H H H H H

1933- -CF ₃ 0-Ph Ph 0 H H H H H

1943- -CF ₃ 0-Ph 2-F-Ph 0 H H H H H

1953- -CF ₃ 0-Ph 4-F-Ph 0 H H H H H

1963- ^■ CF ₃ 0-Ph 2,4-F ₂ -Ph 0 H H H H H

1973- ^■ CF ₃ 0-Ph 2-Cl-Ph 0 H H H H H

1983- ^■ CF ₃ 0-Ph 4-Cl-Ph 0 H H H H H

1993- ^■ CF ₃ 0-Ph 2,4-Cl ₂ -Ph 0 H H H H H

2004-CF ₃ 0-Ph Ph 0 H H H H H

2014-CF ₃ 0-Ph 2-F-Ph 0 H H H H H

2024-CF ₃ 0-Ph 4-F-Ph 0 H H H H H

2034-CF ₃ 0-Ph 2,4-F ₂ -Ph 0 H H H H H

2044-CF ₃ 0-Ph 2-Cl-Ph 0 H H H H H

Table 1 (Continued)

Table 1 (Continued)

2422,5-Cl ₂ -3-thienyl 2,4-F ₂ ~Ph 0 H H H H H

2432,5-Cl ₂ -3-thienyl 2-Cl-Ph 0 H H" H H H

2442,5-Cl ₂ -3-thienyl 4-Cl-Ph 0 H H H H H 2452,5-Cl ₂ -3-thienyl 2,4-Cl ₂ ~Ph 0 H H H H H

2465-bromo-2-thienyl Ph 0 H H H H H

2475-bromo-2-thienyl 2-F-Ph 0 H H H H H

2485-bromo-2-thienyl 4-F-Ph 0 H H H H H

2495-bromo-2-thienyl 2,4-F„-Ph 0 H H H H H *

2505-bromo-2-thienyl 2-Cl-Ph 0 H H H H H

2515-bromo-2-thienyl 4-Cl-Ph 0 H H H H H

2525-bromo-2-thienyl 2,4-Cl ₂ -Ph 0 H H H H H

2532-pyridyl Ph 0 H H H H H 2542-pyridyl 2-F-Ph 0 H H H H H

2552-pyridyl 2-Cl-Ph 0 H H H H H

2563-pyridyl Ph 0 H H H H H

2573-pyridyl 2-F-Ph 0 H H H H H

2583-pyridyl 2-Cl-Ph 0 H H H H H

Table 1 (Continued)

Ex. No. B n R R ^J R ² R ³ R ⁴ M.P.°C

2594-pyridyl

2604-pyridyl

261 4-pyridyl

262 5-Cl-2-pyridyl

263 5-Cl-2-pyridyl

2645-Cl-2-pyridyl

265 2-Cl-3-pyridyl

2662-Cl-3-pyridyl

2672-Cl-3-pyridyl

2682-Cl-3-pyridyl

269 2-Cl-3-pyridyl

2702-Cl-3-pyridyl

271 2-Cl-3-pyridyl

2723-Cl-2-pyridyl

273 3-Cl-2-pyridyl

2743-Cl-2-pyridyl

275 3-Cl-2-pyridyl

2763-Cl-2-pyridyl

277 3-Cl-2-pyridyl

278 3-Cl-2-pyridyl

279 6-Cl-3-pyridyl

280 6-Cl-3-pyridyl

281 6-Cl-3-pyridyl

282 6-Cl-3-pyridyl

283 6-Cl-3-pyridyl

2846-Cl-3-pyridyl

285 6-Cl-3-pyridyl

Table 1 (Continued)

Table 1 (Continued)

Table 1 (Continued)

Table 1 (Continued)

Ex.

No! A B n R R ¹ R ² R ³ R ⁴ M.P.°C

3594-F-Ph 4-F-Ph 0 H H CH _g H H (oil) ^h

3604-F-Ph 4-F-Ph 0 H H CH ₂ CH=CH ₂ H H (oil) ¹

3614-F-Ph 4-F-Ph 0 H H COCHg H H (oil) ^j

3624-F-Ph 4-F-Ph 0 H H C0 ₂ CH ₃ H H

3634-F-Ph 4-F-Ph 0 H H CONHCHg H H 164-167

3644-F-Ph 4-F-Ph 0 H H CONH-nBu H H

3654-F-Ph 4-F-Ph 0 H H CONHPh H H 3664-F-Ph 4-F-Ph 0 H H CONH- H H

(4-F-Ph)

3674-F-Ph 4-F-Ph ■ 0 H H CON(CH ₃ ) ₂ H H

3682-Cl-Ph 4-Cl-Ph 0 H H CHg H H

3692-Cl-Ph 4-Cl-Ph 0 H H CH ₂ CH=CH ₂ H H

3702-Cl-Ph 4-Cl-Ph 0 H H COCH ₃ H H

3712-Cl-Ph 4-Cl-Ph 0 H H C0 ₂ CH ₃ H H

3722-Cl-Ph 4-Cl-Ph 0 H H CONHCHg H H 3732-Cl-Ph 4-Cl-Ph 0 H H CONH-nBu H H

3742-Cl-Ph 4-Cl-Ph 0 H H CONHPh H H

3752-Cl-Ph 4-Cl-Ph 0 H H CONH- H H

(4-F-Ph)

3762-Cl-Ph 4-Cl-Ph 0 H H C0N(CH ₃ ) ₂ H H 3774-Cl-Ph 2,4-Cl ₂ -Ph O H i Cl _j H H

3784-Cl-Ph 2,4-Cl ₂ -Ph 0 H H CH ₂ CH=CH ₂ H H

3794-Cl-Ph 2,4-Cl ₂ -Ph 0 H H COCH ₃ H H

3804-Cl-Ph 2,4-Cl ₂ -Ph 0 H H C0 ₂ CH ₃ H H 3814-Cl-Ph 2,4-Cl ₂ -Ph 0 H H CONHCH ₃ H H

Table 1 (Continued)

Ex. No! A B n R R ¹ R ² R ³ R ⁴ M.P.°C

3824-Cl-Ph 2,4-Cl ₂ -Ph 0 H H CONH-nBu H H

3834-Cl-Ph 2,4-Cl ₂ -Ph 0 H H CONHPh H H

3844-Cl-Ph 2,4-Cl ₂ -Ph 0 H H CONH(4-F-Ph) H H

3854-Cl-Ph 2,4-Cl ₂ -Ph 0 H H C0N(CH ₃ ) ₂ H H

386 Ph 4-F-Ph 0 H H CHg H H

387 Ph 4-F-Ph 0 H H CH ₂ CH=CH ₂ H H

3964-F-Ph 4-F-Ph 0 H H i-C ₃ H ₇ H H

3974-F-Ph 4-F-Ph 0 H H n-C ₄ H _g H H

3984-F-Ph 4-F-Ph 0 H H COC ₂ H ₅ H H

3994-F-Ph 4-F-Ph 0 H H CO-tC ₄ H _g H H

4004-F-Ph 4-F-Ph 0 H H COPh H H

4014-F-Ph 4-F-Ph 0 H H COCH^h H H

4024-F-Ph 4-F-Ph 0 H H CONH ₂ H H

4034-F-Ph 4-F-Ph 0 H H CONH-iC ₃ H ₇ H H

4044-F-Ph 4-F-Ph 0 H H CONHCHgPh H H

4054-F-Ph 4-F-Ph 0 H H CON(CH ₃ )Ph H H

Table 1 (Continued)

Ex. No. B R R ^J r

4064-F-Ph 4-F-Ph 0 H H CONH(4-Cl-Ph)

4074-F-Ph 4-F-Ph 0 H H C0NH(4-CH ₃ -Ph)

4084-F-Ph 4-F-Ph 0 H H CONH(4-CH ₃ -Ph)

4094-F-Ph 4-F-Ph 0 H H CONH(3-CF ₃ -Ph)

4104-F-Ph 4-F-Ph 0 H H CONH(4-N0 ₂ -Ph)

4114-F-Ph 4-F-Ph 0 H H CONH(2-CH ₃ -Ph)

4124-F-Ph 4-F-Ph 0 H H C0NH(2,4-F ₂ -Ph) 4134-F-Ph 4-F-Ph 0 H H C0NH(2,4-Cl ₂ -Ph) H H

4144-F-Ph 4-F-Ph 0 H H CO^Hg H H

4154-F-Ph 4-F-Ph 0 H H C0 ₂ -nC ₄ H _g H H

4164-F-Ph 4-F-Ph 0 H H C0 ₂ -tC ₄ H _{g 417} 4-F-Ph 4-F-Ph 0 H H CO^gPh

4184-F-Ph 4-F-Ph 0 H H COgPh

4194-F-Ph 4-F-Ph 0 H H CF ₂ H

4204-F-Ph 4-F-Ph 0 H H CH ₂ CF ₃

4214-F-Ph 4-F-Ph 0 H H CH^H^H^

4224-F-Ph 4-F-Ph 0 H H CH ₂ CH ₂ CH ₂ CH ₂ C1

423 Ph 2,4-F ₂ -Ph 0 H H CH ₂ -C≡CH

424 Ph 4-Cl-Ph 0 H H CH -C≡CH ²

4254-F-Ph 2-F-Ph 0 H H CH ₂ -C≡CH

4264-F-Ph 4-F-Ph 0 H H CH ₂ -C≡CH

4274-F-Ph 2,4-F ₂ -Ph 0 H H CH ₂ -C≡CH

4284-F-Ph 2-Cl-Ph 0 H H CH„-C≡CH 2

Table 1 (Continued)

4414-Cl-Ph 2,4-Cl ₂ -Ph 1 H H H

4424-Cl-Ph 2,4-Cl ₂ -Ph 2 H H H

4434-Cl-Ph 2,4-Cl ₂ -Ph 3 H H H

4444-Cl-Ph 2,4-Cl ₂ -Ph 4 H H H

H H (oil) H H 94-100 H H 166-168

H H 115-116

H H (foam)1 H H 140-143

453 (CH ₃ ) ₂ N 2,4-Cl ₂ -Ph 1 H H H H H 104-107

454 (CH ₃ ) ₂ N 4-F-Ph 1 H H H H H (oil) ^m

Table 1 Continued

467 1-imidazoyl 2,4-Cl ₂ -Ph 1 H H H H H

468 1-piperidyl

469 1-piperidyl

470 1-piperidyl

471 1-piperidyl

472 1-piperidyl

473 1-piperidyl

474 1-piperidyl

Table 1 (Continued)

No! A B n R R ¹ R ² R ³ R ⁴ M.P.°C

4752,6-(CH ₃ ) ₂ -l-morpholinyl Ph 1 H H H H H

4762,6-(CH ₃ ) ₂ -l-morpholinyl 2-F-Ph 1 H H H H H

4772,6-(CH ₃ ) ₂ -l-morpholinyl 4-F-Ph 1 H H H H H 97-99

478 2,6-(CH ₃ ) ₂ -l-morpholinyl 2,4-F ₂ ~Ph 1 H H H H H

479 2,6-(CH ₃ ) ₂ -l-morpholinyl 2-CI-Ph 1 H H H H H

4802,6-(CH ₃ ) ₂ -l-morpholinyl 4-Cl-Ph 1 H H H H H

481 2,6-(CH ₃ ) ₂ -l-morpholinyl 2,4-Cl ₂ -Ph 1 H H H H H

4824-CH ₃ -l-piperazinyl Ph 1 H H H H H

4834-CH ₃ -l-piperazinyl 2-F-Ph 1 H H H H H

4844-CH ₃ -l-piperazinyl 4-F-Ph 1 H H H H H

4854-CH ₃ -l-piperazinyl 2,4-F ₂ ~Ph 1 H H H H H

4864-CH ₃ -l-piperazinyl 2-Cl-Ph 1 H H H H H

4874-CH ₃ -l-piperazinyl 4-Cl-Ph 1 H H H H H

4884-CH ₃ -l-piperazinyl 2,4-Cl,-,-Ph 1 H H H H H 489 4-n-Bu-l-piperazinyl Ph 1 H H H H H

4904-n-Bu-l-piperazinyl 2-F-Ph 1 H H H H H

4914-n-Bu-l-piperazinyl 4-F-Ph 1 H H H H H

4924-n-Bu-l-piperazinyl 2,4-F ₂ -Ph 1 H H H H H

4934-n-Bu-l-piperazinyl 2-Cl-Ph 1 H H H H H 4944-n-Bu-l-piperazinyl 4-Cl-Ph 1 H H H H H

4954-n-Bu-l-piperazinyl 2,4-Cl ₂ -Ph 1 H H H H H

496 4-acetyl-l-piperazinyl Ph 1 H H H H H

4974-acetyl-l-piperazinyl 2-F-Ph 1 H H H H H

498 4-acetyl-l-piperazinyl 4-F-Ph 1 H H H H H ₄ gg 4-acetyl-l-piperazinyl 2,4-F ₂ ~Ph 1 H H H H H

Table 1 (Continued)

Ex

No. B n R R ¹ R ² R ³ R ⁴ M.P. 'C

5004-acetyl-l-piperazinyl 2-Cl-Ph 1 H H H H H

5014-acetyl-l-piperazinyl 4-Cl-Ph 1 H H H H H

5024-acetyl-l-piperazinyl 2,4-Cl ₂ -Ph 1 H H H H H

¹⁰ 5032-(2-pyridyl)-Ph 4-F-Ph OH H H H H

5042-(3-pyridyl)-Ph 4-F-Ph 0 H H H H H

5052-(4-pyridyl)-Ph 4-F-Ph 0 H H H H H

5063-(2-pyridyl)-Ph 4-F-Ph 0 H H H H H

5073-(3-pyridyl)-Ph 4-F-Ph 0 H H H H H ¹⁵ 5083-(4-pyridyl)-Ph 4-F-Ph 0 H H H H H

5094-(2-pyridyl)-Ph 4-F-Ph 0 H H H H H

5104-(3-pyridyl)-Ph 4-F-Ph 0 H H H H H

5114-(4-pyridyl)-Ph 4-F-Ph 0 H H H H H

5122-(lH-l,2,4-triazol-l-yl)-Ph 4-F-Ph 0 H H H H H ²⁰ 5133-(1H-1,2,4-triazol-l-yl)-Ph 4-F-Ph 0 H H H H H

5144-(lH-l,2,4-triazol-l-yl)-Ph 4-F-Ph 0 H H H H H

5152-(imidazol-l-yl)-Ph 4-F-Ph 0 H H H H H

5163-(imidazol-l-yl)-Ph 4-F-Ph 0 H H H H H

5174-(imidazol-l-yl)-Ph 4-F-Ph 0 H H H H H ²⁵ 5182-(4-methylpiperazin-l-yl)-Ph 4-F-Ph 0 H H H H H

5193-(4-methylpiperazin-l-yl)-Ph 4-F-Ph 0 H H H H H

5204-(4-methylpiperazin-l-yl)-Ph 4-F-Ph 0 H H H H H

5212-(4-acetylpiperazin-l-yl)-Ph 4-F-Ph 0 H H H H H

5223-(4-acetylpiperazin-l-yl)-Ph 4-F-Ph 0 H H H H H ³⁰ 5234-(4-acetylpiperazin-l-yl)-Ph 4-F-Ph 0 H H H H H

5242-(2-pyridyl)-Ph 2,4-F ₂ ~Ph 0 H H H H H

5252-(3-pyridyl)-Ph 2,4-F ₂ -Ph 0 H H H H H

35

Table 1 (Continued)

Table 1 (Continued)

Ex. No. B n R R ¹ R ² R ³ R ⁴ M.P.°

549 3-(2-pyridyl)-Ph

5503-(3-pyridyl)-Ph

551 3-(4-pyridyl)-Ph

5524-(2-pyridyl)-Ph ₁₀ 5534-(3-pyridyl)-Ph

5544-(4-pyridyl)-Ph

555 2-(1H-1,2,4-triazol-l-yl)

556 3-(1H-1,2,4-triazol-l-yl)

5574-(1H-1,2,4-triazol-l-yl) 15 5582-(imidazol-l-yl)-Ph

559 3-(imidazol-1-y1)-Ph

5604-(imidazol-l-yl)-Ph

561 2-(4-methylpiperazin-l-yl

5623-(4-methylpiperazin-l-yl) 20 5634-(4-methylpiperazin-l-yl)

5642-(4-acetylpiperazin-l-yl)

565 3-(4-acetylpiperazin-l-yl)

5664-(4-acetylpiperazin-l-yl)

567 2-C1-3-(3-pyridyl)-Ph 25 5682-(2-pyridyl)-Ph

569 2-(3-pyridyl)-Ph

5702-(4-pyridyl)-Ph

571 3-(2-pyridyl)-Ph

30 5723-(3-pyridyl)-Ph

573 3-(4-pyridyl)-Ph

5744-(2-pyridyl)-Ph

575 4-(3-pyridyl)-Ph

5764-(4-pyridyl)-Ph 5

Table 1 (Continued)

Table 1 (Continued)

Ex. No. B n R R ¹ R ² R ³ R ⁴ M.P.°C

4-I-Ph 0 H H H H H 3,4-F ₂ -Ph 0 H H H H H

3,4-Cl ₂ -Ph 0 H H H H H

2,6-Cl ₂ -Ph 0 H H H H H

3,5-Cl ₂ -Ph 0 H H H H H 142-144

2-Cl-(4-F)-Ph 0 H H H H H 3-Cl-(4-F)-Ph 0 H H H H H 119-124

(dec.)

606 Ph 2,4,6-Cl ₃ -Ph 0 H H H H H

Table 1 (Continued)

Table 1 (Continued)

Ex.

No. B R ^x R R M.P.°C

6504-F-Ph 3,4-F ₂ -Ph H H H

6514-F-Ph 3,4-Cl ₂ -Ph H H H 98-99

6524-F-Ph 2,6-Cl ₂ -Ph H H H

6534-F-Ph 2-Cl-(4-F)-Ph H H H 128-130

6544-F-Ph 2,4,6-Cl ₃ -Ph H H H

6554-F-Ph 2-F-(4-Cl)-Ph H

6564-F-Ph Ph H 124-125

6574-F-Ph 4-Ph-Ph H 116-119

6584-F-Ph 4-CH ₃ -Ph H 145-147

6594-F-Ph 2-CH ₃ -Ph H 145-149

6604-F-Ph 2-CF ₃ -Ph H H H

6614-F-Ph 3-CF ₃ -Ph 0 H H H H H 121-122

6624-F-Ph 2-F-(4-CF ₃ )-Ph H

6634-F-Ph 4-CH ₃ 0-Ph H 112-114

6644-F-Ph 5-Cl-2-pyridyl H

6654-F-Ph 5-Cl-2-thienyl H 114-115

6664-F-Ph 2-Cl-3-thienyl H H

6674-F-Ph 0 H H H H H 74-75 i- ^C 3 ^H 7

6684-F-Ph 0 H H H H H

^C 2 ^H 5 (oil) ^q

6694-Cl-Ph 2-F-Ph 0 H H H H H 130-131

6704-Cl-Ph 3-F-Ph 0 H H H H H

6714-Cl-Ph 2-Cl-Ph 0 H H H H H 137-139

6724-Cl-Ph 3-Cl-Ph 0 H H H H H

6734-Cl-Ph 4-Br-Ph 0 H H H H H 121-123

6744-Cl-Ph 4-I-Ph 0 H H H H H

Table 1 (Continued)

Table 1 (Continued)

Table 1 (Continued)

Table 1 (Continued)

Ex. No. B n R R ¹ R ² R ³ R ⁴ M.P.°C

7463,4-Cl ₂ -Ph 2,4-Cl ₂ -Ph 0 H H H H H

7472,6-Cl ₂ -Ph 2,4-Cl ₂ -Ph 0 H H H H H

7482-Cl-(4-F)-Ph 2,4-Cl ₂ -Ph 0 H H H H H

7492,4,6-Cl ₃ -Ph 2,4-Cl ₂ -Ph 0 H H H H H

7504-CH ₃ -Ph 2,4-Cl ₂ -Ph 0 H H H H H

751 3-CH ₃ -Ph 2,4-Cl ₂ -Ph 0 H H H H H

7522-CH ₃ -Ph 2,4-Cl ₂ -Ph 0 H H H H H

7532-CF ₃ -Ph 2,4-Cl ₂ -Ph 0 H H H H H 133-137

7543-CF ₃ -Ph 2,4-Cl ₂ -Ph 0 H H H H H 77-84

7554-CH ₃ 0-Ph 2,4-Cl ₂ -Ph 0 H H H H H

7562,3-Cl ₂ -Ph 2,4-Cl ₂ -Ph 0 H H H H H

7573,5-Cl ₂ -Ph 2,4-Cl ₂ -Ph 0 H H H H H

7582,5-Cl ₂ -Ph 2,4-Cl ₂ -Ph 0 H H H H H

7593-Br-Ph 2,4-Cl ₂ -Ph 0 H H H H H 171-173

7604-EtO-Ph 2,4-Cl ₂ -Ph 0 H H H H H

761 2,4-(CH ₃ ) ₂ -Ph 2,4-Cl ₂ -Ph 0 H H H H H

7622,4,6-(CH ₃ ) ₃ -Ph 2,4-Cl ₂ -Ph 0 H H H H H

7634-Ph-Ph 2,4-Cl ₂ -Ph 0 H H H H H

7645-Cl-2-thienyl 2,4-Cl ₂ -Ph 0 H H H H H

7652-Cl-3-thienyl 2,4-Cl ₂ -Ph 0 H H H H H

766 1-imidazoyl 2,4-Cl ₂ -Ph 0 H H H H H

Table 1 (Continued)

Ex

No. B n R R ¹ R ² R ³ R ⁴ M.P.'C

767 lH-l,2,4-triazoyl-l-yl 2,4-Cl ₂ -Ph 0 H H H H H

7682-pyridyl 2,4-Cl ₂ -Ph 0 H H H H H

7695-Cl-pyrid-2-yl 2,4-Cl ₂ -Ph 0 H H H H H 10 7703-pyridyl 2,4-Cl ₂ -Ph 0 H H H H H

7714-pyridyl 2,4-Cl ₂ ~Ph 0 H H H H H

772 n-C ₄ F _g 2,4-Cl ₂ ~Ph 0 H H H H H

7734-I-Ph 4-Cl-Ph 0 H H H H H ¹⁵ 7743,4-F ₂ -Ph 4-Cl-Ph 0 H H H H H

7753,4-Cl ₂ -Ph 4-Cl-Ph 0 H H H H H

7762,6-Cl ₂ -Ph 4-Cl-Ph 0 H H H H H

7772-Cl-(4-F)-Ph 4-Cl-Ph 0 H H H H H 207782,4,6-Cl ₃ -Ph 4-Cl-Ph 0 H H H H H

7794-CH ₃ -Ph 4-Cl-Ph 0 H H H H H

7803-CH ₃ -Ph 4-Cl-Ph 0 H H H H H

7812-CH ₃ -Ph 4-Cl-Ph 0 H H H H H

25

7822-CF ₃ -Ph 4-Cl-Ph 0 H H H H H 43-49

7833-CF ₃ -Ph 4-Cl-Ph 0 H H H H H 109-112

7844-CH ₃ 0-Ph 4-Cl-Ph 0 H H H H H 111-113

7852,3-Cl ₀ -Ph 4-Cl-Ph 0 H H H H H 30 2

7863,5-Cl ₂ -Ph 4-Cl-Ph 0 H H H H H

7872,5-Cl ₂ -Ph 4-Cl-Ph 0 H H H H H

7883-Br-Ph 4-Cl-Ph 0 H H H H H 119-121

7894-EtO-Ph 4-Cl-Ph 0 H H H H H 35

Table 1 (Continued)

Table 1 (Continued)

Ex. No. B n R R ¹ R ² R ³ R ⁴ M.P.°C

8142,3-Cl ₂ -Ph 2,4-F ₂ -Ph 0 H H H H H

8153,5-Cl ₂ -Ph 2 0 H H H H H 173-175

8162,5-Cl ₂ -Ph 2 0 H H H H H

8173-Br-Ph 2 0 H H H H H 103-107

8184-EtO-Ph 2 0 H H H H H

8192,4-(CH ₃ ) ₂ -Ph 2 0 H H H H H

8202,4,6-(CH ₃ ) ₃ -Ph 2 0 H H H H H

8214-Ph-Ph 2 0 H H H H H

8225-Cl-2-thienyl 2 0 H H H H H

8232-Cl-3-thienyl 2 0 H H H H H

8241-imidazoyl 2 0 H H H H H

825 lH-l,2,4-triazoyl-1-yl 2 0 H H H H H

8262-pyridyl 2 0 H H H H H

8275-Cl-pyrid-2-yl 2 0 H H H H H

8283-pyridyl 2 0 H H H H H

8294-pyridyl 2 0 H H H H H

830 £-C ₄ F _g 2 0 H H H H H

8312-F-Ph 4-Br-Ph 0 H H H H H

8323-F-Ph 4-Br-Ph 0 H H H H H

8333-Cl-Ph 4-Br-Ph 0 H H H H H

8344-Br-Ph 4-Br-Ph 0 H H H H H

8352,4-F ₂ -Ph 4-Br-Ph 0 H H H H H

8362,4-Cl ₂ -Ph 4-Br-Ph 0 H H H H H

Table 1 (Continued)

Table 1 (Continued)

