PHILLIPS RICHARD BENTON (US)
| US3235361A | 1966-02-15 | |||
| US3309192A | 1967-03-14 | |||
| US2891855A | 1959-06-23 |
CORSON ET AL., J. ORG. CHEM., 1958
J. E. BROWNING: "Agglomeration", CHEMICAL ENGINEERING, 4 December 1967 (1967-12-04), pages 147FF
"Perry's Chemical Engineer's Handbook", 1973, MCGRAW-HILL, pages: 8 - 57FF
G. C. KLINGMAN: "Weed Control as a Science", 1961, JOHN WILEY AND SONS, INC., pages: 81 - 96
J. D. FRYER; S. A. EVANS: "Heed Control Handbook", 1968, BLACKWELL SCIENTIFIC PUBLICATIONS, pages: 101 - 103
| 1. | What is claimed is: A compound of Formula I wherein: X is (CH2)m; Y is (CR3R4)p; Z is (CR3R4)n; p is 0 to 2; m is 0 to 2; n is 1 to 3; R1 is H or a straightchain ^^3 alkyl; SUBSTITUTESHEET R2 is H, CjCg alkyl, C2C4 alkenyl, C2C4 alkynyl, phenyl or C1C4 alkyl substi¬ tuted by halogen, Ph, OH, CN, 0Ra, S02Ra, PhS02, N3, C02Ra, or C02H; R3 is H or C1C3 alkyl; R4 is H or CH3; R3 and R4 can be taken together to form a 5 or 6membered carbocylic ring; W is Z~ is CH2, NR3, 0, S or may be taken to form a double bond with an adjacent carbon; R5 is H, halogen, Ra, ORa, SRa or CN; R6 is H, F, Cl, CH3, OCH3, OH or ORa; Ra is C1C3 alkyl; q1 is 0, 1 or 2; and q is 0 to 2 provided that the sum of q and q is O, 1 or 2 and that if q and q1 is O then Z~~ is CH2. |
| 2. | A compound of Claim 1 wherein: R2 is CLC. |
| 3. | alkyl, C2C3 alkenyl, C C3 alkynyl, or ^^2 alkyl substituted by SUBSTITUTESHEET OH, CN, OCH3, S02CH3, S02Ph or C02CH3; and 5 R5 is H, F, Cl, Br, CH3, OCH3, SCH3 or CN. |
| 4. | 3 A compound of Claim 2 wherein: n is 2; m is 1; 10 p is 0; and R3 is H or CH3. |
| 5. | A compound of Claim 2 wherein: n is 3; 15 m is 2; p is 0; and R3 is H or CH3. |
| 6. | A compound of Claim 2 wherein: 20 n is 1; m is 2; p is 1; and R3 is H or CH3. 25 6. |
| 7. | A compound of Claim 3 wherein:; Z1 is CH2. |
| 8. | A compound of Claim 3 wherein: Z1 is 0.*& 30. |
| 9. | A compound of Claim 3 wherein: Z1 is S. |
| 10. | A compound of Claim 3 wherein: 35 Z1 is NR, SUBSTITUTESHEET . |
| 11. | A compound of Claim 3 wherein: W is W1 W2 W3 *& 15. |
| 12. | W4 W5 W6*& 25. |
| 13. | 7 8 wg SUBSTITUTE SHEET W. |
| 14. | W. |
| 15. | 15 11 The compound of Claim 3 which is: 7oxabicyclo((2.2.1))heptane' 2(2,3 dihydrolHinden1yloxy)lmethy14 (1methylethyl). |
| 16. | 12 The compound of Claim 3 which is: 2(2,3dihydrolHindenlyloxy) l,4diethyl7oxabicyclo[2.2.1]heptane. |
| 17. | 13 A composition suitable for controlling the growth of undesired vegetation which comprises an effective amount of a compound of any one of Claims 1 through 12 and at least one of the following: surfactant, solid or liquid diluent. |
| 18. | 14 A method for controlling the growth of undesired vegetation which comprises applying to the locus to be protected an effective amount of a compound of any one of Claims 1 through 12. |
| 19. | The method of Claim 14 wherein the undesired vegetation is present in rice. |
| 20. | The method of Claim 13 wherein the undesired vegetation is present in rice. |
Related Application This application is a continuation-in-part of my copending application U.S. Serial No. 07/197,181, filed May 23, 1988.
Background of the Invention Field of the Invention
The present invention relates to novel bicyclo ether derivative compounds, to compositions containing these ether derivative compounds, and to methods of using these compounds or compositions to control the growth of undesired vegetation.
Description of Related Art Vieira et al., Helvetica Chimica Acta, 65(6) (1982), pp. 1700-06, teach the preparation of the oxabicyclic cyanohydrin acetates via a Diels-Alder reaction.
Vieria et al.. Helvetica Chimica Acta. 66(6) (1983), pp. 1865-71 teach a chiral variant of the above described reaction which produces oxabicyclic
cyanohydrin esters homologous to those depicted above, but with a (-)-camρhanoyl group instead of an acetate group.
Black et al., Helvetica Chimica Acta, 67 (1984), pp. 1612-15, disclose a method for the preparation of the chiral oxabicyclic ketone via diastereoselective formation of a brucine complex of the corresponding cyanohydrin acetate.
Payne et al., U.S. Patent 4,567,283 and Payne et al., U.S. Patent 4,670,041 disclose a variety of herbicidal bicyclic ethers of the Formula
TUTESHEET
wherein
W is an unsaturated, aromatic or heterocyclic group. This reference also disclosed certain bicyclic and monocyclic intermediates to these compounds.
Payne et al., U.S. Patent 4,525,203, disclose herbicidal bicyclic ethers of the Formula
GB 2188-931 discloses compounds of the following formula as herbicides:
SUBSTITUTESHEET
Summary of the Invention This invention pertains to compounds of Formula I including stereoisomers, suitable agricultural compositions containing them and their use as broad spectrum preemergent and postemergent herbicides.
wherein:
X is (CH 2 ) m ;
Y is (CR 3 R 4 ) p ;
Z is (CR 3 R 4 ) n ; p is 0 to 2; is 0 to 2; n is 1 to 3;
R_ is H or a straight-chain C 1 -C 3 alkyl;
R 2 is H, C -Cg alkyl, C 2 -C 4 alkenyl, C 2 -C 4 alkynyl, phenyl or C 1 -C 4 alkyl substi¬ tuted by halogen, Ph, OH, CN, OR a , S0 2 R a , PhS0 2 , N 3 , C0 2 R a , or C0 2 H;
R 3 is H or C 1 -C 3 alkyl;
R 4 is H or CH 3 ;
R 3 and R 4 may be taken together to form a 5- or 6-membered carbocyclic ring;
W is
Z 1 is CH 2 , NR , 0, S or may be taken to form a double bond with an adjacent carbon;
R 5 is H, halogen, R a , OR a , SR a or CN;
R 6 is H, F, Cl, CH 3 , OCH 3 , OH or OR a ;
R a is CJ-C-J alkyl; q 1 is 0, 1 or 2; and q is 0 to 2 provided that the sum of q and q 1 is O, 1 or 2 and that if q and q 1 is O then Z 1 is CH 2 .
Preferred for either their biological activity or ease of synthesis are:
1. Compounds of Formula I wherein;
R 2 is C-L-C3 alkyl, C 2 -C 3 alkenyl, C 2 -C 3
SUBSTITUTESHEET
alkynyl, or CL-C 2 alkyl substituted by OH, CN, OCH 3 , S0 2 CH 3 , S0 2 Ph or C0 2 CH 3 ; and R 5 is H, F, Cl, Br, CH 3 , OCK 3 , SCH 3 or CN.
2. Compounds of Preferred 1 wherein; n is 2; m is 1; p is O; and
R 3 is H or CH 3 .
3. Compounds of Preferred 1 wherein; n is 3; m is 2; p is 0; and
R 3 is H or CH 3 .
4. Compounds of Preferred 1 wherein; n is 1; m is 2; p is 1; and
R 3 is H or CH 3 .
5. Compounds of Preferred 2, 3 or 4 wherein; Z 1 is CH 2 .
6. Compounds of Preferred 2, 3 or 4 wherein; is O.
7. Compounds of Preferred 2, 3 or 4 wherein; Z 1 is S.
8. Compounds of Preferred 2, 3 or 4 wherein; Z 1 is NR 3 .
9. Compounds of Preferred 2, 3 or 4 wherein; is
W-1 W-2 W-3
15
W-4 W-5 W-6
25
30 W-8 -g
-10 w-11 W-12
SUBSTITUTE SHEET
W-1 3 W-1 4 W-1 5
Specifically preferred are:
exo-2-(2,3-dihydro-lH-inden-l-yloxy)-l-methyl-4- (l-methylethyl)-7-oxabicyclo((2.2.1))heptane; and
exo-2-(2,3-dihydro-lH-inden-l-yloxy)-1,4-diethyl- 7-oxabicyclo[2.2.1]heptane.
Detailed Description of the Invention
The compounds of Formula I exhibit geometrical and optical isomerism and may be prepared in geometrically or optically pure or mixed forms. The various individual optical and geometrical forms and various combinations thereof of the materials of the invention usually have some difference in herbicidal properties. Generally preferred for herbicidal efficacy are 1) those geometrical isomers of Formula I wherein the OW group resides on the same face of the carbocyclic ring as the O-Y bridge and 2) those optical isomers with the absolute configuration depicted in Formula la. The present invention contemplates all of the herbicidally active forms
resulting from synthesis and from deliberately created mixtures.
The compounds of Formula la may be synthesized according to the well known Williamson Ether Synthesis (see N. Baggett in Comprehensive Organic Chemistry, D. Barton and W. D. Ollis eds. , _____________, pp. 819-832, Pergamon Press, N.Y. (1979)) as shown in Scheme I by allowing bicyclic alcohols of Formula IV to react with appropriate alkylating agents represented as W-L where W represents those organic radicals defined previously and LG represents leaving group moieties such as chloride, bromide, iodide, and sulfonate esters. This is outlined in Scheme I.
SUBSTITUTESHEET
Scheme I
IV la
The bicyclic alcohols of Formula IV are known in the art (U.S. 4,670,041; U.S. 4,529,806; U.S. 4,486,219) and the alkylating agents W-LG are prepared in the conventional manners known to those skilled in the art from the alcohols W-OH.
