S P E C I F I C A T I O N

Title of the Invention;

OXIME DERIVATIVES AND HERBICIDES CONTAINING THE SAME AS AN ACTIVE INGREDIENT

Field of the Invention:

The present invention relates to oxime derivatives and herbicidal compositions containing the same as an active ingredient. Particularly, the present invention relates to a heribicide which shows excellent herbicidal activity against broad leaved weeds and narrow leaved weeds, and has selec¬ tive herbicidal activity without any adverse effect on the growth of crop plants by selecting the application methods, treating methods and application rates ^' appropriately.

Description on the Prior Arts:

Herbicides of the type which selectively kills broad- leaved weeds, typified by 2,4-dichlorophenoxyacetiσ acid, are known as selective herbicidally active compounds, the selectivity of the herbicidal activity of 2,4- dichlorophenoxyacetic acid is between narrow-leaved plants including both crop plants and weeds, and broad-leaved plants including both crop plants and weeds. It is known that 2,4-dichlorophenoxyacetic acid has very little or no activity against narrow-leaved plants [see, for example, Nature, 155, 498 (1945)]. It is known, on the other hand, that compounds resulting from introduction of a chloro- or trifluoromethyl-substituted phenoxy group or a chloro- or trifluoromethyl-substituted pyridyloxy group into the aro¬ matic group of the above compound have the activity of selectively killing narrow-leaved plants (see U.S. Patents Nos. 4,270,948; 4,309,562; 4,314,069; 4,332,961 and 3,954,442; British Patent No. 1,579,201, and Japanese Laid-

Open Patent Publication Nos. 125626/1977 and 15825/1977). These compounds, however, also kill useful crops such as rice or corn.

Herbicides containing some kinds of N-phosphonome- thylglycine derivatives as active ingredients are known and commercially available. These N-phosphonomethylglycine derivatives are basically non-selective herbicides, but their herbicidal activity is reduced in a low application rate against perennial weeds such as Cyperus rotundus in Cyperaceae and against broad-leaved weeds such as Chenopodi- um album var. centrorubrum or Amaranthus retroflexas. Par¬ ticularly, they hardly develop herbicidal activity against weeds in Convolvulaceae such as Ipomoea purpurea even 2 weeks after application. Further, the N-phosphonomethylgly- cine derivatives are slow acting and unsuitable for the cases that the weeds are whithered quickly and the next work will be started soon in crop lands or non-crop lands. For example, in a crop land, all of the weeds should be eradi¬ cated before sowing of a crop plant, but the slow acting may cause adverse effects such as delay of sowing time and damage to the crop seeds. Additionally, in non-crop lands, delays in constructions of buildings or railroads or weeding delay in roads may be caused, thus the N-phosphonomethylgly- cine derivatives are unsatisfactory as a non-selective herbicide quick-acting at a low application rate.

Herbicides containing some kinds of glufosinate com¬ pounds as a major active ingredient are known and commer¬ cially available. This type of herbicides also is basically non-selective, but has a disadvantage that a low application rate reduces herbicidal activity against broad-leaved weeds such as Chenopodium album var. centrorubrum, Amaranthus retroflexas or Abutilon theophrasti.

The Objects and Summary of the Invention:

It is an object of the present invention to provide a novel oxime derivative.

Another object of the present invention is to provide a herbicide showing excellent herbicidal effect against broad-leaved weeds and narrow-leaved weeds.

Another object of the present invention is to provide a compound and a herbicide containing the same which selec¬ tively eradicates broad-leaved weeds and narrow-leaved weeds substantially without chemical injury to useful crop plants, especially soybeans and corns, by choosing appropriately the application methods, treating methods and application rates. Another object of the present invention is to provide a compound and a selective herbicide containing the same which can act on plant bodies to kill or inhibit the growth of a plurality of broad-leaved weeds and narrow-leaved weeds substantially without chemical injury to narrow-leaved crops such as corn and broad-leaved crops such as soybean, accord¬ ingly can create a state where crop plants can easier grow than noxious weeds do in an area where both useful crops and noxious weeds are growing.

Another object of the present invention is to provide a selective herbicide which can not only kill or inhibit the growth of the target weeds, but also inhibit the germination of the weeds and kill the grown plants substantially without inhibition of germination and growth of useful crop plants by treating the soil with the herbicide before germination, in other words, to provide a herbicide which can be used by both foliar spraying and soil treatment.

Another object of the present invention is to provide a herbicide which has low toxicity to animals and fish and remains little in the soil.

Another object of the present invention is to provide a herbicidal composition which can kill both narrow-leaved and broad-leaved weeds at a low application rate by combining

the novel oxime derivative according to the present inven¬ tion with known N-phosphonomethylglycine derivative and/or glufosinate derivative to utilize their herbicidal proper¬ ties. Another object of the present invention is to provide novel benzaldehyde derivative as an intermediate which can prepare the oxime derivatives in high yield efficiently in the production of novel oxime derivatives according to the present invention. Further objects of the invention along with its advan¬ tage will become apparent from the following description. According to the study by the inventors, these above objects and advantages of the invention are achieved by the following oxime derivatives. Namely, according to the present invention, oxime derivatives of formula (I)

wherein

X and Y are 'identical or different and each represents a hydrogen atom, a halogen atom, -CF3, or an alk l group having 1 to 5 carbon atoms; Z is =CH- or =N-;

R represents a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms;

₂

R represents a group selected from the following groups shown in a) to g): a) hydrogen atom: b) a saturated or unsaturated aliphatic hydrocar¬ bon group having 1 to 10 carbon atoms which may be optionally substituted by the following substituents:

substituents: i) a halogen atom; ii) a hydroxyl group; iii) an alkoxy group having 1 to 5 carbon atoms; iv) -COR ⁴ ; wherein R is a hydroxyl group, an alkyl group having 1 to 5 carbon atoms which may be substituted by a halogen atom, a phenyl group which may be sub- stituted by a halogen atom, an alkoxy group having 1 to 5carbon atoms, a alkenyloxy group having 1 to 5 carbon atoms or a group of the

formula R^

/ -N

in which R ⁵ and R° are identical or different and each represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms; v) a phenyl group; wherein the phenyl group may be substi- tuted by a halogen atom, a hydroxyl group, -CF3, -NO2, -CN, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, -COR ₄ or R ⁵ -N ⁷

V _; vi) a phenoxy group; wherein the phenoxy group may be substituted by the groups cited in

v) , in addition to phenyl, phenoxy or pyridyloxy group (wherein the phenyl, phenoxy or pyridyloxy group may be substituted by halogen atom or -CF3) vii) R ⁵

/ -N

V wherein R ⁷ is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or -COR ⁴ ; viii) -CN; c) an alkoxy group which may be substituted by the following substituents: substituents: i) a halogen atom; ii) a phenyl group (wherein the phenyl group may be substituted by substitu¬ ents v) in b) ; d) a phenoxy group which may be substituted by the following substituents: substituents: .the same substituents as v) in b); e) an aromatic hydrocarbon group having 6 to 20 carbon atoms which may be substituted by the following substituents: substituents: i) a halogen atom; ii) a hydroxyl group; iv) -N0 ₂ ; v) -CN; vi) an alkyl group having 1 to 5 carbon atoms; vii) an alkoxy group having 1 to 5 carbon atoms; viii)-COR ⁴ ;

ix)

x) -N ⁺ R ⁵ R ^β R ⁸

Q wherein R is an alkyl group having 1 to 5 carbon atoms; xi) a phenyl group wherein the phenyl group may be substi- tuted by the substituents v) in b); xii) a phenoxy group wherein the phenoxy group may be substituted by the substituents vi) in b); xiii)-CH ₂ COR ⁴ ; f) an aromatic heterocyclic group containing at least one nitrogen atom having 3 to 20 carbon atoms which may be substituted by the following substituents: substituents: the same substituents as shown in e);

g) R ⁵

-N

R ^y q wherein R is b) , e) or f); R ^J is a hydrogen atom ; or an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substi¬ tuted by a halogen atom, a hydroxyl group, an alkoxy group, -COR ⁴ or

wherein R and are identical or different and represent a hydrogen atom, an alkyl group having 1

to 5 carbon atoms, or a phenyl group;

O S O

II II II Q represents a direct bond, -C-, -C- or -S-;

0 wherein in case that Q is a direct bond, R is not c), d) or g) ; or their salts are provided.

The oxime derivatives according to the present inven¬ tion have a wide range of herbicidal spectrum, exhibiting excellent herbicidal activity against both broad-leaved weeds and narrow-leaved weeds. Further, the oxime deriva¬ tives according to the present invention can eradicate . broad-leaved weeds and narrow-leaved weeds substantially without chemical injury to useful crops, especially soybeans and corns, accordingly without growth inhibition of these plants, by selecting application methods, treating methods and application rates optimally. The oxime derivatives according to the present invention develops herbicidal effect with a reduced amount of application and have quick- acting herbicidal activity.

The best embodiment of the invention:

The present invention will be illustrated in detail as follows.

In the general formula (I) , X and Y are identical or different and each represents a hydrogen atom, a halogen atom, trifluoromethyl or an alkyl group having 1 to 5 carbon atoms. The halogen atom is, for example, fluorine, chlorine or bromine. The alkyl group having 1 to 5 carbon atoms is straight-chained or branched, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, iso-butyl, t-butyl, or n-pentyl. X and Y are identical or different and each

preferably represents chlorine or trifluoromethyl. In the formula (I), Z is =CH- or =N-. In the formula (I), R represents a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms.

The concrete examples having the alkyl group having 1 to 5 carbon atoms, prescribed here are the same as those cited in the alkyl group having 1 to 5 carbon atoms in context of X and Y. The alkoxy group having 1 to 5 carbon atoms may be straight-chained or branched, and is, for example, methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, sec-butoxy, t- butox , n-pentoxy, etc.