Ex. No. B n R R ¹ R ² R ³ R ⁴ M.P.°C

861 3-(2,4-F ₂ -Ph)-Ph 2,4-Cl ₂ -Ph 0 H H H H H

862 2,4-F ₂ -Ph 4-CH ₃ -Ph 0 H H H H H

863 4-CH ₃ -Ph 4-CH ₃ -Ph 0 H H H H H 178-181.5 864 2-CF ₃ -Ph 4-CH ₃ -Ph 0 H H H H H

865 3-CF ₃ -Ph 4-CH ₃ -Ph 0 H H H H H

866 4-CF ₃ -Ph 4-CH ₃ -Ph 0 H H H H H

867 2-F-Ph 4-CH ₃ 0-Ph 0 H H H H H 868 3-F-Ph 4-CH ₃ 0-Ph 0 H H H H H

869 3-Cl-Ph 4-CH ₃ 0-Ph 0 H H H H H

870 4rBr-Ph 4-CH ₃ 0-Ph 0 H H H H H

871 2,4-F ₂ -Ph 4-CH ₃ 0-Ph 0 H H H H H

872 2,4-Cl ₂ -Ph 4-CH ₃ 0-Ph 0 H H H H H

873 2-CF ₃ -Ph 4- CHgO-: Ph 0 H H H H H

874 3-CF ₃ -Ph 4-CH ₃ 0-Ph 0 H H H H H

875 4-CF,-Ph 4-CH ₃ 0-Ph 0 H H H H H ³

876 Ph 2-CH ₃ 0-Ph 0 H H H H H

877 2-F-Ph 2-CH ₃ 0-Ph 0 H H H H H

878 3-F-Ph 2-CH ₃ 0-Ph 0 H H H H H

879 4-F-Ph 2-CH ₃ 0-Ph 0 H H H H H 56-70

(138-139.5

•H ₂ C ₂ 0 ₄ )

880 2,4-F ₂ -Ph 2-CH ₃ 0-Ph 0 H H H H H

881 2-Cl-Ph 2-CH ₃ 0-Ph 0 H H H H H

Table 1 (Continued)

Table 1 (Continued)

Ex. No. B n R R ¹ R ² R ³ R ⁴ M.P.°C

904 2,4-F ₂ -Ph 3,4-Cl ₂ -Ph 0 H H H H H 905 3-Cl-Ph 0 H H H H H 110-111 906 2,4-Cl ₂ -Ph 0 H H H H H 907 4-Br-Ph 0 H H H H H 908 2-CF ₃ -Ph 0 H H H H H 909 3-CF ₃ -Ph 0 H H H H H 910 4-CF ₃ -Ph 0 H H H H H 911 Ph 0 H H H H H 912 2-F-Ph 0 H H H H H 913 3-F-Ph 0 H H H H H 914 4-F-Ph 0 H H H H H 915 2,4-F ₂ -Ph 0 H H H H H 916 2-Cl-Ph 0 H H H H H 917 3-Cl-Ph 0 H H H H H 918 4-Cl-Ph 0 H H H H H 919 2,4-Cl ₂ -Ph 0 H H H H H 920 4-Br-Ph 0 H H H H H 921 2-CF ₃ -Ph 0 H H H H H 922 3-CF ₃ -Ph 0 H H H H H 923 4-CF ₃ -Ph 0 H H H H H 924 Ph 0 H H H H H 925 2-F-Ph 0 H H H H H 926 3-F-Ph 0 H H H H H

Table 1 (Continued)

Table 1 (Continued)

Table 1 (Continued)

Table 1 (Continued)

Ex. No. B n R R ¹ R ² R ³ R ⁴ M.P.°C

10003-F-Ph PhCH ₂ - 0 H H H H H

10014-F-Ph PhCH ₂ - 0 H H H H H

10022,4-F ₂ -Ph PhCH ₂ - 0 H H H H H

10032-Cl-Ph PhCH ₂ - 0 H H H H H

10043-Cl-Ph PhCH ₂ - 0 H H H H H

10054-Cl-Ph PhCH ₂ - 0 H H H H H

10062,4-Cl ₂ -Ph PhCH ₂ - 0 H H H H H

10074-Br-Ph PhCH ₂ - 0 H H H H H

10082-CF ₃ -Ph PhCH ₂ - 0 H H H H H

10093-CF ₃ -Ph PhCH ₂ - 0 H H H H H

10104-CF ₃ -Ph PhCH ₂ - 0 H H H H H

1011 Ph PhCH(CH ₃ ) 0 H H H H H

10122-F-Ph PhCH(CH ₃ ) 0 H H H H H

10133-F-Ph PhCH(CH ₃ ) 0 H H H H H

10144-F-Ph PhCH(CH ₃ ) 0 H H H H H

10152,4-F ₂ -Ph PhCH(CH ₃ ) 0 H H H H H

10162-Cl-Ph PhCH(CH ₃ ) 0 H H H H H

10173-Cl-Ph PhCH(CH ₃ ) 0 H H H H H

10184-Cl-Ph PhCH(CH ₃ ) 0 H H H H H

10192,4-Cl ₂ -Ph PhCH(CH ₃ ) 0 H H H H H

10204-Br-Ph PhCH(CH ₃ ) 0 H H H H H

10212-CF ₃ -Ph PhCH(CH ₃ ) 0 H H H H H

Table 1 (Continued)

Table 1 (Continued)

Table 1 (Continued)

Table 1 (Continued)

35

Table 1 (Continued)

Table 1 (Continued)

Ex. No. B R R ^J R ² R ³ R ⁴ M.P.°C

11433-CF ₃ -Ph 3-pyridyl

11444-CF ₃ -Ph 3-pyridyl

1145 Ph 4-pyridyl

11462-F-Ph 4-pyridyl ^w '

11473-F-Ph 4-pyridyl

11482,4-F ₂ -Ph 4-pyridyl

11492-Cl-Ph 4-pyridyl

11503-Cl-Ph 4-pyridyl 11514-Cl-Ph 4-pyridyl

11522,4-Cl ₂ -Ph 4-pyridyl

11534-Br-Ph 4-pyridyl

11542-CF ₃ -Ph 4-pyridyl

11553-CF ₃ -Ph 4-pyridyl

11564-CF ₃ -Ph 4-pyridyl

1157 Ph 2-Cl-3-pyridyl

11582-F-Ph 2-Cl-3-pyridyl

11593-F-Ph 2-Cl-3-pyridyl 11604-F-Ph 2-Cl-3-pyridyl

11612,4-F ₂ -Ph 2-Cl-3-pyridyl

11622-Cl-Ph 2-Cl-3-pyridyl

11633-Cl-Ph 2-Cl-3-pyridyl

11644-Cl-Ph 2-Cl-3-pyridyl

11652,4-Cl ₂ -Ph 2-Cl-3-pyridyl

11664-Br-Ph 2-Cl-3-pyridyl

11672-CF ₃ -Ph 2-Cl-3-pyridyl

11683-CF ₃ -Ph 2-Cl-3-pyridyl

Table 1 (Continued)

11694-CF,-Ph 2-Cl-3-pyridyl 0 H H H H H

1170 Ph 3-Cl-2-pyridyl 0 H H H H H

1171 2-F-Ph 3-Cl-2-pyridyl 0 H H H H H

11723-F-Ph 3-Cl-2-pyridyl 0 H H H H H 11734-F-Ph 3-Cl-2-pyridyl 0 H H H H H

11742,4-F ₂ -Ph 3-Cl-2-pyridyl 0 H H H H H

11752-Cl-Ph 3-Cl-2-pyridyl 0 H H H H H

11763-Cl-Ph 3-Cl-2-pyridyl 0 H H H H H 11774-Cl-Ph 3-Cl-2-pyridyl 0 H H H H H

11782,4-Cl ₂ -Ph 3-Cl-2-pyridyl 0 H H H H H

11794-Br-Ph 3-Cl-2-pyridyl 0 H H H H H

11802-CF,-Ph 3-Cl-2-pyridyl 0 H H H H H w

11813-CF,-Ph 3-Cl-2-pyridyl 0 H H H H H ³

11824-CF,-Ph 3-Cl-2-pyridyl 0 H H H H H

11832-F-Ph 5-Cl-2-pyridyl 0 H H H H H

11843-F-Ph 5-Cl-2-pyridyl 0 H H H H H

11852,4-F -Ph 5-Cl-2-pyridyl 0 H H H H H 11863-Cl-Ph 5-Cl-2-pyridyl 0 H H H H H

11872,4-Cl ₂ -Ph 5-Cl-2-pyridyl 0 H H H H H

11884-Br-Ph 5-Cl-2-pyridyl 0 H H H H H

11892-CF,-Ph 5-Cl-2-pyridyl 0 H H H H H 11903-CF ₃ -Ph 5-Cl-2-pyridyl 0 H H H H H

11914-CF ₃ -Ph 5-Cl-2-pyridyl 0 H H H H H

3

1192 Ph 6-Cl-3-pyridyl 0 H H H H H

Table 1 (Continued)

Table 1 (Continued)

Table 1 (Continued)

Table 1 (Continued)

Table 1 (Continued)

Ex. No. B n R R ¹ R ² R ³ R ⁴ M.P.°C

20152-Cl-4-pyridyl 4-Cl-Ph 0 H H H H H (2HC1 salt 170-175)

20162-CH ₃ -Ph 2-Cl-4-F-Ph 0 H H H H H

a NMR: (CDC1 ₃ ) δ 4.70 (q, J=14Hz, 2H) , 4.90 (s, IH), 5.40 (s, IH), 5.55 (s, IH), 6.8-7.0 (m, 4H) , 7.2-7.4 (m, 4H), 7.8 (bs, 2H) .

NMR: (CDCI3) δ 4.8 (q, 2H) , 5.2 (s, IH), 5.3 (s,lH), 5.6 (s, IH), 6.9-7.6 (m, 8H) , 7.8 (s, IH), 8.1 (s, IH).

c NMR: (CDCI3) δ 4.70 (q, J=13Hz, 2H) , 4.85 (s, IH), 5.35 (s, IH), 5.55 (s, IH), 6.85-7.4 (m, 8H), 7.7 (s, H), 7.9 (s, IH).

d NMR: (CDCI3) δ 4.60 (q, J=12Hz, 2H) , 5.0 (s, IH), 5.40 (s, IH), 5.55 (s, IH) , 6.8 (1/2 of ABq, J=10Hz, 2H), 7.00 (m, 2H), 7.3 (1/2 of ABq, J=10Hz, 2H), 7.45 (m, 2H) , 7.80 (s, IH), 7.85 (s, IH).

e NMR: (CDCI3) δ 4.6, 4.8 (ABq, J=l4Hz, 2H) , 4.9 (br s, 3H), 5.3 (s, IH) , 5.6 (s, IH) , 6.8 (d, IH), 7.0 (m, 3H), 7.4 (m, 3H) , 7.8 (s, IH) , 7.9 (s, IH).

f NMR: (CDCI3) δ 1.3 (s, 9H) , 4.7 (q, 2H) , 4.6 (s, IH), 5.0 (s, IH), 5.4 (s, IH) , 6.8-7.4 (9H) , 7.8 (s, IH).

g NMR: (CDCI3) 5 4.7, 4.8 (ABq, J=12Hz, 2H) , 6.7- 7.5 (m, 14H) , 7.9 (s, IH) , 8.0 (s, IH) .

h NMR: (CDCI3) δ 3.45 (s, 3H) , 4.75 (ABq, J=18Hz , 5 14Hz, 2H) , 4.6 (m, 2H) , 6.8-7.0 ( , 4H) , 7.05-

7.25 (m, 4H) , 8.0 (s, IH) , 8.25 (s, IH) .

i NMR: (CDCI3) δ 4.0 (dd, 14, 4flz, IH) , 4.3 (dd, 14, 4Hz, IH), 4.6 (d, 13Hz, IH) , 4.9 (d, 13Hz, ₁₀ IH), 5.1 (d, IH), 5.3 (d, IH) , 5.55 (s, IH) , 5.60

(s, IH), 5.85 (m, IH) , 6.8-7.0 (m, 4H) , 7.05-7.2 (m, 4H), 8.05 (s, IH) , 8.25 (s, IH) .

j NMR: (CDCI3) δ 1.90 (s, 3H), 4.80 (1/2 of ABq, 15 J=l4Hz, IH), 5.65 (1/2 of ABq, J=l4flz, IH), 5.55

(s, IH), 5.60 (s, IH), 6.75-7.0 (m, 4H), 7.0-7.2 (t, 2H), 7.25-7.4 (m, 2H), 7.35 (s, IH), 7.85 (s, IH).

₂₀ NMR: (CDCI3) 54.03, 4.11 (ABq, J=llHz, 2H) , 4.25 (s, IH, OH), 4.39 (s, IH, OH), 4.54, 4.81 (ABq, J=14Hz, 2H), 5.31, 5.33 (2 sharp s, IH each), 7.25-7.40 (m, 4H) , 7.71 (s, IH) , 8.03 (s, IH).

25

NMR: (CDCI3) δ 2.03 (s, IH, OH), 4.0-4.2 (m, 2H), 4.57, 4.85 (ABq, J=15Hz, 2H) , 5.3-5.35 (m, 2H), 5.7-5.9 (broad s, IH, OH), 7.3-7.6 (m. 4H) , 7.75 (s, IH), 8.11 (s, IH) .

30 m NMR: (CDCI3) δ 2.10 (s, 6H) , 2.52, 3.03 (ABq, J=12Hz, 2H), 4.41, 4.78 (ABq, J=15 Hz, 2H) , 5.19 (s, IH), 5.50 (s, IH), 6.9-7.2 (m, 2H) , 7.4-7.6 (m, 2H), 7.80 (s, IH) , 8.36 (s, IH) .

35

n NMR: (CDC1 ₃ ) δ 2.11 (s, 6H) , 2.61, 3.11 (ABq, J=12Hz, 2H), 4.50, 4.90 (ABq, J=13Hz, 2H) , 5.13 (s, IH), 5.50 (s, IH), 7.50 (s, 4H) , 7.86 (s, IH), 8.14 (s, IH).

o NMR: (CDCI3) 52.13 (s, 3H) , 2.19 (s, 3H) , 2.5-

3.1 (m, 2H), 4.44, 4.85 (ABq, J=14Hz, 2H) , 5.0-

5.5 (m, 2H), 7.3-7.8 (m, 9H) , 7.97 (s, IH) , 8.32 (s, IH, OH), 8.50 (s, IH).

10 p NMR: (CDCI3) δ 4.6 (d, 1/2 of ABq, IH) , 4.9 (d, 1/2 of ABq, IH), 5.0 (s, IH) , 5.3 (two s, 2H) , 6.9-7.6 (m, 9H), 7.8 (two s, 2H) .

15 N MMRR:: (CDCI3) 61.0 (t, 3H), 1.2 (s, IH) , 1.6 (m,

2 !HH)), 4.2 (ABq, 2H) , 5.1 (s, IH) , 5.4 (s, IH) ,

65.9-7.1 (m, 4H), 7.9 (s, IH) , 8.0 (s, IH) .

r NMR: (CDCI3) δ 4.6 (AB, 2H) , 4.6 (d, IH) , 5.3 ₂₀ (s, IH), 5.5 (s, IH), 7.2 (m, IH) , 7.6 (m, 7H) ,

7.7 (m, IH), 7.7 (s, IH) , 7.8 (s, IH) .

NMR: (CDCI3) δ 4.6 (1/2 of AB, J=13, IH) , 5.0 (1/2 of AB, J=13, IH), 5.2 (s, IH) , 5.3 (s, IH) ,

25 5.4 (s, IH), 7.0 (m, 2H) , 7.2 (m, IH) , 7.4 (m, 5H), 7.8 (s, IH), 7.82 (s, IH) .

t NMR: (CDCI3) δ 4.6 (1/2 of ABq, IH) , 5.3 (s) ,

5.4 (1/2 of ABq + s + br, 4H total), 7.1 (m, IH) , 30 7.3 (m, IH), 7.5 (m, 5H) , 7.8 (s, 2H) .

u NMR: (CDCI3) δ 4.4 (1/2 of AB, IH) , 5.7 (1/2 of AB, IH), 5.1 (s, IH), 5.3 (s, IH) , 5.4 (s, IH) , 7.2 ( , 3H), 7.3 (m, 2H) , 7.4 (d, IH) , 7.6 (m, 35 IH), 7.7 (s, IH), 7.9 (s, IH) .

v NMR: (CDCI3) δ 4.4 (s, 2H) , 4.8 (s, IH) 5.1 (s, IH), 5.5 (s, IH), 6.3 (d, IH) 6.5 (d, IH) 6.8-7.2 (m, 4fl), 7.6 (s, IH), 7.7 (s, IH) .

5 w NMR: (CDC 3) ^{δ 4} - ⁷ ( ^dd _» 2H), 5.4 (s, IH) , 5.6

(s, IH), 6.7 (d, IH), 7.0 (d, IH) , 7.2 ( ) , 8.0 (s, IH), 8.2 (s, IH).

x NMR: (CDCI3) ^δ 1- ^β ft*© ^s » ^6H total), 4.3 (1/2 ₁₀ of ABq, IH), 4.6 (1/2 of ABq, IH) , 5.0 (d, IH) ,

5.2 (d, IH), 5.3 (s, IH), 6.7-7.6 (m, 8H) , 7.9 (s, IH), 8.1 (s, IH).

<-» y NMR: (CDCI3) δ 4.7 (s, 2H) , 5.3 (s, IH) , 5.8 (s, ₁₅ IH), 6.9 (m, 3H) , 7.1 (m, IH) , 7.2 (m, IH) , 7.4

(s, IH), 7.9 (s, IH), 8.1 (s, IH) .

.8 NMR: (CDCI3) 64.6 (dd, 2H) , 5.2 (s, IH) , 5.4 (s, IH), 5.6 (s, IH), 6.7 (d, IH) , 6.8 (d, IH) , ₂₀ 7.4-7.6 (m, 4H), 7.9 (s, IH) , 7.9 (s, IH) .

aa NMR: (CDCI3) δ 4.6 (d, IH) , 5.0 (d, IH) , 5.2 (s, IH), 5.34 (s, IH), 5.4 (s, IH) , 6.8 (s, IH) , 7.2 (m, 5H), 7.9 (s, 2H) .

25 ab NMR: (CDCI3) δ 4.4 (d, IH) , 5.3 (d, IH) , 5.3 (s,

IH), 5.6 (s, IH), 6.8 (s, IH) , 7.2-7.4 (m, 4H) ,

7.8 (s, IH), 8.1 (s, IH).

30 ac NMR: (CDCI3) δ 4.6 (d, IH) , 5.1 (d, IH) , 5.3 (s,

IH), 5.35 (s, IH), 5.45 (s, IH) , 6.8 (s, IH) , 7.2 (m, 4H), 7.9 (s, IH) , 8.1 (s, IH) .

ad NMR: (CDCI3) 64.6 (d, IH) , 5.3 (d, IH) , 5.3 (s, 35 IH), 5.6 (s, IH), 6.8 (s, IH) , 7.2 (m, 2H) , 7.4

(s, IH), 7.9 (s, IH), 8.1 (s, IH) .

af NMR: (CDCI3) δ 4.7 (bs, IH) , 4.9 (bs, IH) , 5.33 (2s, 2H), 6.75 (d, 2H) , 7.12 (m, 4H) , 7.45 (s, IH), 7.83 (s, IH), 8.00 (s, IH) , 8.33 (d, 2H) .

ag NMR t: (CDCI3) δ 4.6 (s, 2H), 5.4 (s, IH) , 5.5 (s, IH) I, 5.8 (s, IH), 6.8-7.0 (m, 3H) , 7.3-7.4 ( , IH) I, 8.0, 8.1 (two s, 2H).

ah NMR: (CDCI3) δ 4.6 (ABq, 2H) , 5.2 (s, OH), 5.3

10 (s, IH), 5.4 (s, IH), 7.1-7.7 (m, 8H) , 7.7 (s, IH), 7.8 (s, IH).

ai NMR: (CDC1 ₃ ) δ 3.6 (s, 3H) , 4.7-5.0 (ABq, 2H) , 5.4 (s, IH), 5.7 (s, IH), 6.6-7.2 (m) , 7.7 (s, 15 IH), 7.8 (s, IH).

aj NMR: (free base, CDCI3) δ 4.77 (s, 2H) , 5.27 (s, IH), 5.33 (s, IH), 5.73 (s, IH), 6.72 (d, IH) , 7.00 (t, IH), 7.32 (ABq, 4H) , 7.77 (s, IH) , 8.13 20 ( ^s _> ^1H ), 8.18 (d, IH).

ak NMR: (CDCI3) δ 4.63 (d, IH) , 5.03 (d, IH) , 5.30 (s, IH), 5.42 (s, IH), 5.50 (s, IH) , 6.75 (m, 2H), 7.23 (d, IH), 7.43 (q, IH) , 7.67 (dd, IH) , ₂₅ 7.83 (s, IH), 7.88 (s, IH) , 8.28 (d, IH) .

al NMR: (CDCI3) δ 4.67 (d, IH) , 5.40 (s, IH) , 5.46 (s, IH), 5.45 (d, 2H), 7.00-7.27 (m, 3H) , 7.43 (d, IH), 7.67-7.83 (m, 3H) , 8.33 (d, IH) .

30 am NMR: (CDCI3) δ 4.7 (1/2 of ABq, IH) , 5.0 (1/2 of ABq, IH), 5.3 (s, 2H), 6.0 (s, IH) , 6.8 ( , 2H) , 7.3-7.6 (m, 6H), 7.7 (s, IH) , 7.8 (d, IH) , 8.0 (s, IH), 8.6 (d, IH), 8.7 (s, IH) .

35

an NMR: (CDCI3) 5 4.6 (1/2 of ABq, IH) , 5.0 (1/2 of ABq, IH) , 5.2-5.3 (three s, 3H) , 6.8 (m, 2H) , 7.5 (m, 6H) , 7.8 (m, 3H) , 8.6 (d, IH) , 8.8 (s, IH) .

Examples 1276 and 1276a: Preparation of the (S)- enantiomer of Example 49

The compound of Example 49 (1.5 g) and 1.5 g of -L-α-bromocamphor-jr-sulfonic acid was dissolved i ⁿ 75 ml of acetonitrile and refluxed for 2 hours. The solution was allowed to cool to ambient temperature and stand for 14 hours. Filtration of the resulting solids followed by recrystallization from an additional portion of acetonitrile, yielded 1.28 g of white solid, mp 216-217°;

25 [o] _D = -104° (C = 1; DMSO).

The acetonitrile can be evaporated to yield the adduct having a (+)- rotation (Example 1276a) . This compound can be recrystallized from an ether/acetone mixture to yield a solid, that on treatment with aqueous NaHC03 yields material identical by NMR to that of Example 49.

The solid was suspended in 50 ml of saturated

N HCθ3 solution and stirred vigorously until the evolution of gas ceased (1-2 hours) . The mixture was extracted twice with 50 ml of CHCI3. The organic layers were combined, washed with brine, dried over a SU4 and the solvent removed in vacuo. This yielded 750 mg of a white solid (Example 1276) having an 'H NMR identical to that of the compound of Example 49, mp =

82-83°; [ ] ²⁵ = -62° (C = 1; CHCI3) .

These compounds and other compounds which were resolved as described above are shown in Table 2.

Table 2

A

Ex

No. A B n R R ¹ R ² R ³ R ⁴ M.P.°C [α] ²⁵

10

1276 Q- F-©- 0 H H H H H 82-83 -62 ^e

127βa^ φ- F-©- 0 H H H H H 83-84 +60'

₁₂₇₇ (2) _F _^_ _p _ _ o H H H H H 60-61 -67 ^c 15 (HCl salt

181-184)

_1277a (l),(2) m ^t a. _F _^_ _p _ _ o H H H H H 60-62 ₊ 66°

* denotes chiral center

(1) = substitute d-o-bromocamphor-r-sulfonic acid - - (2) = use a 3 parts ether - 1 part acetone mixture as solvent.

Example 1278

25

Preparation of 2-(4-fluorophenyl)-3-pheny1-1-(5- mercapto-lH-1,2, -triazol-l-yl)-3-buten-l-ol

To a solution of 1.24 g (0.004 mol) of 2-(4-fluoro¬

30 phenyl)-3-pheny1-1-(1H-1,2,4-triazol-l-yl)-3-buten- 2-ol in 15 mL of THF at -70° was added 5.2 mL (0.008 mol) of a 1.55 M solution of n-butyllithium in hexanes over 5 minutes. After 30 minutes, 0.13 g (0.004 mol) of sulfur was added and the reaction mixture was allowed to

35

warm to room temperature over 1 h, then quenched with 8 mL of IN HCl. After pouring into saturated NH4CI, the mixture was extracted with 2 x ether and the combined organic layers were washed with brine, dried over Na2SU4 and evaporated. The crude product was purified by flash chromatography using 2:13:85 methanol/ether/methylene chloride to give 0.85 g of the title compound, m.p. 54- 58°: NMR (CDCI3) δ 4.7 (ABq, 2H) , 5.0 (s, IH, OH), 5.3 (s, IH, vinyl), 5.5 (s, IH, vinyl), 7.0 (m, 4H) , 7.2 (m, 3H), 7.5 (m, 2H) , 7.7 (s, IH, triazole proton), 12.5 (brs, IH, SH); IR (methylene chloride) 3500-3000 (br) , 1590, 1500, 1465, 1230, 1162, 1109, 825 cm" ¹ ; MS: highest m/e 341.