The alcohols, WOH, are generally known in the art and are most conveniently prepared through metal hydride (e.g., sodium borohydride) reduction of the corresponding bicyclic ketones which can be derived by Friedel-Crafts type cyclization of derivatives of phenylalkylcarboxylic acid, phenoxyalkylcarboxylic acids, phenylthioalkylcarboxylic acids, benzyloxy- alkylcarboxylic acids, and benzylthioalkylcarboxylic acids. Details may be found in a) T. Laird in Comprehensive Organic Chemistry. D. Barton and W. D. Ollis, eds., Vol. 1. pp. 1165-1168, Pergamon Press, New York (1979); b) M. H. Palmer and N. M. Scollick, J. Chem. Soc.. C.. (1968), 2833; c) C. E. Dalgliesch
^SUBSTITUTESHEET
and Mann, J. Chem. Soc. (1945), 893; d) C. D. Hurd and S. Hayao, J. Am. Chem. Soc.. (1954), _7£, 4299 and 5056; and e) R. Lesser, Chem. Ber.. (1923), ϋ6, 1642. Alternatively, the compounds of Formula la may be prepared by the coupling procedure described in Scheme II, which is used in cases where the standard Williamson ether synthesis proves problematic. This procedure uses a Lewis acidic metal oxide wherein the metal can remove the halide ion by forming an insoluble precipitate. In Example 1, silver (I) oxide is used and the silver halide is the co-product. Alternative metal oxides that may be used are HgO, CaO, MgO. N,N-Dimethylformamide and ethereal solvents, such as diethyl ether, tetrahydrofuran, dioxane, or 1,2-dimethoxyethane are the preferred solvents. Other solvents likely to provide good yields include dipolar aprotic solvents like dimethyl sulfoxide, acetone and N,N'-dimethyl- propyleneurea. Scheme II
SUBSTITUTESHEET
The synthetic procedure shown in Scheme III may be used to prepare compounds of Formula la wherein Z_ is a heteroatom (such as N, O, S) . The coupling substrate is a styrene with an appropriate substituted heteroatom in protected form (such as with a trialkylsilyl, acetate ester, benzoate ester, etc.). A mild halogenating agent such as
N-halosuccinimide, N-haloacetamide, dioxane dihalide, or pyridinium hydrohalide perhalide may be used to form a cyclic halonium ion under optional acid catalysis. The ion is intercepted at the benzylic center to form the benzylic ether. The heteroatom is deprotected and allowed to close in. situ to form the desired heterocyclic ring. The acid catalyst for the initial coupling can be used in either concentrated or diluted form. Scheme III
IV deprotβct n is 0 or 1 cyclize
SUBSTITUTE SHEET
Example 1 (±)-exo-2-(3 ,4-Dihydro-lH-inden-2-yl-oxy)-l-methyl- 4-(l-methvlethyl)-7-0xabicyclor2.2.11heptane
(±)-Exo-1-meth 1-4-(1-methylethyl)-7-oxabicyclo¬ id .2. l]heptane-2-ol (2.51 g, 14.7 mmoles) was dissolved in 7.3 mL of diethyl ether in a one-neck flask. 1-chloroindane (3.37 g, 22.1 mmoles) was then added, followed by silver (I) oxide (Aldrich, 3.41 g, 16.2 mmoles). A reflux condenser was fitted to the flask and the reaction was heated at reflux for 12 hrs. The mixture was allowed to cool and filtered through a pad of Celite Florisil or Si0 2 . The filter cake was washed with diethyl ether, the filtrate was concentrated and chromatographed on Si0 2 (10-20% Et 0/hexane) to obtain 2.12 g (51%) of the desired product as an oil in a 1:1 mixture of diastereomers . 1 H-NMR (CDC1 3 , 200 MHz): 7.40 ( , 1H) ;
7.23 (m, 3H) ; 4.95 (app.t, 1H); 3.75 (m, 1H); 3.10 (m, 1H); 2.80 (m, 1H) ;
2.50-2.00 ( , 4H) ; 2.80-2.40 (m, 8H) ; 1.05 (2d, 6H) .
Example 2
Exo-2- r2,3-dihydrobenzofuran-3-yl-oxy)-l-methyl-4- (l-methylethyl)-7-oxabicyclor2.2.11heptane
2-ethenyl phenol was synthesized according to the procedure of Corson et al. (J. Pro . Chem.. 1958.
2_3 . , 544) and silated by standard procedures. 2-t-butyldimethylsiloxy styrene (550 mg, 2.03 mmoles) was dissolved in tetrahydrofuran (4.0 mL) .
Exo-l-methyl-4-(1-methylethyl)-7-oxabicyclo[2.2.1]- heptane-2-ol (690 mg, 4.06 mmoles) and N-bromosuccinimide were added. One drop of perchloric acid (70%) was added. The reaction was stirred for 1 1/2 hrs after which time a IM solution of tetrabutylaπunoniu fluoride in THF (2.5 mL) (any fluoride source, such as KF, NaF, CaF 2 , HF will suffice) was added and the solution was stirred for an hour. The reaction mixture was diluted with diethyl ether and washed with H 2 0. The organic layer was dried over anhydrous Na 2 S0 4 , filtered, and concentrated. It was then chromatographed on Si0 2 (10-20% Et 2 0/hexane) to obtain 210 mg of the desired product in about 95% purity. l-H- MR (CDC1 3 , 200 MHz): 7.30 (m, 1H) ;
7.25 (app. tdd, 1H) ;
6.90 (m, 2H);
5.10 (td, 1H);
4.85 (m, 2H); 3.70 (2dd, 1H) ;
2.15-1.90 (m, 2H) ;
1.70-1.30 (m, 8H) ;
0.98 (2d, 6H) .
By the general procedures described, or by obvious modifications thereof, the compounds of Tables 1 to 8 can be prepared.
General Structure for Tables 1 to 6
15
20
25
30
35
SUBSTITUTESHEET
16
TABLE 1
R R- *1
CH- CH _ CH 2 H
CH 3 CH 3 CH 2 4-F
CH 3 CH 3 CH 2 4-C1
CH 3 CH 3 CH 2 4-CH 3
CH 3 CH 3 CH 2 6-F
CH 3 C 2 H 5 CH 2 H
CH 3 C 2 H 5 CH 2 4-F
CH 3 C 2 H 5 CH 2 6-F
CH 3 i-C 3 H 7 CH 2 H
CH 3 i-C 3 H 7 CH 2 4-F
CH 3 i-C 3 H 7 CH 2 6-F
CH 3 i-C 3 H 7 CH 4-C1
CH 3 i-C 3 H 7 CH 2 4-CH 3
CH 3 i-C 3 H 7 CH 2 4-0CH ;
CH 3 i-C 3 H 7 CH 2 4-SCH :
CH 3 i-C 3 H 7 CH 2 5-CN
CH 3 CC1(CH 3 ) 2 CH 2 H
CH 3 CC1(CH 3 ) 2 CH- 4-F
CH 3 C(CH 3 ) 2 S0 2 CH 3 CH 2 H
CH 3 C(CH 3 ) 2 OCH 3 CH 2 H
CH 3 C(CH 3 ) 2 CN CH 2 H
CH 3 C(CH 3 ) 2 OH CH' 4-Br
CH 3 C(CH 3 ) 2 OH CH- H
CH 3 C(CH 3 ) 2 S0 2 Ph CH- H
CH. Ph CH- H
SUBSTITUTE SHEET
-~1 E 2 ^1
CH 3 H CH 2 H
CH 3 CH 2 C0 2 ,CH 3 CH 2 H
CH 3 CH 2 C0 2 »H CH 2 4-F
CH 3 CH 2 Ph CH 2 H
CH 3 CH 2 CH= =CH 2 CH 2 H
CH 3 CH 2 CH= =CH 2 CH 2 4-F
CH 3 C(CH 3 )ι=CH 2 CH 2 H
CH 3 CH 2 C(CH 3 )=CH 2 CH 2 H
CH 3 CH 2 C≡CH CH 2 H
C 2 H 5 CH 2 C=CH CH 2 H
C 2 H 5 CH 2 CH= =CH 2 CH 2 4-F
C 2 H 5 CH 2 CH= =CH 2 CH 2 H
C 2 H 5 C 2 H 5 CH 2 4-F
C 2 H 5 C 2 H 5 CH 2 4-C1
C 2 H 5 C 2 H 5 CH 2 6-F
C 2 H 5 C 2 H 5 CH 2 4-CH 3
C 2 H 5 C 2 H 5 CH 2 H
C 2 H 5 C 2 H 5 0 H
C 2 H 5 C 2 H 5 0 4-F
C 2 H 5 C 2 H 5 0 4-C1
C 2 H 5 C 2 H 5 0 4-CH 3
C 2 H 5 C 2 H 5 0 6-F
C 2 H 5 C 2 H 5 0 4,6-di-F
C 2 H 5 CH 2 CH= =CH 2 0 4-F
C 2 H 5 CH 2 CH= =CH 2 0 4-C1
C 2 H 5 CH 2 C(CH 3 )=CH 2 0 H
C 2 H 5 CH 2 C(CH 3 )=CH 2 0 4-F
SUBSTITUTE SHEET
λ E 2 __1 -
C 2 H 5 CH 2 C(CH 3 )=CH 2 0 4-CH 3
CH 3 CH 2 C(CH 3 )=CH 2 0 4-C1
CH 3 CH 2 C(CH 3 )=CH 2 0 4-F
CH 3 CH 2 C(CH 3 )=CH 2 0 H CH 3 i-C 3 H 7 0 H
CH 3 i- C 3 H 7 0 4,6-di-F
CH 3 i-C 3 H 7 0 4-F
CH 3 i-C 3 H 7 0 4-C1
CH 3 i-C 3 H 7 0 4-CH 3 CH 3 i-C 3 H 7 s 4-CH 3
CH 3 i-C 3 H 7 s 4-F
CH 3 i-C 3 H 7 s 4-C1
CH 3 i-C 3 H 7 s 4,6-di-F
CH 3 i-C 3 H 7 s H C 2 H 5 C 2 H 5 s H
C 2 H 5 C 2 H 5 s 4-CH 3
C 2 H 5 C 2 H 5 s 4-F
C 2 H 5 C 2 H 5 s 4-C1
C Hc CH CH=CH s H C 2 H 5 C 2 H 5 NCH 3 H
CH 3 C 2 H 5 NCH 3 H
CK 3 i-C 3 H 7 NCH 3 H
C 2 H5 CH 2 CH=CH 2 NCH 3 H
TABLE 2
Si ~~1 & 1
CH : CH 3 H CH ; CH 3 4-F CH, CH 3 4-C1 CH, CH 3 4-CH 3 CH, CH 3 6-F CH, C 2 H 5 H CH, C 2 H 5 4-F CH, C 2 H 5 6-F CH, i-C 3 H 7 H CH, i-C 3 H 7 4-F CH, i-C 3 H 7 6-F CH, i-C 3 H 7 4-C1 CH, i-C 3 H 7 4-CH 3 CH, i-C 3 H 7 4-0CH 3 CH, i-C 3 H 7 4-SCH 3 CH : i-C 3 H 7 5-CN CH, CC1(CH 3 ) 2 H
CH; CC1(CH 3 ) 2 4-F
CH . C(CH 3 ) 2 S0 2 CH 3 H
SUBSTITUTE SHEEf
- R l % •