R' is preferably a hydrogen atom. In the formula (I), R is a group selected from the groups shown in a) through g) .

In this context, the aliphatic hydrocarbon group is a straight-chained or branched aliphatic hydrocarbon group and an alicyclic hydrocarbon group. The concrete examples of the halogen atoms, alkyl groups having 1 to 5 carbon atoms, and the alkoxy groups having 1 to 5 carbon atoms are the same as those cited in the prescription of X, Y and R' .

The alkenyloxy group having 2 to 5 carbon atoms is, for example, ethenoxy, propenoxy, butenoxy or pentenoxy.

The aromatic hydrocarbon group is benzene, naphthalene or their combinations.

The aromatic heterocyclic group has a structure of, for example, benzene or naphthalene in which at least one of carbon atom is replaced by an oxygen atom, a sulfur atom, a nitrogen atom or the like.

Additionally, R is preferably, in case that Q is a direct bond, an aromatic hydrocarbon group having 6 to 20 carbon atoms which may be substituted by e) or an aromatic

heterocyclic group having 3 to 20 carbon atoms, which con¬ tains at least one nitrogen atom and may be substituted by f), and is preferably a group other than a) a hydrogen atom, in case that 0

II Q is -C-.

• ^* > In R of the formula (I), the aliphatic hydrocarbon group is the one which is substituted by a straight-chained or branched hydrocarbon group, an alicyclic hydrocarbon group and an aromatic hydrocarbon group. The concrete exam¬ ples of the halogen atom, alkoxy group and -COR are the same as those cited in R .

R ³ is preferably methyl, ethyl, propyl, butyl or other aliphatic chained hydrocarbon groups having 1 to 5 carbon atoms,

^3 ^C 2 ^H 5 -CH ₂ -COR ⁴ , -CH-COR ⁴ , -CH-COR ⁴ ,

^3 _t ^C 2 ^H 5 particularly preferably -CH-COR ⁴ , -CH-COR ⁴ , wherein R ⁴ represents a hydroxy, methoxy, thoxy, propoxy or butoxy group.

0 S

In the formula (I), Q is a direct bond, -C-, -C-, or

O 0

II If

-S- , and preferably a direct bond or -C-.

II

0 wherein, in case that Q is a direct bond, R^ is not an alkoxy group which may be substituted by c) , a phenoxy group which may be substituted by d) or

Among the compounds of formula ( ) , the compounds selected from the following table have particularly

excellent herbicidal activity

Examples of the oxime derivatives of formula (I) are shown in the following table.

No. X R'

(1B) -CF- -Cl -CH ^** -H -H -C ₂ H ₅

(2B) -CF. -Cl -CH= -H -H -CHCOOCH- i -

CH-,

(3B) -CF. -Cl -CH= -H

(4B) -CF- -Cl -CH= -H

(5B) -CF, -Cl ^* -CH= -H

(6B) -CF -Cl -CH= -H

(7B) -CF ₃ -Cl -CH= -H

(8B) -CF ₃ -Cl -CH= -H

(9B) -CF-, -Cl -CH= -H -cyclohexyl -CHCOOCH3

CHr

( 1 0B ) -CF3 -Cl -CH= -H -CH ₂ COOC ₂ H ₅ -CHCOOCH3 CHo

No . X R ¹ R' R-

(11B) -CF ₃ -Cl -CH= -H -CH ₂ -CH=CH ₂ -CHCOOCH ₃ CH ₃

(12B) -CF ₃ -Cl (13B) -CF3 -Cl -CH** ^* - -H -CH ₂ -CH ₂ -CH=CH ₃

(14B) -CF3 -Cl -CH= -H -CH ₂ -CH=CH ₂

(15B) -CF3 -Cl -CH= -H -CH ₂ -CH=CH ₂

(16B) -CF3 -Cl -CH= -CH3 -H -CHCOOCH3 CH ₃

(17B) -CF3 -Cl -CH= -CH3 -CH3 -CHCOOCH3

CH ₃

(18B) . -CF ₃ -Cl -CHa -H -benzyl -CHCOOCH3

CH ₃

(19B) -CF ₃ -Cl -CH= -H -phenyl ^_C 2 ^H 5

(20B) -CF ₃ -Cl -CH= -H -phenyl -CHCOOCH3

CH ₃

(21B) -CF3 -Cl -CH= -H -4-fluorophenyl -CHCOOCH3

CH ₃

No . R ¹ R' R-

(22B) -CF ₃ -Cl -CH= -H -2-fluorophenyl -CHCOOCH3 CH ₃

(23B) -CF ₃ -Cl -CH= -H -3-fluorophenyl -CHCOOCH3

CH ₃

(24B) -CF ₃ -Cl -CH= -H -4-chlorophenyl -CHCOOCH3

CH3

(25B) -CF ₃ -Cl -CH= -H -4-cyanophenyl -CHCOOCH3

CH,

(26B) -CF ₃ -Cl -CH= -H -4-nitroρhenyl -CHCOOCH3

CH ₃

(27B) -CF ₃ -Cl -CH= - -H -3-nitrophenyl -CHCOOCH3 CH ₃

»

(28B) -CF ₃ -Cl -CH= -H -3-trifluoro- -CHCOOCH3 ethylphenyl CH3

(29B) -CF ₃ -Cl -CH= -H -3-methoxyphenyl -CHCOOCH3

CH ₃

(30B) -CF3 -Cl -CH= -H -4-methylphenyl -CHCOOCH3

CH ₃

(31B) -CF ₃ -Cl -CH= -H -4-ρhenylphenyl -CHCOOCH3

CH ₃

(32B) -CF3 -Cl -CH= -H -4-(4-trifluoro- -CHCOOCH3 ethylphenoxy)- CH3 phenyl

No. X R' R-

(33B) -CF ₃ -Cl -CH= -H -3,4-dichloro- -CHCOOCH- phenyl CH3

(34B) -CF ₃ -Cl -CH= -H -2,4-dinitro- -CHCOOCH3 phenyl CH3

(35B) -CF3 -Cl -CH= -H -2-chloro-4- -CHCOOCH3 trifluoromethyl- CH3 phenyl

(36B) -CF3 -Cl -CH= -H -3,5-dimethoxy- -CHCOOCH3 phenyl CH3

(37B) -CF ₃ -Cl -CH= -H -3,5-dimethyl- -CHCOOCH3 phenyl CH3

(38B) -Cl -Cl -CH= -H -phenyl -CHCOOCH 3

CH ₃

(39B) -Cl -Cl -CH= -H -4-fluorophenyl

(4OB) -Cl -Cl -CH= -H -4-nitrophenyl -CHCOOCH3

CH ₃

(41B) -Cl -Cl -CH= -H -3-methoxyphenyl -CHCOOCH3 CH ₃

(42B) -Cl -Cl -CH= -H -3-trifluoro- -CHCOOCH-,

I - ³ methylphenyl CHo

No . X '

(43B) -Cl -Cl -CH= -H -4-methylphenyl -CHCOOCH CH ₃

(44B) -Cl -Cl -CH= -H -4-cyanophenyl -CHCOOCH-, i ° CH ₃

(45B) -Cl -Cl -CH= -H -2-chloro-4- -CHCOOCH-, trifluoromethyl- CH phenyl

(46B) -CF3 -H -CH= -H -phenyl -CHCOOCH CH,,

(47B) -CF3 -H -CH= -H -4-fluorophenyl -CHCOOCH3

CH ₃

(48B) -CF3 -H -CH= -H -4-chlorophenyl -CHCOOCH3

CH ₃ .