The compounds shown in Table 3 were prepared or can be prepared by the methods described above.

Table 3 (continued)

Table 3 (continued)

Table 3 (continued)

Table 3 (continued)

Table 3 (continued)

Table 3 (continued)

Table 3 (continued)

Table 3 (continued)

Ex. No. B R R ¹ R ² R ⁴ Q M.P.°C

(oil)f

0

1473 4-F-Ph 2-F-Ph H H H H SCNH-allyl

0

1474 4-F-Ph 2-F-Ph H H H H SCNH-i-Pr

0

1475 4-F-Ph 2-F-Ph H H H H SCNHPh

1476 4-F-Ph 2-F-Ph H H H H SCNH-(4-Cl-Ph)

0

1477 4-F-Ph 2-F-Ph H H H H SCNHCH ₀ Ph

0

1478 4-F-Ph 2-F-Ph H H H H SCNHCH ₂ -(4-CH ₃ 0-Ph)

0

1479 4-F-Ph 2-F-Ph H H H H CCH

Table 3 (continued)

♦All compounds in this table are compounds in which E is a bond except 1468 and 1469 in which E is an oxygen atom.

a NMR: (CDC1 ₃ ) <54.9 (s, 2H) ; 5.1 (s, IH) ; 5.2 (s, IH); 5.3 (s, IH); 6.7 (m, 2H) ; 6.9 (m, 2H); 7.2 (m, 2H); 7.5 (m, IH) ; 7.6 (s, IH) ; 12.2 (brs, IH) .

b NMR: (CDCI3) δ 4.7 (ABq, 2H) ; 5.3 (s, 2H) ; 5.8 (s, IH); 6.7 (m, 2H) ; 6.9 ( , 2H) ; 7.3 (m, 2H) ; 7.5 (m, IH); 7.8 (s, IH) .

c NMR: (CDCI3) δ 3.8 (ABq, 2H) ; 4.7 (ABq, 2H) ; 5.2 (s, IH); 5.3 (two s, 2H) ; 6.9-7.2 (m, 4H) ; 7.2-7.4 (m, 3H); 7.5 ( , IH) ; 7.8 (s, IH) .

d NMR: (CDCI3) 5 0.92 (t, 3H) ; 1.4-1.7 (m, 4H) ; 3.1 (t, 2H) ; 4.5 (ABq, 2H) ; 5.4 (two s, 2H) ; 5.8 (s, IH) ; 7.0 (m, 4H) ; 7.2 (m, 3H) ; 7.5 (m, 2H) ; 7.8 (s, IH) .

5 e NMR: (CDCI3) δ 2.7-3.5 (m, 2H) ; 4.3 (s, IH) ; 4.4 (m, 2H) ; 5.2 (m, 2H) ; 6.8-7.4 (m, 8H) ; 7.9 (m, IH) .

10 f NMR: (CDCI3) δ 2.7-3.4 (m, 2H) ; 4.2 (d, IH) ; 4.5

(ABq, 2H) ; 5.3 (m, 2H) ; 6.8-7.4 (m, 8H) ; 7.9 (d, IH) .

15

20

25

30

35

Example 1487

Preparation of 2,3-bis(4-fluorophenyl)- 1-(1H-1,2,4-triaι.ol-l-yl)-3,4-epoxy-2-butanol

2,3-Bis(4-fluorophenyl)-1-(1H-1,2,4-triazol-l-yl)- 3-butene-2-ol (1.0 g) was dissolved in 50 ml of anhydrous benzene and stirred under nitrogen. To this solution was added .012 g of vanadium acetonyl- acetonate. The solution was then refluxed and tert- butyl hydroperoxide (0.44 g dissolved in 5 ml of anhydrous benzene) was added dropwise over 10 minutes. The reaction was refluxed for one additional hour and then cooled to ambient temperature. The benzene was removed in vacuo and the residue chromatographed on silica gel (2% MeOH/CH ₂ Cl2) . This yielded a total of 650 mg of diastereomeric products in a 3:1 ratio. Further chromatography resulted in the separation of the diastereomers. The major isomer was a waxy white solid. NMR (CDCI3/TMS) δ 2.60 (d, J=6Hz, IH) ; 3.48 (d, J=6Hz, IH); 4.70 (q, J=7Hz, 2H) ; 5.25 (s, IH) ; 6.8-7.3 (m, 8H) ; 7.55 (s, IH); 7.90 (s, IH) .

The minor isomer was an amorphous white solid. NMR (CDCI3/TMS) 52.55 (d, J=6H, IH) ; 2.75 (d, J=6Hz, IH) ; 4.80, (q, J=7Hz); 5.0 (s, IH) ; 6.85 - 7.10 (m, 4fl) ; 7.15-7.45 (m, 4H) ; 7.80 (s, IH) ; 8.05 (s, IH) .

The epoxides shown in Table 4 were prepared or can be prepared by the method described in Example 1487.

Table 4

Table 4 (continued)

Ex.

No. B n R R ¹ R ² R ³ R ⁴ M.P.°C

4-CF ₃ -Ph 0 H H H H H

2-F-Ph 0 H H H H H 2-Cl-Ph 0 H H H H H

5- ^C 4 ^F 9 0 H H H H H

4-F-Ph 0 H H H H H

2,4-Cl ₂ -Ph 0 H H H H H -*

4-Cl-Ph 0 H H H H H 149-150 Low Rf isomer

141-143 High Rf isomer

2,4-F„-Ph 0 H H H H H 138-140 Isomer A

152-156 Isomer B

4-CF ₃ -Ph 0 H H H H H

2-F-Ph 0 H H H H H 2-Cl-Ph 0 H H H H H

H- ^{C F} 9 0 H H H H H

4-F-Ph 0 H H H H H

2,4-Cl ₂ -Ph 0 H H H H H

4-Cl-Ph 0 H H H H H

2,4-F ₂ -Ph 0 H H H H H

4-CF ₃ -Ph 0 H H H H H

2-F-Ph 0 H H H H H

2-Cl-Ph 0 H H H H H π-C ₄ F ₉ 0 H H H H H

4-F-Ph 0 H H H H H 88-94

2,4-Cl ₂ -Ph 0 H H H H H

4-Cl-Ph 0 H H H H H 156-158

2,4-F„-Ph 0 H H H H H 87-90 Low Rf isomer

² 148-150 High Rf isomer

4-CF ₃ -Ph 0 H H H H H 2-F-Ph 0 H H H H H

Table 4 (Continued)

No. A B n R R ¹ R ² R ³ R ⁴ M.P .

1627 1-imidazoyl 2,4-Cl ₂ -Ph 1 H H H H H

1628 1-imidazoyl 2,4-Cl ₂ -Ph 2 H H H H H

1629 1-imidazoyl 4-F-Ph 3 H H H H H

16301-imidazoyl 4-F-Ph 4 H H H H H

1631 lH-l,2,4-triazoyl-l-yl 4-F-Ph 1 H H H H H

1632 lH-l,2,4-triazoyl-l-yl 4-F-Ph 2 H H H H H

1633 lH-l,2,4-triazoyl-l-yl 4-F-Ph 3 H H H H H

1634 lH-l,2,4-triazoyl-l-yl 4-F-Ph 4 H H H H H

1635 lH-l,2,4-triazoyl-l-yl 2,4-Cl ₂ -Ph 1 H H H H H 1636 Ph 2,5-F ₂ -Ph 0 H H H H H

3-F-Ph 0 H H H H H

2,5-Cl ₂ -Ph 0 H H H H H

3-Cl-Ph 0 H H H H H

4-Br-Ph 0 H H H H H

4-I-Ph 0 H H H H H

3,4-F ₂ -Ph 0 H H H H H

3,4-Cl ₂ -Ph 0 H H H H H

2,6-Cl ₂ -Ph 0 H H H H H

2-Cl-(4-F)-Ph 0 H H H H H

2,4,6-Cl ₃ -Ph 0 H H H H H

2-F-(4-Cl)-Ph 0 H H H H H

Ph 0 H H H H H 4-CH ₃ -Ph 0 H H H H H

3-CH ₃ -Ph 0 H H H H H

2-CH ₃ -Ph 0 H H H H H

2-CF ₃ -Ph 0 H H H H H 3-CF ₃ -Ph 0 H H H H H

Table 4 (Continued)

Table 4 (Continued)

Table 4 (Continued)

Table 4 (Continued)

No. A B n R R ¹ R ² R ³ R ⁴ M.P.°C

17542-CF ₃ -imidazol-l-yl

1755 4-(i-C ₃ H _? 0)-Ph

17564-I-Ph 17573,4-F ₂ -Ph

17583,4-Cl ₂ -Ph

1759 2,6-Cl ₂ -Ph

17602-Cl-(4-F)-Ph 1761 2,4,6-Cl ₃ -Ph

17624-CH ₃ -Ph

1763 3-CH ₃ -Ph

17642-CH ₃ -Ph 17652-CF ₃ -Ph

1766 3-CF ₃ -Ph

17674-CH ₃ 0-Ph

1768 2,3-Cl ₂ -Ph

17693,5-Cl ₂ -Ph

17702,5-Cl ₂ -Ph

1771 3-Br-Ph

17724-C ₂ H ₅ 0-Ph

1773 2,4-(CH ₃ ) ₂ -Ph

17742,4,6-(CH ₃ ) ₃ -Ph

1775 4-Ph-Ph

1776 5-Cl-2-thienyl 1777 2-Cl-3-thienyl

Table 4 (Continued)

Table 4 (Continued)

No! A B n R R ¹ R ² R ³ R ⁴ M.P.°

18032,4,6-(CH ₃ ) ₃ -Ph 2,4-Cl ₂ -Ph 0 H H H H H

18044-Ph-Ph 2,4-Cl ₂ -Ph 0 H H H H H

18055-C1-2-thienyl 2,4-Cl ₂ -Ph 0 H H H H H

18062-C1-3-thienyl 2,4-Cl ₂ -Ph 0 H H H H H

1807 1-imidazoyl 2,4-Cl ₂ -Ph 0 H H H H H

1808 lH-l,2,4-triazoyl-l-yl 2,4-Cl ₂ -Ph 0 H H H H H

18092-pyridyl 2,4-Cl ₂ -Ph 0 H H H H H

18105-Cl-2-pyridyl 2,4-Cl ₂ -Ph 0 H H H H H

18113-pyridyl 2,4-Cl ₂ -Ph 0 H H H H H

18124-pyridyl 2,4-Cl ₂ -Ph 0 H H H H H

0 H H H H H

0 H H H H H

0 H H H H H

0 H H H H H

0 H H H H H

0 H H H H H

0 H H H H H

0 H H H H H

0 H H H H H

0 H H H H H

0 H H H H H

0 H H H H H

Table 4 (Continued)

Ex. No. B n R R ¹ R ² R ³ R ⁴ M.P.°C

18262,3-Cl ₂ -Ph 4-Cl-Ph 0 H H

18273,5-Cl ₂ -Ph 4-Cl-Ph 0 H H

18282,5-Cl ₂ -Ph 4-Cl-Ph 0 H H

18293-Br-Ph 4-Cl-Ph 0 H H

18304-EtO-Ph 4-Cl-Ph 0 H H

18312,4-(CH ₃ ) ₂ -Ph 4-Cl-Ph 0 H H

18322,4,6-(CH ₃ ) ₃ -Ph 4-Cl-Ph 0 H H

18334-Ph-Ph 4-Cl-Ph 0 H H

18345-Cl-2-thienyl 4-Cl-Ph 0 H H

18352-Cl-3-thienyl 4-Cl-Ph 0 H H

18361-imidazoyl 4-Cl-Ph 0 H H

1837 lH-l,2,4-triazoyl-l-yl 4-Cl-Ph 0 H H

18382-pyridyl 4-Cl-Ph 0 H H

18395-Cl-2-pyridyl 4-Cl-Ph 0 H H

18403-pyridyl 4-Cl-Ph 0 H H

18414-pyridyl 4-Cl-Ph 0 H H

1842 n-C ₄ F _g 4-Cl-Ph 0 H H

18434-I-Ph 2,4-F ₂ -Ph 0 H H

18443,4-F ₂ -Ph 2,4-F ₂ -Ph 0 H H

18453,4-Cl ₂ -Ph 2,4-F ₂ -Ph 0 H H

18462,6-Cl ₂ -Ph 2,4-F ₂ -Ph 0 H H

18472-Cl-(4-F)-Ph 2,4-F ₂ -Ph 0 H H

18482,4,6-Cl ₃ -Ph 2,4-F ₂ -Ph 0 H H

18494-CH ₃ -Ph 2,4-F ₂ -Ph 0 H H

18503-CH ₃ -Ph 2,4-F ₂ -Ph 0 H H

Table 4 (Continued)

Ex. No. B n R R ¹ R ² R ³ R ⁴ M.P.°C

1851 2-CH ₃ -Ph 2,4-F ₂ -Ph 0 H H H H H

18522-CF ₃ -Ph 2,4-F ₂ -Ph 0 H H H H H

18533-CF ₃ -Ph 2,4-F ₂ -Ph 0 H H H H H

18544-CH ₃ 0-Ph 2,4-F ₂ -Ph 0 H H H H H

18552,3-Cl ₂ -Ph 2,4-F ₂ -Ph 0 H H H H H

18563,5-Cl ₂ -Ph 2,4-F ₂ -Ph 0 H H H H H

18572,5-Cl ₂ -Ph 2,4-F ₂ -Ph 0 H H H H H

18583-Br-Ph 2,4-F ₂ -Ph 0 H H H H H

18594-C ₂ H ₅ 0-Ph 2,4-F ₂ -Ph 0 H H H H H

18602,4-(CH ₃ ) ₂ -Ph 2,4-F ₂ -Ph 0 H H H H H

18612,4,6-(CH ₃ ) ₃ -Ph 2,4-F ₂ -Ph 0 H H H H H

18624-Ph-Ph 2,4-F ₂ -Ph 0 H H H H H

18635-Cl-2-thienyl 2,4-F ₂ -Ph 0 H H H H H

18642-Cl-3-thienyl 2,4-F ₂ -Ph 0 H H H H H

1865 1-imidazoyl 2,4-F ₂ -Ph 0 H H H H H

1866 lH-l,2,4-triazoyl-l-yl 2,4-F ₂ -Ph 0 H H H H H

18672-pyridyl 2,4-F ₂ -Ph 0 H H H H H

18685-Cl-2-pyridyl 2,4-F ₂ -Ph 0 H H H H H

18693-pyridyl 2,4-F ₂ -Ph 0 H H H H H

18704-pyridyl 2,4-F ₂ -Ph 0 H H H H H

1871 n-C ₄ F _g 2,4-F ₂ -Ph 0 H H H H H

NMR: (CDC1 ₃ ) δ 2.7 (m, 2H) , 4.4 (1/2 of ABq, J=12, IH), 4.9 (1/2 of ABq, J=12, IH) , 5.0 (br s, IH, OH), 6.7 (m, 2H) , 7.0 (m, 2H) , 7.4 (m, 3H), 7.8 (s, IH), 8.0 (s, IH) .

Example 1930 2-(2,4-Difluorophenyl)-3-(2-chlorophenyl)-1-(1H- 1,2,4-imidazol-l-y1)-3-buten-2-ol

₅ A mixture of 10.2 g (0.035 mol) of 2-(2,4- difluorophenyl)-2-[1-(2-chlorophenyl)ethenyl]oxirane; 6.20 g (0.091 mol) of imidazole and 12.44 g (0.091 mol) of potassium carbonate in 100 mL of DMSO was heated overnight at 100°, then cooled and poured into 800 mL θ of H ₂ 0. The aqueous mixture was extracted with 4x500 mL Et 0, and the organic extracts were washed with water (2x) and brine, dried over MgS04 and evaporated to give 7.8 g of a yellow-brown solid. Flash chromatography and trituration with Et 0 gave 4.0 g of ₅ a white powder, mp 139-142°: NMR: (CDCI3) δ 3.9 (br, OH), 4.2 (1/2 of ABq, IH) , 4.7 (1/2 of ABq, IH, CH ₂ - imidazole) , 5.3 (s, IH, vinyl), 5.5 (s, IH, vinyl), 6.7 (m, 4H), 7.0-7.5 (m, 6H) ; IR (nujol) 3400-2600 (br), 1614, 1512, 1501, 1111, 1075, 852, 819, 768, 743, 623 cm -1

The compounds shown in Table 4A were prepared or can be prepared by the methods described above.

Table 4A

19232,4-F ₂ -Ph 2,4-F ₂ -Ph 0 H H H H

19242,4-F ₂ -Ph 2-Cl-Ph 0 H H H H

19252,4-F ₂ -Ph 4-Cl-Ph 0 H H H H

19262,4-F ₂ -Ph 2,4-Cl ₂ -Ph 0 H H H H

19272-Cl-Ph Ph 0 H H H H

19282-Cl-Ph 2-F-Ph 0 H H H H

19292-Cl-Ph 4-F-Ph 0 H H H H

19302-Cl-Ph 2,4-F ₂ -Ph 0 H H H H 139-142 (HCl salt 215-217)

1931 2-Cl-Ph 2-Cl-Ph 0 H H H H

19322-Cl-Ph 4-Cl-Ph 0 H H H H 160-162 (HCl salt 170-173)

19332-Cl-Ph 2,4-Cl ₂ -Ph 0 H H H H

Table 4A (continued)

No. ^' A B n R R ¹ R ² R ³ R ⁴ M.P.°C

1976 2-CF ₃ -Ph Ph 0 H H H H H 177-179

1977 2-CF ₃ -Ph 2-F-Ph 0 H H H H H 185-187

1978 2-CF ₃ -Ph 4-F-Ph 0 H H H H H 170-172

1979 2-CF ₃ -Ph 2,4-F ₂ -Ph 0 H H H H H

1980 2-CF ₃ -Ph 2-Cl-Ph 0 H H H H H

1981 2-CF ₃ -Ph 4-Cl-Ph 0 H H H H H 159-161

1982 2-CF ₃ -Ph 2,4-Cl ₂ -Ph 0 H H H H H

1983 3-CF ₃ -Ph Ph 0 H H H H H 1984 3-CF ₃ -Ph 2-F-Ph 0 H H H H H

1985 3-CF ₃ -Ph 4-F-Ph 0 H H H H H

1986 3-CF ₃ -Ph 2,4-F ₂ -Ph 0 H H H H H

1987 3-CF ₃ -Ph 2-Cl-Ph 0 H H H H H ιg88 3-CF ₃ -Ph 4-Cl-Ph 0 H H H H H

1989 3-CF ₃ -Ph 2,4-Cl ₂ -Ph 0 H H H H H

1990 4-CF ₃ -Ph Ph 0 H H H H H

1991 4-CF ₃ -Ph 2-F-Ph 0 H H H H H

1992 4-CF3-Ph 4-F-Ph 0 H H H H H

1993 4-CF ₃ -Ph 2,4-F ₂ -Ph 0 H H H H H

1994 4-CF ₃ -Ph 2-Cl-Ph 0 H H H H H

1995 4-CF ₃ -Ph 4-Cl-Ph 0 H H H H H

1996 4-CF -Ph 2,4-Cl2~Ph 0 H H H H H a NMR: (CDC1 ₃ ) ό ^" 4.5 (ABq, 2H) , 4.8 (br s,

IH), 5.5 (two s, 2H), 6.7 (s, IH) , 6.9 (s,

IH), 7.0-7.6 (m, 10H)

Pharmaceutical Utility

In vitro activity (Table 5) is expressed in terms of the minimal inhibitory concentration (MIC) of the test compound which inhibits the growth of yeasts and fungi.

The target organisms, Candida albicans ATCC 11651 and Aspergillus fumigatus ATCC 28214 are standardized, [Y. Bezjak, J. Clinical Micro., 21 509-512 (1984)] to a concentration of 10' organisms/ml and maintained at -70 o until use. Test compounds are solubilized in dimethyl sulfoxide (DMSO) and diluted in Eagle's Minimum Essential Medium (EMEM) broth to achieve a final concentration of 200 /Jg/ml. Stock solutions of standard antifungal agents are stored at -70° and diluted in EMEM as required.

The ^n vitro assay utilizes a microtiter broth dilution technique [L. Polonelli and G. Morace, Mycopathologia, 86, 21-28 (1984)] and C. Hughes, et. al. Antimicrob. Ag. and Chemo., 25, 560-562(1984)]. Test compounds are serially diluted in EMEM to give graded concentrations ranging from 100 to 0.4 g/ml. The appropriate wells are inoculated with the required organism (C. albicans at 1 x 10^ organisms/ml and A. fumigatus at 5 x 10^ organisms/ml) and the assay incubated at 30° for 24 hours. The extent of fungal growth is determined at an optical density equal to 540 nm using a scanning spectrophotometer (Flo ^ MCC) and MIC values, representing the minimal concentration of a compound which inhibited growth, are determined, [Y. Grenta, et al. Antimicrob. Ag. and Chemo. , 22, 151-153 (1982)].

The in vivo activity of test compounds is based on the percent (%) survival of infected animals receiving test or standard agent compared to that in an infected untreated group (Table 6) . The ^n vivo assays are chronic systemic infections lethal to mice within 7 days post infection, [J. Barnes, et al. Lab Investigation, 49460-467 (1963) , and T. Rogers and E. Balish, Infection and Immunity, 1433-38 (1976)].

Candida albicans ATCC 11651, from a frozen stock culture (10^ organisms/ml) maintained at -70°, is diluted in saline to 1 x 10' organisms/ml and 0.2 ml inoculated intravenously (caudal vein) into 20.0 gm CF-1 female mice (Charles River) .

Test compounds are routinely solubilized in 0.25X (w/v) methylcellulose (Methocel®) but for those compounds difficult to solubilize 10S (w/v) Emulophor® (EL620 GAF Corp.) is used. The standard antifungal agents, amphotericin B (Fungizone^) in water and ketoconazole (Nizoral®) in Methocel®, are administered at 1.0 mg/kg/day and 150 mg/kg/day, respectively.

In a primary assay, mice (10 per group) are infected with C. albicans, and receive test compounds at 50 or 150 mg/kg/day via the subcutaneous route. Animals are dosed with the test compound at 1 and 6 hour post- infection and then once daily for the next three days. Survival of mice in each group is recorded for 21 days.

Compounds which protect >7055 of the infected animals for 14 days at a dose 150 mg/kg/day or less are viewed as active.

Table 5

In Yitro Antifungal Results

10

15

20

25

30

35

Table 5 (Continued)

10

15

20

25

30

35

Table 5 (Continued)

10

15

20

25

30

35

Table 5 (Continued)

Example MIC values (tg/ml)

Number C. albicans A. fumi atus

724

726

815

905 ⁰ 1258

1260 1276 1276a 1277 ⁵ 1277 HCl salt

1277a 1278 1300 1377 0 1451

1459 1487 1527

25

Standards*

Amphotericin B Nystatin ** 5-Fluorocytosine Ketoconazole Miconazole

*MIC values of the standard drugs are the mean ° of five determinations

+ Standard deviation

TABLE 6

In Vivo Antifungal Results

% Survival (150 mg/kg per day) o Primary Assay

TABLE 6 (continued)

In Vivo Antifungal Results

% Survival (150 mg/kg per day) Primary Assay

Standards

Amphotericin B 100 100 100 Ketoconazole 100 80 50

N.T. : Not Tested

DOSAGE FORMS The antimycotic agents of this invention can be administered by any means that effects contact of the active ingredient with the agent's site of action in the body. The compounds can be administered by any conventional means available for use in conjunction with pharmaceuticals, either as individual therapeutic agents or in a combination of therapeutic agents. They can be administered alone, but are generally administered with a pharmaceutical carrier selected on the basis of the chosen route of administration and standard pharmaceutical practice.

The dosage administered will, of course, vary depending on the use and known f ctors such as the pharmacodynamic characteristics of the particular agent, and its mode and route of administration: age, health, and weight of the recipient; nature and extent of symptoms, kind of concurrent treatment, frequency of treatment, and the effect desired.

Dosage forms (compositions) suitable for administration contain from about 200 milligram to about 2000 milligrams of active ingredient per unit. In these pharmaceutical compositions, the active ingredient will ordinarily be present in an amount of about 0.5-9555 by weight based on the total weight of the composition. For use in the treatment of said diseases, a daily dose of active ingredient can be about 10 to 50 milligrams per kilogram of body weight. The composition of the invention may be in a conventional pharmaceutical form suitable for oral administration, for example a tablet, a capsule, an emulsion or an aqueous or oily solution or suspension, or suitable for topical application, for example a cream, ointment or gel. It can also be administered parenterally in sterile liquid dosage forms.

Gelatin capsules contain the active ingredient and powdered carriers, such as lactose, starch, cellulose derivatives, magnesium stearate, stearic acid and the like. Similar diluents can be used to make compressed tablets. Both tablets and capsules can be manufactured as sustained release products to provide for continuous release of medication over a period of hours. Compressed tablets can be sugar coated or film coated to mask any unpleasant taste and protect the tablet from the atmosphere, or enteric coated for selective disintegration in the gastrointestinal tract.