CH 3 C(CH 3 ) 2 OCH 3 H
CH 3 C(CH 3 ) 2 CN H
CH 3 C(CH 3 ) 2 OH 4-Br
CH 3 C(CH 3 ) 2 OH H
CH 3 C(CH 3 ) 2 S0 2 Ph H
CH 3 Ph H
CH 3 H H
CH 3 CH 2 C0 2 CH 3 H
CH 3 CH 2 C0 2 H 4-F
CH 3 CH 2 Ph H
CH 3 CH 2 CH=CH 2 4-F
CH 3 C(CH 3 )=CH 2 H
CH 3 CH 2 C(CH 3 )=CH 2 H
CH 3 CH 2 C=CH H
C 2 H 5 CH 2 C=CH H
C 2 H 5 CHnCH=CH 2 4-F
C 2 H 5 CH 2 CH=CH — H
C 2 H 5 C 2 H 5 4-F
C 2 H 5 C 2 H 5 6-F
C 2 H 5 C 2 H 5 4-CH 3
C 2 H 5 C 2 H 5 H
22
__! -
E l *__
CH 3 C(CH 3 ) 2 ,C1 CH 2 H
CH3 C(CH 3 )= :CH 2 CH2 H
CH 3 i-C 3 H 7 CH 2 5-OCH 3
CH 3 i-C 3 H 7 CH 2 5-CN
CH 3 i-C 3 H 7 CH 2 5-SCH 3
CH 3 i-C 3 H 7 CH 2 H colorless oil; MS (SP/CI) 153 (9%), 135 (11%), 131 (100%)
CCHH 3 ,, ii--CC 33 HH 77 CH 2 5-C1
CH 3 i-C 3 H 7 CH 2 5-CH 3
CH 3 i-C 3 H 7 CH 2 5-F
CH 3 i-C 3 H 7 CH 2 5,7-di-F
CH 3 CH 2 CH—CH 2 CH 2 H
CCHH 3 ^ CCHH 2 CCHH—==CCHH 2 n CH 2 5-F
CH 3 CHnCH—CH—> CH 2 5-CH 3
CH 3 CH 2 CH=CH 2 CH 2 5-C1
CH 3 CHoCH-=CH S 5-C1
CH 3 CH CH=CH S 5-F
CH 3 CHτCH=CH 2 S H
C 2 H 5 CHoCH=CH 2 S H
C 2 H 5 CH 2 CH=CH 2 S 5-F
C 2 H 5 CH 2 CH=CH S 5-CH 3
C 2 H 5 C 2 H 5 S 5-CH 3
S 5-F
C 2 H 5 C 2 H 5
C 2 H 5 C 2 H 5 S H
S 5,7-di-F
C 2 H 5 C 2 H 5
CH 3 C 2 H 5 S H
CH 3 i-C 3 H 7 S H
E 2 H R J_
CH i-C 3 H 7 S 5-F CH i-C 3 H 7 S 5-Cl CH i-C 3 H 7 ε 5-CH 3 CH i-C 3 H 7 s 5,7-di-F CH, i-C 3 H 7 NCH 3 H
TABLE 4
CH 3 i-C 3 H 7 S H
CH 3 i-C 3 H 7 S 5-F
CH 3 i-C 3 H 7 s 5-Cl
CH 3 i-C 3 H 7 s 5-CH 3
CH 3 i-C 3 H 7 s 5,7-di- -F
CH 3 CH CH=CH 2 s 5,7-di- -F
CH 3 CH 2 CH=CH — s 5-F
CH 3 CH 2 CH=CH 2 s H
C 2 H 5 CH CH=CH s H
C 2 H 5 CH —CH=CH — s 5-F
C 2 H 5 CH CH='CHn s 5,7-di- -F
C 2 H 5 C 2 H 5 s 5,7-di- -F
C 2 H 5 C 2 H 5 s H
C 2 H 5 C 2 H 5 s 5-Cl
C 2 H 5 C 2 H 5 s 5-CH 3
C 2 H 5 C 2 H 5 s 5-F
C 2 H 5 C 2 H 5 0 5-F
C 2 H 5 C 2 H 5 0 5-Cl
C 2 H 5 C 2 H 5 0 5-CH 3
C 2 H 5 C 2 H 5 0 H
C 2 H 5 C 2 H 5 0 5,7-di- -F
C 2 H 5 CH 2 CH=CH 2 0 H
C 2 H 5 CH 2 C=CH 0 H
C 2 H 5 CH 2 C=CH 0 5-F
CH 3 CH 2 C=CH 0 5-F
SUBSTITUTE SHEET
CH 3 CH 2 C≡CH 0 H
CH 3 i-C 3 H 7 0 H
CH 3 i-C 3 H 7 0 5-Cl
CH 3 i-C 3 H 7 o 5-CH 3
CH 3 i-C 3 H 7 0 5-F
CH 3 i-C 3 H 7 0 5,7-di-F
CH 3 i-C 3 H 7 NC 2 H 5 H
CH 3 i-C 3 H 7 NH H
CH 3 i-C3H7 NCH 3 H
C 2 H 5 C 2 H 5 NCH 3 H
C 2 H 5 CH 2 CH=CH 2 NCH 3 H
TABLE 5
E __ E 2 __! 3. ^ %
C 2 H 5 C 2 H 5 CH 0 H H
C 2 H 5 C 2 H 5 CH 0 5-F H
C 2 H 5 C 2 H 5 CH 0 5 , 7-di-F H
C 2 H 5 CH CH=» CH CH 0 5-CH 3 H
C 2 H 5 CH CH=CH CH 0 5-F __
C 2 H 5 CH CH=CH CH 0 H H CH 3 CH 2 CH=CH CH 0 H H
CH 3 CH CH=CH 2 CH 0 5-F H
CH 3 i-C 3 H 7 CH 0 5-F H '
CH 3 i-C 3 H 7 CH 0 5 , 7-di-F H
CH 3 i-C 3 H 7 CH 0 H H
CH 3 i-C 3 H 7 CH 1 H H
CH 3 CH 2 CH=CH 2 CH 1 H H
C 2 H 5 CH 2 CH=CH CH 1 H H
C 2 H 5 C 2 H 5 CH 1 H H
C 2 H 5 C 2 H 5 N 1 H H
C 2 H 5 CH CH=CH 2 N 1 H H CH 3 CH CH=CHτ N 1 H H
CH 3 i-C 3 H 7 N 1 H H
CH _ i-C 3 H 7 N 1 H OCH,
SUBSTITUTE SHEET
TABLE 6
E l R-
C 2 H 5 C 2 H 5 H
C 2 H 5 C 2 H 5 OCH 3
C 2 H 5 CH 2 CH=CH 2 OCH 3 2 H 5 CH 2 CH=CH 2 H CH 3 CH 2 CH=CH 2 H
CH. CH 2 CH=CH 2 0CH 3
CH- i-C 3 H 7 OCH 3 CH, i-C 3 H 7 H
TABLE 7
III E __ Zl
CH_ H CH 2 (C 2 H 5 2 CH 2 CH 2 CH,
C 2 H 5 H CH, C(C 2 H 5 ) 2 CH 2 CH 2 CH ' CH 3 H CH 2 C(CH 3 ) 2 CH 2 CH 2
CH 3 H CH- C(C H 5 2 CH 2 CH-
CH 3 H C(CH 3 ) 2 CH CH CH '
CH 3 CH 3 CH ' CH 2 CH 2 CH CH '
CH 3 H CH 2 CH 2 C(CH 3 ) 2 CH CH 2
CH. H CH 2 CH 2 C ( 2 H 5 ) 2 CHn CH<j
SUBSTITUTE SHEET
R- R- Y Α 1
CH 3 H CH 2 CH 2 C(CH 3 ) 2 CH- CH :
C 2 H 5 H CH 2 CH 2 C(CH 3 ) 2 CH- CH ;
C 2 H 5 H CH 2 CH 2 C(C 2 H 5 ) 2 CH- CH ;
CH 3 H CH 2 CH 2 C(C 2 H 5 ) 2 CH- CH-
CH 3 CH, CH CH 2 CH 2 CH 2 CH CH; C 2 H 5 C 2 H 5 CH 2 CH 2 CH 2 CH 2 CH 2 CH; C 2 H 5 CH 2 CH= ■CH 2 CH 2 CH 2 CH 7 CHoCHτ CH; CH. CH(CH 3 >2 C CHH; 2 CH 2 CHTCHOCHT CH;
CH- H CH- C(CH 3 ) 2 CH 2 CH 2 0
CH,, CH- C(C 2 H 5 ) CH 2 CH 2 0
E 2
C 2 H 5 H CH 2 ( 2H 5 ) 2 CH-jCHo 0
CH 3 H CH 2 C(CH 3 ) 2 CH 2 0
CH 3 H CH 2 C(C 2 H 5 ) 2 CH2 0
CH 3 H - C(CH 3 ) 2 CH 2 CH 2 0
CH 3 H CH 2 CH 2 - - • . CHOCHTCHΠ 0
CH 3 H CH 2 CH 2 C(CH 3 ) 2 CH 2 0
CH 3 H CH 2 CH 2 C(CH 3 ) 2 CH 2 0
C 2 H 5 H CH 2 CH 2 C(CH 3 ) 2 CH 2 0
C2H 5 H CH 2 CH 2 C(CH 3 )2 CH 2 0
C2H 5 H CH 2 CH 2 C(C 2 H 5 ) 2 CH 2 p
CH 3 H CH 2 CH 2 C(C 2 H 5 ) 2 CH 2 0
E l
CH 3 CH 3 CHnCHo 2 2 2 0
C 2 H 5 C 2 H 5 CH CH 2 2 2 0
C 2 H 5 CH 2 CH=CH 2 CH 2 CH 2 2 2 2 0
TABLE 8
R λ R
CH, H CH- C(CH 3 ) 2 CH 2 CH CH. H CH- (C 2 H 5 )2 CH 2 CH 2
C 2 H 5 H CH 2 C(C 2 H 5 ) 2 CH 2 CH 2
CH 3 H CH 2 C(CH 3 ) 2 CH 2
CH 3 H - C(CH 3 ) 2 CH 2 CH
CH 3 CH 3 CH 2 - 2 2 2
CH 3 H CH 2 CH 2 C(CH 3 ) 2 CH 2
CH 3 H CH 2 CH C(C 2 H 5 ) 2 CH 2
CH 3 H CH 2 CH 2 C(CH 3 ) 2 CH 2
C 2 H 5 H CH 2 CH C(CH 3 ) 2 CH 2 '
C 2 H 5 H CH 2 CH 2 C(CH 2 CH 3 ) CH 2
CH 3 H CH 2 CH 2 C ( C H 5 ) 2 CH 2
SUBSTITUTE SHEET
l
CH 3 CH 3 CH 2 CH __ CH 2 CH 2 CH 2
C 2 H 5 C 2 H 5 CHoCHo - CH , 2 CH 2 CH 2
C 2 H 5 CH 2 CH S =CH 2 CH CH 2 - CH 2 CH CH 2
SUBSTITUTE SHEET
TABLE 9
*_ __
CH, H CH 2 C(CH 3 ) 2 CH 2 CH CH 2 CH
CH. H CH 2 C(C 2 H 5 )2 CH 2 CH CH 2 CH 2
CH 2 CH . CH CH
C 2„H n 5 H CH 2 (C 2 H5) 2 CH CH CHτCH
CH, H CH 2 C(CH 3 ) 2 CH 2 CH 2 CH 2 CH Ξ H CH 2 C(C 2 H 5 ) 2 CH 2 CH CH 2 CH 3 H - C(CH 3 ) 2 CH 2 CH 2 CH CH 2 CH 2 CH 3 CH 2 - CH 2 CH CH 2 CH 2 CH 2 CH 3 H CH 2 CH 2 C(CH 3 ) 2 CH 2 CH 2 CH 2 CH. H CH 2 CH 2 C(C 2 H 5 ) 2 CH 2 CHτCH 2
TE SHEET
E l R- Zl
CH 3 H CH CH C(CH 3 ) 2 CH CH 2 C
C 2 H 5 H CH 2 CH 2 C(CH 3 ) 2 CH CH 2 C
C 2 H 5 H CH 2 CH 2 C(C 2 H 5 )2 CH CH 2 C
CH 3 H CH CH 2 ( 2H 5 ) 2 CH CH 2 C
CH 3 CH 3 CH 2 CH 2 CH CH 2 CHn CH 2 C
C 2 H 5 C 2 H 5 CH 2 CH 2 CH CH 2 CHp CH 2 C
C 2 H 5 CH 2 CH= ■CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 C
SUBSTITUTE SHEET
C 2 H 5 H CH 2 C ^ C 2 H 5^2 CH 2 CH CH 2 0
CH 3 H CH 2 C(CH 3 ) 2 CH 2 CH 2 0
CH 3 H CH 2 C 2 H 5 )2 CH2 CH 2 0
CH 3 H — C(CH 3 ) 2 CH CH 2 CH 2 0
CH 3 H CH 2 CH 2 - CH 2 CH 2 CH 2 CH 2 0
CH 3 H CH 2 CH 2 C(CH 3 ) 2 CH 2 CH 2 0
CH 3 H CH CH 2 C(C 2 H 5 2 CH 2 CH 2 0
CH 3 H CH 2 CH 2 C(CH 3 ) 2 CH 2 CH 2 0
C 2 H 5 H CH 2 CH 2 C(CH 3 ) 2 CH 2 CH 2 0
C2H 5 H CH CH 2 C(CH 3 )2 CH 2 CH 2 0
C2H 5 H CH 2 CH (C 2 H 5 )2 CH 2 CH 2 0
CH 3 H CH 2 CH 2 (C H 5 )2 CH 2 CH 2 0
C 2 H 5 H CH 2 CH 2 CH 2 CH 2 0
SUBSTITUTE SHEET
E l E __ Σ_ zl
CH 3 CH 3 _»H —_Η — CH 2 CH 2 CH 2 CH 2 0
C 2 H 5 C 2 H 5 CH 2 CH CH 2 CH 2 CH 2 CH 2 0
C 2 H 5 CH 2 CH= =CH 2 CHnCH CH 2 CH 2 CH CHpO
SUBSTITUTE SHEET
Formulations
Useful formulations of- the compounds of Formula I can be prepared in conventional ways. They include dusts, granules, pellets, solutions, suspensions, emulsions, wettable powders, e ulsifiable 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 a few liters to several hundred liters per hectare. High strength compositions are primarily used as intermediates for further formulation. The formulations, broadly, contain about 0.1% to 99% by weight of active ingredient(s) and at least one of
(a) about 0.1% to 20% surfactant(s) and (b) about 1% to 99.9% solid or liquid diluent(s). More specifically, they will contain these ingredients in the following approximate proportions:
Table 9
Weight Percent* Active Ingredient Diluent(s) Surfactant(s)
Wettable Powders 5-60 39-94 1-10
Emulsifiable 3-80 20-95 0-20
Concentrates
Dusts 1-25 70-99 0-5
Granules and Pellets 0.1-50 50-99.9 0-15
* Active ingredient plus at least one of a Surfactant or a Diluent equals 100 weight percent.