(49B) -CFo -H -CH= -H -3-trifluoro- -CHCOOCH- - ^> 1 methylphenyl CH-,

(5OB) -CF ₃ -Cl -CH= -H -2-pyridyl -CHCOOCH3

CH ₃

(51B) -CF3 -Cl -CH= -H -6-methoxy-2- -CHCOOCH3 pyridyl CH3

(52B) -CF ₃ -Cl -CH= -H -3-chloro-2- -CHCOOCH3 pyridyl CH3

(53B) -CF ₃ -Cl -CH= -H -2-pyrazyl -CHCOOCH3

CH ₃

No . X R ¹ R' R-

(54B) -CF o -Cl -CH= -H -3,6-dimethyl- -C1HCOOCH ₃ 2-pyrazyl CH3

(55B) -CF ₃ -Cl -CH= -H -2-quinolyl -CHCOOCH3

CH ₃

(56B) -CF ₃ -Cl -CH= -H -6-chloro-3- -CHCOOCH3 pyridazyl CH,

(57B) -Cl -Cl -CH= -H -6-chloro-2- -CHCOOCH 3 pyridyl CH-

(58B) -Cl -Cl -CH= -H -3,6-dimethyl- -CHCOOCH3

2-pyrazyl CH,

(59B) -CF, -H -CH= -H -6-chloro-2- -CHCOOCH ^J I pyridyl CH,

(60B) -CF ₃ -Cl -CH= -H -6-methoxy-2- -CHCOOCH3 pyridyl CH3

(61B) -Cl -Cl -CH= -H -3-chloro-2- -CHCOOCH,

1 - ^■ pyridyl CH3

(62B) -Cl -H -CH= -H -phenyl -CHCOOCH3

CH ₃

(63B) -CF, -Cl -CH= -H -phenyl -CHCOOH

^•■ 1

CH,

(64B) -CF3 -Cl -CH= -H -phenyl -H

No. X R ¹ R-

(65B) -CF ₃ -Cl -N= -H -phenyl -CHCOOCH- i CH,

(66B) -CF-, -Cl -CH= -H -CH,-CH=CH- -CH ₂ COOCH ₃

(67B) -CF ₃ -Cl -CH= -H -CH ₂ -CH=CH ₂ -CH ₂ COOC ₂ H ₅

(68B) -CF ₃ -Cl -CH= -H -phenyl -CH ₂ COOCH ₃

(69B) -CF ₃ -Cl -CH= -H -phenyl -CH ₂ COOC ₂ H ₅

(70B) -CF ₃ -Cl -CH= -H —CH,—CH=CH, -CHCOO ⁿ C ₄ Hg CH,

(71B) -CF ₃ -Cl -CH= -H -phenyl -CHCOOC 2H ⁿ 5

CH,

(72B) -CF ₃ -Cl

(73B) -CF ₃ -Cl -CH= -H -H -CHCOOCH-

I

^C 5 ^H 11

(74B) -CF ₃ -Cl -CH= -H -phenyl -CHCOO ⁿ C ₄ H ₉ CH,

(75B) -CF, -Cl -CH= -H -H -CH ₂ COOCH ₃

(76B) -CF ₃ -Cl -CH= -H -phenyl -CHCONH ^1SO C ₃ H ₇ CH,

No . X

(77B) -CF3 -Cl -CH= -H -H -CHCOOCH3 C ₂ H ₅

(78B) -Cl -Cl -CH= -H -H -CHCOOCH, CH ₃

(79B) -CF ₃ -Cl -CH= -CH3 -4-nitrophenyl -CHCOOCH3

CH ₃

(80B) -CF ₃ -Cl -CH= -H -4-nitrophenyl -CHCONHP(OCH ₃ ) ₂

CH ₃ 0

(81B) -CF, -Cl -CH= -H -phenyl -CHCOOH

^J I, phenyl

(82B) -CF3 -Cl -CH= -H -4-chloro-2- -CHCOOCH nitrophenyl CH

(83B) -CF ₃ -Cl -CH= -H -2-nitrophenyl -CHCOOCH3

CH,

(84B) -CF ₃ -Cl -CH= -H -2-methylthio- -CHCOOCH3 pyrimidine CH3

(85B) -CF ₃ -Cl -CH= -H -4-nitrobenzyl

(86B) -CF ₃ -Cl -N= -H -4-nitrophenyl -CHCOOCH3

I C 'H ^l 3-

(87B) -CF ₃ -Cl -N= -H -4-fluorophenyl -CHCOOCH3

CH ₃

No . X R" R-

(88B) -CF3 -Cl

(89B) -CF ₃ -Cl -CH= -H -1-nitro-2-naphthyl -CHCOOCH3

CH ₃

(90B) -CF ₃ -Cl -CH= -H -4-nitrophenyl -CHC0NH ₂

CH,

(91B) -CF ₃ -Cl -CH= -H -4-(2,2-dimethyl- -CHCOOCH3 ethyl) henyl CH3

(92B) -CF ₃ -Cl -CH= -OCH3 -CH ₂ COOCH ₂ CH=CH ₂ -CHCOOCH3

CH ₃

(93B) -CF ₃ -Cl -CH= -OCH3 -4-nitrophenyl -CHCOOCH3 CH ₃

(94B) -CF3 -Cl -CH= -OCH3 -CH ₂ COOC ₂ H ₅ -CHCOOCH3

_. CH ₃

(95B) -CF ₃ -Cl -CH= -H -4-methoxy- -CHCOOCH3 carbonylmeth l-2- CH3 nitrophenyl

(96B) -CF3 -Cl -CH= -H -4-methoxy- -CHCOOCH3 carbonylphenyl CH3

(97B) -CF3 -Cl -CH= -H -4-trifluoro- -CHCOOCH3 methylphenyl CH3

No . X R ¹ R' R-

(98B) -CF ₃ -Cl -CH= -H -4-nitrophenyl -CH ₂ COOCH ₃

(99B) -CF ₃ -Cl -CH= -H -4-nitrophenyl -CHCOOCH3

00B) -CF ₃ -Cl -CH= -H -4-nitrophenyl -CHCOOCH3

^C 5 ^H 11

o. X R-

(143B) -CF3 -Cl -CH= -H 6-chloro-2- -CHCOOCH- i quinoxalyl CH,

(144B) -CF ₃ -Cl -CH= -H 4-acetylamino- -CHCOOCH. phenyl CH,

(145B) -CF ₃ -Cl -CH= -CH3 -H -CHCOOCH. CH,

(146B) -CF ₃ -Cl -CH= -H 4-nitrophenyl -H

(154B) -CF3 -Cl -CH= -OH 4-nitrophenyl -CHCOOCH- 1 CH,

(155B) -CF3 -Cl -CH= -OH -CH ₂ COOC ₂ H ₅ -CHCOOCH- CH,

(156B) -CF3 -Cl -CH= -OH -CH ₂ COOCH ₂ CH=CH ₂ -CHCOOCH3

I

CH-

(157B) -CF ₃ -Cl -CH= -H -phenyl -CHC00 ^1SO C3H ₇ CH,

(158B) -CF ₃ -Cl -CH= -H -phenyl -CHCONH-

I

CH,

(159B) -CF ₃ -Cl -CH= -H -phenyl -CHCON(CH ₃ ) ₂

CH-

(160B) -CF3 -Cl -CH= -H -phenyl -CHCON(C ₂ H ₅ ) ₂

CH-

No . X R Q

(101B) -CF, -Cl -CH= -H -4-nitrophenyl -CHCOOCH, 0

^J I - ^J I I

CH ₃ -C-

(102B) -CF, -Cl -CH= -H -3,5-dinitro- -CHCOOCH-, 0

^J I -> II phenyl CH3 -C-

(103B) -CF, -Cl -CH= -H -2,4-dinitro- -CHCOOCH, 0

-> i - ^■ I I phenyl CH3 -C-

(104B) -CF, -Cl -CH= -H -4-fluorophenyl -CHCOOCH, 0

^J I ^• - ιι CH ₃ -C-

(105B) -CF, -Cl -CH= -H -4-methoxy- -CHCOOCH, 0 carbonyl- CH ₃ - -C- 2,3,5,6-tetra- chlorophenyl

(106B) -CF, -Cl -CH= -H 2-nitro-5-(2- -CHCOOCH, 0

^J i ^J II chloro-4- CH3 -C- trifluoromethyl- phenoxy)pheny1

(107B) -CF ₃ -Cl -CH= -H -4-pyridyl -CHCOOCH3 0

CH ₃ -C-

(108B) -CFo, -Cl -CH= -CHo, -4-nitrophenyl -CiHCOOCH-,3 _M 0

CH ₃ -C-

No . R ¹

(109B) -CF ₃ -Cl -CH= -H -4-(N,N-dimethyl -CHCOOCH3 0 amino) henyl CH3 -C-

(11OB) -CF, -Cl -CH= -H -4-(N,N,N-tri- -CHCOOCH, 0

^J I ^■*• * II methylammonium CH3 -C- iodo)phenyl

(111B) -CF, -Cl -CH= -H -4-trifluoro- -CHCOOCH, 0 ^•■ i ^J ii methylphenyl CH3 -C-

(112B) -CF, -Cl -CH= -H -4-cyanophenyl -CHCOOCH, 0 C ¹ H ₃ -"C-

(113B) -CF-, -Cl -N= -H -4-nitrophenyl -CHCOOCH, 0 ^J i - ^* - il

CH ₃ -C-

(114B) -CF, -Cl -CH= -H -4-nitrophenyl -CHCOOCH, 0 n ¹ "

^C 5 ^H 11 ^~C~

(115B) -CF ₃ -Cl -CH= -H -4-nitrophenyl -CHCOOCH, 0

I ^**** II C ₂ H ₅ -C-

(116B) -CF, -Cl -CH= -H -4-nitrophenyl -CH,COOCH, 0

*- ^J ) l

-C-

( 1 1 7B) -CF, -Cl -CH= -H -4-phenoxy

( 1 1 8B ) -CF, -Cl -CH= -H -3 , 4-dichloro- -CHCOOCH, O

. ₇ . I ^ό n anilmo CH3 -C-

No . X R ¹ R"

(119B) -CF ₃ -Cl -CH= -H -4-chloro¬ -C IHCOOCH-,J 0I I anilino CH- -C-

(120B) -CF ₃ -Cl -CH= - H -3-chloro- -CHCOOCH, 0 anilino CH- -C-

(121B) -CF ₃ -Cl -CH= -H -4-fluoro- -CHCOOCH- 0

I II anilino CH, -C-

(122B) -CF ₃ -Cl -CH= -H -4-nitroanilino -CHCOOCH- O i II CH, -C-

(123B) -CF ₃ -Cl -CH= -H -4-chloroanilino -CHCOOCH- S

I - II CH, -C-

(124B) -CF ₃ -Cl -CH= -H -2,4-dichloro- -CHCOOCH- 0 l II phenyl CH, -C-

(125B) -CF ₃ -Cl -CH= -H -2,4-dichloro- -CHCOOCH, 0 l II phenoxymethyl CH, -C-

(126B) -CF, -Cl -CH= -H 1 -[4-(3-chloro-5- -CHCOOCH- O ^•■ I II trifluoromethyl-2- CH3 -C- py idyloxy)phenoxy- ethyl