The pharmaceutical compositions which are ointments, creams and gels can, for example, contain the usual diluents, e.g. animal and vegetable fats, waxes, paraffins, starch, tragacanth, cellulose derivatives, polyethylene glycols, silicones, bentonites, silicic acid, talc and zinc oxide or mixtures of these substances.

In general, water, a suitable oil, saline, aqueous dextrose (glucose), and related sugar solutions and glycols such as propylene glycol or polyethylene glycols are suitable carriers for parenteral solutions. Solutions for parenteral administration preferably contain a water soluble salt of the active ingredient, suitable stabilizing agents, and if necessary, buffer substances. Antioxidizing agents such as sodium bisulfite, sodium sulfite, or ascorbic acid, either alone or combined, are suitable stabilizing agents.

All the pharmaceutical compositions according to the invention can also contain coloring and flavoring to increase patient acceptance.

Also used are citric acid and its salts and sodium EDTA. In addition, parenteral solutions can contain

preservatives, such as benzalkonium chloride, methyl or propyl-paraben, and chlorobutanol.

Suitable pharmaceutical carriers are described in Remington's Pharmaceutical Sciences, A. Osol, a standard reference text in this field.

Useful pharmaceutical dosage forms for administration of the compounds of this invention can be illustrated as follows:

Capsules A large number of unit capsules are prepared by filling standard two-piece hard gelatin capsules each with 100 milligrams of powdered active ingredient, 150 milligrams of lactose, 50 milligrams of cellulose, and 6 milligrams magnesium stearate. Soft Gelatin Capsules

A mixture of active ingredient in a digestable oil such as soybean oil, cottonseed oil or olive oil is -prepared and injected by means of a positive displacement pump into gelatin to form soft gelatin capsules containing 100 milligrams of the active ingredient. The capsules are washed and dried.

Tablets A large number of tablets are prepared by conventional procedures so that the dosage unit is 100 milligrams of active ingredient, 0.2 milligrams of colloidal silicon dioxide, 5 milligrams of magnesium stearate, 275 milligrams of microcrystalline cellulose, 11 milligrams of starch and 98.8 milligrams of lactose. Appropriate coatings may be applied to increase palatability or delay absorption.

Injectable A parenteral composition suitable for administration by injection is prepared by stirring 1.5% by weight of active ingredient in 10% by volume propylene glycol. The solution is made to volume with water for injection and sterilized.

141

Suspension

An aqueous suspension is prepared for oral administration so that each 5 milliliters contain 100 milligrams of finely divided active ingredient, 100 milligrams of sodium carboxymethyl cellulose, 5 milligrams of sodium benzoate, 1.0 grams of sorbitol solution, U.S.P., and 0.025 milliliters of vanillin.

Cream

A cream for topical application is prepared by incorporating 100 milligrams of the finely pulverized active ingredient in 5 grams of a cream base which comprises 40% white petrolatum, 3% microcrystalline wax, 10% lanolin, 5% Span^O, 0.3% Tween^O and 41.7% water.

Agricultural Formulations

The compounds of this invention when used for agricultural purposes will generally be used in formulation with a liquid or solid diluent or with an organic solvent. Useful formulations of the compounds of Formula I can be prepared in conventional ways. They include dusts, granules, pellets, solutions, emulsions, wettable powders, emulsifiable concentrates and the like. Many of these may be applied directly. Sprayable formulations can be extended in suitable media and used at spray volumes of from about one to several hundred liters per hectare. High strength compositions are primarily used as intermediates for further formulation. The formulations, broadly, contain about 1% to 99% by weight of active ingredient(s) and at least one of a) about 0.1% to 35% surf ctant(s) and b) about 5% to 99% solid or liquid inert diluent(s). More specifically, they will contain these ingredients in the following approximate proportions: Percent by Weight

Active In redient Diluent s Surf ctant s

Lower or higher levels of active ingredient can, of course, be present depending on the intended use and the physical properties of the compound. Higher ratios of surfactant to active ingredient are sometimes

desirable, and are achieved by incorporation into the formulation or by tank mixing.

Typical solid diluents are described in Watkins, et al. , "Handbook of Insecticide Dust Diluents and Carriers", 2nd Ed., Dorland Books, Caldwell, New Jersey. The more absorptive diluents are preferred for the wettable powders and the denser ones for dusts. Typical liquid diluents and solvents are described in Marsden, "Solvents Guide," 2nd Ed., Interscience, New York, 1950. Solubility under 0.1% is preferred for suspension concentrates; solution concentrates are preferably stable against phase separation at 0°C. "McCutcheon's Detergents and Emulsifiers Annual", MC Publishing Corp., Ridgewood, New Jersey, as well as Sisely and Wood, "Encyclopedia of Surface Active Agents", Chemical Publ. Co., Inc., New York, 1964, list surfactants and recommended uses. All formulations can contain minor amounts of additives to reduce foam, caking, corrosion, microbiological growth, etc. Preferably, ingredients should be approved by the U.S. Environmental Protection Agency for the use intended.

The methods of making such compositions are well known. Solutions are prepared by simply mixing the ingredients. Fine solid compositions are made by blending and, usually, grinding as in a hammer or fluid energy mill. Suspensions are prepared by wet milling (see, for example, Littler, U.S. Patent 3,060,084). Granules and pellets may be made by spraying the active material upon preformed granular carriers or by agglomeration techniques. See J. E. Browning,

"Agglomeration", Chemical Engineering, Dec. 4, 1967, pp. 147ff. and "Perry's Chemical Engineer's Handbook", 4th Edn., McGraw-Hill, N.Y., 1963, pp. 8-59ff.

For further information regarding the art of formulation, see for example:

H. M. Loux, U.S. Patent 3,235,361, Feb. 15, 1966, Col. 6, Line 16 through Col. 7, Line 19 and Examples 10 through 41.

R. W. Luckenbaugh, U.S. Patent 3,309,192, March 14, 1967, Col. 5, Line 43 through Col. 7, Line 62 and Examples 8, 12, 15, 39, 41, 52, 53, 58, 132, 138- 140, 162-164, 166, 167, 169-192. H. Gysin and E. Knusli, U.S. Patent 2,891,855,

June 23, 1959, Col. 3, Line 66 through Col. 5, Line 17 and Examples 1-4.

G. C. Klingman, "Weed Control as a Science", John Wiley and Sons, Inc., New York, 1961, pp. 81-96. J. D. Fryer and S. A. Evans, "Weed Control Hand¬ book", 5th Edn. Blackwell Scientific Publications, Oxford, 1968, pp. 101-103.

Examples of useful formulations of compounds of the present invention are as follows. Wettable Powder

2-(2,4-difluorophenyl)-3-(4-fluorophenyl)-1-(1H-1,2,4- triazol-l-yl)-3-buten-l-ol; and the (S) enantiomer thereof 80% sodium alkylnaphthalenesulfonate 2% sodium ligninsulfonate 2% synthetic amorphous silica 3% kaolinite 13%

The ingredients are blended, hammer-milled, re- blended and packaged. Granule wettable powder of above example 15% gypsum 69% potassium sulfate 16%

The ingredients are blended in a rotating or fluid bed mixer and water sprayed on to accomplish granulation. When most of the material has reached the

desired range of 1.0 to 0.42 mm. (U.S.S. No. 18 to 40 sieves) , the granules are removed, dried, and screened. Oversize material is crushed to produce additional material in the desired range. High Strength Concentrate

2-(2-fluorophenyl)-3-(4-fluorophenyl)-1-(1H-1,2,4- triazol-l-yl)-3-buten-2-ol; and the (S) enantiomer thereof 98.5% silica aerogel 0.5% synthetic amorphous fine silica 1.0%

The ingredients are blended and ground in a hammer-mill to produce a high strength concentrate essentially all passing a U.S.S. No. 50 sieve (0.3 mm openings) . This material may then be formulated in a variety of ways.

Aqueous Suspension

2-(2,4-difluorophenyl)-3-phenyl-l-(1H-1,2,4- triazol-l-yl)-3-buten-2-ol; and the (S) enantiomer thereof 25% hydrated attapulgite 3% crude calcium ligninsulfonate 10% sodium dihydrogen phosphate 0.5% water 61.5%

The ingredients are ground together in a ball, sand, or roller mill until the solid particles have been reduced to diameters under 10 microns. Solution

2-(2,4-difluorophenyl)-3-(4-chlorophenyl)-1-(1H- l,2,4-triazol-l-yl)-3-buten-2-ol; and the (S) enantiomer thereof 30% dimethylformamide 70%

The ingredients are combined and stirred to produce a solution, which can be used for low volume applications.

Emulsifiable Concentrate

2-(2,4-difluorophen l)-3-(4- luorophenyl)-1-(1H- 1,2,4-triazol-l-yl)-3-buten-2-ol; and the (S) enantiomer thereof 15% blend of calcium sulfonates and nonionic surfactants 25% xylene 60%

The ingredients are combined and stirred until the active is dissolved. A fine screen filter is included in packaging operation to insure the absence of any extraneous undissolved material in the product.

Utility

The compounds of this invention are useful as plant disease control agents. They are effective in controlling a broad spectrum of plant diseases, particularly foliar pathogens of ornamental, vegetable, field, cereal and fruit crops, such as Puccinia recondita, Erysiphe cichoracearum, Erysiphe graminis, Venturia inaequalis, Cercospora arachidicola, and Monilinia fructicola, Rhizoctonia solani, Pyricularia oryzae, Botrytis cinerea, Pseudocercosporella herpotrichlorides, and Cercosporidium personatum. They also control seed pathogens.

Disease control is ordinarily accomplished by applying an effective amount of the compound either pre- or post-infection to the portion of the plant to be protected, such as the roots, stems, foliage, fruit, seeds, tubers or bulbs, or to the media (soil or sand) in which the plants to be protected are growing. The compound may also be applied to the seed from which the plants to be protected are to be grown.

Rates of application for these compounds can be influenced by many factors of the environment and should be determined under actual use conditions. Foliage can normally be protected when treated at a rate of from less than 1 g/ha to 5000 g/ha of active ingredient. Plants growing in soil treated at a concentration from 0.1 to about 20 kg/ha can be protected from disease. Seed and seedlings can normally be protected when seed is treated at a rate of from 0.06 to about 3 grams per kilogram of seed.

The compounds of this invention can be mixed with fungicides, bactericides, acaricides, nematicides, insecticides, or other biologically active compounds in order to achieve desired results with a minimum

expenditure of time, effort and material. Amounts of these biologically active materials added for each part by weight of the composition of this invention may vary from 0.05 to 25 parts by weight. Suitable agents of this type are well-known to those skilled in the art. Some are listed below:

Fungicides methyl 2-benzimidazolecarbamate (carbendazim) tetramethylthiuram disulfide (thiuram) n-dodecylguanidine acetate (dodine) manganese ethylenebisdithiocarba ate ( aneb)

1,4-dichloro-2,5-dimethoxybenzene (chloroneb)methyl

1-(butylcarbamoyl)-2-benzimidazolecarbamate (benomyl) 2-cyano-N-ethylcarbamoyl-2-methoxyiminoacetamide (cymoxanil)

N-trichloromethylthiotetrahydrophthalamide (captan) N-trichloromethylthiophthalimide (folpet) dimethyl 4,4'-(o-phenylene)bis(3-thioallophanate)- (thiophanate-methyl) 2-(thiazol-4-yl)benzimidazole (thiabendazole) aluminum tris(0-ethyl phosphonate) (phosethyl aluminum) tetrachloroisophthalonitrile (chlorothalonil)

2,6-dichloro-4-nitroaniline (dichloran)

N-(2,6-dimethylpheny1)-N-(methoxyacetyl) lanine methyl ester (metalaxyl) cis-N-[1,1,2,2-tetrachloroethyl)thio]cyclohex-4-ene-

1,2-dicarbioximide (captafol) 3-(3,5-dichlorophenyl)-N-(1-methylethyl)-2,4-dioxo-l- imidazolidine carboxamide (iprodione) 3-(3,5-dichlorophenyl)-5-ethenyl-5-methyl-2,4-oxazoli- dinedione (vinclozolin) kasugamycin

0-ethyl-S,S-diphenylphosphorodithioate(edifenphos) 4-(3-(4-(1,1-dimethyl-ethyl)phenyl)-2-methyl)propyl- 2,6-dimethylmorpholine (Fenpropimorph) 4-(3-4(1,1-dimethyl-ethyl)phenyl)-2- methyl)propylpiperidine (Fenpropidine)

Bactericides tribasic copper sulfate streptomycin sulfate oxytetracycline

Acaricides senecioic acid, ester with 2-sec-butyl-4,6-dinitro- phenol (binapacryl) 6-methyl-l,3-dithiolo[2,3-B]quinonolin-2-one (oxythio- quinox) 2,2,2-trichloro-l,1-bis(4-chlorophenyl)ethanol-

(dicofol) bis(pentachloro-2,4-cyclopentadien-l-yl) (dienochlor) tricyclohexyltin hydroxide (cyhexatin) hexakis(2-methyl-2-phenylpropyl)distannoxane (fenbutin oxide)

Nematicides 2-[diethoxyphosphinylimino]-1,3-diethietane (fosthietan) S-methyl-1-(dimethylcarbamoyl)-N-(methylcarba oyloxy)- thioformimidate(oxamyl) S-methyl-1-carbamoyl-N-(methylcarbamoyloxy)thio- formimidate

N-isopropylphosphoramidic acid, O-ethyl-0'-[4-(methyl- thio)-m-tolyl]diester (fenamiphos)

Insecticides 3-hydroxy-N-methylcrotonamide(dimethylphosphate)ester (monocrotophos) methylcarbamic acid, ester with 2,3-dihydro-2,2- dimethyl-7-benzofuranol (carbofuran) 0-[2,4,5- richloro-α-(chlorome hy1)benzyl]phosphoric acid, 0',0'-dime hyl ester (tetrachlorvinphos)

2-mercaptosuccinic acid, diethyl ester, S-ester with thionophosphoric acid, dimethyl ester (malathion) phosphorothioic acid, 0,0-dimethyl, 0-p_-nitrophenyl ester (methyl parathion) methylcarbamic acid, ester with α-naphthol

(carbaryl) methyl N-[[(methylamino)carbonyl]oxy]ethanimidothio- ate (methomyl) '-(4-chloro-£-tolyl)-N, -dimethylformamidine (chlordimeform)

0,O-diethyl-0-(2-isopropyl-4-methyl-6-pyrimidyl)- phosphorothioate (diazinon) octachlorocamphene (toxaphene)

0-ethyl 0-p_-nitrophenyl phenylphosphonothioate (EPN) cyano(3-phenoxypheny1)-methyl 4-chloro-α-(l-methyl- ethyl)benzeneacetate (fenvalerate) (3-phenoxyphen 1)meth l (+)-cis,trans-3-(2,2-dichloro- ethenyl)-2,2-dimethylcyclopropanecarboxylate

(permethrin) dimethyl N,N'-[thiobis(N-methylimmo)carbonyloxy]]- bis[ethanimidothioate] (thiodicarb) phosphorothiolothionic acid, 0-ethyl-0-[4-(methyl- thio)phenyl]-S-n-propyl ester (sulprofos) α-cyano-3-phenoxybenzyl 3-(2,2-dichlorovinyl)-2,2- dimethylcyclopropane carboxylate (cypermethrin) cyano(3-phenoxyphenyl)methyl 4-(difluoromethoxy)- a-(methylethyl)benzeneacetate (flueythrinate) 0,O-diethyl-0-(3,5,6-trichloro-2-pyridyl)phosphoro¬ thioate (chlorpyrifos) 0,O-dimethyl-S-[(4-oxo-l,2,3-benzotriazin-3-(4H)-yl)- methyl]phosphorodithioate (azinphos-methyl) 5,6-dimethyl-2-dimethylamino-4-pyrimidinyl dimethyl carbamate (pirimicarb) S-(N-formyl-N-methylcarbamoylmethyl)-0,O-dimethyl phosphorodithioate (formothion)

S-2-(ethylthioethyl)-0,O-dimethyl phosphiorothioate

(demeton-S-methyl) α-cyano-3-phenoxybenzyl cis-3-(2,2-dibromovinyl)- 2,2-dimethylcyclopropane carboxylate (deltamethrin) cyano(3-phenoxyphenyl)methyl ester of N-(2-chloro-4- trifluoromethylphenyl)alanine (fluvalinate)

Test results indicate that the compounds of the present invention are also active preemergent or postemergent herbicides or plant growth regulants. Some of them have utility for broad-spectrum pre- and/or postemergence weed control in areas where complete control of all vegetation is desired, such as around industrial storage areas, parking lots, drive-in theaters, around billboards, highway and railroad structures. Other compounds have utility for selective weed control in crops such as rice, wheat, barley, corn, soybeans, sugarbeets and cotton. Some of the compounds are useful as selective herbicides for rice. They may be used either in direct seeded or transplanted rice. Alternatively, the subject compounds are useful to modify plant growth.

The rates of application for the compounds of the invention are determined by a number of factors, including their use as plant growth modifiers or as herbicides, the crop species involved, the types of weeds to be controlled, weather and climate, formulations selected, mode of application, amount of foliage present, etc. In general terms, the subject compounds should be applied at levels of around 0.050 to 20 kg/ha, the lower rates being suggested for use on lighter soils and/or those having a low organic matter content, for plant growth modification or for situations where only short-term persistence is required, such as a herbicide for fallow land.

The compounds of the invention may be used in combination with any other commercial herbicide, non- limiting examples of which are those below:

Common Name Chemical Name acifluorfen 5-[2-chloro-4-(trifluoromethyl)- phenoxy]-2-nitrobenzoic acid acrolein acrolein alachlor 2-chloro-2',6'-diethyl-N- (methoxymethyl)-acetanilide ametryn 2-(ethylamino)-4-(isopropylamino)-6- methylthio)- -triazine amitrole 3-amino-s-triazole AMS ammonium sulfa ate asulam methyl sulfanilylcarbamate atrazine 2-chloro-4-(ethylamino)-6- (isopropylamino)-ss-triazine barban 4-chloro-2-butynyl m- chlorocarbanilate benefin N-butyl-N-ethyl-α,α,α-trifluoro-2,6- dinitro-£-toluidine bensulide 0,O-diisopropyl phosphorodithioate S-ester with N-(2-mercaptoethyl)- benzenesulfonamide bentazon 3-isopropyl-lH-2,1,3- benzothiadiazin-4(3H)-one 2,2- dioxide benzipram 3,5-dimethyl-N-(1-methylethyl)-N- (phenylmethyl)benzamide benzoylprop N-benzoyl-N-(3,4-dichloropheny1)-DL- alaine bifenox methyl 5-(2,4-dichlorophenoxy)-2- nitrobenzoate bromacil 5-bromo-3-sec-butyl-6-methyluracil

Common Name Chemical Name bromoxynil 3,5-dibromo-4-hydroxybenzonitrile butachlor N-(butoxymethyl)-2-chloro-2',6'- diethylacetanilide butam 2,2-dimethyl-N-(1-methylethyl)-N- (phenylmethyl)propanamide buthidazole 3-[5-(1,1-dimethylethyl)-1,3,4- thiadiazol-2-yl]-4-hydroxy-l- methyl-2-imidazolidinone butralin 4-(1,1-dimethylethyl)-N-(1-methyl- propyl)-2,6-dinitrobenzenamine butylate S-ethyl-diisobutylthiocarbamate cacodylic acid hydroxydimethylarsine oxide carbetamide D-N-ethyllactamide carbanilate (ester)

CDAA N-N-diallyl-2-chloroacetamide CDEC 2-chloroallyl diethyldithiocarbamate chlorbromuTon 3-(4-bromo-3-chlorophenyl)-1- methoxy-1-methylurea chloroxuron 3-[£-(£-chlorophenoxy)phenyl]-1,1- dimethylurea chlorpropham isoproyl m-chlorocarbanilate chlorsulfuron 2-chloro-N-[(4-methoxy-6-methyl- 1,3,5-triazin-2-yl)amino- carbonyl]benzene-sulfonamide chlortoluron N'-(3-chloro-4-meth lpheny1-N' , '- dimehylurea cisanilide cis-2,5-dimethyl-N-phenyl-l- pyrrolidine-carboxamide

CMA calcium ethanearsonate cyanazine 2-[[4-chloro-6-(ethylamino)-s- triazin-2-yl]amino]-2- methylpropionitrile cycloate S-ethyl N-ethylthiocyclohexane- carbamate

Common Name Chemical Name cycluron 3-cyclooctyl-l,1-dimethylurea cyperquat l-methyl-4-phenylpyridinium cyprazine 2-chloro-4-(cyclopropylamino)-6- (isopropylamino)- -triazine cyprazole N-[5-(2-chloro-l,1-dimethylethyl)- 1,3,4-thiadiazol-2-yl] cyclopropanecarboxamide cypromid 3',4'-dichlorocyclopropanecar- boxanilide dalapon 2,2-dichloropropionic acid dazomet tetrahydro-3,5-dimethyl-2H-l,3,5- thiadiazine-2-thione

DCPA dimethyl tetrachloroterephthalate desmetryn 2-(isopropylamino)-4-(methylamino)- 6-methylthio)- -triazine diallate S-(2,3-dichloroallyl)diisopropyl- thiocarbamate dicamba 3,6-dichloro-o-anisic acid dichlobenil 2,6-dichlorobenzonitrile dichlorprop 2-(2, -dichlorophenoxy)propionic acid diclofop 2-[4-(2,4-dichlorophenoxy)phenoxyl]- propanoic acid diethatyl N-(chloroacetyl)-N-(2,6- diethylphenyl)-glycine difenzoquat 1,2-dimethy1-3,5-diphenyl-lH- pyrazolium dinitramine N ⁴ ,N ⁴ -diethyl-α, ,α-tri luoro-3,5- dinitrotoluene-2,4-diamine dinoseb 2-sec-butyl-4,6-dinitrophenol diphenamide N,N-dimethy1-2,2-diphenylacetamide dipropetryn 2-(ethylthio)-4,6-bis(isopropyl¬ amino)-s_-triazine

Common Name Chemical Name diquat 6,7-dihydrodipyrido[1,2-α:2' ,1'-c]- pyrazinediium ion diuron 3-(3,4-dichloropheny1)-1,1- dimethylurea

DSMA disodium methanearsonate endothall 7-oxabicyclo[2.2.1]heptane-2,3- dicarboxylic acid erbon 2-(2,4,5-trichlorophenoxy)ethyl 2.2- dichloropropionate ethafluralin N-ethyl-N-(2-methyl-2-propenyl)-2,6- dinitro-4-(tri luoromethyl)- benzenamine ethofumesate (+)-2-ethoxy-2,3-dihydro-3,3- dimethyl-5-benzofuranyl methanesulfonate fenac (2,3,6-trichlorophenyl)acetic acid fenoxaprop ethyl 2-(4-(6-chloro-2-benzoxazolyl- oxy)phenoxy) ropanoate fenuron 1,l-dimethyl-3-phenylurea fenuron TCA 1,2-dimethyl-3-phenylurea mono(trichloroacetate) flamprop N-benzoyl-N-(3-chloro-4- luorophenyl)-DL-aniline fluchloralin N-(2-chloroethyl)-2,6-dinitro-N- propyl-4-(trifluoromethyl)aniline fluometuron 1,l-dimethyl-3- ( , ,α-trifluoro-m- tolyl)-urea fluorodifen £-nitrophenyl α, a, a-trifluoro-2- nitro-£-tolyl ether fluridone l-methyl-3-phenyl-5-[3-(trifluoro¬ methyl)phenyl]-4-(IH)-pyridinone fomesafen 5-(2-chloro-4-tri luoromethyl- phenoxy)-N-methylsulfonyl-2- nitrobenzamide

Common Name Chemical Name fosa ine ethyl hydrogen (aminocarbonyl)- phosphonate glyphosate N-(phosphonomehy1)glycine hexaflurate potasium hexafluoroarsenate hexazinone 3-cyclohexyl-6-(dimethylamino)-1- methyl-1,3,5-triazine-2, (IH, 3H)- dione lπ-azaquin 2-(4,5-dihydro-4-methyl-4-(1-methyl- ethyl)-5-oxo-lH-imidazol-2-yl)-3- quinolinecarboxylic acid ioxynil 4-hydroxy-3,5-diiodobenzonitrile isopropalin 2,6-dinitro-N,N-dipropylcumidine karbutilate tert-butylcarbamic acid ester with 3-(m-hydroxyphenyl)-1,1- dimethylurea lactofen 1'-(carboethoxy)ethyl-5-(2-chloro-4- (trifluoromethyl)phenoxy)-2- nitrobenzoate lenacil 3-cyclohex l-6,7-dihydro-lH- cyclopentapyrimidine-2,4(3H,5H)- dione

[[(trifluoromethyl)- sulfonyl]amino]phenyl]acetamide

Common Name Chemical Name methalpropalin N-(2-methyl-2-propenyl)-2.6-dinitro- N-propyl-4-(trifluoromethyl)- benzenamide methabenzthiazuron 1,3-dimethyl-3-(2-benzothiazolyl) urea etham sodium methyldithiocarbamate methazole 2-(3,4-dichlorophenyl)-4-methyl- 1,2,4-oxadiazolidine-3,5-dione methoxuron N'-(3-chloro-4-methoxyphenyl)N,N- dimethylurea metolachlor 2-chloro-N-(2-ethyl-6-methylphenyl)- N-(2-methoxy-l-methylethyl)- acetamide metribuzin 4-amino-6-tert-butyl-3-(methylthio)- as-triazine-5(4H)-one metsulfuron methyl 2-[[(4-methoxy-6-methyl-l,3,5- triazine-2-yl)aminocarbonyl]amino- sulfonyl]benzoic acid, methyl ester molinate S-ethyl hexahydro-lH-azepine-1- carbothioate monolinuron 3-(£-chlorophenyl)-1-methoxy-l- methylurea monuron 3-(£-chlorophenyl)-1,1-dimethylurea monuron TCA 3-(£-chlorophenyl)-1,1-dimethylurea mono(trichloroacetate)