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 some¬ times 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, but other solids, either mined or manufac¬ tured, may be used. The more absorptive diluents are preferred for 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 Publishing Co., Inc., New York, 1964, list surfactants and recommended uses. All formulations can contain minor amounts of additives to reduce foaming, caking, corrosion, micro¬ biological growth, etc.
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, December 4, 1967, pp. 147ff. and "Perry's Chemical
Engineer's Handbook", 5th Ed., McGraw-Hill, New York, 1973, pp. 8-57ff.
For further information regarding the art of formulation, see for example: H. M. Loux, U.S. Patent 3,235,361, February 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 and 169-182;
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; and
J. D. Fryer and S. A. Evans, "Weed Control Hand¬ book", 5th Ed., Blackwell Scientific Publications, Oxford, 1968, pp. 101-103.
In the following examples, all parts are by weight unless otherwise indicated.
Example A Wettable Powder 7-oxabicyclo((2.2.1))heptane' 2-(2,3-dihydro- lH-inden-l-yloxy)-l-methyl-4-(l-methylethyl) 60% sodium alkylnaphthalenesulfonate 2% sodium ligninsulfonate 2% synthetic amorphous silica 36%
The active ingredient is first sprayed onto the amorphous silica, then the ingredients are blended, hammer-milled until all the solids are essentially under 50 microns, reblended, and packaged.
Example B
Wettable Powder
7-oxabicyclo((2.2.1))heptane' 2-(2,3-dihydro- lH-inden-l-yloxy)-l-methyl-4-(l-methylethyl) 50% sodium alkylnaphthalenesulfonate 2% low viscosity methyl cellulose 2% diatomaceous earth 46%
The active ingredient is first sprayed onto the diatomaceous earth then the ingredients are blended, coarsely hammer-milled and then air-milled to produce particles essentially all below 10 microns in diameter. The product is reblended before packaging.
Example C Granule
Wettable Powder of Example 4 5% attapulgite granules 95%
(U.S.S. 20-40 mesh; 0.84-0.42 mm) A slurry of wettable powder containing 25% solids is sprayed on the surface of attapulgite granules in a double-cone blender. The granules are dried and packaged.
Example D Emulsifiable Concentrate
7-oxabicyclo((2.2.1))heptane' 2-(2,3-dihydro- lH-inden-l-yloxy)-l-methyl-4-(l-methylethyl) 40% Atlox 3403F 3%
Atlox 3404F 3% xylene 54% The active ingredient and Atlox emulsifiers are dissolved in the solvent, filtered and packaged. Atlox 3403F and 3404F are blends of anionic and ionic emulsifiers from ICI Americas, Inc.
Example E
Low Strength Granule
7-oxabicyclo((2.2.1))heptane' 2-(2,3-dihydro- lH-inden-1-yloxy)-l-methyl-4-(1-methylethyl) 5% attapulgite granules 95% (U.S.S. 20-40 mesh)
The active ingredient is dissolved in a solvent and the solution is sprayed upon dedusted granules in a double-cone blender. After spraying of the solution has been completed, the material is warmed to evaporate the solvent. The material is allowed to cool and then packaged.
Example F Granule 7-oxabicyclo((2.2.1))heptane' 2-(2,3-dihydro- lH-inden-l-yloxy)-l-methyl-4-(1-methylethyl) 50% wetting agent 1% crude ligninsulfonate salt (containing 10% 5-20% of the natural sugars) attapulgite clay 39%
The ingredients are blended and milled to pass through a 100 mesh screen. This material is then added to a fluid bed granulator, the air flow is adjusted to gently fluidize the material, and a fine spray of water is sprayed onto the fluidized material. The fluidiza- tion and spraying are continued until granules of the
desired size range are made. The spraying is stopped, but fluidization is continued, optionally with heat, until the water content is reduced to the desired level, generally less than 1%. The material is then discharged, screened to the desired size range, generally 14-100 mesh (1410-149 microns), and packaged for use.
Example G Concentrated Emulsion
7-oxabicyclo((2.2.1))heptane' 2-(2,3-dihydro- lH-inden-l-yloxy)-l-methy1-4-(1-methylethyl) 25% xylene 25%
Atlox 3404F 5%
G1284 5% ethylene glycol 8% water 32% The active ingredient, solvent and emulsifiers are blended together. This solution is added to a mixture of the ethylene glycol and water with stirring.
Example H Solution
7-oxabicyclo((2.2.1))heptane' 2-(2,3-dihydro- lH-inden-l-yloxy)-l-methy1-4-(1-methylethyl) 5% water 95%
The compound is added directly to the water with stirring to produce the solution, which may then be packaged for use.
Example I Dust 7-oxabicyclo((2.2.1))heptane' 2-(2,3-dihydro- lH-inden-l-yloxy)-l-methy1-4-(1-methylethyl) 10%
___
attapulgite 10%
Pyrophyllite - 80% The active ingredient is sprayed onto the attapulgite and then passed through a hammer-mill to produce particles substantially all below 200 microns. The ground concentrate is then blended with powdered pyrophyllite until homogeneous.
Utility
Test results indicate that compounds of this invention are highly active preemergent and/or postemergent herbicides or plant growth regulants. These compounds are useful for postemergence grass control in agronomic crops and are particularly useful for preemergence broad-spectrum grass and selected small-seeded broadleaf weed control in agronomic crops. Agronomic crops such as barley {Hordeum vulgare) , corn {Zea mays) , cotton {Gossypium hirsutum) , rape {Brassica napus) , rice {Oryza satiυa) , sorghum {Sorghum bicolor) , soybean {Glycine max) , sugar beet {Beta υulgaris), and wheat {Triticum aestivum) show little or no injury when treated with application rates necessary for weed control for many of the compounds in this invention. Many of the compounds of this invention are also particularly suitable for barnyardgrass {Echinochloa crus-galli) control in transplanted rice. Troublesome weed species that are suppressed or controlled are grass weeds such as barnyardgrass {Echinochloa crus-galli) , blackgrass {Alopecurus myosuroides) , cheatgrass {Bromus secalinus) , crabgrass {Digitaria spp.), downy brome {Bromus tectorum) , foxtail {Sctaria spp.), johnsongrass {Sorghum halepense) , and wild oat {Avena fatua) ; broadleaf weeds such as lambsquarters
{Chenopodium album) and velvetleaf {Abutilon iheophrasti) ; and sedge {Cyperus spp.). Test results also indicate that compounds of this invention have utility for broad-spectrum pre- and/or postemergence weed control in other areas where control of vegetation is desired, such as around storage tanks, parking lots, drive-in theaters, billboards, highways, and railroad structures and in fallow areas of crop production such as in wheat, barley, and in plantation crops such as palm, pineapple, plantin, banana, citrus, rubber, sugarcane, etc. Rates of application for compounds of this invention are determined by a number of factors. These factors include: formulation selected, method of application, amount of vegetation present, growing conditions, etc. In general terms, the subject compounds should be applied at rates from 0.01 to 20 kg/ha with a preferred rate range of from 0.05 to 1 kg/ha. One skilled in the art can easily determine rates needed for the desired level of weed control.
Compounds of this invention may be used alone or in combination with other commercial herbicides, insecticides, or fungicides. The following list exemplifies some of the herbicides suitable for use in mixtures. A combination of a compound from this invention with one or more of the following herbicides may be particularly useful for weed control.
Common Name Chemical Name acetochlor 2-chlorό-B-(e_hoxymethyl)-N-(2-e_hyl- 6-me hylphenyl)acetamide acifluorfen 5-[2-chloro-4-(trifluoromethylJphenoxy]- 2-nitrobenzoic acid acrolein 2-propenal alachlor 2-chloro-2,6-diethylphenyl-N-(methoxy methyl)acetanilide ametryn N-ethyl-N'-l(1-methylethyl)-6-(methyl- thio)-1,3,5-triazine-2,4-diamine amitrole lH-l,2,4-triazol-3-amine AMS ammonium sulfamate asulam methyl [(4-aminophenyl)sulfonyl]carbamate atrazine 6-chloro-N-ethyl-N'-(lmethylethyl)-1,3,5- triazine-2,4-diamine barban 4-chloro—2-butynyl 3-chlorophenylcarbamat benefin N-butyl-N-ethyl-2.6-dinitro-4-(tri- fluorome hyl)benzenamine bensulfuron 2-[[[[[(4,6-dimethoxy-2-pyrimidinyl)- methyl a ino]carbonyl]amino]sulfonyl]methyl]- benzole acid, methyl ester bensulide 0,0-bis(1-methylethyl)S-[2-[(phenylsulfon amino]ethyl]phosphorodithioate bentazon 3-(1-methylethyl)-(1H)-2,23-benzothiadiaz 4(3H)-one 2,2-dioxide benzofluor N-[4-(ethylthio)-2-(trifluoromethyl)pheny methanesulfonamide benzoylprop N-benzoyl-N-(3,4-dichlorophenyl)-DL- alaine bifenσx methyl 5-(2,4-dichlorophenox )-2- nitrobenzoate bromacil 5-bromo-6-methyl-3-(l-methylpropyl)-2,4- (1H,3H)pyrimidinedione bromoxynil 3,5-dibromo-4-hydroxybenzonitrile