(127B) -CF3 -Cl -CH= = -H -CH- -CHCOOCH- O I II CH, -c-

(128B) -CF3 -Cl -CH= -H 1-[4-(5-tri- -CHCOOCH- O

I II fluoromethyl-2- CH, -C- pyridyloxy)phenoxy- ethvl

No. X R" R

(129B) -CF ₃ -Cl -CH= -H -OC ₂ H ₅ -CHCOOCH-, 0 i ^J II CH, -C-

(130B) -CF ₃ -Cl -CH= -H n CgH- _j -CHCOOCH- 0

I II CH, -C-

(131B) -CF, -Cl -CH= -H -CC1 ₂ CH ₃ -CHCOOCH, 0

II CH ₃ -C-

(132B) -CF ₃ -Cl -N= -H -CH3 -CHCOOCH- 0

II CH, -C-

(133B) -CF3 -Cl -CH= -H -0CH ₂ CC1 ₃ -CHCOOCH- 0

I - II CH, -C-

(134B) -CF3 -Cl -CH= -H -NH-(CH ₂ )3CH3 -CHCOOCH3 0 II

CH- -c-

(135B) -CF ₃ -Cl -CH= -H -3-aminophenyl -CHCOOCH-, 0

II CH, -C-

(136B) -CF, -Cl -CH= -H -3-(N,N-dimethyl- -CHCOOCH, 0

⁰ I - ^■ II carbamoylamino) - CH3 -C- phenyl

(137B) -CF ₃ -Cl -CH= -H -4-ethoxycarbonyl- -CHCOOCH3 ° aminophenyl CH, C-

No . X R ' R- Q

( 1 38B ) -CF, -Cl -CH= -H -phenyl -CHCOOCH, 0

° I I I CH ₃ -C-

(139B) -CF, -Cl -CH= -H -2,4,6-trimethyl- -CHCOOCH, 0

° | * ^■ * II phenyl CH, -S-

- ⁵ II

0

(140B) -CF, -Cl -CH= -H 4-tert-butyl- -CHCOOCH, 0 phenyl CH ₃ -C-

(141B) -CF ₃ -Cl -CH= -H 4-chloroacetyl- -CHCOOCH3 0 aminophenyl CH ₃ -C-

(142B) -CF, -Cl -CH= -H 4-(1 ,1 -dimethyl- -CHCOOCH, 0 propionylammo)- CH3 -C- phenyl

No. X R ¹ R^ R-

(147B) -CF, -Cl -CH= -H 1 ,1-dimethyl- -CHCOOCH- ^J I propionylamino CH,

(148B) -CF ₃ -Cl -CH= -H 4-nitrophenyl -CHCOOCH3

CH-

(149B) -CF ₃ -Cl -CH= -H 4-fluorobenzoyl- -CHCOOCH- 1 amino CH,

(150B) -CF ₃ -Cl -CH= -H ethenyl -CHCOOCH- i CH,

(151B) -CF ₃ -Cl -CH= -H ethoxycarbon l- -CHCOOCH- i - amino CH,

(152B) -CF ₃ -Cl -CH= -H trichloroacetyl- -CHCOOCH- amino CH-

(153B) -CF3 -Cl -CH= -H 3-fluorobenzyl- -CHCOOCH. amino CH,

The compound of formula (I) can be produced, for exam pie, by the processes shown by the following reaction schemes (i) and (ii). The processes are not limited only to them.

method ( i )

method (ii)

method (iii)

method (iv)

OR-

wherein X, Y, Z, R ¹ , R ² , R ³ , R ⁹ and Q are the same as in formula (I) and X ¹ means a halogen atom.

The formylation reaction in processes (i) and (ii) can be conducted by the Gattermann reaction in which, for example, hydrogen cyanide or zinc cyanide are used together with hydrogen chloride, if necessary, in the presence of aluminum trichloride or zinc chloride to produce a pre¬ scribed aldehyde derivative [see, for example, Organic Reactions, , 37 (1957); Ber. , 31, 1149 (1898); Ber., 32_, 284 (1899); Ann., 35_, 313 (1907); J. Am. Chem. Soc. , 45, 2373 (1932)], or the dichloromethyl alkyl ether method in which a dichloromethyl alkyl ether such as dichloromethyl methyl ether, dichloromethyl ethyl ether or dichloromethyl butyl ether is allowed to react with in the presence of titanium tetrachloride or aluminum trichloride followed by hydrolysis [see, for example, Chem. Ber., ^3_, 88 (1960); Ann., 662, 105 (1963); Chem. Ber., 9β_, 308 (1963)3, or the Reimer-Tiemann reaction in which a formylation reagent such as chloroform, bromofor , trichloracetic acid or chloral hydrate is allowed to react in the presence of an alkali such as an alkali hydroxide, or an alkali carbonate [see, for example, Ber., 9_, 423 (1876); J. Chem. Soc, 1929, 469; Organic Syntheses, III, 463 (1955)], or the orthoformate method in which an orthoformate such as methyl orthoformate or ethyl orthoformate is allowed to react with in the presence of aluminum trichloride, zinc chloride or titanium tetrachloride and the acetal produced is hydrolyzed to give a prescribed aldehyde [see, for example, Chem. Ber., 96_, 308 (1963)], or the Duff method in which hexamethylenetetra ine is allowed to react with in the presence of glycerol-boric acid or acetic acid-formic acid, and the Schiff base formed is hydrolyzed to produce the aldehyde [see, for example, J. Chem. Soc, 1945, 276], or the N-methylformanilide method in which a formyl group is introduced by allowing N-methyl¬ formanilide to react with in the presence of phosphorus oxychloride [see, for example, Ber., 60, 119 (1927)], or the

dimethylformamide method in which dimethylformamide is used instead of the above-cited N-methylformanilide to introduce a for yl group [see, for example, J. Am. Chem. Soc, 75_, ⁹⁸⁹ (1953)].

A benzaldehyde derivative of formula (II)

wherein

X, Y, Z, R , and R ³ have the same meanings as in formu- ι la (I), wherein, in case that Z is =CH-, R is not an alkyl group having 1 to 5 carbon atoms, and R is not an aliphatic hydrocarbon group having 1 to 1.0 carbon atoms which is substituted by -COR , and its salt are used as an intermediate of a compound of formula (I) .

The examples of benzaldehyde of formula (II) are shown in the following table.

No . X R-

-CH= -H

-CH= -H

-CH= -H

-CH= -H

-N= -H

-N= -H

-CH= -CH-

-CH= -C ₂ H ₅

-CH= -CH ₂ COOCH ₃

-CH= -CH ₂ COOC ₂ H ₅

-CH= -CHCOOCH,

CH,

( 1 2A) -CF- -Cl -CH= -CHCOOC ₂ H ₅ CH ₃

(13A) -CF- -Cl -CH= -CHCOO ⁿ C ₄ H _g

CH-

No. R-

(14A) -CF ₃ -H -CH= -CHCOOCH3

CH,

(15A) -Cl -H -CH=

(16A) -Cl -Cl -CH= -CHCOOCH3 CH ₃

(17A) -CF3 -Cl -N=

(18A) -CF ₃ -H -N=

(19A) -CF3 -Cl -CH= -CHCOOCH3

CH ₃

(20A) -CF ₃ -Cl -CH= -CHCOOCH3

C ₂ H ₅

(21A) -CF3 -Cl -CH= -CHCOOCH3 ^C 5 ^H 11

(22A) -CF, -CL -CH= -CHCONHP(OCH,)

CH ₃ 0

The oxime derivatives of formula (I) according to the present invention have the property of affecting the metabo¬ lism of plants, for example, to inhibit the growth of a certain kind of plants, regulate the growth of a certain kind of plants, dwarf a certain kind of plants, or kill a certain kind of plants.

The compounds of formula (I) according to the present invention can be applied to seeds of plants, as well as to plants in various growth stages through foliage and/or roots. In other words, the compounds provided by the present invention are applied, either as such or in the form of a composition, to the plants whose growth is to be inhibited, namely whose metabolism is to be regulated, to seeds of such plants, to a locus where such plants are growing or a locus where such plants are expected to grow in application amounts sufficient to control the metabolism of such plants.

The compounds according to the present invention can control the metabolism of plants at a rate of, for example, 0.001 to 20 kg/ha, preferably 0.005 to 10 kg/ha, particular- ly preferably 0.01 to 5kg/ha.

The compounds according to the present invention can be used in a usual formulation such as a solution, an emulsi- fiable concentrate, a suspension, a dust, a paste or gran¬ ules. Such formulations are prepared by using at least one agriculturally acceptable diluent. Examples include solid carriers such as talc, bentonite, clay, kaolin, diatomaceous earth, white carbon, vermiculite, slaked lime, ammonium sulfate and urea; liquid carriers such as water, alcohols, dioxane, acetone, xylene, cyclohexane, methylnaphthalene, dimeth lformamide, N-methylpyrrolidone, dimethyl sulfoxide, cyclohexanone, methyl ethyl ketone, methyl isobutyl ketone; surfactant, emulsifiers or dispersants such as alkyl sul¬ fate, alkylsulfonic acid salts, ligninsulfonic acid salts,

polyoxyethylene glycol ethers, polyoxyethylene alkylaryl ethers, polyoxyethylene sorbitan monoalkylates and dinaph- thylmethanedisulfonic acid salts; and a variety of adjuvants such as carboxymethyl cellulose and gum arabic For example, such a formulation can be prepared by mixing the compound according to the invention with the aforesaid carrier and/or emulsifier, etc.

The compound according to the invention may be present in a proportion of usually 0.01 to 99% by weight, preferably 0.1 to 96% by weight, in the formulation.

The compound according to the invention can be applied to plants in usual methods such as spraying, atomizing or dusting, as such or in the form of a mixture with other active compounds or in such a formulation as aforesaid. When it is desired to inhibit the growth of, or eradi¬ cate hazardous plants, the compound according to the inven¬ tion can be applied, either as such or in the form of a composition, to the plants or seeds directly or to the soil in an amount sufficient to inhibit the growth of or eradi- cate the hazardous plants in a locus where useful plants or their seeds and hazardous plants or their seeds are present together or likely to grow together.