MSMA monosodium methanearsonate napropamide 2-( -naphthoxy)-N,N- diethylpropionamide naptalam N-1-naphthylphthalamic acid neburon l-butyl-3-(3,4-dichlorophenyl)-1- methylurea nitralin 4-(methylsulfony1)-2,6-dinitro-N,N- dipropylaniline

Common Name Chemical Name nitrofen 2, -dichlorophenyl £-nitrophenyl ether nitro luorofen 2-chloro-l-(4-nitrophenoxy)-4- (trifluoromethyl)benzene norea 3-(hexahydro-4.7-methanoindan-5-yl)- 1.1-dimethylurea norflurazon 4-chloro-5-(methylamino)-2-(α, ,α- trifluoro-m-tolyl)-3(2H)- pyridazinone oryzalin 3, -dinito-N,N-dipropylsul anilamide oxadiazon 2-tert-buty1-4-(2,4-dichloro-5- isopropoxyphenyl)Δ2-1,3,4- oxadiazolin-5-one oxyfluorfen 2-chloro-l-(3-ethoxy-4-nitro- phenoxy)-4-(tri luoro¬ methyl)benzene paraquat 1,1'-dimethyl-4, '-bipyridinium ion

PBA chlorinated benzoic acid pendimethalin N-(1-ethylpropy1)-3,4-dimethyl-2,6- dinitrobenzenamine perfluidone 1,1,1-trifluoro-N-[2-methyl-4- (phenylsulfonyl)phenyl]methane- sulfonamide picloram 4-amino-3,5,6-trichloropicolinic acid procyazine 2-[[4-chloro-6-(cyclopropylamino)- 1,3,5-triazine-2-yl]amino]-2- methylpropanenitrile profluralin N-(cyclopropylmethyl) -a, a, a- trifluoro-2,6-dinitro-N-propyl-£- toluidine prometon 2, -bis(isopropylamino)-6-methoxy-s- triazine prometryn 2, -bis(isopropylamino)-6- (methylthio)-s-triazine

Common Name Chemical Name pronamide 3,5-dichloro N-(l,l-dimβthyl-2- propyn-yl)enzamide propachlor 2-chloro-N-isopropylacetanilide propanil 3' ,4'-dichloroprionalide propazine 2-chloro-4,6-bis(isopropylamino)-s_- triazine propham isopropyl carbanilate prosulfalin N-[[4-(dipropylamino)-3,5- dinitrophenyl]sulfonyi]-S,S- dimethylsulfilimine prynachlor 2-chloro-N-(l-methyl-2- propynyl) cetanilide quinofop ethyl 2-[4-(6-chloroquinoxalin-2-yloxy)- phenoxypropanoic acid, ethyl ester secbumeton N-ethyl-6-methoxy-N' (1- methylpropyl)-1,3,5-triazine-2,4- diamine sethoxydim 2-[1-(ethoxyimino)butyl]-5-[2- (ethylthio)propyl]-3-hydroxy-2- cyclohexene-1-one siduron 1-(2-methylcyclohexyl)-3-phenylurea simazine 2-chloro-4,6-bis(ethylamino)-s- triazine simetryn 2,4-bis(ethylamino)-6-(methylthio)- s-triazine supriox 2-[1-(2,5-dimethylphenyl)- ethylsulfonyl]-pyridine-N-oxide

TCA trichloroacetic acid tebuthiuron N-[5-(1,1-dimethylethyl)-1,3,4- thiadiazol-2-yl]-N,N'-dimethylurea terbacil 3-tert-butyl-5-chloro-6-methyluracil terbuchlor N-(butoxymethyl)-2-chloro-N-[2-(1.1- dimethylethyl)-6-methylphenyl]- aceamide terbuthylazine 2-(tert-butylamino)-4-chloro-6- (ethylamino)-s-triazine

Common Name Chemical Name terbutol 2,6-di-tert-butyl-p-tolyl methylcarbamate terbutryn 2-(tert-butylamino)-4-(ethylamino)- 6-(methylthio)-s-triazine tetra luron N,N-dimethyl-N'-[3-(1,1,2,2- tetrafluoroethoxy)phenyl]urea thiobencarb S-[(4-chlorophenyl)methyl] diethylcarbamothioate triallate S-(2,3,3-trichloroallyl)- diisopropylthiocarbamate trifluralin a, a,α-tifluoro-2,6-dinitro-N,N- propyl-£-toluidine trimeturon 1-(£-chlorophenyl)-2,3,3- trimethylpseudourea vernolate S-propyl dipropylthiocarbamae ethyl 5-[2-chloro-4-(trifluoromethyl)- phenoxy]-2-nitrobenzoic acid

2,3,6-TBA 2,3,6-trichlorobenzoic acid 2,4-D (2,4-dichlorophenoxy)acetic acid 2,4-DB 4-(2,4-dichlorophenoxy)butyric acid 2,4-DEP tris[2-(2, -dichlorophenoxy)ethyl] phosphite

Trade Name or Code Number Chemical Name

"Cinch" exo-l-methyl-4-(1-methylethyl)-2-[2- methylphenyl)methoxy]7- oxabicyclo[2.2.1]heptane

AC 263,499 2-[4,5-dihydro-4-methyl-4-(1-methyl¬ ethyl)-5-oxo-lH-imidazol-2-yl]-5- ethyl-3-pyridinecarboxylic acid

Harmony TM 3-[[(4-methoxy-6-methyl-l,3-5- triazin-2-yl)aminocarbonyl]amino- sul onyl]-2-thiophenecarboxylic acid, methyl eser

Trade Name or Code Number Chemical Name

PPG-1013 5-(2-chloro-4-(trifluoromethyl)- phenoxy)propanoic aicd, methyl ester

FMC 57020 2-(2'-chloropheny1)meth 1-4,4- dimethyl-3-isoxazolidinone AC 222,293 6-(4-isopropyl-4-methyl-5-oxo-2- imidazolin-2-yl)-m-toluic acid,meth l ester and 6-(4- isopropyl-4-methyl-5-oxo-2- imidazolin-2-yl-£-toluic acid, methyl ester

The herbicidal properties of the subject compounds were discovered in a number of greenhouse tests. The test procedures and results follow.

This invention is further illustrated by the following examples.

Example A The test compounds were dissolved in acetone in an amount equal to 6% of the final volume and then suspended at a concentration of 100 or 20 ppm in purified water containing 250 ppm of the surfactant TREM 014 (polyhydric alcohol esters) . This suspension was sprayed to the point of run-off on apple seedings. The following day plants were inoculated with a spore suspension of Venturia inaequalis, the causal agent of apple scab, and incubated in a saturated humidity chamber at 20°C for 24 hours and then in a growth chamber at 22°C for 11 days, when disease ratings were made.

Example B The test compounds were dissolved in acetone in an amount equal to 6% of the final volume and then suspended at a concentration of 100 or 20 ppm in purified water containing 250 ppm of the surfactant

TREM 014 (polyhydric alcohol esters) . This suspension was sprayed to the point of run-off on peanut seedlings. The following day plants were inoculated with a spore suspension of Cercosporidium personatum, the causal agent of Peanut Late Leafspot, and incubated in a saturated humidity chamber at 22°C for 24 hours, then in a high humidity chamber at 27°C for 7 days, and then in a growth chamber at 29°C for 7 days, when disease ratings were made.

Example C

The test compounds were dissolved in acetone in an amount equal to 6% of the final volume and then suspended at a concentration of 100 or 20 ppm in puri ied water containing 250 ppm of the surfactant

TREM 014 (polyhydric alcohol esters) . This suspension was sprayed to the point of run-off on broad bean

seedlings. The following day plants were inoculated with a spore suspension of Botrytis cinerea, the causal agent of bean grey mold, and incubated in a saturated humidity chamber at 20°C for 24 hours when disease ratings were made.

Example D The test compounds were dissolved in acetone in an amount equal to 6% of the final volume and then suspended at a concentration of 100 or 20 ppm in purified water containing 250 ppm of the surfactant TREM 014 (polyhydric alcohol esters) . This suspension was sprayed to the point of run-off on wheat seedlings. The following day plants were inoculated with a spore dust of Erysiphe graminis f. sp. tritici, the causal agent of wheat powdery mildew, and incubated in a growth chamber at 20°C for 6 days, when disease ratings were made.

Example E

The test compounds were dissolved in acetone in an amount equal to 6% of the final volume and then suspended at a concentration of 100 or 20 ppm in purified water containing 250 ppm of the surfactant TREM 014 (polyhydric alcohol esters) . This suspension was sprayed to the point of run-off on rice seedlings. The following day plants were inoculated with a spore suspension of Pyricularia oryzae, the causal agent of rice blast, and incubated in a saturated humidity chamber at 27°C for 24 hours and then in a growth chamber at 29°C for 4 days, when disease ratings were made.

Example F The test compounds were dissolved in acetone in an amount equal to 6% of the final volume and then suspended at a concentration of 100 or 20 ppm in purified water containing 250 ppm of the sur actant TREM 014 (polyhydric alcohol esters) . This suspension was sprayed to the point of run-off on rice seedlings. The following day plants were inoculated with a spore suspension of Rhizoctonia solani, the causal agent of rice sheath blight, and incubated in a saturated humidity chamber at 27°C for 48 hours and then in a growth chamber at 29 ^β C for 4 days, when disease ratings were made.

Example G The test compounds were dissolved in acetone in an amount equal to 6% of the final volume and then suspended at a concentration of 100 or 20 ppm in purified water containing 250 ppm of the surfactant

TREM 014 (polyhydric alcohol esters) . This suspension was sprayed to the point of run-off on wheat seedlings. The following day plants were inoculated with a spore suspension of Puccinia recondita, the causal agent of wheat leaf rust, and incubated in a saturated humidity chamber at 20°C for 24 hours and then in a growth chamber at 20°C for 8 days, when disease ratings were made.

Example H

The test compounds were dissolved in acetone in an amount equal to 6% of the final volume and then suspended at a concentration of 100 or 20 ppm in purified water containing 250 ppm of the surfactant TREM 014 (polyhydric alcohol esters) . This suspension was sprayed to the point of run-off on tomato seedlings. The following day plants were inoculated

with a spore suspension of Phytophthora infestans, the causal agent of tomato late blight, and incubated in a saturated humidity chamber at 20°C for 24 hours and then in a growth chamber at 20°C for 5 days, when disease ratings were made.

Example I The test compounds were dissolved in acetone in an amount equal to 6% of the final volume and then suspended at a concentration of 100 or 20 ppm in purified water containing 250 ppm of the surfactant TREM 014 (polyhydric alcohol esters) . This suspension was sprayed to the point of run-off on grape seedlings. The following day plants were inoculated with a spore suspension of Plasmorpara viticola, the causal agent of grade downy mildew, and incubated in a saturated humidity chamber at 20°C for 24 hours, then in a growth chamber at 20°C for 7 days and then held in a saturated humidity chamber at 20°C for 24 hours, when disease ratings were made.

Example J The test compounds were dissolved in acetone so that 1 ml of solution yielded a concentration of 0.5 kilogram/hectare when added to cucumber seeds and soil in pots. Seeds and soil were then inoculated with a mixture of sand, cereal and mycelium of the fungus Pythium aphanadermaturn, causal agent of cucumber damping off, and incubated in a growth chamber at 30°C for 14 days. Disease ratings were then made.

Example K The test compounds were dissolved in acetone so that 1 ml of solution yielded a concentration of 0.5

kilogram/hectare when added to cotton seeds and soil in pots. Seeds and soil were then inoculated with a mixture of sand, cereal and mycelium of the fungus Rhizoctonia solani, causal agent of cotton blight, and incubated in a growth chamber at 30°C for 14 days. Disease ratings were then made.

Example L The test compounds were dissolved in acetone so that 1 ml of solution yielded a concentration of 0.5 kilogram/hectare when added to cucumber seeds and soil in pots. Seeds and soil were then inoculated with a mixture of sand, cereal and mycelium of the fungus Fusarium oxysporum . sp. cucumerinum, causal agent of cucumber wilt, and incubated in a growth chamber at 30°C for 14 days. Disease ratings were then made.

Example M The test compounds were dissolved in acetone so that 1 ml of solution yielded a concentration of 0.5 kilogram/hectare when added to lima bean seeds and soil in pots. Seeds and soil were then inoculated with a mixture of sand, cereal and mycelium of the fungus Sclerotium rolfsii, causal agent of southern blight, 3-3--- incubated in a growth chamber at 30°C for 14 days. Disease ratings were then made.

Results for Examples A-M are given in Table 7. In this table, a rating of 100 indicates 100% disease control and a rating of 0 indicates no disease control relative to the controls. A - entry indicates that no test was performed with the specified compound. A P entry indicates that disease control was not measured due to phytoxicity.

Table 7 (Continued)

Table 7 (Continued)

Ex. Ex. Ex. Ex. J K L M

P P P P 0 P P P 0 20 0 0

0 0 0 0 0 0 0 0

Test A

Seeds of crabgrass (Digitaria spp.), barnyardgrass (Echinochloa crusgalli), giant foxtail (Setaria faberii) , wild oats (Avena fatua) , cheatgrass (Bromus secalinus) , Yβlvetleaf (AbutiIon theophrasti) , morningglory (Ipomoea spp.) , cocklebur (Xanthium pensylvanicum) , sorghum, corn, soybean, sugarbeet, cotton, rice, wheat, barley and purple nutsedge (Cyperus rotundus) tubers were planted and treated preemergence with the test chemicals dissolved in a non-phytotoxic solvent. At the same time, these crop and weed species were treated with a soil/foliage application. At the time of treatment, the plants ranged in height from 2 to 18 cm. Treated plants and controls were maintained in a greenhouse for sixteen days, after which all species were compared to controls and visually rated for response to treatment. The ratings, summarized in Table A, are based on a numerical scale extending from 0 = no injury, to 10 = complete kill. The accompanying descriptive symbols have the following meanings:

C = chlorosis/necrosis; B = burn; D = defoliation; E = emergence inhibition;

G = growth retardation; H = formative effect; U = unusual pigmentation; X = axillary simulation; S = albinism; and

Y = abscised buds or flowers.

TABLE A

TABLE A (CONTINUED)

CMPD 56

CMPD 56 (salt)

RΛTE--KG/HA 0. 4

POSTEMERGEHCE RATE--KG/HA 0.4 COKER COTTON 7P,9G POSTEMERGEHCE CULT MORNINGLRY 4C,9β COKER COTTON 4H COCKLEBUR 3H.SG CULT MORNINGLRY 3C.7G

PURPLE NUTSEDGE 0 COCKLEBUR 2C LARGE CRABGRASS 4G PURPLE NUTSEDGE 0 BARNYARDGRASS 5G LARGE CRABGRASS 0 WILD OATS 0 BARNYARDGRASS 0

ERA WHEAT 0 WILD OATS 0

G4646 CORN 0 ERA WHEAT 0

WILLMS SOYBEANS 3C,»G 64646 CORN 0 BICE DRY SEEDED 0 WILLMS SOYBEANS 1C G522 SORGHUM 0 RICE DRY SEEDED 0 CHEAT GRASS 0 G522 SORGHUM 0 USH11 SUGARBEET 5H,5I USH11 SUGARBEET 2H

VELVETLEAF 7G VELVETLEAF 2G GIANT FOXTAIL 0 GIANT FOXTAIL 0 KLAGES BARLEY 0 KLAGES BARLEY 0 DOWNY BROKE 0

CMPD 56

RATE■ G/HA 0.4 CMPD 56 PREEMERGENCE BATEoKG/HA 0.4

COKER COTTON 5 _G PREEMERGENCE

CULT MORNINGLRY 4C.9G COKER COTTON 0

COCXLEBUR 26 CULT MORNINGLRY 0

PURPLE NUTSEDGE 56 COCKLEBUR 0

LARGE CRABGRASS 4C.9G PURPLE NUTSEDGE 0

BARNYARDGRASS 7C.9H LARGE CRABGRASS 9G WILD OATS 0 BARNYARDGRASS 0

ERA WHEAT 0 WILD OATS 0

G4646 CORN 0 ERA WHEAT 0

WILLMS SOYBEANS 7G G4646 CORN 0 RICE DRY SEEDED 0 WILLMS SOYBEANS 0

G522 SORGHUM 7G BICE DRY SEEDED 0

CHEAT GRASS 5G 6522 SORGHUM .0

USH11 SUGARBEET 6G USH11 SUGARBEET 3K

VELVETLEAF 4C.9G VELVETLEAF 0

GIANT FOXTAIL 9H GIANT FOXTAIL 4C.96

KLAGES BARLEY 0 KLAGES BARLEY 0 DOWNY BROKE 0

174

TABLE A (CONTINUED)

CMPD 57 CMPD 58

BATE-KG/HΛ 0.4 RATE»KG/HA 0.4 POSTEMERGEHCE POSTEMERGENCE

10 COKER COTTON 10P,9G COKER COTTON 10P.9G CULT MORNINGLRY 5C.9G CULT MORNINGLRY 2C.36 COCKLEBUR IH COCKLEBUR 2C.8H PURPLE NUTSEDGE 5G PURPLE NUTSEDGE 0 LARGE CRABGRASS 9C LARGE CRABGRASS 2C.SH BARNYARDGRASS 7H BARNYARDGRASS 0 WILD OATS 0 WILD OATS 0 ERA WHEAT 0 ERA WHEAT 0 G4646 CORN 0 G4646 CORN 0 WILLMS SOYBEANS 4C,9β WILLMS SOYBEANS 4C.9G

15 BICE DRY SEEDED 0 RICE DRY SEEDED 0 G522 SORGHUM 0 G522 SORGHUM 0 CHEAT GRASS 0 CHEAT GRASS 0 USHll SUGARBEET 4H-5I USHll SUGARBEET 3H,7G VELVETLEAF 4C.9G VELVETLEAF 2C,8G GIANT FOXTAIL 9G GIANT FOXTAIL 0 KLAGES BARLEY 0 KLAGES BARLEY 0

CMPD 57 CMPD 58

RATE----G/HΛ 0.4 BΛTE->KG/HA 0.4 PREEMERGENCE PREEMERGENCE

20 COKER COTTON 7G COKER COTTON 86 CULT MORNINGLBY 4C.9G CULT MORNINGLRY 8G COCKLEBUR 0 COCKLEBUR 3G PURPLE NUTSEDGE 0 PURPLE NUTSEDGE 0 LARGE CRABGRASS 4C,9G LARGE CRABGRASS 96 BARNYARDGRASS 9C BARNYARDGRASS 4C.9H WILD OATS 0 WILD OATS 0 ERA WHEAT 2G ERA WHEAT 0 G4646 CORN 2G G46 6 CORN 3G WILLMS SOYBEANS 3C,9G WILLMS SOYBEANS 4G

25 BICE DRY SEEDED 0 RICE DRY SEEDED 0 G522 SORGHUM 8G G522 SORGHUM 7G CHEAT GRASS 9G CHEAT GRASS 3G USHll SUGARBEET 7H USHll SUGARBEET 96 VELVETLEAF 5C.9G VELVETLEAF 5G GIANT FOXTAIL 9H GIANT FOXTAIL 3C.96 KLAGES BARNEY 2G KLAGES BARLEY

30

35

TABLE A (CONTINUED)

CMPD 59 CMPD 61

RATE-K6/HA 0.4 RATE-KG/HA 0.4

POSTEHERGENCE POSTEMERGEHCE COKER COTTON 2B CULT MORNINGLRY • * r COCKLEBUR 1C PURPLE NUTSEDGE 0 LARGE CRABGRASS 0 BARNYARDGRASS 0 WILD OATS 0 ERA WHEAT 0 G4646 CORN 0 WILLMS SOYBEANS 3H RICE DRY SEEDED 0 G522 SORGHUM 0 USHll SUGARBEET 3H VELVETLEAF 3C.5G GIANT FOXTAIL 0 KLAGES BARLEY 0 DOWNY BROME 0

59 CMPD 61

BATE--KG/HΛ 0.4 PREEMERGENCE COKER COTTON 0 CULT MORNINGLRY 0 COCKLEBUR 0 PURPLE NUTSEDGE 0 LARGE CRABGRASS 0 BARNYARDGRASS 0 WILD OATS 0 ERA WHEAT 0 64646 CORN 0 WILLMS SOYBEANS 0 RICE DRY SEEDED 0 G522 SORGHUM 0 USHll SUGARBEET 0 VELVETLEAF 0 GIANT FOXTAIL 76 KLAGES BARLEY 0 DOWNY BROME 0

TABLE A (CONTINUED)

CMPD 66 CMPD 67

RΛTE--KG/KA 0.4 RATE-K6/HA 0.4 POSTEMERGEHCE COKER COTTON 10P.9G CULT MORNINGLRY 2C.26 COCKLEBUR 2C,56 PURPLE NUTSEDGE 0 LARGE CRABGRASS 46 BARNYARDGRASS 0 WILD OATS 0 ERA WHEAT 0 G4646 CORN 0 WILLMS SOYBEANS 1C.4H RICE DRY SEEDED 0 6522 SOR6HUM 0 CHEAT 6RASS 0 USHll SUGARBEET 7H.5I VELVETLEAF 2C,56 GIANT FOXTAIL 0 KLAGES BARLEY 0

CMPD 67

RATE--KG/HA 0.4 PREEMERGENCE COKER COTTON 0 CULT MORNINGLRY 0 COCKLEBUR 0 PURPLE NUTSEDGE 0 LARGE CRABGRASS 7G BARNYARDGRASS 3G WILD OATS 0 ERA WHEAT 0 G4646 CORN 0 WILLMS SOYBEANS IH RICE DRY SEEDED 0 G522 SORGHUM 0 CHEAT GRASS 3G USHll SUGARBEET 7G VELVETLEAF 0 GIAHT FOXTAIL 5G KLAGES BARLEY 0

TABLE A (CONTINUED)

CMPD 99 CMPD 101

RATE-KG/HA 0.4 RATE-KG/HA 0.4

POSTEMERGEHCE POSTEMERGEHCE

99 01

TABLE A (CONTINUED)

CMPD 106

RΛTE=-KG/HA 0.4 POSTEMERGEHCE COKER COTTON 46 CULT MORNINGLRY 2C-8G COCKLEBUR 2C,2H PURPLE NUTSEDGE 5G LARGE CRΛBGRASS 26 BARNYARDGRASS SH WILD OATS 0 ERA WHEAT 0 G4646 CORN 0 WILLMS SOYBEANS 2C.5G RICE DRY SEEDED 0 6522 SORGHUM 0 CHEAT GRASS 0 USHll SUGARBEET 5G VELVETLEAF 3C,7G GIANT FOXTAIL 0 KLAGES BARLEY 0

CMPD 106

RATE-KG/HA 0.4 PREEMERGENCE COKER COTTON 0 CULT MORNINGLRY 0 COCKLEBUR 0 PURPLE NUTSEDGE 0 LARGE CRABGRASS 4C.9H BARNYARDGRASS 0 WILD OATS 0 ERA WHEAT 0 G4646 CORN 0 WtLLMS SOYBEANS 2G RXCE DRY SEEDED 0 G522 SORGHUM 0 CHEAT 6RASS 0 USHll SUGARBEET 3H VELVETLEAF 0 GIANT FOXTAIL 3C,96 KLAGES BARLEY 36

179

TABLE A (CONTINUED)

10

15

20

25

30

35

TABLE A f mNTINUED)

RATE-KG/HA POSTEMERGEHCE COKER COTTON CULT MORNINGLRY COCKLEBUR LARGE CRABGRASS BARNYARDGRASS WILD OATS ERA WHEAT G4646 CORN WILLMS SOYBEANS RICE DRY SEEDED 6522 SORGHUM CHEAT GRASS USHll SUGARBEET VELVETLEAF GIANT FOXTAIL KLAGES BARLEY

RATE-KG/HA PREEMERGENCE COKER COTTON CULT MORNINGLRY COCKLEBUR PURPLE NUTSEDGE LARGE CRABGRASS BARNYARDGRASS WILD OATS ERA WHEAT G4646 CORN WILLMS SOYBEANS RICE DRY SEEDED 6522 SORGHUM CHEAT GRASS USHll SUGARBEET VELVETLEAF GIANT FOXTAIL KLAGES BARLEY

TABLE A (CONTINUED.