SUBSTITUTE SHEET
Common Name Chemical Name butachlor N-(butoxymethyl)-2-chloro-N-(2,6-diethyl- phenyl)acetamide buthidazole 3-[5-(l,l-dimethylethyl)-l,3,4-thiadia- zol-2-yl]-4-hydroxy-l-methyl-2-imida- zolidinone butralin 4-(l,l-dimethyle_hyl)-N-(l-methyl- propyl)-2,6-dinitrobenzenamine butylate S-ethyl-bis(2-methylpropyl)carbamothioate cacodylic dimethyl arsinic acid acid
CDAA 2-chloro-N,N-di-2-propenylacetamide
CDEC 2-chloroallyl diethyldithiocarbamate chloramben 3-amino-2,5-dichlorobenzoic acid chlorbromuron 3-(4-bromo-3-chlorophenyl)-l-methoxy-l- me hylurea chlorimuron 2-[[[[ -chloro-δ-methoxy-Σ-pyrimidinylJ- ethyl aminoJcarbonylJaminoJsulfonylJbenzoic- acid, ethyl ester chloroxuron N'-[4-(4-chlorophenoxy)phenyl]-N,N- dimethylurea chlorpropham 1-methylethyl 3-chlorophenylcarbamate chlorsulfuron 2-chloro-N-[(4-methoxy-6-methyl-l,3,5- triazin-2-yl) mino]carbonyl]benzene- sulfonamide chlortoluron '-(3-chloro-4-methylphenyl- ,N- dimethylurea cinmethylin exo-l-methyl-4-(1-methylethyl)-2- [(2-me hylphenyl)methoxy)-7- oxabicyclo[2.2.1]heptane clethodim (E,E)-(_)-2-t[(3-chloro-2-propenyl)oxy]- imino]propyl]-5-[2-(ethylthio)-propyl]- 3-hydroxy-2-cyclohexan-l-one clomazone 2-[(2-chlorophenyl)methyl]- ,4-dimethyl- 3-isoxazolidinone
Common Name Chemical Name
cloproxydim (E,E)-2-[l-[[(3-chloro-2-propenyl)oxy) imino]butyl]-5-[2-(ethylthio)proρyl]- 3-hydroxy-2-cyclohexen-1-one clopyralid 3,6-dichloro-2-pyridinecarboxylic acid
CMA calcium salt of MAA cyanazine 2-[[4-chloro-6-(ethylamino)-1,3,5- triazin-2-yl]amino]-2-me hyl- propanenitrile cycloate S-e hyl cyclohexylethylcarbamothioate cycluron 3-cyclooctyl-l,1-dimethylurea cyperquat l-methyl-4-phenylpyridinium cyprazine 2-chloro-4-(cyclopropylamino)-6-(iso- propylamino)-__-triazine cyprazole N-_5-(2-chloro-l,l-dimethylethyl)-l,3,4- thiadiazol-2-yl]cyclopropanecarbox- a ide cypromid 3',4'-dichlorocyclopropanecarboxanilide dalapon 2,2-dichloropropionic acid dalapon 2,2-dichloropropanoic acid dazomet tetrahydro-3,5-dimethyl-2H-l,3,5-thia- diazine-2-thione
DCPA dimethyl 2,3,5,6-tetrachloro-1,4- benzenedicarboxylate desmediphan ethyldesmetryn[3-[[(phenylamino)- carbonyl]oxy]phenyl]carbamate desmetryn 2-Cisopropylamino)-4-(methylamino)-6- methylthio)-j_.-triazine diallate S-(2,3-dichloro-2-propenyl) bis(1-methyl¬ ethyl)carbamothioate dicamba 3,6-dichloro-2-methoxybenzoic acid
Common Name Chemical Name
dichlobenil 2,6-dichlorobenzonitrile dichlorprop C.)-2-(2,4-dichlorσphenoxy)proρanoic ac diclofop (%)-2-[4-(2,4-dichlorophenox )phenox ]- propanoic acid diethatyl N-(chloroacetyl)-N-(2,6-diethylphenyl)- glycine difenzoquat l,2-d_methyl-3,5-diphenyl-lH-pyrazolium dinitramine N 3 ,N 3 -diethyl-2,4-dinitro-6-(tri- fluoromethyl)-l,3-benzenediamine dinoseb 2-(1-methylρropyl)-4,6-dinitrophenol diphenamide N,N-dimethyl-a-phenylbenzeneacetamide dipropetryn 6-(ethyl hio)-N,N'-bis(1-methylethyl)- 1,3,5-triazine-2,4-diamine diquat 6,7-dihydrodipyrido[l,2-a:2',l'-c]- pyrazinediium ion diuron N'-(3,4-dichlorophenyl)-N,N-dimethylure
DNOC 2-methyl-4,6-dinitrophenol
DPX-M6316 3-DSMAt[[[(4-methoxy-6-methyl-l,3,5- triazin-2-yl)amino]carbonyl]amino]- sulfonyl]-2-thiophenecarboxylic acid, methyl ester
DPX-V9360 2-[[[t(4,6-dimethoxypyrimidin-2-yl)- amino]carbonyl]amino]sulfonyl]- 3-pyridinecarboxylic acid, N,N-dimethylamide
DSMA disodium salt of MAA
Common Name Chemical Name endothall 7-oxabicyclo[2.2.1]heptane-2,3-dicarbox- ylic acid
EPTC S-ethyl dipropylcarbamothioate ethafluralin N-ethyl-N-(2-methyl-2-propenyl)-2,6- dinitro-4-( rifluoromethyl)benzen- amine ethofu esate (+)-2-ethoxy-2,3-dihydro-3,3-dimethyl- 5-benzofuranyl methanesulfonate Express* 2-[[[[N-(4-methoxy-6-methyl-
1,3,5-triazine-2-yl)-N-methylamino]- carbonyl]amino]sulfonyl]benzoic acid, methyl ester fenac 2,3,6-trichlorophenylacetic acid fenoxaprop C-)-2-[4-[6-chloro-2-benzoxazolyl- ethyl oxy]phenoxy]propanoic acid fenuron N,N-dimethyl-N'-phenylurea fenuron TCA Salt of fenuron and TCA flamprop N-benzoyl-N-(3-chloro-4-fluorophenyl)- DL-alanine fluazifop C-)2-[4-[[5-(trifluoromethyl)-2- pyridinyl]oxy]phenoxy] ropanoic acid fluazifop-P (R)-2-[4-[[5-(trifluoromethyl)-2- pyridinyl]oxy]phenoxy]propanoic acid fluchloralin N-(2-chloroethyl)-2,6-dinitro-N-propyl- 4—( rifluorome hyl)benzenamine fluometuron N,N-dimethyl-N'-[3-trifluoromethyl) phenyl]urea fluoro- 3-chloro-4-(chloromethyl)-l-[3- chloridone (trifluoromethyl)phenyl]-2-pyrroli- dinone fluorodifen p_-nitrophenyl a,a,a-trifluoro-2-nitro- p_-tolyl ether
Common Name .he ical Name
fluorogly- carboxyπtethyl 5-[2-chloro-4-(tri- cofen fluoromethyl)phenoxy]-2-nitro- benzoate fluridone 1-methyl-3-phenyl-5-[3-(tri luoro¬ methyl)phenyl]-4(1H)-pyridinone fomesafen 5-[2-chloro-4-trifluoromethyl) henoxy]- N-(methylsulfonyl)-2-nitrobenzamide fosamine ethyl hydrogen (aminocarbonyl)phosphate glyphosate N-(phosρhonomethyl)glycine halozyfop 2-[4-[[3-chloro-5-(trifluoromethyl)- 2-pyridinyl]oxy]phenoxy]propanoic acid hexaflurate potassium hexafluoroarsenate hexazinone 3-cyclohexyl-6-(dimethyl_mino)-l-methyl■ l,3,5-triazine-2,4(lH,3H)-dione imazametha- 6-(4-isoρroρyl-4-methyl-5-oxo-2- benz imidazolin-2-yl)-_n-toluic acid, methyl ester α azapyr (%)-[4,5-dihydro-4-methyl-4-(1-methyl¬ ethyl)-5-oxo-lH-imidazol-2-yl]-3- pyridinecarboxylic acid imazaquin 2-[4,5-dihydro-4-methyl-4-(1-methyl¬ ethyl)-5-oxo-lH-imidazol-2-yl]-3- guinolinecarboxylic acid imazethapyr {%)-2-[4,5-dihydro-4-methyl-4-(1-methyl¬ ethyl)-5-oxo-lH-imidazol-2-yl]-5- ethyl-3-pyridinecarboxylic acid ioxynil 4-hydroxy-3,5-diiodobenzonitrile isopropalin 4-(1-methylethyl)-2,6-dinitro-N,N- dipropylbenzenamine
Common Name Chemical Name isoproturon N-(4-isopropylρhenyl)-N' , '-dimethylurea isouron '-[(1,1-dimethylethyl)-3-isoxazolyl]- N,N-dimethylurea isoxaben N-[3-(l-ethyl-l-methylpropyl)-5- isoxazolyl]-2,6-dimethoxybenzamide karbutilate 3-[[(dimethylamino)carbonyl] mino]- phenyl (1,1-dimethylethyl)- carbamate lactofen ( _)-2-ethoxy-l-methyl-2-oxoethyl 5-[2- chloro-4-(trifluoromethylJphenoxy]- 2-nitrobenzoate lenacil 3-cyclohexyl-6,7-dihydro-lH-cyclopenta- pyrimidine-2,4(3H,5H)-dione linuron N'-(3,4-dichlorophenyl)-N-methoxy-N- methylurea
MAA methylarεonic acid MAMA monoammonium salt of MAA MCPA (4-chloro-2-methylphenoxy)acetic acid MCPB 4-(4-chloro-2-methylphenoxy)butanoic acid mecoprop (.)-2-(4-chloro-2-methylphenoxy)- propanoic acid mefluidide N-[2,4-dimeth l-5-[[(trifluoromethyl)- sulfonyl]amino]phenyl]acetamide methal- N-(2-methyl-2-ρropenyl)-2,6-dinitro-N- propalin propyl-4-(trifluoromethyl)benzenamide methabenz- l,3-dimethyl-3-(2-benzothiazolyl)urea thiazuron metham methylcarbamodithioic acid methazole 2-(3,4-dichlorophenyl)-4-methyl-l,2,4- oxadiazolidine-3,5-dione methoxuron N'-(3-chloro-4-methoxyphenyl)N,N- dimethylurea
Common Name Chemical Name
metolachlor 2-chloro-N-(2-ethyl-6-methylphenyl)-N- (2-methoxy-l-methylethyl)acetamide metribuzin 4-amino-6- ( l , l-dimethylethyl ) -3-(methyl thio ) -l, 2 , 4-triazin-5( 4H) -one metsulfuron 2-[[[ [(4-methoxy-6-methyl-l,3,5- triazin-2-yl)amino]carbonyl]amino]- sulfonylJbenzoic acid, methyl ester
MH 1,2-dihydro-3,6-pyridazinedione molinate S-e hyl hexahydro-lH-azeρine-1-carbo- thioate onolinuron 3-(_>-chloroρhenyl)-l-methoxy-l-methyl- urea monuron '-(4-chlorophenyl)-N,N-dimethylurea monuron TCA salt of monuron and TCA MSMA monosodium salt of MAA napropamide N,N-diethyl-2-(l-naphthalenyloxy)- propanamide naptalam 2-[(1-naρhthalenylamino)carbonyl]- benzole acid neburon l-butyl-3-(3,4-dichlorophenyl)-1-methyl- urea nitralin 4-(methylsulfonyl)-2,6-dinitro-N,N- dipropylaniline nitrofen 2,4-dichloro-l-(4-nitrophenoxy)benzene nitrofluorfen 2-chloro-l-(4-nitrophenoxy)-4-(tri- fluoromethyl)benzene norea N,N-dimethyl-N * -(octahydro-4,7-methano- lH-inden-5-yl)urea 3aa,4a,5a,7a,7aa- isomer norflurazon 4-chloro-5-(methylamino)-2-(3-(tri- fluoromethyl)phenyl)-3(2H)-pyridaz- inone
Common Name Chemical Name oryzalin 4-(diprόpyla ino)-3,5-dinitrobenzene- sulfona ide oxadiazon 3-[2,4-dichloro-5-(l-methylethoxy)- phenyl]-5-(1,1-dimethylethyl-1,3,4- oxadiazol-2-(3H)-one oxyfluorfen 2-chloro-l-(3-ethoxy-4-nitrophenox )-4- (trifluoro ethyl)benzene paraquat 1,1'-dimethyl-4,4'-dipyridinium ion pebulate S-propyl butylethylcarbamothioate pendimethalin N-(1-ethylpropyl)-3,4-dimethyl-2,6- dinitrobenzenamine perfluidone l,l,l-trifluoro-N-[2-methyl-4-(phenyl- sulfonyl)phenylJmethanesulfonamide phenmedipham 3-[(methoxycarbonyl)aminoJphenyl- (3-methylphenyl)carbamate picloram 4-amino-3,5,6-trichloro-2-pyridine- carboxylic acid