The hazardous plants may be defined as plants which come into an environment created by man, such as a paddy or an upland farm, from the surrounding nature, and grow there and which are considered by man to be useless in that envi¬ ronment or do harm to it. Such hazardous plants are general¬ ly called weeds. Examples of the weeds are shown below. Amaranthaceae Amaranthus retroflexas Amaranthus lividus

Convolvulaceae

Ipomoea purpurea

Cuscuta japonica

Polygonaceae

Polygonum convolvulus Polygonum hydropiper

Polygonum lapathifolium Rumex obtusifolius Rumex crispus Rumex bidens

Chenopodiaceae

Chenopodium album

Chenopodium album var. centrorubrum Chenopodium ficifolium

Cruciferae

Brassica kaber Capsella bursa-pastoris Thlaspi arvense Raphanus raphanistrum

Portulacaceae

Portulaca oleracea

Oeguminosae

Cassia ob usifolia

Desmodium tortuosum

Sesbania exaltata

Daubentonia texana

Asclepiadaceae

Asclepias syriaca

Labiatae

Lamium amplexicaule

Malvaceae Abutiloή theophrasti Sida spinosa

Solanaceae

Solanum nigrum Datula stramonium

Solanum carolinense

^" Plantaginaceae

Plantago lanceolata Plantago major

Plantago rugelii

Compositae

Erigeron annuus Ambrosia artemisiaefolia var. elator

Xanthium strumarium

Cirsium arvense var. etosum

Brdens pilosa

Helianthus sp. Sonchus oleraceus

Matricaria chamomilla

Taraxacum officinale

Rubiaceae Galium aparine

Gramineae

Sorghum halepense Avena fatua

Digitaria adscendens

Setaria faberi

Agropyron repens

Panicum texanum Echinochloa crus-galli

Setaria viridis

Poa annua

Eleusine indica

Axonopus affinis Bachiaria platyphylla

Bromus tectorum

Cynodon dactylon

Panicum dichotomiflorum

Paspalum dilatatum Echinochloa colona

Panicum capillare

Setaria faberi

Alopecurus acqualis var. amurensis

Dactyloctenium Imperata cylindrica

Pennisetum alopecuroides

Alopecurus myosuroides

Bromus secalinus

Agrostis alba Apera spica-venti

Avena ludoviciana

Bromus sterilis

Brachiaria eruciformis

Cenchrus pauciflorus Digitaria ischaemum

Caryophyllaceae

Stellaria media

Euphorbiaceae

Euphorbia sp.

Scrophulariaceae Veronica didyma

Cyperaceae

Cyperus rotundus Ceperus microiria Cyperus serotinus Scirpus hotarui Eleocharis acicularis var. longiseta

Alismataceae Sagittaria pygmaea

Pontederiaceae

Monochoria vaginalis

Moreover, the compounds of formula (I) also can be used as a selective herbicide which can eradicate both broad- leaved weeds and narrow-leaved weeds substantially without chemical injury to useful crops, especially soybeans and corns, accordingly without growth inhibition of these plants, by selecting the application methods, treating methods and application rates.

For example, the compounds of the invention or composi¬ tions containing the compounds of the invention can be used as a selective herbicide which can not only eradicate the target weeds or inhibit their growth by foliar application, but also can inhibit germination and growth of the weeds by applying them before germination, substantially without inhibition of germination and growth of useful crops.

The compounds of formula (I) provided by this invention

may be used in combination with various herbicidal compounds known per se. At this time, the compounds of formula (I) according to the invention are combined with another com¬ pounds showing excellent herbicidal activity against narrow-leaved weeds so that it may manifest satisfactorily herbicidal effects against both broad-leaved weeds and narrow-leaved weeds. Thus, there can be obtained a herbici¬ dal composition which is effective against both broad-leaved weeds and narrow-leaved weeds. Thus, the present invention provides a herbicidal composition comprising, as a herbicidal ingredient, a combi¬ nation of the compound of formula (I) and an N-phosphonome- thylglycine derivative of formula (III)

R ²¹ -P-CH ₂ -NHCH ₂ -COR ²³ (III)

R ²²

wherein

2*1 ? ^Δ and R ^ώώ are identical or different and each repre¬ sents a hydroxyl or -OR ²⁴ ,

R ²³ represents a hydroxyl , -OR ²⁴ or -NR ²⁵ R ²⁶ , wherein R represents an alkyl group having 1 to 5 carbon atoms, a cyclohexyl group, a haloalkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms or an alkoxyalkyl group or a haloalkoxyal- kyl group or an alkoxyalkoxyalkyl group (wherein each of the alkoxy, haloalkoxy, and alkyl groups has 1 to 5 carbon atoms), and a phenoxy group; 2c 2β " and R are identical or different and each repre¬ sents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a hydroxyalkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or

R" and R ² , together with the nitrogen atom to which they are attached, may form a morpholino group, a piperidino group or a pyrrolidino group, and/or a glufosinate compound of formula (IV) 0 R ³¹

II I ,,

CH ₃ -P-(-CH ₂ -) ₂ -C-COR- ³ ^ (IV)

OH NH

wherein is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms,

R ³² is -OH, -NH ₂ , -NHNH ₂ , -NHCgH ₅ or an alkoxy group having 1 to 12 carbon atoms which may be substituted by -OH, or its acid addition salt or a salt thereof with a base, additionally a carrier and/or a surfactant.

In the formula (III), R ²¹ and R ²² are identical or different and each represents -OH, or -OR ²⁴ , R ²³ represents -OH, -OR ²⁴ or -NR ²⁵ R ²⁶ , wherein

^■ " R ² represents an alkyl group having 1 to 5 carbon atoms, a cyclohexyl group, a haloalkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms or an alkoxyalkyl, haloalkoxyalkyl or alkoxyalkoxyalkyl group (wherein each of the alkoxy, haloalkoxy, and alkyl groups has 1 to 5 carbon atoms), and a phenoxy group,

R ²⁵ and R ² are identical or different and each repre¬ sents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a hydroxyalkyl group having 1 to 5 carbon atoms, and an alkenyl group having 2 to 5 carbon atoms, or

2c (- and R^ , together with the nitrogen atom to which they are attached, may form a morpholino group, a piperidino or a pyrrolidino group.

Examples of the alkyl group for R ²⁴ , R ²⁵ and R ²⁶ may be the same as those given hereinabove with regard to X and Y in formula ( ) .

Examples of the haloalkyl group having 1 to 5 carbon atoms for R ² include halomethyl, haloethyl, dihaloethyl, halopropyl, halobutyi, and halopentyl groups. The halogen atoms may be, for example, fluorine, chlorine or bromine.

Examples of the alkenyl group having 2 to 5 carbon atoms for R ² , R ²⁵ and R ²⁶ include vinyl, propenyl, butenyl and pentenyl groups.

Examples of preferred alkoxyalkyl groups for R are methoxymethyl and ethoxyethyl groups. Examples of preferred haloalkoxyalkyl groups for R ² are chlorethoxyethyl and chloromethoxyethyl groups. Examples of preferred alkoxyalkoxyalkyl groups for R are methoxyethoxyethyl and ethoxyethoxyethyl groups.

Examples of preferred hydroxyalkyl groups having 1 to 5

2c 2fϊ carbon atoms for R ^J and R ^ΛO are hydroxymethyl, hydroxyethyl and hydroxypentyl groups. Compounds of formula (III) are disclosed in the Japa¬ nese Patent Published Specification No.6401/(1981 ) (U.S. Patent No. 7,123,057) and are known per se.

The compound of formula (III) also may be used in the form of its acid addition salt or its salt with a base in the composition of this invention.

Strong acids with a pKa of, for example, not more than 2.5 are preferred as acids for forming the acid adducts. As such an acid, are cited hydrochloric acid, sulfuric acid, phosphoric acid, trifluoroacetic acid, and trichloroacetic acid.

The salt with a base is formed, for example, as a salt with a cation such as an alkali metal, an alkaline earth metal, copper, zinc, ammonium or an organic ammonium or trimethylsulfonium, triethylsulfonium, tripropylsulfonium,

trimethylsulfoxonium, triethylsulfoxonium, tripropylsulfoxo- nium, when at least one of R ^Λ 2 ^* 1 , R"27 and R"? ^■ -? represent -OH.

The alkali metal represents, for example, lithium, sodium and potassium, and the alkaline earth metal repre- sents, for example, magnesium and calcium.

The organic ammonium salt is produced from an organic a ine having a low molecular weight of less than about 300.

Examples of the organic amine include alkylamines, alkylenepolyamines, and alkanolamines, such as methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, secondary butylamine, n-amylamine, isoamyla- mine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, undecylamine, dodecylamine, tridecylamine, tetradecylamine, pentadecylamine, hexadec lamine, heptadecy- lamine, octadecylamine, methylethylamine, methylisopropyla- mine, methylhex lamine, methylnonylamine, meth lpentadecyla- mine, methyloctadecylamine, ethylbutylamine, ethylheptyla¬ mine, ethyloctylamine, hexylheptylamine, hexyloct lamine, dimethylamine, diethylamine, di-n-propylamine, diisopropyla- mine, di-n-am lamine, di-isoamylamine, dihexylamine, dihep- tylamine, dioctylamine, trimethylamine, triethylamine, tri-n-propylamine, tri-isopropylamine, tri-n-butylamine, tri-isobutylamine, tri-secondary butylamine, tri-n- amylamine, ethanolamine, n-propanolamine, isopropanolamine, diethanolamine, N,N-diethylethanolamine, N-ethylethanol- amine, N-but lethanolamine, allylamine, n-butenyl-2-amine, n-pentenyl-2-amine, 2,3-dimethylbutenyl-2-amine, di-butenyl-2- amine, n-hexenyl-2-amine, and propylenedia- mine, primary arylamines, such as aniline, methoxyaniline, ethox aniline, o, m, p-toluidine, phenylenediamine, 2,4,6- tribromoaniline, benzidine, naphthylamine, and o, m, p- chloroaniline; and heterocyclic amines such as pyridine, morpholine, piperidine, pyrrolidine, indoline, and azepine. Preferred compounds of formula (II) are those in which

one or two of R ²¹ , R ²² , and R ²³ are -OH, -OH salt or -OR ²⁴ , and the remainder of R ²¹ , R ²² and R ²³ is -OH or its salt.