CMPD 598

RATE=KG/HA 0.4 POSTEMERGENCE

COKER COTTON 8G CULT MORNINGLORY 0 COCKLEBUR 2C PURPLE NUTSEDGE 3G LARGE CRABGRASS 2G BARNYARDGRASS 0 WILD OATS 2G ERA WHEAT 3G G4646 CORN 0 WILLMS SOYBEANS 2C,2H RICE DRY SEEDED 0 G522 SORGHUM 0 CHEAT GRASS 0 USHll SUGARBEET 4G,5I VELVETLEAF 0 GIANT FOXTAIL 3G KLAGES BARLEY 0

CMPD 598

RATE=KG/HA 0.4 PREEMERGENCE

COKER COTTON 0 CULT MORNINGLORY 0 COCKLEBUR 2G PURPLE NUTSEDGE 0 LARGE CRABGRASS 3C, 9G BARNYARDGRASS 2G WILD OATS 0 ERA WHEAT 0 G4646 CORN 0 WILLMS SOYBEANS 0 RICE DRY SEEDED 0 G522 SORGHUM 0 CHEAT GRASS 0 USHll SUGARBEET 7H VELVETLEAF 5G GIANT FOXTAIL 9G KLAGES BARLEY 0

TABLE A (CONTINUED)

CMPD 603

RATE-KG/HA 0.4 POSTEMERGENCE COKER COTTON 0 CULT MORNINGLRY 3B COCKLEBUR IB PURPLE NUTSEDGE 0 LARGE CRABGRASS 0 BARNYARDGRASS 0 WILD OATS 0 ERA WHEAT 0 G4646 CORN 0 WILLMS SOYBEANS 0 RICE DRY SEEDED 0 6522 SORGHUM 0 CHEAT GRASS 0 USHll SUGARBEET 0 VELVETLEAF IB 6IANT FOXTAIL 0 KLAGES BARLEY 0

CMPD 603

RATE-KG/HA 0.4 PREEMERGENCE COKER COTTON 0 CULT MORNINGLRY 0 COCKLEBUR 0 PURPLE NUTSEDGE 0 LARGE CRABGRASS 0 BARNYARDGRASS 0 WILD OATS 0 ERA WHEAT 0 64646 CORN 0 WILLMS SOYBEANS 0 RICE DRY SEEDED 0 6522 SORGHUM 0 CHEAT 6RASS 0 USHll SUGARBEET 0 VELVETLEAF 0 GIAHT FOXTAIL 0 KLAGES BARLEY 0

TABLE A (CONTINUED)

TABLE A (CONTTNITF-

CMPD 620 CMPD 624

RATE-KG/HA 0.4 RATE-KG/HA 0.4

POSTEMERGENCE POSTEMERGENCE COKER COTTON CULT MORNINGLRY COCKLEBUR PURPLE NUTSED6E LARGE CRABGRASS BARNYARDGRASS WILD OATS ERA WHEAT G4646 CORN WILLMS SOYBEANS RICE DRY SEEDED G522 SOR6HUM CHEAT 6RASS USHll SUGARBEET VELVETLEAF GIANT FOXTAIL KLAGES BARLEY

624

RATE-KG/HA PREEMERGENCE COKER COTTON CULT MORNINGLRY COCKLEBUR PURPLE NUTSEDGE LARGE CRABGRASS BARNYARDGRASS WILD OATS BRA WHEAT G4646 CORN WILLMS SOYBEANS RICE DRY SEEDED G522 SORGHUM CHEAT GRASS USHll SUGARBEET VELVETLEAF GIANT FOXTAIL KLAGES BARLEY

TABLE A (CONTINUED)

10

CMPD 644

RATE-K6/HA

POSTEMERGENCE CULT MORNINGLRY 6C,9G COCKLEBUR 5C.8H PURPLE NUTSEDGE 8G,5X

15 LARGE CRABGRASS 3C,9G BARNYARDGRASS 5C.9H WILD OATS 3C,6G ERA WHEAT 4C.86 G4646 CORN 3C,6H WILLMS SOYBEANS 9C RICE DRY SEEDED 3C.86 6522 SORGHUM 3C.9H CHEAT GRASS 2C.S6 USHll SUGARBEET 5G,5I

20 VELVETLEAF 96 GIANT FOXTAIL 3C.96 KLAGES BARLEY 2C.9G

RATE-KG/HA PREEMERGENCE COKER COTTON 9a CULT M0RNIN6LRY 96 COCKLEBUR 3C,7Q

25 PURPLE NUTSEDGE IP" LARGE CRABGRASS 9H BARNYARDGRASS 9C WILD OATS 4C,8G ERA WHEAT 9G G4646 CORN 2C,8H WILLMS SOYBEANS 86 RICE DRY SEEDED 66 6522 SOR6HUM 3C,96 CHEAT 6RASS 76 USHll SUGARBEET 96

30 VELVETLEAF 6C,96 GIANT FOXTAIL 9H KLΛGES BARLEY 36

35

TABLE A ( C-ONTINUED)

CMPD 644 CMPD 646

RATE-KG/HA 0.1 0.4 RATE-KG/HA 0.4 POSTEMERGENCE POSTEMERGENCE COKER COTTON 5G 2C.7G CULT MORNINGLRY 3C,3G 3C.56 COCKLEBUR 0 2C PURPLE NUTSEDGE 0 0 LARGE CRABGRASS 0 0 BARNYARDGRASS 0 0 WILD OATS 0 0 ERA WHEAT 0 0 G4646 CORN 0 0 WILLMS SOYBEANS 2C,2H 2C,5B RICE DRY SEEDED 0 1C G522 SORGHUM 0 0 USHll SUGARBEET 2G 76 VELVETLEAF 36 2C.6G GIANT FOXTAIL 0 2C.36 KLAGES BARLEY 0 0 DOWNY BROME 0 0

CMPD 644 646

RATE-KG/HA 0.1 0.4 PREEMERGENCE COKER COTTON 0 CULT MORNINGLRY 2C COCKLEBUR 0

PURPLE NUTSEDGE 10E loε LARGE CRABGRASS 3C.7H 5C, 9H BARNYARDGRASS 0 5C .9H WILD OATS 0 2C , 5β ERA WHEAT 0 0 64646 CORN 0 0 WILLMS SOYBEANS 0 0 RICE DRY SEEDED 0 0 G522 SORGHUM 0 4G USHll SUGARBEET 0 6H VELVETLEAF 0 2C GIΛNT FOXTAIL 3C.9H 5C.9H KLAGES BARLEY 0 0 DOWNY BROME 0 3C.56

TABLE A (CONTINUED)

CMPD 648 CMPD 651

RATE-KG/HA 0.4 RATE-KG/HA 0.4 POSTEMERGENCE POSTEMERGENCE COKER COTTON 9P.9G COKER COTTON 0 CULT MORNINGLRY 1C CULT MORNINGLRY 2C COCKLEBUR 2C COCKLEBUR 1C PURPLE NUTSEDGE 0 PURPLE NUTSEDGE 0 LARGE CRΛBGRASS 0 LARGE CRABGRASS 0 BARNYARDGRASS 0 BARNYARDGRASS 0 WILD OATS 0 WILD OATS 0 ERA WHEAT 0 ERA WHEAT 0 G4646 CORN 0 G4646 CORN 2G WILLMS SOYBEANS 2C WILLMS SOYBEANS ΪC RICE DRY SEEDED 0 RICE DRY SEEDED 0 G522 S0R6HUM 0 6522 SORGHUM 0 CHEAT 6RASS 0 CHEAT 6RASS 0 USHll SUGARBEET 46,51 USHll SUGARBEET IH VELVETLEAF 2C.56 VELVETLEAF 0 GIANT FOXTAIL 0 GIANT FOXTAIL 0 KLAGES BARLEY 0 KLAGES BARLEY 0

CMPD 648 CMPD 651

RATE-KG/HA 0.4 RATE-KG/HA 0.4 PREEMERGENCE PREEMERGENCE COKER COTTON 0 COKER COTTON 0 CULT MORNINGLRY 0 CULT MORNINGLRY 0 COCKLEBUR 0 COCKLEBUR 0

PURPLE NUTSEDGE 0 PURPLE NUTSEDGE 0

LARGE CRΛBGRASS 3C,8G LARGE CRABGRASS 0 BARNYARDGRASS 0 BARNYARDGRASS 0 WILD OATS 0 WILD OATS 0

ERA WHEAT 0 ERA WHEAT 0

G4646 CORN 26 G4646 CORN 0 WILLMS SOYBEANS 0 WILLMS SOYBEANS 0 RICE DRY SEEDED 0 RICE DRY SEEDED 0 G522 SORGHUM 0 6522 S0R6HUM 0

CHEAT 6RASS 26 CHEAT 6RASS 0

USHll SUGARBEET 7H USHll SUGARBEET 0

VELVETLEAF 4G VELVETLEAF 0

GIANT FOXTAIL 2C,96 GIANT FOXTAIL 0

KLAGES BARLEY 3G KLAGES BARLEY 0

TABLE A (CONTINUED)

CMPD 653 CMPD 656

RATE-KG/HA 0.4 RATE-KG/HA 0.4 POSTEMERGENCE P ^OS TEMεRGENCE COKER COTTON 10P.96 COKER COTTON 76 CULT MORNINGLRY 2C CULT MORNINGLRY 2C,3H COCKLEBUR 2C,5G COCKLEBUR 2C LARGE CRABGRASS 5C,96 PURPLE NUTSEDGE 2G BARNYARDGRASS 0 LARGE CRABGRASS 2G WILD OATS 0 BARNYARDGRASS 0 ERA WHEAT 0 WILD OATS 0 G4646 CORN 26 ERA WHEAT 0 WILLMS SOYBEANS 3C.76 64646 CORN 0 RICE DRY SEEDED 0 WILLMS SOYBEANS 2C 6522 SORGHUM 0 MCE DRY SE8D8D 0 CHEAT GRASS 0 6522 SORGHUM 0 USHll SUGARBEET 2C.7H CHEAT GRASS 0 VELVETLEAF 1C USHll SUGARBEET 4H GIANT FOXTAIL 2C,7H GIANT FOXTAIL 0 KLAGES BARLEY 0 KLA6ES BARLEY 0

CMPD 653 CMPD 656

RATE-KG/HA 0.4 RATE-KG/HA 0.4 PREEMERGENCE PREEMER6ENCE COKER COTTON 56 COKER COTTON 0 CULT MORNINGLRY 2C.5G CULT MORNINGLRY 0 COCKLEBUR 2H COCKLEBUR 0 PURPLE NUTSEDGE 0 PURPLE NUTSEDGE 26 LARGE CRABGRASS 9C LARGE CRABGRASS 5C _f 9H BARNYARDGRASS 3C,9G BARNYARDGRASS 0 WILD OATS 0 WILD OATS 0 ERA WHEAT 2G ERA WHEAT 0 G4 46 CORN 0 64646 CORN 0 WILLMS SOYBEANS 0 WILLMS SOYBEANS 0 RICE DRY SEEDED 0 SICE DRY SEEDED 0 6522 SOR6HUM 76 6522 S0R6HUM 0 CHEAT 6RASS 86 CHEAT 6RASS 0 USHll SU6ΛRBEET 8H USHll SUGΛRBEεT 2H VELVETLεAF 5C.96 VELVETLEAF 0 GIANT FOXTAIL 5C.9H GIANT FOXTAIL 4C,9H KLAGES BARLEY 0 KLAGES BARLEY 0

TABLE A ( CONTINUED)

CMPD 659

RATE-KG/HA 0.4 POSTEMERGENCE COKER COTTON 0 CULT MORNINGLRY 3C.6G COCKLEBUR 2'- ' PURPLE NUTSEDGE 0 LARGE CRABGRASS 0 BARNYARDGRASS 0 WILD OATS 0 ERA WHEAT 0 G4646 CORN 0 WILLMS SOYBEANS 3C RICE DRY SEEDED 0 G522 SORGHUM 0 CHEAT GRASS 0 USHll SUGARBEET 0 VELVETLEAF 2C.5G GIANT FOXTAIL 0 KLAGES BARLEY 0

CMPD 659

190

TABLE A (CONTINUED)

10

CMPD 669

RATE-KG/HA

POSTEMERGENCE

15

20

669

25

30

35

TABLE A (CONTINUED)

CMPD 673 CMPD 675

RATE-KG/HA 0.4 RATE-KG/HA 0.4 POSTEMERGENCE POSTEMERGENCE

673 675

TABLE A (CONTINUED)

CMPD 724

RATE-KG/HA 0.4 POSTEMERGENCE COKER COTTON 66 CULT MORNINGLRY 3C,5H COCKLEBUR 3C,4H PURPLE NUTSEDGE 2C.8H LARGE CRABGRASS 96 BARNYARDGRASS 2C,3H WILD OATS 0 ERA WHEAT 0 G4646 CORN 0 WILLMS SOYBEANS 4C.8H RICE DRY SEEDED 56 6522 SOR6HUM 0 CHEAT GRASS 0 USHll SUGARBEET 7H VELVETLEAF 9H GIANT FOXTAIL 96 KLAGES BARLEY 0

CMPD 724

RATE-KG/HA 0.4 PREEMERGENCE COKER COTTON 0 CULT HORNIN6LRY 2C.8H COCKLEBUR 0 PURPLE NUTSEDGE 0 LARGE CRABGRASS 2C.9H BARNYARDGRASS 5C,9H WILD OATS 0 ERA WHEAT 0 64646 CORN 0 WILLMS SOYBEANS 0 RICE DRY SEEDED 0 G522 SORGHUM 0 CHEAT GRASS 0 USHll SUGARBEET 5H VELVETLEAF 96 GIANT FOXTAIL 3C.9H KLAGES BARLEY 0

TABLE A (CONTINUED)

CMPD 724 CMPD 726

RATE-KG/HA 0.4 RATE-KG/HA 0.4

POSTEMERGENCE POSTEMERGENCE

724 726

TABLE A (CONTINUED)

CMPD 754

CMPD 753

RATE-KG/HA 0.4.

RATE-KG/HA 0.4 POSTEMERGENCE POSTEMERGENCE COKER COTTON 2H COKER COTTON 10P.96 CULT MORNIN6LRY 5C.96 CULT MORNINGLRY 4C.9G COCKLEBUR 2C.3H COCKLEBUR 2C,66 PURPLE NUTSED6E 0 PURPLE NUTSEDGE 0 LARGE CRABGRASS 0 LARGE CRABGRASS 4C,96 BARNYARDGRASS 0 BARNYARDGRASS 5H WILD OATS 0 WILD OATS 0 ERA WHEAT 0 ERA WHEAT 0 G4646 CORN 0 G4646 CORN 0 WILLMS SOYBEANS 2C,3H WILLMS SOYBEANS 9C BICE DRY SEEDED 0 RICE DRY SEEDED 0 G522 SORGHUM 0 G522 SOR6HUM 26 USHll SUGARBEET 76 CHEAT 6RASS 0 VELVETLEAF 36 USHll SUGARBEET 8H GIANT FOXTAIL 0 VELVETLEAF 3C,8G KLAGES BARLEY 0 GIANT FOXTAIL 2C,96 DOWNY BROME 0 KLAGES BARLEY 0

CMPD 754

CMPD 753 RATE-KG/HA 0.4

RATE-KG/HA 0.4 PREEMERGENCE PREEMERGENCE COKER COTTON 0 COKER COTTON 36 CULT H0RNIN6LBY 0 CULT MORNINGLRY 96 COCKLEBUR 0 COCKLEBUR 3H PURPLE HUTSED6E 0 PURPLE NUTSEDGE 96 LARGE CRABGRASS 8G LARGE CRΛBGRASS 9G BARNYARDGRASS 2B BARNYARDGRASS SG WILD OATS 0 WILD OATS 0 ERA WHEAT 0 ERA WHEAT 0 G4646 CORN 0 G4646 CORN 0 WILLMS SOYBEANS 0 WILLMS SOYBEANS 36 RICE DRY SEEDED 0 RICE DRY SEEDED 0 6522 SOR6HUM 0 G522 SORGHUM 56 USHll SUGARBEET 36 CHEAT GRASS 0 VELVETLEAF 0 USHll SUGARBEET 8H GIANT FOXTAIL 76 VELVETLEAF 46 KLAGES BARLEY 0 6IANT FOXTAIL 3C.9G DOWNY BROME 0 KLAGES BARLEY 0

TABLE A (CONTINUED)

CMPD 782

RATE-KG/HA 0.4 POSTEMERGENCE COKER COTTON L0P,9G CULT MORNINGLRY 5C,9G COCKLEBUR 8G PURPLE NUTSED6E 0 LARGE CRABGRASS 5C.96 BARNYARDGRASS 7H WILD OATS 0 ERA WHEAT 0 64646 CORN 0 WILLMS SOYBEANS 86 RICE DRY SEEDED 0 G522 SORGHUM 0 CHEAT GRASS 0 USHll SUGARBEεT 7H.5I VELV8TLEAF 8G 6IANT FOXTAIL 7G KLAGES BARLEY 0

CMPD 782

RATE-KG/HA 0.4 PREEMERGENCE COKER COTTON 0 CULT MORNINGLRY 3C,9H COCKLEBUR 0 PURPLE NUTSEDGE 0 LARGE CRABGRASS 3C,9G BARNYARDGRASS 2C.9H WILD OATS 0 ERA WHEAT 0 G4646 CORN 0 WILLMS SOYBEANS 3G RICE DRY SEEDED 0 G522 SOR6HUM 66 CHEAT GRASS 0 USHll SUGARBEET 96 VELVETLEAF 2C,86 GIANT FOXTAIL 9H KLAGES BARLEY 0

196

■CONTTNHTCn

CMPD (11

CMPD 810

RATE-KG/HA 0.4 POSTEMERGENCE

810 811

_TA BLE A (CONTINUED)

10

CMPD 815 CMPD 863

RATE-KG/HA 0.4 RATE-KG/HΛ 0.4 POSTEMERGENCE POSTEMERGENCE

COKER COTTON 2C,6G

CULT M0RNIN6LRY 1C,26

COCKLEBUR 2C PURPLE NUTSEDGE 0

15 LARGE CRABGRASS 0 BARNYARDGRASS 0 WILD OATS 0

ERA WHEAT 0

G4646 CORN 0

WILLMS SOYBEANS 2C RICE DRY SEEDED 0 6522 S0R6HUM 0 CHEAT GRASS 0 USHll SUGARBEET 0

20 VELVETLEAF 2C GIΛNT FOXTAIL 0 KLAGES BARLEY 0

CMPD 863

RATE-KG/HA 0.4 PREEMERGENCE

COKER COTTON 5G CULT M0RNIN6LRY 0

COCKLEBUR 26

25 PURPLE NUTSED6Z 46

LAR6E CRΛB6RASS 46

BARNYARDGRASS 36

WILD OATS 26 ERA WHEAT 0

64646 CORN 0

WILLMS SOYBEANS 0 RICE DRY SEEDED 0 6522 SOR6HUM 0

CHEAT GRASS 26 USHll SUGARBEET 0

30 VELVETLEAF 0 GIANT FOXTAIL 8G KLAGES BARLEY 0

35

198

TABLE A (CONTINUED)

10

CMPD 905

RATE-KG/HA 0.4 POSTEMERGENCE COKER COTTON 0

15 CULT MORNINGLRY 2C COCKLEBUR 0 PURPLE NUTSEDGE 0 LARGE CRABGRASS 0 BARNYARDGRASS 0 WILD OATS 0 ERA WHEAT 0 64646 CORN 0 WILLMS SOYBEANS 0 BICE DRY SEEDED 0

20 6522 SOR6HUM 0 CHEAT GRASS 0 USHll SUGARBEET 0 VELVETLEAF 0 GIANT FOXTAIL 0 KLAGES BARLEY 0

CMPD 905

RATE-KG/HA 0.4 PREEMERGENCE COKER COTTON 0

25 CULT MORNINGLBY 0 COCKLEBUR 0 PURPLE NUTSED6E 0 LARGE CRABGRASS 0 BARNYARDGRASS 0 WILD OATS 0 ERA WHEAT 0 G4646 CORN 0 WILLMS SOYBEANS 0 RICE DRY SEEDED 0

30 6522 SORGHUM 0 CHEAT GRASS 0 USHll SUGARBEET 0 VELVETLEAF 0 GIANT FOXTAIL 0 KLAGES BARLEY

35

TABLE A ( CONTINUED)

10

CMPD 1276 CMPD 1276 ( salt)

RATE-KG/HA 0.4 RATE-KG/HA 0.4 POSTEMERGENCE POSTEMERGENCE

15

20

25

30

35

TABLE A (CONTINUED)

RATE-KG/HA POSTEMERGENCE COKER COTTON CULT MORNINGLRY COCKLEBUR LARGE CRABGRASS BARNYARDGRASS WILD OATS ERA WHEAT G4646 CORN WILLMS SOYBEANS RICE DRY SEEDED G522 SORGHUM CHEAT GRASS USHll SUGARBEET VELVETLEAF GIANT FOXTAIL KLAGES BARLEY

BATE-KG/HA PBEEMERGENCε COKER COTTON CULT M0RNIN6LRY COCKLEBUR

PURPLE NUTSEDGE LARGE CRABGRASS BARNYARDGRASS WILD OATS ERA WHEAT G4646 CORN WILLMS SOYBEANS RICE DRY SEEDED G522 SORGHUM CHEAT GRASS USHll SUGARBEET VELVETLEAF GIANT FOXTAIL KLAGES BARLEY

TABLE A (CONTINUED)

RATE-KG/HA POSTEHERGENCE COKER COTTON CULT MORNIN6LRY COCKLEBUR PURPLE NUTSEDGE LARGE CRABGRASS BARNYARDGRASS WILD OATS ERA WHEAT G4646 CORN WILLMS SOYBEANS RICE DRY SEEDED G522 SORGHUM CHEAT GRASS USHll SUGARBEET VELVETLεAF GIANT FOXTAIL KLAGES BARLEY

RATE-KG/HA PREEMERGENCE COKER COTTON CULT MORNINGLRY COCKLEBUR PURPLE NUTSEDGE LARGE CRABGRASS BARNYARDGRASS WILD OATS ERA WHEAT G4646 CORN WILLMS SOYBEANS RICE DRY SEEDED 6522 SORGHUM CHEAT GRASS USHll SUGARBEET VELVETLEAF GIANT FOXTAIL KLAGES BARLEY

TABLE A (CONTINUED)

CMPD 1280

RATE-KG/HA

RATE-KG/HA 0.4 POSTEMERGENCE POSTEMERGENCE COKER COTTON COKER COTTON 76 CULT MORNINGLRY CULT MORNIN6LRY 2H COCKLEBUR COCKLEBUR 4H PURPLE NUTSEDGE PURPLE NUTSEDGE 0 LARGE CRABGRASS LARGE CRABGRASS 9H BARNYARDGRASS BARNYARDGRASS 5H WILD OATS WILD OATS 0 ERA WHEAT ERA WHEAT 0 64646 CORN 64646 CORN 0 WILLMS SOYBEANS WILLMS SOYBEANS 5C.96 BICE DRY SEEDED RICE DRY SEEDED 0 6522 S0R6HUM G522 SORGHUM 2G CHEAT GRASS CHEAT GRASS 0 USHll SUGARBEET USHll SUGARBEET 8H VELVETLEAF VELVETLEAF 7H 6IΛNT FOXTAIL GIANT FOXTAIL 9H KLAGES BARLEY KLAGES BARLEY 0

CMPD 1280 RATE-KG/HA

RATE-KG/HA 0.4 PBEEMEBGENCE PREEMERGENCE COKER COTTON COKER COTTON 26 CULT MORNINGLRY CULT MORNIN6LRY 2H COCKLEBUR COCKLEBUR 0 PURPLE NUTSEDGE PURPLE NUTSEDGE 0 LARGE CRABGRASS LARGE CRAB6RASS 9H BARNYARDGRASS BARNYARDGRASS 36 WILD OATS WILD OATS 0 ERA WHEAT ERA WHEAT 0 G4646 CORN 64646 CORN 0 WILLMS SOYBEANS WILLMS SOYBEANS 0 RICE DRY SEEDED RICE DRY SEEDED 0 6522 SORGHUM G522 S0R6HUM 0 CHEAT GRASS CHEAT 6RASS 0 USHll SUGARBEET USHll SUGARBEET 56 VELVETLEAF VELVETLEAF 5G GIANT FOXTAIL GIANT FOXTAIL 9H KLAGES BARLEY KLAGES BARLEY 0

TABLE A ( CONTINUED!