PPG-1013 5-(2-chloro-4-(trifluoromethyl)phenoxy)- 2-nitroacetophenone oxime-O-acetic acid, methyl ester procyazine 2-[[4-chloro-6-(cyclopropylamino)-l,3,5- triazine-2-yl]amino]-2-methylproρane- nitrile profluralin N-(cyclopropylmethyl)-2,6-dinitro-N- propyl-4-(trifluoromethyl)benzen- amine prometon 6-methoxy-N, '-bis(1-methylethyl)- 1,3,5-triazine-2,4-diamine prometryn N,N'-bis(1-methylethyl)-6-(methyl- thio)-1,3,5-triazine-2,4-diamine pronamide 3 , 5-dichloro N-(l, l-dimethyl-2-propyn- yDbenz amide propachlor 2-chloro-N-(l-methylethyl-N-phenyl- acetamide
' SUBSTITUTE SHEET
Common Name Chemical Name
propanil N-(3,4-dichlorophenyl)propanamide propazine 6-chloro-N,N*-bis(1-methylethyl)- 1,3,5-triazine-2,4-diamine propham 1-methylethyl phenylcarbamate prosulfalin N-t[4-(dipropylamino)-3,5-dinitro- phenyl]sulfonyl]-S,S-dimethylsulfi1- imine prynachlor 2-chloro-N-(l-methyl-2-ρropynyl)ace - anilide pyrazon 5-amino-3-chloro-2-phenyl-3(2H)- pyridazinone quizalofop (°-)-2-[4[(6-chloro-2-quinoxalinyl)]- oxy]phenoxy]propanoic acid secbumeton N-ethyl-6-methoxy- ' (1-methylpropyl)- 1,3.5-triazine-2,4-diamine sethoxydim 2-[l-(ethoxyimino)butyl]-5-[2-(ethyl- thio)propyl]-3-hydroxy-2-cyclohexene- 1-one siduron N-(2-methylcyclohexyl)- '-phenylurea simazme 6-chloro-N,N'-diethyl-1,3,5-triazine- 2,4-diamine sulfometuron 2-[_[[<4,6-dimethyl-2-ρyrimidinyl)- methyl amino]carbonyl]amino]sulfonyl]- benzole acid, methyl ester
TCA trichloroacetic acid tebuthiuron N-[5-(1,1-dimethylethyl)-1,3,4-thiadi- azol-2-yl]-N,N'-dimeth lurea terbacil 5-chloro-3(l,1-dimethylethyl)-6- methyl-2,4(1H,3H)-pyri idinedione terbuchlor N-(butoxy ethyl)-2-chloro-N-[2-(1,1- di ethylethyl)-6-methylphenyl]- acetamide
Common Name Chemical Name
terbuthyl- 2-(tert-butylamino)-4-chloro-6-(ethyl- azine amino)-ϋ-triazine terbutol 2,β-di-ig i-butyl-E-tolyl methylcar- ba ate terbutryn N-(l,l-dimethylethyl)-N'-ethyl-6- methylthio)-1,3,5-triazine-2,4- diamine thiameturon 3-[[[[(4-methoxy-6-methyl-1,3,5- methyl triazin-2-yl)amino]carbonyl]amino]- sulfonyl]2-thiophenecarboxylic acid, methyl ester thiobencarb S-[(4-chlorophenyl)methyl]diethylcar- bamothiσate triallate S-(2,3,3-trichloro-2-propenyl)bis(1- methylethyl)carbamothioate triclopyr [(3,5,6-trichloro-2-pyridinyl)- oxy]acetic acid tridiphane 2-(3,5-dichlorophenyl)-2-(2,2,2- trichloroethyl)oxirane trifluralin 2,6-dinitro-N,N-dipropyl—4-(tri- fluoromethyl)benzena ine trimeturon 1-(jj-chlorophenyl)-2,3,3-trimethylpseu- dourea
2,4- (2,4-dichlorophenoxy)acetic acid 2,4-B 4-(2,4-dichlorophenoxy)butanoic acid vernolate S-propyl dipropylthiocarbamothioate xylachlor 2-chloro-N-(2,3-dimethylphenyl)-N- (1-methylethyl)acetamide
Herbicidal properties of the subject compounds were discovered in a number of greenhouse tests. Test procedures and results follow.
SUBSTITUTE SHEET
TABLE A Biological Testing
Coπpound 1
15
25 Corrpound 2
Corrpound 3 Corrpound 4
Corrpound 5
15
Corrpound 6 Coπpound 7
25
Coπpound 8 Corrpound 9
su BST rαrn- SHEET
Corrpound 1 0 Corrpound 1 1
15
Coπpound 12
25
35
TEST A
Seeds of barley (Hordeum vulgare) , barnyardgrass {Echinochloa crus-galli) , cheatgrass {Bromus secalinus) , cocklebur {Xanthium pensylυanicum) , corn {Zea mays) t cotton {Gossypium hirsutum) , crabgrass {Digitaria spp.), giant foxtail {Setaria faberi) , morningglory {Ipomoea spp.), rice {Oryza sativa) , sorghum {Sorghum bicolor) , soybean {Glycine max) , sugar beet {Beta υulgaris) , velvetleaf {Abutilon theophrasti) , wheat {Triticum aestivum) , and wild oat {Aυena fatua) and purple nutsedge {Cyperus rotundus) tubers were planted and treated preemergence with test chemicals dissolved in a non-phytotoxic solvent. At the same time, these crop and weed species were also treated with postemergence applications of test chemicals. Plants ranged in height from two to eighteen cm (two to three leaf stage) for postemergence treatments. Treated plants and controls were maintained in a greenhouse for approximately sixteen days, after which all species were compared to controls and visually evaluated. Plant response ratings, summarized in Table A, are based on a scale of 0 to 10 where 0 is no effect and 10 is complete control. A dash (-) response means no test result. The accompanying descriptive symbols have the following meanings:
B = burn injury;
C - chlorosis/necrosis;
E = inhibition of emergence;
G = growth retardation;
H = formative effect; P = terminal bud injury; and
S - albinism.
SUBSTITUTESHEET
Table A
Cmpd 1
RATE (g/ha) 400 100 POSTEMERGENCE Barley 0 0
Barnyardgrass 9H 0 Cheatgrass 2G 0 Cocklebur 2H 0 Corn 2G 0 Cotton 0 0 Crabgrass 8H 5G Giant foxtail 9H 5H Morningglory 0 0 Nutsedge 0 0 Rice 3G 0 Sorghum 2G 0 Soybean 2H 0 Sugar beet 7G 0 Velvetleaf 5G 5G Wheat 2G 0 Wild oat 5G 0
PREEMERGENCE Barley 0 0
Barnyardgrass 10H 10H Cheatgrass 9E 7G Cocklebur 0 0 Corn 9H 2G Cotton 0 0 Crabgrass 10H 10H Giant foxtail 10H 10H Morningglory 0 0 Nutsedge 10E 0 Rice 5G 0 Sorghum 10H 9H Soybean 0 0 Sugar beet 5H 0 Velvetleaf 6H 2H Wheat 0 0 Wild oat 6G 0
Cmpd 2
RATE (g/ha) 400 100
POSTEMERGENCE
Barley 0 0
Barnyardgrass 5H 0
Cheatgrass 0 0
Cocklebur 1C 1C
Corn 0 0
Cotton 0 0
Crabgrass 2S, 5G 0
Giant foxtail 3G 0
Morningglory 0 0
Nutsedge 0 0
Rice 0 0
Sorghum 0 0
Soybean 0 0
Sugar beet 0 0
Velvetleaf 1C, 4G 3G
Wheat 0 0
Wild oat 0 0
PREEMERGENCE
Barley 0 0
Barnyardgrass 10H 10H
Cheatgrass 4G 0
Cocklebur 1C 0
Corn 2G 0
Cotton 0 0
Crabgrass 9H 6G
Giant foxtail 9H 8G
Morningglory 0 0
Nutsedge 0 0
Rice 0 0
Sorghum 2C, 6G 0
Soybean 0 0
Sugar beet 4G 0
Velvetleaf 7G 4G
Wheat 0 0
Wild oat 3C,' 7H 2C,5G
Cmpd 3 Cmpd 4
RATE (g/ha) 100 400 100
POSTEMERGENCE
Barley 0 0 0
Barnyardgrass 9H 5C, 9H 4H
Cheatgrass 0 0 0
Cocklebur 1H 3C, 5H 2C
Corn 2G 2C, 6G 0
Cotton 0 0 0
Crabgrass 0 9H 4H
Giant foxtail 8H 9H 9H
Morningglory 2C 0 0
Nutsedge 3G 0 0
Rice 0 0 0
Sorghum 0 3G 0
Soybean 2H 0 0
Sugar beet 0 0 0
Velvetleaf 1C,3G 4H 0
Wheat 2G 0 0
Wild oat 0 0 0
PREEMERGENCE Barley 0 7H 0
Barnyardgrass 10H 10H 10H
Cheatgrass 3G 2G 0
Cocklebur 2G 0 0
Corn 2G 3C, 6H 4H
Cotton 0 0 0
Crabgrass 4C-,9H 9H 9H
Giant foxtail 9H 10H 5C,9H
Morningglory 0 0 0
Nutsedge 0 0 0
Rice 0 0 0
Sorghum 8H 3C, 9H 6H
Soybean 0 2G 0
Sugar beet 0 0 0
Velvetleaf 8H 7H 4H
Wheat 3G 0 0
Wild oat 0 9H 2G
SUBSTITUTE SHEET
Cmpd 5
RATE (g/ha) 400 50 POSTEMERGENCE Barley 0 0
Barnyardgrass 9C 2H Cheatgrass 2G 0 Cocklebur 2C,4H 2C Corn 2C,2G 0 Cotton 7H " 0 Crabgrass 9H 8H Giant foxtail 9H 7H Morningglory 0 0 Nutsedge 2C,3G 0 Rice 0 0 Sorghum 0 0 Soybean 4H 0
Sugar beet 0 0 Velvetleaf 6H 0 Wheat 0 0 Wild oat 0 . 0
PREEMERGENCE Barley 0 0
Barnyardgrass 10H 10H Cheatgrass 3G 2G Cocklebur 3H - Corn 5C,8H 0 Cotton 0 0 Crabgrass 10H 10H Giant foxtail 10H 10H Morningglory 0 0 Nutsedge 0 0 Rice 3G 0 Sorghum 3C,7H 2G Soybean 0 0 Sugar beet 0 0 Velvetleaf 8H 3H Wheat 5H * 0 Wild oat 7H 0
Cmpd 6 Cmpd 7
RATE (g/ha) 400 100 400 100
POSTEMERGENCE
Barley 0 0 0 0
Barnyardgrass 5H 0 3H 0
Cheatgrass 0 0 0 0
Cocklebur 2C 1C 1C,3G 0
Corn 0 0 0 0
Cotton 6H 0 0 0
Crabgrass 0 0 7H 0
Giant foxtail 0 0 3G 0
Morningglory 0 0 0 0
Nutsedge 0 0 0 0
Rice 1C 0 0 0
Sorghum 0 0 0 0
Soybean 1C,7G 0 0 0
Sugar beet 0 0 0 0
Velvetleaf 4G 2G 0 0
Wheat 0 0 0 0
Wild oat 0 0 0 0
PREEMERGENCE
Barley 0 0 0 0
Barnyardgrass 10H 8H 10H 7H
Cheatgrass 2G 0 4G 0
Cocklebur 5G 0 0 0
Corn 3G 0 0 0
Cotton 0 0 0 0
Crabgrass 2G 0 9H 5G
Giant foxtail 9H 3G 9H 7G
Morningglory 2H 0 0 0
Nutsedge 0 0 0 0
Rice 0 0 0 0
Sorghum 5G 0 0 0
Soybean 0 0 0 0
Sugar beet 0 0 0 0
Velvetleaf 7H 0 3C,5H 1H
Wheat 0 0 0 0
Wild oat 0 0 2C 0
Cmpd 8 Cmpd 9
RATE (g/ha) 400 100 400 100
POSTEMERGENCE
Barley 0 0 8H 2G
Barnyardgrass 9C 3C,9H 9C 9C
Cheatgrass 2G 0 9H 2G
Cocklebur 2C 1C 2C,6H 2C
Corn 0 0 3C,7H 3C,5H
Cotton 8H 0 3H 3H
Crabgrass 9H 9H 9H 9H
Giant foxtail 4C, 9H 3C,9H 5C,9H 9H
Morningglory 0 0 1H 0
Nutsedge 0 0 3C,9H 0
Rice 0 0 9C 2G
Sorghum 0 0 5H 3H
Soybean 1C, 3H 1H 6C,9H 6H
Sugar beet 5H 2H 5C,9H 0
Velvetleaf 3C, 7H 1H 3C,9H 6H
Wheat 0 0 9G 2G
Wild oat 0 0 9H 4G
PREEMERGENCE Barley 0 0 8H 0
Barnyardgrass 10H 10H 10H 10H
Cheatgrass 0 0 9H 6H
Cocklebur 0 0 0 0
Corn 0 0 4C,8H 4G
Cotton 0 0 8H 0
Crabgrass 10H 9H 10H 10H
Giant foxtail 10H 10H 10H 10H
Morningglory 0 0 0 0
Nutsedge 0 0 3C,9G 5G
Rice 0 0 3G 2G
Sorghum 3C, 8H 0 9H 9H
Soybean 0 0 9H 8H
Sugar beet 3H 2H 3H 2H
Velvetleaf 8H 6H 4C,9H 8H
Wheat 0 0 7G 3G
Wild oat 0 0 8H 2G
Cmpd 10 Cmpd 11
RATE (g/ha) 400 100 400 100
POSTEMERGENCE
Barley 8G 0 0 0
Barnyardgrass 9C 4C, 9G 3C, 9H 8H
Cheatgrass 9G 1C 3G 2G
Cocklebur 2C, 5H 1C, 2H 3C 2C
Corn 3C, 8H 5H 2G 0
Cotton 10P, 8G 0 2C 0
Crabgrass 9H 9H 9G 9G
Giant foxtail 4C, 9G 4C, 9G 9G 2G
Morningglory 1H 0 0 0
Nutsedge - 0 - 0
Rice 8G 0 0 0