There can also be cited compounds of formula (III) in which one or two of R ^2"1 , R ²² and R ²³ are salts of -OH, and the remainder of R ²¹ , R ²² and R ²³ is -OH. Examples of the salts of -OH are ammonium or organic ammonium salts in which the organic ammonium group is selected from monoalk lammoni¬ um, dialkylammonium, trialk lammonium, monoalken lammonium, dialken lammonium, trialken lammonium, monoalkyn lammonium, dialkynylammonium, trialkyn lammonium, monoalkanolammonium, dialkanolammonium, trialkanolammonium, heterocyclic ammonium and arylammonium, and contains 1 to 18 carbon atoms.

The salts of the compounds of formula (III) with acids or bases can be produced by methods known per se from the compounds of formula (III) with the acids or bases.

Examples of the compounds of formula (III) and their acid addition salts or their salts with bases are shown below. (101) N-phosphonomethylglycine. (102) N-phosphonodimethylglyσine sodium salt.

(103) N-phosphonomethylglycine ammonium salt.

(104) N-phosphonomethylglycine calcium salt monohydrate.

(105) N-phosphonomethylglycine magnesium salt.

(106) N-phosphonomethylglycine potassium salt. (107) N-phosphonomethylglycine dimethylammonium salt.

(108) N-phosphonomethylglycine copper salt.

(109) N-phosphonomethylglycine zinc salt.

(110) N-phosphonomethylglycinamide.

(111) meth l N-phosphonomethylglycinate. (112) ethyl N-phosphonomethylglycinate.

(113) n-propyl N-phosphonomethylglycinate.

(114) n-butyl N-phosphonomethylglycinate.

(115) cyclohexyl N-phosphonomethylglycinate.

(116) chloroethyl N-phosphonomethylglycinate.

(117) N-phosphonomethylglycine isopropylammonium salt.

(118) N-phosphonomethylglycine methylammonium salt.

(119) N-phosphonomethylglycine diisopropylammonium salt.

(120) N-phosphonomethylglycine pyridinium salt. (121) N-phosphonomethylglycine anilinium salt.

(122) N-phosphonomethylglycine trimethylsulfonium salt.

(123) N-phosphonomethylglycine trimethylsulfoxonium .salt.

In the formula (IV), R ³ ' is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ³² is -OH, -NH ₂ , -NHNH ₂ , -NHCgH ₅ or an alkoxy group having 1 to 12 carbon atoms which may be substituted by -OH. Examples of the alkyl group for R ³¹ may be alkyl groups having 1 to 4 carbon atoms among the alkyl groups exemplified for X and Y in formula (I). The alkoxy group for R ³² may be straight-chained or branched, and includes, for example, methoxy, ethoxy, n- propoxy, iso-propoxy, n-butoxy, sec-butoxy, iso-butoxy, tert-butoxy, n-pentoxy, n-hexoxy, n-heptoxy, n-octoxy, n- nonanoxy, n-decanoxy, n-undecanox , and dodecanoxy groups. These alkoxy groups may be substituted by -OH, thus, for

,2 example, R ^J may represent a hydroxyethoxy group.

Compound of formula (IV) are disclosed in Japanese Patent Publication No. 26564/1982 (U. S. Patent No. 4,168,963) and believed to be known. The compound of formula (IV) may be used in the compo¬ sition of this invention, as an acid addition salt or a salt with a base.

Examples of acids for forming the acid addition salts may be those exemplified hereinabove with regard to the acid addition salts of the compound of formula (IV). It is be¬ lieved that the acid addition salts are formed at the primary amino group in formula (IV).

Examples of the bases for forming the salt may be those exemplified above with regard to the compounds of formula

(III).

In the formula (IV), R ³¹ is preferably a hydrogen atom and R ³² is preferably -OH, -NH ₂ , -NHNH ₂ , an alkoxy group having 1 to 4 carbon atoms, and a hydroxyalkoxy group having 2 to 4 carbon atoms.

Examples of preferred salts of the compounds of formula (IV) include salts with Na, K, Cu, Mg, Ca, Zn, Ni, Mn or Fe, ammonium salts, salts with bases such as mono-, di-, or tri-alklylamine having 1 to 4 carbon atoms in each alkyl moiety, or aniline, acid adducts with acids such as hydro¬ chloric acid, sulfuric acid, hydrobromic acid, chloric acid, or oxalic acid.

The salts of the compounds of formula (IV) with the acids or bases may be produced by known methods from the compounds of formula (III) and the acids or bases.

Examples of the compounds of formula (IV) and their acid adducts or their salts with bases which are preferably used in this invention are shown below.

(500) [ (3-amino-3-carboxy)-ρropyl-1 -methyl-phosphinic acid (501 ) [(3-amino-3-carboxy)-propyl-1 -methyl-phosphinic acid monosodium salt.. (502) [ (3-amino-3-carboxy)-propyl-1 -methyl-phosphinic acid monopotassium salt. (503) [(3-amino-3-carboxy)-propyl-1 -methyl-phosphinic acid monoammonium salt.

(504) [(3-amino-3-carboxy)-propyl-1 -methyl-phosphinic acid diammonium salt.

(505) [(3-amino-3-carboxy)-propyl-1 -methyl-phosphinic acid magnesium salt.

(506) [ (3-amino-3-carboxy)-prop l-1 -methyl-phosphinic acid monopropylammonium salt.

(507) [ (3-amino-3-carboxy)-propyl-1 -methyl-phosphinic acid mono(diisoprop lammonium) salt

(508) [ (3-amino-3-carbomethoxy)-propyl-1 ]-methyl-phosphinic acid.

(509) [ (3-amino-3-carbomethoxy)-propyl-1 ]-methyl-phosphinic acid sodium salt. (510) [ (3-amino-3-carbomethoxy)-propyl-1 ]-methyl-phosphinic acid diisopropylammonium salt.

(511 ) [ (3-amino-3-carbamido)-propyl-1 ]-methyl-phosphinic acid.

(512) [ (3-amino-3-carbamido)-propyl-1 ]-methyl-phosphinic acid sodium salt.

(513) [ (3-amino-3-carbamido)-propyl-1 ]-methyl-phosphinic acid ammonium salt.

(514) [ (3-amino-3-methyl-3-carboxy)-propyl-1 ]-methyl- phosphinic acid. (515) [ (3-amino-3-methyl-3-carboxy)-propyl-1 ]-methyl- phosphinic acid monosodium salt. (516) [ (3-amino-3-methyl-3-carboxy)-propyl-13-methyl- phosphinic acid monoammonium salt.

Bialaphos also may be used as a similar compound of formula (IV) for mixing with the compound of formula (I). Further, a triazine herbicide (simazine, atrazine, cyana- zine, simetryn, prometrin or metribuzin) can be mixed with the compound of formula (I) of the invention in addition to the compounds of formulas (III) and (IV).

The composition according to the present invention contains the compound of formula (I) and other herbicides in a (I) : the other compounds weight ratio of from 1 : 500 to 500 : 1, more preferably from 1 : 200 to 200 :1, especially preferably from 1 : 100 to 100 : 1.

The amount of the composition to be actually applied varies depending upon many factors, for example, the type of a plant whose growth is to be controlled. Suitably, it is generally 0.01 to 10 kg/ha, preferably 0.05 to 5 kg/ha. Any

one skilled in the art can easily determine the suitable proportions and amount of the composition by an ordinary standardized test without conducting many experiments.

The composition of this invention may be applied in the form of a composition comprising the active ingredient and a carrier of a solid or liquid diluent. The composition may also include an additive such as surfactant. Examples of such diluents, carriers and surfactants may be those which have been cited hereinabove. The composition of this invention can be used as a usual formulation, for example, as a solution, an emusifia- ble concentrate, a suspension, a dust or a paste in combina¬ tion with a carrier and/or a surfactant.

The composition of this invention can be prepared, for example, by mixing the compound (I) and the other herbicidal compounds and then with a carrier or other additives, and formulating the resulting mixture, or by separately prepar¬ ing a composition comprising the compound (I) and another composition comprising the other herbicidal compositions, adding a carrier or the like as required, then mixing these compositions, and formulating the mixture.

According to the present invention, there is also provided a method of eradicating weeds, which comprises applying the compound of formula (I) and the other herbici- dal compounds, simultaneously or successively, to a locus where weeds are growing in an amount effective for eradicat¬ ing the weeds.

In this method, the compound of formula (I) and the other herbicidal compounds may be applied simultaneously to the aforesaid locus, as the composition comprising these compounds, or as the composition of the compound (I) and the composition of the other herbicidal compounds separately prepared.

Alternatively, the composition of the compound (I) and

the composition of the other herbicidal compounds, separate¬ ly prepared, may be applied to the aforesaid locus succes¬ sively.

The sequence of application of the composition of the compound (I) and the composition of the other herbicidal compounds is not limited.

After one of the compositions is applied, the other may preferably be applied, while the active compound or com¬ pounds still remain on the foliage of the weeds. Usually, after one of the composition is applied, the other may preferably be applied immediately or within 2 to 3 days, al¬ though this period may vary depending upon the type of the plant to be controlled, the climatic conditions, etc.

According to the present invention, the compound of formula (I) and the other herbicidal compounds, for example, may be applied to a locus where a crop is cultivated before emergence of the crop. As a result, weeds growing in the locus before emergence of the crop can be killed.

The amount of the composition to be applied is deter- mined suitably as a measure of the amount of these compounds described in the compositions.

Advantageously, according to the method of this inven¬ tion, both broad-leaved weeds and narrow-leaved weeds can be eradicated at a low application rate. Moreover, the compounds of formula (I) according to the present invention also can be applied in combination with a variety of pesticides such as insecticides or herbicides which are known per se. Examples of such insecticides in¬ clude organophosphate insecticipdes such as parathion, fenitrothion, diazinon, or fenthion; carbamate insecticides such as carbaryl, dioxacarb, carbanolate; pyrethroid insec¬ ticides such as permethrin, allethrin, fenvalerate, cyperme- thrin, bifenthrin, flucythrinate, cyhalothrin or tefluthrin; diphenyl insecticides such as DDT, methoxychlor, dicofol,

chlorobenzilate, or bromopropylate; additionally, cyhexatin, lindane, dinochlor, chlordane and others.