RATE-KG/HA POSTEMER6ENCE COKER COTTON CULT M0RNIN6LBY COCKLEBUR PURPLE NUTSED6E LARGE CRAB6RASS BARNYARDGRASS WILD OATS ERA WHEAT G4646 CORN WILLMS SOYBEANS RICE DRY SEEDED 6522 SOR6HUM CHEAT 6RASS USHll SU6ΛRBEET VELVETLEAF 61ANT FOXTAIL KLAGES BARLEY DOWNY BROME

BATE-KG/HA PREEMERGENCE COKER COTTON CULT MORNINGLRY COCKLEBUR PURPLE NUTSEDGE LARGE CRABGRASS BARNYARDGRASS WILD OATS ERA WHEAT G4646 CORN WILLMS SOYBEANS RICE DRY SEEDED 6522 SOR6HUM CHEAT GRASS USHll SUGARBEET VELVεTLEAF GIANT FOXTAIL KLAGES BARLEY DOWNY BROME

TABLE (CONTINUED ₎

CMPD CMPD

RATE-KG/HA 0.4 RATE-KG/HΛ 0.4

POSTEMERGENCE POSTEMERGENCE COKER COTTON 3H COKER COTTON 3C.9H CULT M0RNIN6LRY 1C.1H CULT MORNINGLRY 4C,8H COCKLEBUR 1C,36 COCKLEBUR 3C.8H PURPLE NUTSEDGE 0 PURPLE NUTSEDGE 56 LARGE CRABGRASS 0 LARGE CRABGRASS 96 BARNYARDGRASS 0 BARNYARDGRASS 2C,8H WILD OATS 0 WILD OATS 0 ERA WHEAT 0 ERA WHEAT 0 64646 CORN 26 G4646 CORN 2G WILLMS SOYBEANS 2C,3H WILLMS SOYBEANS 4C.86 RICE DRY SEEDED 0 RICB DRY SEEDED 56 6522 SORGHUM 0 6522 S0R6HUM 5G CHEAT GRASS 0 CHEAT GRASS 56 USHll SUGARBEET 86 USHll SUGARBEET 6H VELVETLEAF 0 VELVETLεAF 2C,8H GIANT FOXTAIL Q GIANT FOXTAIL 9G KLAGES BARLEY 0 KLAGES BARLEY 0

CMPD CMPD

RATE-KG/HA 0.4 RATE-KG/HA 0.4 PREEMERGENCE PREEMERGENCE COKER COTTON 0 COKER COTTON 8G CULT M0RNIN6LBY 0 CULT MORNIN6LRY 9H COCKLEBUR 0 COCKLEBUR 0 PURPLE NUTSEDGE 56 PURPLE NUTSEDGE 0 LARGE CRΛBGRASS 4C,96 LARGE CRABGRASS 9C BARNYARDGRASS IC BARNYARDGRASS 1 WILD OATS 0 oc WILD OATS 0 ERA WHEAT 2G ERA WHEAT 0 G4646 CORN 0 64646 CORN 0 WILLMS SOYBEANS 26 WILLMS SOYBEANS 0 RICE DRY SEEDED 36 BICE DRY SEEDED 0 6522 S0R6HUH 0 6522 SORGHUM 9H CHEAT GRASS 0 CHEAT GRASS 0 USHll SUGARBEET 4H USHll SUGARBEET VELVETLEAF 56 8H VELVETLEAF GIANT FOXTAIL 3C,9H 7H GIANT FOXTAIL KLAGES BARLEY 0 3C.9B KLAGES BARLEY 0

TABLE A (CONTINUED)

CMPD 11

CMPD

BATE-KG/HA

RATE-KG/HA 0.1 0.4 POSTEMERGENCE POSTEMERGENCE COKER COTTON CULT MORNINGLRY COCKLEBUR PURPLE NUTSEDGE LARGE CRABGRASS BARNYARDGRASS WILD OATS ERA WHEAT G4646 CORN WILLMS SOYBEANS RICE DRY SEEDED 6522 S0R6HUM USHll SUGARBEET VELVETLEAF GIANT FOXTAIL KLAGES BARLEY DOWNY BROME

11

RATE-KG/HA PREEMERGENCE COKER COTTON CULT MORNINGLRY COCKLEBUR PURPLE NUTSEDGE LARGE CRABGRASS BARNYARDGRASS WILD OATS BRA WHEAT 64646 CORN WILLMS SOYBEANS RICE DRY SEEDED 6522 SOR6HUM USHll SUGARBEET VELVETLεAF GIANT FOXTAIL KLAGES BARLEY DOWNY BROME

TABLE A (CONTINUED)

CMPD 15

RATE-KG/HA POSTEMERGENCE 0.4 COKER COTTON CULT MORNINGLRY 7G COCKLEBUR 2C,4H PURPLE NUTSEDGE 2C LARGE CRABGRASS 0 BARNYARDGRASS 0 WILD OATS 36 ERA WHEAT 0 G4646 CORN 0 WILLMS SOYBEANS 0 RICε DRY SEEDED 3C.5H 6522 S0R6HUM 0 USHll SUGARBEET 0 VELVETLEAF 0 GIANT FOXTAIL 5H KLAGES BARLEY 66 DOWNY BROME 0

0

RATE-KG/HA CMPD 15 PREEMERGENCE 0.4 COKER COTTON CULT MORNINGLRY 0 COCKLEBUR 0 PURPLE NUTSEDGE 0 LARGE CRABGRASS 96 BARNYARDGRASS 3C,9H WILD OATS 0 ERA WHEAT 0 G4646 CORN 0 WILLMS SOYBEANS 0 RICE DRY SEEDED 0 G522 SORGHUM 0 USHll SUGARBEET 0 VELVETLεAF 0 GIANT FOXTAIL 0 KLAGES BARLEY 66 DOWNY BBOME 0 0

TABLE A ( CONTINUED)

CMPD 17

CMPD 16

0.4 RATE-KG/HA 0.4

RATE-KG/HA POSTEMERGENCE P _O STEMERGENCE COKER COTTON 3H

COKER COTTON 8G CULT MORNIN6LRY 3C,4G

CULT MORNINGLRY 4C.9G COCKLEBUR 2C.5G * COCKLEBUR 2C,6G PURPLE NUTSED6E 0

PURPLE NUTSEDGE 0 BARNYARDGRASS 0

LARGE CRABGRASS 8G WILD OATS 0

BARNYARDGRASS 0 ERA WHEAT 0

WILD OATS 0 0 64646 CORN 0

ERA WHEAT WILLMS SOYBEANS 1C,2H

64646 CORN 0 RICE DRY SEEDED IC

WILLMS SOYBEANS 2C,2B 6522 SOR6HUM 0 RICE DRY SEEDED 2C CHEAT GRASS 0 6522 SORGHUM 0 USHll SUGARBEET 7H CHEAT GRASS 0 VELVETLEAF 0 USHll SUGARBEET 2G 6ZANT FOXTAIL 36 VELVETLεAF 66 KLAGES BARLEY 0 GIANT FOXTAIL 76 KLAGES BARLEY 0 CMPD 17

CMPD 16 RATE-KG/HA 0.4 PREEMERGENCE

RATE-KG/HA 0.4 COKER COTTON 0 PREEMERGENCE CULT MORNINGLRY 0 COKER COTTON 56 COCKLEBUR 0 _C ULT MORNINGLRY 0 PURPLE NUTSEDGE 10E COCKLEBUR u LARGE CRABGRASS 96

PURPLE NUTSEDGE 10E BARNYARDGRASS 36 LARGE CRABGRASS 8G BARNYARDGRASS 5G WILD OATS 0 WILD OATS 0 ERA WHEAT 0 ERA WHEAT 0 G4646 CORN 0 WILLMS SOYBEANS 0 G4646 CORN 26 RICE DRY SEEDED 0 WILLMS SOYBEANS 0

RICE DRY SEEDED 26 6522 SOR6HUM 0

G522 SORGHUM 0 CHEAT 6RASS 0 USHll SUGARBEET 0

CHEAT GRASS 0

USHll SUGARBEET 6G VELVETLEAF 26

VELVETLEAF 5G GIANT FOXTAIL 6G KLAGES BARLEY 0

GIANT FOXTAIL 9H

KLAGES BARLEY 0

20S

TABLE A (CONTINUED)

CMPD 18 CMPD 23

18 23

TABLE A (CONTINUED ⁾

CMPD 34

CMPD 33

RATE-KG/HA 0.4

RATE-K6/HA 0 . 4 POSTEMERGENCE P _O STEMERGENCE COKER COTTON 10P.8G COKER COTTON 10P , 9G CULT MORNINGLRY 3C,10P CULT MORNINGLRY 2C , 56 COCKLEBUR 2C.2H COCKLEBUR 3C 4H PURPLE NUTSEDGE 0 PURPLE NUTSEDGE 0 LARGE CRABGRASS 3G LARGE CRABGRASS 5C , 96 BARNYARDGRASS 0 BARNYARDGRASS 0 WILD OATS 0 WILD OATS 0 ERA WHEAT 0 ERA WHEAT 0 G4646 CORN 0 G4646 CORN 26

4C,96 WILLMS SOYBεANS 4C.96 WILLMS SOYBEANS RICε DRY SEEDED 2G RICE DRY SEEDED 0 G522 SOR6HUM 0 G522 SORGHUM 0 USHll SUGARBEET 7H CHEAT 6RASS 0 ,5I VELVETLEAF 5C,86 USHll SUGARBEET 8H GIANT FOXTAIL 0 VELVETLEAF 3C.86 KLAGES BARLEY 0 GIANT FOXTAIL 96 DOWNY BROME 3G KLAGES BARLEY 0

CMPD 33 CMPD 34

BATE-KG/HΛ 0.4

RATE-KG/HA 0.4 PREEMERGENCE PREEMERGENCE COKER COTTON 0 COKER COTTON SG CULT MORNINGLRY 66 CULT MORNINGLRY 76 COCKLEBUR 0 COCKLEBUR 26 PURPLE NUTSED6E 0 PURPLE NUTSEDGE 0 LARGE CRABGRASS 3C.96 LARGE CRABGRASS 86 BARNYARDGRASS 2C,8H BARNYARDGRASS 56 WILD OATS 0 WILD OATS 0 ERA WHEAT 0 ERA WHEAT 0 G4646 CORN 0 G4646 CORN 0 WILLMS SOYBEANS 0 WILLMS SOYBEANS 46 RICE DRY SEEDED 0 RICE DRY SEEDED 26 G522 SORGHUM 56 6522 S0R6HUM H USHll SUGARBEET 5H CHEAT GRASS 0 USHll SUGARBEET 76 VELVETLEAF 76 GIANT FOXTAIL 3C.9H VELVETLEAF 26 GIANT FOXTAIL 9H KLAGES BARLEY 0 DOWNY BROME 0 KLAGES BARLEY 0

210

TABLE A (CONTINUED)

CMPD 34 CMPD 34

RATE-KG/HA 0.4 RATE-KG/HA 0.4 POSTEMERGENCE POSTEMERGENCE COKER COTTON 4G CULT M0RNIN6LRY 0 COCKLEBUR 2C,3H PURPLE NUTSEDGE 0 LARGE CRABGRASS 56 BARNYARDGRASS 5H WILD OATS 0 ERA WHEAT 0 G4646 CORN 0 WILLMS SOYBEANS 4C.76 RICE DRY SEEDED 0 6522 SORGHUM 0 USHll SUGARBEET 66 VELVETLEAF 5C.96 GIANT FOXTAIL 0 KLAGES BARLEY 0 DOWNY BROME 0

34 CMPD 34

RATE-KG/HA 0.4 PREEMERGENCE COKER COTTON 0 CULT MORNINGLRY 2C,86 COCKLEBUR 0 PURPLE NUTSEDGE 0 LARGE CRABGRASS 4C.9G BARNYARD6RASS 3C,86 WILD OATS 0 ERA WHEAT 0 64646 CORN 26 WILLMS SOYBEANS 0 RICE DRY SEEDED 0 G522 SORGHUM 0 USHll SUGARBEET 4B VELVETLEAF 5C,86 GIANT FOXTAIL 3C.9G KLAGES BARLEY 0 DOWNY BROME 36

211

TABLE A (CONTINUED)

CMPD 35 CMPD 35 (salt)

RATE-KG/HA 0.4 RATE-KG/HA POSTEMERGENCE POSTEMERGENCE COKER COTTON COKER COTTON 10P.96 CULT MORNINGLRY CULT MORNINGLRY 5C,96 COCKLEBUR COCKLEBUR 4C.9H PURPLE NUTSEDGε PURPLE NUTSEDGE 86 LARGE CRABGRASS LARGE CRABGRASS 3C,9G BARNYARDGRASS BARNYARDGRASS 5C,9G WILD OATS WILD OATS 0 ERA WHEAT ERA WHEAT 0 G4646 CORN 64646 CORN 3C,7H WILLMS SOYBEANS WILLMS SOYBEANS 4C,96 RICE DRY SEEDED RICE DRY SEEDED 46 6522 S0R6HUM 6522 S0R6HUM 76 CHEAT GRASS CHEAT GRASS 4G USHll SUGARBEET USHll SUGARBEET 3H,76 VELVETLEAF VELVETLEAF 7C,96 GIANT FOXTAIL GIANT FOXTAIL 3C.9G KLAGES BARLEY KLAGES BARLEY 6G

35

RATE-KG/HA

PREEMERGENCE COKER COTTON CULT MORNINGLRY COCKLEBUR PURPLE NUTSEDGE LARGE CRABGRASS BARNYARDGRASS WILD OATS ERA WHEAT G4646 CORN WILLMS SOYBEANS RICE DRY SEEDED GS22 SORGHUM CHEAT GRASS USHll SUGARBEET VELVETLEAF GIANT FOXTAIL KLAGES BARLEY

TABLE A (CONTINUED)

CMPD 35 (salt) CMPD 35 (salt)

RATE-KG/HA 0.4 RATE-KG/HA 0.4 POSTEMERGENCE POSTEMERGENCE COKER COTTON 3H COKER COTTON 0 CULT MORNIN6LRY 3C.8G CULT MORNIN6LRY 0 COCKLEBUR 2C.1H COCKLEBUR 0 PURPLE NUTSEDGE 0 PURPLE NUTSEDGE 0 LARGE CRABGRASS 0 LARGE CRAB6RASS 0 BARNYARDGRASS 0 BARNYARDGRASS 0 WILD OATS 0 WILD OATS 0 ERA WHEAT 0 ERA WHEAT 0 G4646 CORN 2H 64646 CORN 0 WILLMS SOYBEANS 3C.96 WILLMS SOYBBANS 26 RICE DRY SEEDED 0 BICE DRY SEEDED 0 6522 SOR6HUM 0 6522 S0R6HUM 0 USHll SUGARBEET 76 USHll SUGARBEET 26 VELVETLεAF 3C.56 VELVETLεAF 0 GIANT FOXTAIL 2G GIANT FOXTAIL 0 KLAGES BARLEY 0 KLAGES BARLEY 0 DOWNY BROME 0 DOWNY BROME 0

CMPD 35 CMPD 35

RATE»KG/HΛ 0.4 RATE-KG/HA 0.4 PREEMERGENCE PREEMERGENCE CULT MORNINGLRY 8G COKER COTTON 0 COCKLEBUR 0 CULT MORNINGLRY 0 PURPLE NUTSEDGE 0 COCKLEBUR 0 LARGE CRABGRASS 3C.96 PURPLE NUTSED6E 0 BARNYARDGRASS 7H LARGE CRABGRASS 0 WILD OATS 0 BARNYARDGRASS 0 ERA WHEAT 0 WILD OATS 0 G4646 CORN 0 ERA WHEAT 0 WILLMS SOYBBANS 0 G4646 CORN 0 RICE DRY SEEDED 0 WILLMS SOYBEANS 0 6522 SOR6HUH 0 RICE DRY SEEDED 0 USHll SUGARBEET 3H 6522 SORGHUM 0 VELVETLEAF 5C,96 USHll SUGARBEET 0 GIANT FOXTAIL 9H εLv TLεAF 0 KLAGES BARLEY 0 GIANT FOXTAIL 0 DOWNY BROME 0 KLA6ES BARLEY 0 DOWNY BROME 0

TABLE A (CONTINUED)

_C M _PD 35 (salt) CMPD 39

RATE-KG/HA 0 .4 RATE-K6/HA 0.4 POSTEHERGENCE P _O STEMERGENCE COKER COTTON 9P , 8G COKER COTTON 86,10P CULT MORNINGLRY 2C , 2H CULT MORNINGLRY 2C COCKLEBUR 2C . 2H COCKLEBUR 2C PURPLE NUTSEDGE 0 PURPLE NUTSED6E 0 LARGE CRABGRASS 0 LAR ₆ E CRΛB6RASS BARNYARDGRASS 5H BARNYARDGRASS 0 WILD OATS 0 WILD OATS 0 ERA WHEAT 0 ERA WHEAT 0 G4646 CORN 26 G4646 CORN 0 WILLMS SOYBEANS 96,51 WILLMS SOYBEANS 2C RICE DRY SEEDED 0 RICE DRY SEEDED 0 6522 SORGHUM 0 G522 S0R6HUM 0 CHEAT GRASS 0 _C HEAT 6RASS 0 USHll SUGARBEET 4H U _S Hll SU6ARBEET 4H VELVETLEAF 3C,8H VELVETLEAF 4H GIANT FOXTAIL 0 GIANT FOXTAIL 0 KLAGES BARLEY 0 KLAGES BARLEY 0

CMPD 35 CMPD 39

RATE-KG/HA 0.4 RATE-KG/HA 0.4 PREEMERGENCE PREEMERGENCE COKER COTTON 86 COKER COTTON 0 CULT MORNINGLRY 66 CULT MORNIN6LRY 0 COCKLEBUR 0 COCKLEBUR 0 PURPLE NUTSEDGE 0 PURPLE NUTSEDGE 0 LARGE CRABGRASS 3C.96 LARGE CRΛB6RASS 66 BARNYARDGRASS 3C,96 BARNYARDGRASS 2G WILD OATS 2G ERA WHEAT 0 WILD OATS 0 ERA WHEAT 0 G4646 CORN 0 G4646 CORN 0 WILLMS SOYBEANS 9G WILLMS SOYBEANS 0 BICE DRY SEEDED 46 RICE DRY SEEDED 0 6522 SOR6HUM 5G CHEAT 6RASS 56 6522 S0R6HUM 0 CHEAT GRASS 0 USHll SUGARBEET 5H U _S Hll SUGARBEET 2H VELVεTLελF 7G GIANT FOXTAIL 3C,96 VELVETLEAF 0 GIANT FOXTAIL 66 KLAGES BARLEY 0 KLAGES BARLEY 0

TABLE A (CONTINUED ⁾

CMPD 42 CMPD 47

RATE-KG/HA 0.4 RATE-KG/HA 0.4 POSTEMERGENCE POSTEMERGENCE COKER COTTON 10P,8G CULT MORNIN6LRY IC COCKLEBUR IC PURPLE NUTSEDGE 0 LARGE CRABGRASS 0 BARNYARDGRASS 0 WILD OATS 0 ERA WHEAT 0 64646 CORN 26 WILLMS SOYBEANS 2C.2H RICE DRY SEEDED 0 6522 SOR6HUM 0 CHEAT GRASS 0 USHll SUGARBEET 0 VELVεTLεAF 0 GIANT FOXTAIL 0 KLAGES BARLEY 0

42 CMPD 47

RATE-KG/HA 0.4 PREEMERGENCE COKER COTTON 0 CULT MORNINGLRY 0 COCKLEBUR 0 PURPLE NUTSEDGE 0 LARGE CRABGRASS 96 BARNYARDGRASS IB WILD OATS 0 ERA WHEAT 0 G4646 CORN 36 WILLMS SOYBEANS 0 BICE DRY SEEDED 0 6522 S0R6HUM 0 CHEAT 6RΛSS 0 USHll SUGARBEET 4B VELVETLEAF 0 GIANT FOXTAIL 3C.9H KLAGES BARLEY 0

TABLE A (CONTINUED.

SUBSTITUTE SHEET

Test B Postemergence

Three round pans (25 cm diameter by 12.5 cm deep) were filled with Sassafras sandy loam soil. One pan was planted with nutsedge (Cyperus rotundus) tubers, crabgrass (Digitaria sanguinalis) , sicklepod (Cassia obtusifolia), ji sonweed (Datura stramonium), velvetleaf (Abutilon theophrasti) , lambsquarters (Chenopodiu album), rice (Oryza sativa), and teaweed (Sida spinosa) . the second pot was planted with green foxtail (Setaria viridis) , cocklebur (Xanthium pensylvanicum), morningglory (Ipomoea hederacea) , cotton (Gossypiu hirsutum) , johnsongrass (Sorghum halepense) , barnyardgrass (Echinochloa crusgalli) , corn (Zea mays) , soybean (Glycine max) , and giant foxtail

(Setaria faberi) . The third pot was planted with wheat (Triticum aestivum) , barley (Hordeum vulgare) , wild buckwheat (Polygonum convolvulus L.), cheatgrass (Bromus secalinus .) , sugarbeet (Beta vulgaris) , wild 0-a.t (Avena fatua L.), common chickweed (Stellaria media), blackgrass (Alopecurus myosuroides) , and rape (Brassica napus) . The plants were grown for approximately fourteen days, then sprayed postemergence with the chemicals dissolved in a nonphytotoxic solvent.

Premergence

Three round pans (25 cm diameter by 12.5 cm deep) were filled with Sassafras sandy loam soil. One pan was planted with nutsedge tubers, crabgrass, sicklepod,jimsonweed, velvetleaf, lambsquarters, rice and teaweed. The second pot was planted with green foxtail, cocklebur, morningglory cotton, ohnsongrass, barnyardgrass, corn, soybean, and giant foxtail, he third pot was planted with wheat, barley, wild

buckwheat, cheatgrass, sugarbeet, wild oat, viola, blackgrass, and rape. The thee pans were sprayed preemergence with the chemicals dissolved in a nonphytotoxic solvent. Treated plants and controls were maintained in the greenhouse for approximately 24 days, then all rated plants were compared to controls and visually rated for plant response.

Response ratings are based on a scale of 0 to 100 where 0 = no effect, and 100 = complete control. A dash (-) response means no test.

Response ratings are contained in Table B.

TABLE B CMPD 51 RΛTE-G/HA 0250 0125 0062

10

15

20

25

30

35

TABLE B

CMPD 51

RATE=G/HA 1000 0500 0250 0125 0062

PRE

GIANT FOXTAIL VELVETLEAF

USHll SUGARBEET LARGE CRABGRASS PRICKLY SIDA JIMSONWEED RICE DRY SEEDED COCKLEBUR COKER COTTON WILLMS SOYBEANS BARNYARDGRASS WILD OATS IVY MORNINGLORY ERA WHEAT SICKLEPOD JOHNSONGRASS PURPLE NUTSEDGE G4646 CORN WILD BUCKWHEAT BLACKGRASS ALTEX RAPE KLAGES BARLEY GREEN FOXTAIL

CHEAT GRASS

FIELD VIOLET

LAMBSQUARTER 100 100 90 80 70

TABLE B

CMPD 669

RATE=G/HA 2000 1000 0500 0250 POST GIANT FOXTAIL VELVETLEAF USHll SUGARBEET LARGE CRABGRASS PRICKLY SIDA JIMSONWEED RICE DRY SEEDED COCKLEBUR COKER COTTON WILLMS SOYBEANS BARNYARDGRASS WILD OATS IVY MORNINGLORY ERA WHEAT SICKLEPOD JOHNSONGRASS PURPLE NUTSEDGE G4646 CORN WILD BUCKWHEAT BLAC RASS ALTEX RAPE KLAGES BARLEY GREEN FOXTAIL CHEAT GRASS FIELD VIOLET LAMBSQUARTER

221

10

15

20

25

30

35

TABLE B

CMPD 35

10

15

20

25

30

35

TABLE B

CMPD 35

0250 0062

70 30 70 50 60 50 90 30 70 50 50 0

0 0 50 30 30 20 60 20 30 0

0 0 50 30

0 0 50 30 50 30

0 0

0 0 50 30 30 0 50 30

0 0 60 30

0 0

0 0 70 50

TABLE B

10 CMPD 35

RATE=G/HA - _{n n Λ}

PRE ²⁰⁰⁰ 1000 0250 0062

GIANT FOXTAIL 100 inn

^V ELVETLEAF _{9 Q} "° 100 ₉₀

^US Hll ^S UGARBEET 60 In ^? ° ⁶⁰

LAR ^G E ^C RABGRASS 100 ₁₀₀ , ° °

PRICKLY SIDA go A ¹⁰ ° "0

JIMSONWEED 1 ₀₀ f° ⁷⁰ 60

, _c ^Rχ CE DRϊ SEEDED 0 n ⁸ ° ⁶⁰

15 ^C OCKLEBUR c ₀ ° 0 ₀

^CO KER COTTON an ,« ³⁰ 0

^W ILLM ^S SOYBEANS 90 _«n ⁶ ° 30

B ^A R ^N Y ^A RD ^G RASS 100 ion , ³ ° 0

WILD OATS o ¹⁰ ° 60

IVY MORNINGLORY 80 ° 0

ERA WHEAT « _« ^{0 S} ICKLEPOD on ° . 0 ₀

^JO HN ^SO NGRASS 1 _{00 1 0 0} ³ ° °

P ^U RPLE NUTSEDGE _{0 n} ⁹⁰ 70 0 ^{G4646 C} O N 60 A ° 0

WILD BUCKWHEAT 80 ?„ ²⁰ 0

BLA ^C KGRASS ₉ n J° ⁵⁰ 30

ALTEX RAPE ₉ " f0 60 ₃₀

KL ^AG ES BARLEY _{0 n} ⁵⁰ 30

^G REE ^N F ^O XTAIL 100 I _Q O --° °

^C HEAT GRASS 60 , _« ¹⁰ ° "0 F -I-.E--L--DI- VVIIOOLLEETT ₈ 800 _i n ° 0 LAM8S ^Q UARTER _{100 100} " 30

90 80 5

30

35

TABLE B

CMPD. 52

RATE=»G/HA 2000 1000 0250 0062 POST GIANT FOXTAIL VELVETLEAF USHll SUGARBEET LARGE CRABGRASS PRICKLY SXDA JIMSONWEED RICE DRY SEEDED COCKLEBUR COKER COTTON WILLMS SOYBEANS BARNYARDGRASS WILD OATS IVY MORNINGLORY ERA WHEAT SICKLEPOD JOHNSONGRASS PURPLE NUTSEDGE G4646 CORN WILD BUCKWHEAT BLACKGRASS ALTΞX RAPE KLAGES BARLEY GREEN FOXTAIL CHEAT GRASS FIELD VIOLET LAMBSQUARTER