Sorghum 8H 0 0 0
Soybean 6H 0 1C 0
Sugar beet 6H 1H 0 0
Velvetleaf 8H 7H 2C, 6H 2C,3H
Wheat 2G 0 0 0
Wild oat 5H 2G 0 0
PREEMERGENCE
Barley 8H 0 3G 0
Barnyardgrass 10H 10H 10H 9H
Cheatgrass 9H 9G 6G 5G
Cocklebur 5G 0 1C, 2H 0
Corn 10H 3C, 8H 4C, 8H 3G
Cotton 0 0 2G 0
Crabgrass 10H 10H 10H 8H
Giant foxtail 10H 10H 10H 8H
Morningglory 0 0 0 0
Nutsedge 2C, 8G 10E 0 0
Rice 8H 0 2C, 2G 0
Sorghum 10H 3C, 9H 4C, 8G 4G
Soybean 4H 0 0 0
Sugar beet 4H 2H 0 0
Velvetleaf 5H 2C, 6H 5H 2H
Wheat 2C, 5G 0 2G 0
Wild oat 9H 2G 2C, 8H 2H
Cmpd 12
RATE (g/ha) 400 100
POSTEMERGENCE
Barley 0 0
Barnyardgrass 0 0
Cheatgrass 0 0
Cocklebur 1C 0
Corn 0 0
Cotton 0 0
Crabgrass 0 0
Giant foxtail 2G 0
Morningglory 0 0
Nutsedge 0 0
Rice 0 0
Sorghum 0 0
Soybean 0 0
Sugar beet 0 0
Velvetleaf 0 0
Wheat • 0 0
Wild oat 0 0
PREEMERGENCE
Barley 0 0
Barnyardgrass 0 0
Cheatgrass 0 0
Cocklebur 0 0
Corn 0 0
Cotton 0 0
Crabgrass 3G 0
Giant foxtail 4G 0
Morningglory . 0 0
Nutsedge 0 0
Rice 0 0
Sorghum 0 0
Soybean 0 0
Sugar beet 0 0
Velvetleaf 0 0
Wheat 0 0
Wild oat 0 0
Cmpd 13
RATE (g/ha) 400 100
POSTEMERGENCE
Barley 0 0
Barnyardgrass 1H 0
Cheatgrass 0 0
Cocklebur - 0
Corn 0 0
Cotton 0 0
Crabgrass 0 0
Giant foxtail 3G 0
Morningglory 0 0
Nutsedge 0 0
Rice 0 0
Sorghum 0 0
Soybean 0 0
Sugar beet 0 0
Velvetleaf 0 0
Wheat 0 0
Wild oat 0 0
PREEMERGENCE
Barley 0 0
Barnyardgrass. 2C,8G 2C,5G
Cheatgrass 0 0
Cocklebur 0 0
Corn 0 0
Cotton 0 0
Crabgrass 5G 0
Giant foxtail 3G 0
Morningglory 0 0
Nutsedge 10E 0
Rice 0 0
Sorghum 2G 0
Soybean 0 0
Sugar beet 2G 0
Velvetleaf 4H 0
Wheat 0 0
Wild oat 0 0
TEST B Seeds of barley {Hordeum υulgare) , barnyardgrass
{Echinochloa crus-galli) , blackgrass {Alopecurus myosuroides) , chickweed {Stellaria media) , cocklebur {Xanthium pensylυanicum) , corn {Zea mays) , cotton {Gossypium hirsutum) , crabgrass {Digitaria spp . ) , downy brome {Bromus tectorum) , giant foxtail {Setaria faberi) , green foxtail {Setaria viridis) , j imsonweed {Datura stramonium) , j ohnsongrass {Sorghum halepense) , lambsquarters {Chenopodium album) , morningglory {Ipomoea spp . ) , rape {Brassica napus) , rice {Oryza sativa) , sicklepod {Cassia obtusifolia) , soybean {Glycine max) , sugar beet {Beta υulgaris) , teaweed {Sida spinosa) , velvetleaf {Abutilon theophrasti) , wheat {Triticum aestivum) , wild buckwheat {Polygonum convolvulus) , and wild oat {Aυenafatua) and purple nutsedge {Cyperus rotundus) tubers were planted and treated preemergence with test chemicals dissolved in a non-phytotoxic solvent . At the same time, these crop and weed species were also treated with postemergence applications of test chemicals . Plants ranged in height from two to eighteen cm ( two to three leaf stage) for postemergence treatments . Treated plants and controls were maintained in a greenhouse for approximately 24 days , after which all species were compared to controls and visually evaluated . Preemergence and postemergence application rates for each compound are listed in Table B . Plant response ratings , summarized in Table B , are based on a scale of 0 to 100 where 0 is no effect and 100 is complete control . A dash (-) response means no test result .
SUBSTITUTE SHEET
Table B
Cmpd 1
RATE (g/ha) 500 250
POSTEMERGENCE
Barley 0 0
Barnyardgrass 85 80
Blackgεass 30 20
Chickweed 0 0
Cocklebur 0 0
Corn 20 - 0
Cotton 0 0
Crabgrass 90 50
Downy brome 0 0
Giant foxtail 90 90
Green foxtail 40 30
Jimsonweed 0 0
Johnsongrass 30 20
Lambsquarters 40 30
Morningglory 0 0
Nutsedge 60 0
Rape 0 0
Rice 0 0
Sicklepod 0 0
Soybean 0 0
Sugar beet 60 20
Teaweed 0 0
Velvetleaf 60 40
Wheat 0 0
Wild buckwheat 0 0
Wild oat 30 20
Cmpd " 1
RATE (g/ha) 500 250 125 62
PREEMERGENCE
Barley 0 0 0 0
Barnyardgrass 100 100 100 30
Blackgrass 100 100 70 40
Chickweed 0 0 0 0
Cocklebur 20 0 0 0
Corn 30 20 20 0
Cotton 0 0 0 0
Crabgrass 100 100 100 100
Downy brome 90 90 90 30
Giant foxtail 100 100 100 50
Green foxtail 100 100 100 100
Jimsonweed 0 0 0 0
Johnsongrass 80 70 70 40
Lambsquarters 80 80 - 70
Morningglory 0 0 0 0
Nutsedge 30 • 0 0 0
Rape 20 0 0 0
Rice 40 10 0 0
Sicklepod 0 0 0 0
Soybean 0 0 0 0
Sugar beet 30 20 0 0
Teaweed 50 40 30 20
Velvetleaf 80 70 40 20
Wheat 0 0 0 0
Wild buckwheat 90 60 40 30
Wild oat 100 60 40 30
SUBSTITUTE SHEET
Cmpd 2
RATE (g/ha) 250 125 62 31
POSTEMERGENCE
Barley 0 0 0 0
Barnyardgrass 90 90 90 50
Blackgrass 0 0 0 0
Chickweed 0 0 0 0
Cocklebur 0 0 0 0
Corn 30 20 0 0
Cotton 0 0 0 0
Crabgrass 70 20 0 0
Downy brome 0 0 0 0
Giant foxtail 40 30 0 0
Green foxtail 40 20 0 0
Jimsonweed 0 0 0 0
Johnsongrass 0 0 0 0
Lambsquarters 80 20 0 0
Morningglory 0 0 0 0
Nutsedge 0 0 0 0
Rape 30 20 0 0
Rice 0 0 0 0
Sicklepod 0 0 0 0
Soybean 0 0 0 0
Sugar beet 0 0 0 0
Teaweed 0 0 0 0
Velvetleaf 40 20 0 0
Wheat 0 0 0 0
Wild buckwheat 0 0 0 0
Wild oat 0 0 0 0
Cmpd " 2
RATE (g/ha) 250 125 62 31
PREEMERGENCE
Barley 0 0 0 0
Barnyardgrass 100 100 100 100
Blackgrass 40 30 30 30
Chickweed 0 0 0 0
Cocklebur 0 — 0 0
Corn 0 0 0 0
Cotton 0 0 0 0
Crabgrass 100 100 100 90
Downy brome 0 0 0 0
Giant foxtail 100 100 80 70
Green foxtail 90 80 70 30
Jimsonweed 0 0 0 0
Johnsongrass 50 30 20 20
Lambsquarters 90 80 50 50
Morningglory 0 0 0 0
Nutsedge 0 0 0 0
Rape 0 0 0 0
Rice 30 0 0 0
Sicklepod 100 40 0 0
Soybean 0 0 0 0
Sugar beet 0 0 0 0
Teaweed 60 60 60 0
Velvetleaf 70 50 20 0
Wheat 0 0 0 0
Wild buckwheat 0 0 0 0
Wild oat 0 0 0 0
Cmpd 4
RATE (g/ha) 250 125 62 31 POSTEMERGENCE Barley 30 0 0 0
Barnyardgrass 70 65 60 40 Blackgrass 100 90 70 40 Chickweed 0 0 0 0 Cocklebur 30 0 0 0 Corn 0 0 0 0 Cotton 0 0 0 0 Crabgrass 90 80 70 60 Downy brome 0 0 0 0 Giant foxtail 90 60 30 0 Green foxtail 70 60 40 30 Jimsonweed 50 30 0 0 Johnsongrass 0 0 0 0 Lambsquarters 80 70 60 30 Morningglory 50 0 0 0 Nutsedge Rape 80 50 0 0 Rice 0 0 0 0
Sicklepod 30 0 0 0 Soybean 0 0 0 0 Sugar beet 0 0 0 0 Teaweed 0 0 0 0 Velvetleaf 70 30 30 0 Wheat 0 0 0 0
Wild buckwheat 30 0 0 0 Wild oat 0 0 0 0
Cmpd ' 4
RATE (g/ha) 250 125 62 31
PREEMERGENCE
Barley 50 30 0 0
Barnyardgrass 100 100 100 100
Blackgrass 100 100 60 60
Chickweed 70 70 30 0
Cocklebur 100 0 0 -
Corn 100 ' 80 50 20
Cotton 30. 30 0 0
Crabgrass 100 100 100 100
Downy brome 100 100 40 20
Giant foxtail 100 100 100 100
Green foxtail 100 100 100 100
Jimsonweed 80 40 30 0
Johnsongrass 100 80 75 40
Lambsquarters 0 0 0 0
Morningglory 0 0 0 0
Nutsedge 20 0 0 0
Rape 20- - 0 0 0
Rice 40 0 0 0
Sicklepod 50 30 0 0
Soybean 0 0 0 0
Sugar beet - 50 30 30
Teaweed 80 - 70 0
Velvetleaf 90 80 50 0
Wheat 30 0 0 0
Wild buckwheat 0 0 0 0
Wild oat 40 30 30 0
Cmpd 5
RATE (g/ha) 250 125 62 31 POSTEMERGENCE Barley 0 0 0 0
Barnyardgrass 60 50 30 0 Blackgrass 30 0 0 0 Chickweed 0 0 0 0 Cocklebur 0 0 0 0 Corn 0 0 0 0 Cotton 0 0 0 0 Crabgrass 70 - 30 0 Downy brome 0 0 0 0 Giant foxtail 90 80 60 30 Green foxtail 60 0 0 0 Jimsonweed 30 0 0 0 Johnsongrass 30 0 0 0 La bsquarters 90 60 30 0 Morningglory 0 0 0 0 Nutsedge Rape 0 0 0 0 Rice 70 20 0 0
Sicklepod 30 0 0 0 Soybean 0 0 0 0 Sugar beet 30 0 0 0 Teaweed 0 0 0 0 Velvetleaf 30 30 0 0 Wheat 0 0 0 0
Wild buckwheat 0 0 0 0 Wild oat 0 0 0 0
SUBSTITUTESHEET
Cmpd ' 5 RATE (g/ha) 250 125 62 31
PREEMERGENCE Barley 0 0 0 0
Barnyardgrass 100 100 100 100 Blackgrass 100 100 100 85 Chickweed 30 20 0 0 Cocklebur 50 0 — — Corn 70 50 0 0 Cotton 30 " 20 0 — Crabgrass 100 100 100 100 Downy brorrte 60 40 0 0 Giant foxtail 100 100 100 100 Green foxtail 100 100 100 100 Jimsonweed 0 0 0 0 Johnsongrass 100 100 100 100 Lambsquarters 80 60 50 30 Morningglory 0 0 0 0 Nutsedge Rape 0 0 0 0 Rice 0 0 0 0
Sicklepod 50 30 0 0 Soybean 20 0 0 0 Sugar beet 50 30 0 0 Teaweed 70 30 0 0 Velvetleaf 100 100 80 30 Wheat 0 0 0 0
Wild buckwheat 0 0 0 0 Wild oat 40 30 20 0
TEST C
Plastic pots were partially filled with silt loam soil. The soil was then saturated with water. Indica and Japonica rice {Oryza satiυa) seedlings at the 2.0 to 2.5 leaf stage, seeds of barnyardgrass {Echinochloa crus-galli) , bulrush {Scirpus mucronatus) , and umbrella sedge {Cyperus difformis) , and sprouted tubers of arrowhead {Sagittaria spp.) and waterchestnut {Eleocharis spp.) were planted into this soil. Several days after planting, water levels were raised to 3 cm above the soil surface and maintained at this level throughout the test. Chemical treatments were formulated in a non-phytotoxic solvent and applied directly to the paddy water. Treated plants and controls were maintained in a greenhouse for approximately 21 days, after which all species were compared to controls and visually evaluated. Plant response ratings, summarized in Table C, are based on a scale of 0 to 100 where 0 is no effect and 100 is complete control. A dash (-) response means no test result.