In addition to triazine herbicides, glyphosate and glufosinate aforementioned, following herbicides also can be combined: cyclohexadione herbicides such as alloxydim, sethoxy- dim, cloproxydim or cycloxydim; phenoxyacetic acid herbi¬ cides such as fluazifop, dichlofop, guinofop, poppenate, trifopsime, haloxyfop, chlorazifop, fenoxaprop, fenthiaprop, 2,4-D or MCP; benzoic acid herbicides such as 2,3,6-TBA, dinoben, Chloramben, dicamba, or chlorthal; carbamate herbi¬ cides such as chlorpropham, phenmedipham, asulam, molinate, benthiocarb, or ethiolate; amide herbicides such as propa- nil, naptalam, allidochlor, metolachlor, alachlor or buta- chlor; nitrile herbicides such as bromofenoxim, ioxynil or dichlobenil; urea herbicides such as diuron, linuron, fenu- ron or benzthiazuron; diphenyl ether herbicides such as nitrofen, acifluorfen or chlomethoxynil; further diquat, praquat, trifluralin or dinoseb. The following examples illustrate the present invention in greater detail.

In these examples, all parts means parts by weight, unless otherwise noted. The herbicidal activity was evaluat- ed on a scale of 6 degrees. In other words, 0 means the state where the plants are as sound as before the applica¬ tion of the active compound, while 5 is the state where the plants are withered or killed by application of the active compound, and 1, 2, 3 and 4 mean varying degrees of the enfeebled state of the plants between 0 and 5.

Example 1A

Synthesis of 2-Hydroxy-4-(2-chloro-4-trifluoromethylphe- noxy)benzaldehyde (1A)

3-(2-Chloro-4-trifluorometh lphenoxy)phenol (52 parts) was dissolved in dichloromethane (900 parts by volume) and TiCl^ (39.6 parts by volume) was added to the solution, as they were cooled with ice. Then, dichloromethyl methyl ether (34.1 parts) was added dropwise, as the reaction temperature was kept at about 0°C. After completion of addition, stir- ring was continued for 15 minutes, then 5 % HCl (113 parts by volume) was added cautiously. The reaction mixture was extracted with ether, the organic phase was washed with water, dried over anyhydrous sodium sulfate, evaporated under reduced pressure. The residue was purified by silica- gel chromatography to give the subject compound (1 ) (42 parts). The product melted at 37 to 40°C. The IR and NMR spectraldata are given in Table 1A.

Examples 2A through 5A Syntheses- of compounds (2A) through (5A)

Instead of 3-(2-chloro-4-trifluoromethylphenox )phenol in Example 1A, phenol derivatives shown in Table 2A were used in the same molar amount to react and treated as in Example 1A. The yields of products are given in Table 2A and the IR and NMR spectral data are shown in Table 1 .

Table 2A Example Phenol derivative Compound Yield

No. No. (parts) 2A 3-(4-Trifluoromethylphenoxy)phenol 3A 3-(4-Chlorophenoxy)phenol 4A 3-(2,4-Dichlorophenoxy)phenol 5A 3-(3-Chloro-5-trifluoromethyl-2- pyridyloxy)phenol

Example 6A

Synthesis of 2-ethoxy-4-(2-chloro-4-trifluoromethyl¬ phenoxy)benzaldehyde (8A) A mixture of the compound synthesized in Example 1A (2.0 parts), ethyl iodide (1.0 part), anhydrous potassium carbonate (1.7 part) , and methyl ethyl ketone (30 parts by volume) was refluxed for about 5 hours. The reaction mixture was filtered, then the filtrate was washed with water, dried over anhydrous sodium sulfate, and concentrated under re¬ duced pressure. The crude product was purified by silica gel chromatography to give the subject compound 8A (1.8 part) . The IR and NMR spectral data are given in Table 1A.

Example 7A

Synthesis of 2-methoxycarbonylmethoxy-4-(2-chloro-4- trifluoromethylphenoxy)benzaldehyde (9A)

The compound obtained in Example 1A (1.5 part) was mixed with methyl α-bromoacetate (0.73 part), anhydrous potassium carbonate (1.3 part), and methyl ethyl ketone (25 parts by ^"' volume) , and the mixture was refluxed for about 2 hours. After filtration of the reaction mixture, the fil¬ trate was washed with water, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The crude product was purified on silica gel chromatography to give the subject compound (9A) (1.6 part). The IR and NMR spec¬ tral data are shown in Table 1 .

Example 8 Synthesis of 2-ethoxycarbonylmethoxy-4-(2-chloro-4- trifluoromethylphenoxy)benzaldehyde (10A)

Example 7A was repeated except that ethyl α-bromoace¬ tate (0.79 part) was used instead of methyl α-bromoacetate. The yield of the compound (10A) was 1.7 part. The IR and NMR

spectral data are shown in Table 1 .

Example 9A Synthesis of 2-(1 -methoxycarbonylethoxy)-4-(2-chloro-4- trifluoromethylphenoxy)benzaldehyde (11A)

The compound obtained in Example 1A (8.2 part) was mixed with methyl α-bromopropionate (5.2 part), anhydrous potassium carbonate (7.2 part), and methyl ethyl ketone (lOOparts by volume), and the mixture was refluxed for about 3 hours. After filtration of the reaction mixture, the filtrate was concentrated under reduced pressure, the crude product was purified by silica gel chromatography to give the subject compound (11A) (9.5 part). The melting point of the product was 77 to 79°C and the IR and NMR spectral data are shown in Table 1 .

Example 10A

Synthesis of 2-(1-ethoxycarbonylethoxy)-4-(2-chloro-4- trifluoromethylphenoxy)benzaldehyde (12A) Example 9A was repeated except that ethyl α-bromopropi- onate (5.6 parts) was used instead of methyl α-bromopropion¬ ate. The yield of the compound (12A) was 9.6 parts. The IR and NMR spectral data are shown in Table 1A.

Example 11A

Synthesis of 2-(1-n-butoxycarbonylethoxy)-4-(2-chloro-4- trifluoromethylphenoxy)benzaldehyde (13A)

Example 9A was repeated except that n-butyl α-bromo¬ propionate (6.5 parts) was used instead of methyl α-bromo- propionate. The yield of the compound (13A) was 9.7 parts. The IR and NMR spectral data are shown in Table 1A.

Examples 12A through 15A syntheses of compounds (12A) through (15A)

Example 9A was repeated except that aldehyde deriva¬ tives of (2A) through (5A) were used instead of 2-hydroxy-4-(2-chloro-4-trifluoromethylphenoxy)benzaldehyde (1A) in the same molar amount as in (1A). The reaction yields are shown in Table 3A. The IR and NMR spectral data are given in Table 1A.

Table 3A

The compound (11A) synthesized in Example 9A (0.5 part) was dissolved in a mixed solvent of methanol (6 parts by volume) and water (0.4 part by volume), the solution was combined with 1N KOH (2.48 parts by volume) and allowed to stand 1 overnight at room temperature. Methanol is removed under reduced pressure, the residue was acidified with hydrochloric acid and the liberating product was taken into ether. The organic layer was washed with water, dried over anhydrous sodium sulfate, and concentrated under reduced pressure to give the subject compound (19A) (0.4 part). The IR and NMR spectral data are shown in Table 1 .

Example 17A

Synthesis of compound (5A)

2,3-Dichloro-5-trifluoromethylpyridine (2.16 parts) , 2,4-dihydroxybenzaldehyde (1.41 part), and dimethylsulfoxide

(10 parts by volume) were mixed, combined with 60% strength sodium hydride (0.42 part), stirred at 120°C for 5 hours, cooled down to room temperature, then poured into ice water, and extracted with diethyl ether. The organic phase is dried over anhydrous sodium sulfate, the ether is evaporated under reduced pressure, the residue was purified by silica-gel chromatography to give the subject compound (5A) (2.5 parts). The IR and NMR spectral data are shown in Table 1A.

Examples 18A through 20A

Syntheses of compounds (20A) through (22A)

The subject compounds were obtained by using halogen compounds described in the following Table 4A instead of methyl α-bromopropionate in Example 9A. The IR and NMR spectral data of these products are given in Table 1A.

Table 1A

Table 1A (continued)

Table 1A (continued)

Table 1A (continued)

Example 1B

Synthesis of 2-ethoxy-4-(2-chloro-4-trifluoromethylphe¬ noxy)benzaldehyde oxime (1B)

A solution of hydroxylamine hydrochloride (0.7 part) in water (5 parts) was added to a solution of 2-ethoxy-4-(2- chloro-4-trifluoromethylphenoxy)benzaldehyde (8A) (3.45 parts) in tetrahydrofuran (20 parts), then potassium carbon¬ ate (0.76 part ) was added to the solution with stirring at room temperature, and stirring was additionally continued at room temperature for 1 hour. Tetrahydrofuran was removed under reduced pressure, combined with water (20 parts), and extracted with ether. The ether layer was dried over anhy¬ drous sodium sulfate, then ether was removed. The residue was purified by silica-gel chromatography to give compound (1B) (3.2 parts) . The IR and NMR spectral data of the com¬ pound are shown in Table 1B.

Example 2B Synthesis of 2-(1-methoxycarbonylethoxy)-4-(2-chloro- 4-trifluoromethylphenoxy)benzaldehyde oxime (2B)

Example 1B was repeated except that 2-(1-methoxycarbo- nylethoxy)-4-(2-chloro-4-trifluoromethylphenox )benzaldehyde (11A) (4.03 parts) was used instead of 2-ethoxy-4-(2-chloro- 4-trifluoro-methylphenoxy)benzaldehyde (8A) (3.45 parts). There was obtained compound (2B) (3.85 parts). The IR and NMR spectral data of the compound are given in Table 1B.