TABLE B CMPD 52 RATE=G/HA ^' 2000 1000 0250 0062

60

30 0

80

70

50 0

30 0 0

30 0 0 0 0

50 0 0 0

30 0 0

70 0 0 80

TABLE B

CMPD 18

TABLE B

CMPD 35

RATE=G/HA 0250 POST

GIANT FOXTAIL 80

VELVETLEAF 70

USHll SUGARBEET 60

LARGE CRABGRASS 80

PRICKLY SIDA 80

JIMSONWEED 50 RICE DRY SEEDED 0

COCKLEBUR 30

COKER COTTON 90

WILLMS SOYBEANS 30

BARNYARDGRASS 90 WILD OATS 0

IVY MORNINGLORY 70 ERA WHEAT 0

SICKLEPOD 20

JOHNSONGRASS 90 PURPLE NUTSEDGE 0 G4646 CORN 0

WILD BUCKWHEAT 50

BLACKGRASS 40

ALTEX RAPE 50 KLAGES BARLEY 0

GREEN FOXTAIL 80

LAMBSQUARTER 60 CHICKWEED SPP. 0 DOWNY BROME 0

10

TABLE B CMPD 35 RATE--G/HA 0250 0125 0062

PRE

^G IA ^N T FOXTAIL 100 100 _l oo

^V ELVETLEAF _ "°

^US Hll SUGARBEET 50 20

LARGE CRABGRASS 100 ₁₀₀

15 PRICKLY SIDA _ , 7«0 °

JIMSONWEED 0 u 60 0

RICE DRY SEEDED 30 10 0

COCKLEBUR 0 00

C ^O KER COTTON 50 20 0

WILLMS SOYBEANS 40 10 0

BARNYARDGRASS 80 30 10

WILD OATS 10 0 0

IVY MORNINGLORY 50 40 40

ERA WHEAT 0 0

__ SICKLEPOD 90 40 30

20 JOHNSONGRASS 70 10 0

PURPLE NUTSEDGE 0 0 0

G4646 CORN 0

WILD BUCKWHEAT 40

BLACKGRASS 50 - 10

ALTEX RAPE 40 40 30

KLAGES BARLEY 10 0 0

GREEN FOXTAIL 100 100 70

LAMBSQUARTER 100 70 60

CHICKWEED SPP. 40 30 0 25 DnnOtW-rMNvY BHRe-O _* M--E _" 30 10

30

35

TABLE B

CMPD 33

RATE=G/HA 0500 0250 0125 POST

GIANT FOXTAIL 30 0 0

VELVETLEAF 90 70 60

USHll SUGARBEET 90 80 70

LARGE CRABGRASS 70 60 50

PRICKLY SIDA 70 60 50

JIMSONWEED 90 70 50

RICE DRY SEEDED 0 0 0 COCKLEBUR 30 20 0

COKER COTTON 30 30 30

WILLMS SOYBEANS 60 50 40

BARNYARDGRASS 0 0 0

WILD OATS 30 0 0

IVY MORNINGLORY 80 70 50

ERA WHEAT 0 0 0

SICKLEPOD 50 30 20

JOHNSONGRASS 0 0 0

PURPLE NUTSEDGE 0 0 0 G4646 CORN 0 0 0

WILD BUCKWHEAT 60 30 0

BLACKGRASS 30 0 0

ALTEX RAPE 70 50 30

KLAGES BARLEY 0 0 0

GREEN FOXTAIL 30 0 0

CHEAT GRASS 0 0 0

FIELD VIOLET 90 60 30

LAMBSQUARTER 80 70 50

TABLE B CMPD 33

RATE=G/HA 0500 0250 0125 PRE

GIANT FOXTAIL 100 90 80

VELVETLEAF 90 80 70

USHll SUGARBEET 80 50 30

LARGE CRABGRASS 90 70 50

PRICKLY SIDA 60 30 0

JIMSONWEED 70 50 30

RICE DRY SEEDED 0 0 0 COCKLEBUR 30 0 0

COKER COTTON 30 0 0 ^•

WILLMS SOYBEANS 0 0 0

BARNYARDGRASS 100 90 80

WILD OATS 0 0 0

IVY MORNINGLORY 60 40 20

ERA WHEAT 0 0 0

SICKLEPOD 50 30 0

JOHNSONGRASS 50 30 0

PURPLE NUTSEDGE 0 0 0 G4646 CORN 0 0 0

WILD BUCKWHEAT 0 0 0

BLACKGRASS 30 0 0

ALTEX RAPE 90 80 70

KLAGES BARLEY 0 0 0

GREEN FOXTAIL 100 90 80

CHEAT GRASS 0 0 0

FIELD VIOLET 70 50 30

LAMBSQUARTER 100 100 100

TABLE B

CMPD 35

RATE=G/HA 0500 0250 0125 0062 OST

GIANT FOXTAIL VELVETLEAF USHll SUGARBEET LARGE CRABGRASS PRICKLY SIDA JIMSONWEED RICE DRY SEEDED COCKLEBUR COKER COTTON WILLMS SOYBEANS BARNYARDGRASS WILD OATS IVY MORNINGLORY ERA WHEAT SICKLEPOD

JOHNSONGRASS PURPLE NUTSEDGE G4646 CORN WILD BUCKWHEAT BLACKGRASS ALTEX RAPE KLAGES BARLEY GREEN FOXTAIL CHEAT GRASS LAMBSQUARTER

CHICKWEED SPP.

TABLE B

CMPD 35

RATE=G/HA 0500 0250 0125 0062 PRE GIANT FOXTAIL VELVETLEAF USHll SUGARBEET LARGE CRABGRASS

PRICKLY SIDA JIMSONWEED RICE DRY SEEDED COCKLEBUR COKER COTTON WILLMS SOYBEANS BARNYARDGRASS WILD OATS IVY MORNINGLORY ERA WHEAT SICKLEPOD JOHNSONGRASS PURPLE NUTSEDGE G4646 CORN WILD BUCKWHEAT BLACKGRASS ALTEX RAPE KLAGES BARLEY GREEN FOXTAIL CHEAT GRASS LAMBSQUARTER

CHICKWEED SPP.

236

238

TABLE B

CMPD 1304 0250 0125 0062

RATE=G/HA PRE _G IANT FOXTAIL 100 100 70

_V ELVETLEAF 30 0 0 _U SHll SUGARBEET 5 ^" 0 ^" 30

L _A R _G E CRABGRASS 100 90 80

PRI _C KLY SIDA 70 50 -»v

_J IMS _O NWEED 30 ⁰

RICE DRY SEEDED 0 J »

_CO CKLEBUR

_C OKER COTTON 0 0 o _W ILLMS SOYBEANS 0 0 o B _A RNYARDGRASS 70 30 0 WILD OATS 50 30 0

0 0 0

IVY MORNINGLORY

ERA WHEAT 30 0 0

SICKLEPOD 0 0 0

JOHNSONGRASS 40 0 0

P _U RPLE NUTSEDGE 0 0 0

G4646 CORN 0 0 0

WILD BUCKWHEAT 70 50 30

BLACKGRASS 50 30 0

ALTEX RAPE 0 0 0 KLAGES BARLEY 0 0 ^" 0

GREEN F _O XTAIL 100 100 70

LAMB _S QUARTER 50 30 0

_C HICKWEED SPP. 0 0 0

DOWNY BROME 0 0 0

iσ

TABLE B

CMPD 810

15

zσ

25-

3D

35

TABLE B

CMPD 810

RATE=G/HA 0500 0250 0125 0062

PRE

VELVETLEAF USHll SUGARBEET LARGE CRABGRASS

PRICKLY SIDA JIMSONWEED RICE DRY SEEDED COCKLEBUR COKER COTTON WILLMS SOYBEANS BARNYARDGRASS WILD OATS IVY MORNINGLORY ERA WHEAT SICKLEPOD JOHNSONGRASS PURPLE NUTSEDGE G4646 CORN WILD BUCKWHEAT BLACKGRASS ALTEX RAPE KLAGES BARLEY GREEN FOXTAIL CHEAT GRASS LAMBSQUARTER CHICKWEED SPP.

242

TABLE B

CMPD

RATE=G/HA 0500 0250 0125 0062 PRE GIANT FOXTAIL VELVETLEAF USHll SUGARBEET LARGE CRABGRASS PRICKLY SIDA JIMSONWEED RICE DRY SEEDED COCKLEBUR COKER COTTON WILLMS SOYBEANS BARNYARDGRASS WILD OATS IVY MORNINGLORY ERA WHEAT SICKLEPOD JOHNSONGRASS PURPLE NUTSEDGE G4646 CORN WILD BUCKWHEAT BLACKGRASS ALTEX RAPE KLAGES BARLEY GREEN FOXTAIL LAMBSQUARTER CHICKWEED SPP. DOWNY BROME

TABLE B

CMPD 107

RATE=G/HA 0500 0250 0125 POST GIANT FOXTAIL VELVETLEAF USHll SUGARBEET LARGE CRABGRASS PRICKLY SIDA JIMSONWEED RICE DRY SEEDED COCKLEBUR COKER COTTON WILLMS SOYBEANS BARNYARDGRASS WILD OATS IVY MORNINGLORY ERA WHEAT SICKLEPOD JOHNSONGRASS PURPLE NUTSEDGE G4646 CORN WILD BUCKWHEAT BLACKGRASS ALTEX RAPE KLAGES BARLEY GREEN FOXTAIL LAMBSQUARTER CHICKWEED SPP. DOWNY BROME

245

5 -

10

15

20

25

30

35

TABLE B

CMPD 13

RATE=G/HA 0250 0125 POST

GIANT FOXTAIL

VELVETLEAF

USHll SUGARBEET

LARGE CRABGRASS PRICKLY SIDA

JIMSONWEED

RICE DRY SEEDED

COCKLEBUR

COKER COTTON

WILLMS SOYBEANS

BARNYARDGRASS

WILD OATS

IVY MORNINGLORY

ERA WHEAT SICKLEPOD

JOHNSONGRASS

PURPLE NUTSEDGE

G4646 CORN

WILD BUCKWHEAT

BLACKGRASS

ALTEX RAPE

KLAGES BARLEY

GREEN FOXTAIL

LAMBSQUARTER

CHICKWEED SPP.

DOWNY BROME

Test C

Sixteen cm diameter Airlite plastic pots were partially filled with Ta a silt loam soil and the soil saturated with water. Japonica and Indica rice seedlings a the 2.0 to 2.5 leaf stage were transplanted into 1/3 of the pots. Into another third of the pots were transplanted seedling or sprouted tubers of water plantain (Alisma trivale), Scripus (Scirp_us paludosus) , Cyperus (Cyperus esculentus), and arrowhead (Sagittaria ^S PP•) • The remaining pots were planted with barnyardgrass (Echinochloa crusgalli) seeds and sprouted tubes of water chestnut (Eleocharis spp.) . These weeds all represent major rice weeds or genera of weeds important in rice. Three to four days after planting, the water level was raised to 3 cm (about

1200 ml/pot) and maintained a this level throughout the test. Chemical treatments were applied directly to the paddy water, within 24 hours of raising the water, after being formulated in a nonphytotoxic solvent. The pots were maintained in the greenhouse. Rates of application and plant response ratings made 21 days after treatment are summarized in Table C.

TABLE C

CMPD 669

RATE=G/HA 1000 0500 0250 0125 0064

BARNYARDGRASS 100 90 98 98 90 WATERCHESTNUT 0 0 0 0 0 ARROWHEAD 0 0 0 0 0 SCIRPUS 30 0 0 0 0

YELLOW NUTSEDGE 80 60 0 0 0 WATER PLAINTAIN 0 0 0 0 0 RICE JAP EFF 0 0 0 0 0 RICE INDICA EFF 0 0 0 0 0

CMPD 35

RATE=G/HA 1000 0500 0250 0125 0064

BARNYARDGRASS 95 100 80 100 70

WATERCHESTNUT 0 0 60 40 60

ARROWHEAD 95 50 40 0 0

SCIRPUS 50 0 0 0 0

YELLOW NUTSEDGE 100 95 60 0 0

WATER PLAINTAIN 60 40 40 0 0

RICE JAP EFF 20 0 0 0 0

RICE INDICA EFF 20 0 0 0 0

CMPD 35

RATE--G/HA 2000 0500 0125 0032

RICE JAP TOL 50 50 20 0 RICE INDICA TOL 60 55 55 0

TABLE C

CMPD 18

RATE=G/HA 1000 0500 0250 0125 0064

BARNYARDGRASS 60 40

WATERCHESTNUT 50 40

ARROWHEAD 35 20

SCIRPUS 0 0

WATER PLAINTAIN 40 20

RICE JAP EFF 70 SO

RICE INDICA EFF 50 30

CMPD 50

RATE--G/HA 1000 0500 0250 0125 0064

BARNYARDGRASS 70 70 60 0 0

WATERCHESTNUT 0 0 0 0 0

ARROWHEAD 50 30 0 0 0

SCIRPUS 0 0 0 0 0

YELLOW NUTSEDGE 50 30 0 0 0

WATER PLAINTAIN 0 0 0 0 0

RICE JAP EFF 70 60 30 0 0

RICE INDICA EFF 80 70 30 40 0

CMPD 33

RATE=G/HA 1000 0500 0250 0125 0064

BARNYARDGRASS 95 70 80 10 0

WATERCHESTNUT 0 0 0 0 0

ARROWHEAD 0 0 0 0 0

SCIRPUS 0 0 0 0 0

YELLOW NUTSEDGE 40 0 0 0 0

WATER PLAINTAIN 0 0 0 0 0

RICE JAP EFF 60 30 0 0 0

RICE INDICA EFF 70 30 0 0 0

TABLE C

CMPD 1381

RATE=G/HA 1000 0500 0250 0125 0064

BARNYARDGRASS 100 100 60 55 55

WATERCHESTNUT 0 0 0 0 0

ARROWHEAD 0 0 0 0 0

SCIRPUS 30 0 0 0 0

YELLOW NUTSEDGE 50 40 0 0 0

WATER PLAINTAIN 0 0 0 0 0

RICE JAP EFF 60 40 20 0 0

RICE INDICA EFF 60 40 20 0 0

CMPD 1304

RATE=G/HA 1000 0500 0250 0125 0064

BARNYARDGRASS 100 98 100 100 85 WATERCHESTNUT 50 0 0 0 0 ARROWHEAD 30 0 0 0 0 SCIRPUS 80 70 65 0 0

YELLOW NUTSEDGE 0 0 0 0 0 WATER PLAINTAIN 65 0 0 0 0 RICE JAP EFF 40 0 0 0 0 RICE INDICA EFF 40 0 0 0 0

CMPD 107

RATE=G/HA 1000 0500 0250 0125 0064

BARNYARDGRASS 80 90 40 0 0

WATERCHESTNUT 30 60 40 0 0

ARROWHEAD 70 95 0 0 0

SCIRPUS 80 80 60 0 0

YELLOW NUTSEDGE 95 30 50 0 0

WATER PLAINTAIN 80 60 0 0 0

RICE JAP EFF 50 40 30 0 0

RICE INDICA EFF 50 40 30 0 0

Test D the Corn and Sorghum Herbicide Test included the following species in both the preemergence and postemergence evaluations:

SPECIES

Postemergence plantings were grown in Sassafras sandy loam soil. Corn and soybeans were grown in separate 25 cm diameter containers. Sorghum and the seven grass weed species were grown in two 18 cm diameter containers, 4 species per container. The seven broadleaf weed species were also grown in two 18 cm diameter containers, 4 species in one container, 3 species in the second container. One additional planting of corn in an 18 cm diameter container was made. One additional planting of corn in an 18 cm diameter container was made. The soil surface of this additional container of corn was covered with the absorbent, perlite, before spray treatment so that test chemicals would enter the plant only via the foliage.

The plants were grown 10-21 days, dependent upon the species and then sprayed postemergence with the test chemicals dissolved in a nonpytotoxic solvent.

Postemergence

Preemergence plantings were grown in fertilized Tama silt loam soil. These plantings are identical to those described in the postemergence section, with the exception of the corn planting having perlite covering the soil surface. These plantings were made the day of or the day before spraying the test chemicals dissolved in a nonphytotoxic solvent.

Evaluation Treated plants and controls were maintained in the greenhouse for 2 to 4 weeks. Visual planting response ratings were made on a percentage scale of 0 to 100 in comparison with a control where 0 = no injury, and 100 = death.

The results are shown in Table D,

TABLE D

CMP D 50

RATE GM/HA 0500 0250 0125 0064 PREEMERGENCE

TABLE D

CMPD 33

RATE GM/HA 1000 0500 0250

PREEMERGENCE

10

TABLE D

CMPD 35

RATE GM/HA 0500 0250 0125 0064 PREEMERGENCE

G4646 CORN 0 0 0 0

WILLMS SOYBEANS 0 0 0 0

GREEN FOXTAIL 100 80 70 30

155 GIANT FOXTAIL 100 80 50 0

FALL PANICUM 100 80 50 0

LARGE CRABGRASS 100 95 70 50

BARNYARDGRASS 100 40 60 0

JOHNSONGRASS 100 100 30 30

G522 SORGHUM 0 0 0 0

PURPLE NUTSEDGE 50 0 0 -

VELVETLEAF 100 100 70 60

COCKLEBUR 20 0 0 0

LADY SMARTWEED 100 50 30 0

20 LAMBS _Q UARTER 80 60 30 30

REDROOT PIGWEED 98 50 0 0

IVY MORNINGLORY 30 0 0 0

JIMSONWEED 30 80 0 0

CMPD 35 RATE GM/HA 0500 0250 POSTEMERGENCE G4646 CORN 0 0 WILLMS SOYBEANS 30 10 2gr GREEN FOXTAIL 40 0

GIANT FOXTAIL 60 0 LARGE CRABGRASS ^" 30 ^{" ,} 3 ⁿ 0 BARNYARDGRASS 60 40 JOHNSONGRASS 50 0 G522 SORGHUM 50 0 PURPLE NUTSEDGE 0 0 VELVETLEAF 90 60 COCKLEBUR 30 0 LADY SMARTWEED 50 50 ,_. LAMBSQUARTER 20 0

_« *" REDROOT PIGWEED 70 30

IVY MORNINGLORY ^, 3 ⁿ 0 3200 JIMSONWEED 20 20 PERLITE CORN 0 0

35

258

TABLE E

10 CMPD 51

RATE GM/HA 0500 0250 0125 0064 POSTEMERGENCE PARK WHEAT 0 0 0 0 BONANZA BARLEY 0 0 0 0 BLACK NIGHTSHAD 60 40 0 0 CMN CHICKWEED 0 0 0 0 LAMBSQUARTER 40 20 0 0 CTCHWD BEDSTRAW 50 0 0 0

IB KOCHIA 0 0 0 0

SNTLS CHAMOMILE 60 40 20 0 REDROOT PIGWEED 90 60 50 30 PERSN SPEEDWELL' 40 20 0 0 WILD BUCKWHEAT 0 0 0 0 MUSTARD SPP. 30 30 30 0 WILD RADISH 60 30 30 0 ANN. BLUEGRASS 50 20 0 0 ITALN. RYEGRASS 0 20 20 0 BLACKGRASS 0 0 0 0 GREEN FOXTAIL 0 0 0 0

2D WILD OATS 0 0 0 0 JET RAPE 20 0 0 0

CMPD 51

RATE GM/HA 0500 PREEMERGENCE PARK WHEAT 0 BONANZA BARLEY 30

BLACK NIGHTSHAD 100

CMN CHICKWEED 0

25 LAMBSQUARTER 100

CTCHWD BEDSTRAW 0

KOCHIA 70

SNTLS CHAMOMILE 100

REDROOT PIGWEED 70

PERSN SPEEDWELL 20

WILD BUCKWHEAT 0

MUSTARD SPP. 0

WILD RADISH 0

ANN. BLUEGRASS 20

30 ITALN. RYEGRASS 0

BLACKGRASS 0

GREEN FOXTAIL 100

WILD OATS 20

JET RAPE 0

35

257

Test E

Seeds of the following crops and weeds are sown into 15 cm pots containing Sassafras sandy loam * 5 soil: wheat (Triticum aestivu cv. Park), barley

(Hordeum vulgare cv. Bonanza) , sugarbeet (Beta vulgaris cv. USH-11) , rapeseed (Brassica napus cv. Jet Neuf) , black nightshade (Solanum nigrum) , chickweed (Stellaria media) , lambsquarter (Chenopodiu album) , Galium

10 aparine, knotweed (Polygonum aviculare) , Kochia scoparia, Matricaria indora, redroot pigweed (Amaranthus retroflexus) , smartweed (Polygonum persicaria) , speedwell (Veronica persica) , wild buckwheat (Polygonum convolvulus) , wild mustard

15 (Brassica spp.) , wild radish (Raphanus raphanistrum) , annual bluegrass (PO annua), annual ryegrass (Lolium multiflorum) , blackgrass (Alopercurus mysuroides) , green foxtail (Setaria viridis) , and wild oats (Avena fatua) . Compounds are ormulated in a nonphytotoxic

20 solvent and applied to the plants as a foliar spray or applied to the soil surface. Plants are treated at two stages: preemergence, or postemergence when the sugarbeets are at the 2-3 true leaf stage. Plants are grown in a temperature-controlled greenhouse for the

25 duration of the test.

Weed control and crop injury are evaluated visually at 3-4 weeks after compound application, using a scale of 0 to 100%, where 0 = no injury and 100 = complete death of the plant. All plants are rated with

30 respect to untreated plants (checks) grown in the * greenhouse under identical conditions to the treated plants.

The results are shown in Table E.

35

TABLE E

CMP D 644

RATE GM/HA 0500 0250 0125 0064 POSTEMERGENCE

TABLE E

CMPD 52

RATE GM/HA 0500 0250 0125 0064 POSTEMERGENCE

CTCHWD BEDSTRAW 100

KOCHIA 0

SNTLS CHAMOMILE 100

REDROOT PIGWEED 100

PERSN SPEEDWELL 100

WILD BUCKWHEAT 20

MUSTARD SPP. 50

WILD RADISH 50

ANN. BLUEGRASS 100

ITALN. RYEGRASS 70

BLACKGRASS 20

GREEN FOXTAIL 100

WILD OATS 70

JET RAPE 20

TABLE E

CMPD

RATE GM/HA 0500 0250 0125 0064 POSTEMERGENCE

KOCHIA 100

SNTLS CHAMOMILE 100

REDROOT PIGWEED 100

LADY SMARTWEED 100

PERSN SPEEDWELL 90

WILD BUCKWHEAT 40

MUSTARD SPP. 50

WILD RADISH 50

ANN. BLUEGRASS 100

ITALN. RYEGRASS 70

BLACKGRASS 90

GREEN FOXTAIL 100

WILD OATS 90

JET RAPE 40

TABLE E

CMPD 107

RATE GM/HA 0250 PREEMERGENCE

PARK WHEAT 30

BONANZA BARLEY 30

BLACK NIGHTSHAD 80

CMN CHICKWEED 0

LAMBSQUARTER 90

CTCHWD BEDSTRAW 0

KOCHIA 70

SNTLS CHAMOMILE 70

REDROOT PIGWEED 100

PERSN SPEEDWELL 100

WILD BUCKWHEAT 0

MUSTARD SPP. 20

WILD RADISH 60

ANN. BLUEGRASS 20

ITALN. RYEGRASS 0

BLACKGRASS 20

GREEN FOXTAIL 100

WILD OATS 0

JET RAPE 30

Test F

Weed species were planted 3 or 4 per 15-cm diameter pot in Sassafras sandy loam (pH 6.8; 1% OM) . Cotton was planted separately in the same sized pot. Postemergence plantings were made 12-16 days prior to treating so plants were in the 2- to 3-leaf stage (5-12 cm tall) . Preemergence plantings were made the day before treating. Compounds were sprayed in a suitable non-phytotoxic solvent at 3741/ha, then after 3 weeks of growth in a greenhouse, plant responses were visually rated on a percent scale where 0 = no injury and 100 = plant death. The following species were included:

Planting Depth Common Name Latin Name (cm)

Cotton (Coker 315) Gossypium hirsutum 2

Barnyardgrass Echinochloa crus-galli 1

Bermudagrass Cynodon dactylon 1

Broadleaf signalgrass Brachiari platyphylla 1

Crabgrass Digitaria sanguinalis 1 Fall panicum Panicum dichotomiflorum 1

Goosegrass Eleusine indica 1

Johnsongrass Sorghum halepense 1

Nutsedge Cyperus rotundus 3

Cocklebur Xanthium pensylvanicum 3

Ivy leaf morningglory Ipomoea hederacea 3 Lambsquarters Chenopodiu album 1

Pigweed Amaranthus retroflexus 1

Prickly sida Sida spinosa 1

Purslane Portulaca oleracea 1

Sicklepod Cassia obtusifolia 3

Smartweed Polygonum persicaria 1

Velvetleaf Abutilon theophrasti 3 Ground cherry Physalis heterophylla 1

The results are shown in Table F.

TABLE F

CMPD

RATE GM/HA 0500 0250 0125 0064 0032 PREEMERGENCE