Table C
Cmpd 1
RATE (g/ha) 1000 500 250 125 64
Arrowhead 70 90 70 60 30
Barnyardgrass 100 100 100 100 100
Bulrush 95 95 95 90 0
Rice (Indica) 50 20 0 0 0
Rice (Japonica) 30 20 0 0 0
Umbrella sedge 100 100 100 100 95
Waterchestnut 100 100 100 100 100
Cmpd 2
RATE (g/ha) 1000 500 250 125 64
Arrowhead 0 0 0 0 0
Barnyardgrass 100 100 100 100 100
Bulrush 90 90 0 0 0
Rice (Indica) 30 30 0 0 0
Rice (Japonica) 20- - 0 0 0 0
Umbrella sedge 100 100 100 100 0
Waterchestnut 100 70 100 0 0
Cmpd 3
RATE (g/ha) 500 250 125 64 32
Arrowhead
Barnyardgrass 100 100 100 95 95
Bulrush 90 90 90 - 90 90
Rice (Indica) 80 80 40 30 0
Rice (Japonica) 90 80 50 20 0
Umbrella sedge 100 100 100 100 100
Waterchestnut 90 60 50 70 40
Cmpd 5
RATE (g/ha) 500 250 125 64 32
Arrowhead 90 0 0 0 0
Barnyardgrass 100 100 100 100 100
Bulrush 95 95 95 95 80
Rice (Indica) 50 30 20 0 0
Rice (Japonica) 40 30 0 0 0
Umbrella sedge 100 100 100 100 100
Waterchestnut 95 0 0 0 0
'SUBSTITUTESHEET
Cmpd 7
RATE (g/ha) 500 250 125 64
Arrowhead 0 0 0 0
Barnyardgrass 100 100 100 100
Bulrush 95 0 0 0
Rice (Indica) 0 0 0 0
Rice (Japonica) 0 0 0 0
Umbrella sedge 100 100 100 100
Waterchestnut 0 0 0 0 Cmpd 10
RATE (g/ha) 500 250 125 64
Arrowhead 95 95 60 95
Barnyardgrass 100 100 100 100 1
Bulrush 95 95 90 60
Rice (Indica) 60 40 0 0
Rice (Japonica) 70 50 0 0
Umbrella sedge 100 100 100 100 1
Waterchestnut 95 95 95 0
TEST D
Seeds of spring and winter barley {Hordeum vulgare) , black nightshade {Solanum nigrum) , blackgrass {Alopecurus myosuroides) , bluegrass {Poa annua) , catchweed bedstraw {Galium aparine), cheatgrass {Bromus secalinus) , downy brome {Bromus tectorum) , field pennycress {Thlaspi ' arvense) , field violet {Viola arυens is) , green foxtail {Setaria viridis) , Italian ryegrass {Lolium multiflorum) , ivyleaf speedwell {Veronica hederaefolia) , jointed goatgrass {Aegilops cylindrica) , kochia {Kochia scoparia) , lambsquarters {Chenopodium album) , Persian speedwell {Veronica persica) , rape {Brassica napus) , Russian thistle {Salsola kali) , scentless chamomile {Matricaria inodora) , sugar beet {Beta vulgaris) , spring and winter wheat {Triticum aestivum) , wild buckwheat {Polygonum convolvulus) , and wild oat {Avena fatua) were planted and treated preemergence with test chemicals dissolved in a non-phytotoxic solvent. Postemergence applications of test chemicals were also applied to these same crop and weed species. Plants ranged in height from two to twenty-four cm (two to three leaf stage) for postemergence treatments. Blackgrass and wild oat were treated postemergence at two growth stages — the first stage being at two to three leaves and the second stage being approximately at four leaves or in the initial stages of tillering. Treated plants and controls were maintained in a greenhouse for approximately 21 days, after which all species were compared to controls and visually evaluated. Rates of application of each compound are listed in Table D. Plant response ratings, summarized in Table D, are based on a scale of 0 to 100 where 0 is no effect and 100 is complete control.
Table D
Cmpd 1
RATE (g/ha) 500 250 125 64
POSTEMERGENCE
Barley (Spring) 0 0 0 0
Barley (Winter) 0 0 0 0
Black nightshade 10 0 0 0
Blackgrass 10 0 0 0
Blackgrass (Stage 2) 0 0 0 0
Bluegrass 50 50 20 0
Catchweed bedstraw 0 0 0 0
Cheatgrass 0 0 0 0
Downy brome 0 0 0 0
Field pennycress 10 0 0 0
Field violet 0 0 0 0
Green foxtail 60 60 0 0
Italian ryegrass 0 0 0 0
Ivyleaf speedwell 0 0 0 0
Jointed goatgrass 0 0 0 0
Kochia 0 0 0 0
Lambsquarters 10 0 0 0
Persian speedwell 0 0 0 0
Rape 50 10 0 0
Russian thistle 0 0 0 0
Scentless chamomile 0 0 0 0
Sugar beet 10 0 0 0
Wheat (Spring) 0 0 0 0
Wheat (Winter) 0 0 0 0
Wild buckwheat 0 0 0 0
Wild oat 0 0 0 0
Wild oat (Stage 2) 0 0 0 0
Cmpd 1
RATE (g/ha) 500 250 125 64 DOu ~~ , J~c?.i~Ά_~~.'K~~IΓ_-i_~._~-<Γ_.~_~_ ~ Barley (Spring) 20 10 0 0
Barley (Winter) 20 0 0 0
Black nightshade 0 0 0 0
Blackgrass 100 100 20 0
Bluegrass 100 100 50 10
Catchweed bedstraw 20 0 0 0
Cheatgrass 70 20 0 0
Downy brome ■ 90 60 50 10
Field pennycress 30 0 0 0
Field violet 40 20 20 0
Green foxtail 100 100 100 100
Italian ryegrass 90 80 20 20
Ivyleaf speedwell 60 0 0 0
Jointed goatgrass 20 10 0 0
Kochia 100 80 40 20
Lambsquarters 60 60 50 40
Persian speedwell 20 20 0 0
Rape 50 10 0 0
Russian thistle - • • 20 0 0 0
Scentless chamomile 40 40 10 10
Sugar beet 70 40 40 20
Wheat (Spring) 10 0 0 0
Wheat (Winter) 20 10 0 0
Wild buckwheat 10 0 0 0
Wild oat 30 0 0 0
Cmpd 2
RATE (g/ha) 500 250 125 64
POSTEMERGENCE
Barley (Spring) 0 0 0 0
Barley (Winter) 0 0 0 0
Black nightshade 10 0 0 0
Blackgrass 20 0 0 0
Blackgrass (Stage 2) 0 0 0 0
Bluegrass 20 0 0 0
Catchweed bedstraw 20 10 0 0
Cheatgrass 0 0 0 0
Downy brome 0 0 0 0
Field pennycres.;- 10 0 0 0
Field violet 0 0 0 0
Green foxtail 20 0 0 0
Italian ryegrass 0 0 0 0
Ivyleaf speedwell 0 0 0 0
Jointed goatgrass 0 0 0 0
Kochia 20 0 0 0
Lambsquarters 10 0 0 0
Persian speedwell 0 0 0 0
Rape 10 0 0 0
Russian thistle 0 0 0 0
Scentless chamomile 0 0 0 0
Sugar beet 20 0 0 0
Wheat (Spring) 0 0 0 0
Wheat (Winter) 0 0 0 0
Wild buckwheat 0 0 0 0
Wild oat 0 0 0 0
Wild oat (Stage 2) 0 0 0 0
Cmpd
RATE (g/ha) 500 250 125 64 PREEMERGENCE Barley (Spring) 0 0 0 0 Barley (Winter) 0 0 0 0 Black nightshade 0 0 0 0 Blackgrass 90 30 10 10 Bluegrass 100 90 60 50
Catchweed bedstraw 0 0 0 .0 Cheatgrass 10 0 0 0 Downy brome 70 20 0 0 Field pennycress 60 50 20 0 Field violet 100 70 20 0 Green foxtail 100 100 100 100 Italian ryegrass 80 60 20 0 Ivyleaf speedwell 50 10 0 0 Jointed goatgrass 10 0 0 0 Kochia 30 20 0 0
Lambsquarters 50 50 20 0 Persian speedwell 10 0 0 0 Rape 80 70 60 30
Russian thistle 10 0 0 0 Scentless chamomile 0 0 0 0 Sugar beet 70 50 30 30 Wheat (Spring) 0 0 0 0 Wheat (Winter) 0 0 0 0 Wild buckwheat 0 0 0 0 Wild oat 10 10 0 0
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