Example 3B Synthesis of 2-(1-ethoxycarbonylethoxy)-4-(2-chloro-4- trifluoromethylphenoxy)benzaldehyde oxime (3B)

Example 1B was repeated except that 2-(1-ethoxy-carbo- nylethoxy)-4-(2-chloro-4-trifluoromethylphenoxy)benzalde¬ hyde (12A) (4.16 parts) was used instead of 2-ethoxy-4-(2- chloro-4-trifluoromethylphenoxy)benzaldehyde (8A) (3.45

parts) to produce the subject compound (3.90 parts). The IR and NMR spectral data of the compound are given in Table 1B.

Example 4B Synthesis of 2-ethoxy-4-(2-chloro-4-trifluoromethyl¬ phenoxy)benzaldehyde O-methyloxime (4B)

Example 1B was repeated except that O-methylhydroxyl- amine hydrochloride (0.7 part) was used instead of hydroxy- lamine hydrochloride (0.7 parts) to produce the subject compound (3.80 parts). The IR and NMR spectral data of the compound are given in Table 1B.

Example 5B Synthesis of 2-(1-methoxycarbonylethoxy)-4-(2-chloro-4- trifluoromethylphenoxy)benzaldehyde O-methyloxime (5B)

Example 2B was repeated except that O-methylhydroxyl- amine hydrochloride (0.84 part) was used instead of hydroxy- lamine hydrochloride (0.7 part) to produce the subject compound (3.85 parts) (5B). The IR and NMR spectral data of the compound are given in Table 1B.

Examples 6B through 13B Syntheses of compounds (6B) through (13B)

A solution of 2-(1-methoxycarbonylethoxy)-4-(2-chloro- 4-trifluoromethylphenoxy)benzaldehyde (11A) (4.03 parts) in tetrahydrofuran (20 parts) is combined with an aqueous solution containing an equimolar amount of O-substituted hydroxylamine given in Table 1B and the mixture was stirred at room temperature for additional 1 hour. Then, tetrahy- drofuran was removed under reduced pressure, the residue was mixed with water (20 parts), extracted with ether, the ether layer was dried over anhydrous sodium sulfate, and ether was evaporated off. The residue was purified by silica-gel chromatography to give the products in weights given in

Table 2B. The IR and NMR spectral data of the compounds are given in Table 1B.

Table 2B

Example 14B

Synthesis of 2-(1-ethoxycarbonylethoxy)-4-(2-chloro-4- trifluoromethylphenoxy)benzaldehyde O-allyloxime (14B)

Example 11B was repeated except th ^' at 2-(1-ethoxycarbo- nylethoxy)-4-(2-chloro-4-trifluoromethylphenox )benzaldehyde (12A) (4.16 parts) was used instead of 2-(1-methoxy¬ carbonylethoxy)-4-(2-chloro-4-trifluoromethylphenox )ben- zaldehyde (11A) (4.03 parts) to produce the subject compound (14B) (3.90 parts). The IR and NMR spectral data of the compound are given in Table 1B.

Example 15B

Synthesis of 2-(1-methoxycarbonylethoxy)-4-(2-chloro-4- trifluoromethylphenoxy)benzaldehyde O-propargyloxime (15B)

Example 6B was repeated except that O-propargylhydroxy- lamine hydrochloride was used as an O-substituted hydroxyla- mine to produce the subject compound (3.0 parts) (15B) . The IR and NMR spectral data of the compound are given in Table 1B.

Example 16B

Synthesis of 2-(1-methoxycarbonylethoxy)-4-(2-chloro-4- trifluoromethylphenoxy)acetophenone oxime (16B) Example 1B was repeated except that 2-(1-methoxycarbo¬ nylethoxy)-4-(2-chloro-4-trifluoromethylphenox )acetophenone (21 A) (4.17 parts) was used instead of 2-ethoxy-4-(2-chloro -4-trifluoromethylphenoxy)benzaldehyde (8A) to produce the subject compound (3.0 parts) (16B). The IR and NMR spectral data of the compound are given in Table 1B.

Example 17B

Synthesis of 2-(1-methoxycarbonylethoxy)-4-(2-chloro-4- trifluoromethylphenoxy)acetophenone O-methyloxime (17B) Example 16B was repeated except that O-methylhydroxyl- amine hydrochloride (0.84 part) was used instead of hydrox - lamine hydrochloride (0.74 part) to produce ^' the subject compound (3.1 parts) (17B) . The IR and NMR spectral data of the compound are given in Table 1B. -- ^.

Example 18B

Synthesis of 2-(1-methoxycarbonylethoxy)-4-(2-chloro-4- trifluoromethylphenoxy)benzaldehyde O-benzyloxime (18B)

O-Benzylhydroxylamine (1.23 part) was added to a solu- tion of 2-(1-methoxycarbonylethox )-4-(2-chloro-4-trifluoro¬ methylphenoxy)benzaldehyde (11A) in tetrahydrofuran (20 parts) and stirred at room temperature for 2 hours, then tetrahydrofuran was evaporated under reduced pressure. The residue was purified by silica-gel chromatography to give

the subject compound (18B) (4.67 parts). The IR and NMR spectral data of the compound are given in Table 1B.

Example 19B Synthesis of 2-ethoxy-4-(2-chloro-4-trifluoromethyl¬ phenoxy)benzaldehyde O-phenyloxime (19B)

Example 18B was repeated except that 2-ethoxy-4-(2- chloro-4-trifluoromethylphenox )benzaldehyde (8 ) (3.45 parts) was used instead of 2-(1-methoxycarbonylethoxy)- 4-(2-chloro-4-trifluoromethylphenoxy)benzaldehyde (11A)

(4.03 parts), and O-phenylhydroxylamine (1.10 part), instead of O-benzylhydroxylamine (1.23 part) to give the subject compound (19B) (3.70 parts). The IR and NMR spectral data of the compound are shown in Table 1B.

Examples 20B through 37B Syntheses of compounds (20B) through (37B)

2-(1-Methoxycarbonylethoxy)-4-(2-chloro-4-trifluoro¬ methylphenoxy)benzaldehyde (11A) (4.03 parts) was dissolved in tetrahydrofuran (20 parts). Then, an equimolar amount of O-substituted hydroxylamines given in the following table 3B were added to the solution, and they were stirred at room temperature for 2 to 5 hours, respectively. Tetrahydrofuran was evaporated under reduced pressure, the residue was purified by silica-gel chromatography to give the product. The yields of individual products were given in Table 3B. The IR and NMR spectral data of the products are shown in Table 1B.

Table 3B

Examples O-substituted hydroxylamines No.

20B O-phenylhydroxylamine 21B O-4-fluorophenylhydroxylamine 22B O-2-fluorophenylhydroxylamine 23B 0-3-fluorophenylhydroxylamine 24B 0-4-chlorophenylhydroxylamine 25B 0-4-cyanophenylhydroxylamine 26B O-4-nitrophenylhydroxylamine 27B 0-3-nitrophenylhydroxylamine 28B 0-3-trifluoromethylphenylhydroxyl amine 29B 0-3-methoxy henylhydroxy1amine 30B 0-4-me hylphenylhydroxylamine 31B 0-4-phenylphenylhydroxylamine 32B 0-4-(4-trifluoromethylphenoxy)- phenylhydroxylamine 5.0 (32B) 33B 0-3,4-dichlorophenylhydroxyl amine

34B 0-2,4-dinitrophenylhydroxylamine 35B 0-2-chloro-4-trifluoromethyl phenylhydroxylamine 36B 0-3,5-dimethoxyphenylhydroxyl amine

37B 0-3,5-dimethylphenylhydroxyl amine

Examples 38B through 45B

Syntheses of compounds (38B) through (45B)

Example 20B was repeated except that 2-(1-methoxy¬ carbonylethoxy)-4-(2,4-dichlorophenoxy)benzaldehyde (16A) (3.70 parts) was used instead of 2-(1-methoxycarbony-

lethoxy)-4-(2-chloro-4-trifluoromethylphenoxy)benzaldehyde (11A) (4.03 parts) and O-substituted hydroxylamines given in the following table 3B were used to give the products in yields shown in Table 3B, respectively. The IR and NMR spectral data are given in Table 1B.

Table 4B Examples O-substituted hydroxylamines No. 38B O-phenylhydroxylamine

39B O-4-fluorophenylhydroxylamine

40B O-4-nitrophenylhydroxylamine

41B O-3-methoxyphenylhydroxylamine

42B 0-3-trifluoromethylphenyl hydroxylamine

43B 0-4-methylphenylhydroxyamine

44B 0-4-cyanophenylhydroxylamine

45B 0-2-chloro-4-trifluoromethyl phenylhydroxylamine 5.0 (45B)

Examples 46B through 49B Syntheses of compounds (46B) through (49B)

Example 20B was repeated except that 2-(1-methoxycar- bonylethoxy)-4-(2-chloro-4-trifluoromethylphenoxy)benzalde- hyde (14A) (3.68 parts) was used instead of 2-(1-methoxycar¬ bonylethoxy)-4-(2-chloro-4-trifluoromethylphenoxy)- benzaldehyde (11A) (4.03 parts) and O-substituted hydroxyla¬ mines given in the following table 5B were used to give the products in yields shown in Table 5B, respectively. The IR and NMR spectral data are given in Table 1B.

Table 5B

Examples O-substituted hydroxylamines No.

46B O-phenylhydroxylamine 47B O-4-fluorophenylhydroxylamine 48B O-4-chlorophenylhydroxylamine 49B 0-3-trifluoromethylphenyl hydroxylamine 4.5 (49B)

Examples 50B through 56B Syntheses of compounds (50B) through (56B)

Example 20B was repeated except that O-substituted hydroxylamines given in the following table 6B were used to give the products in yields shown in Table 6B, respectively. The IR and NMR spectral data are given in Table 1B.

Table 6B

Examples O-substituted hydroxylamines Yields Compounds No. (parts) No.

50B O-pyrid-2-ylhydroxylamine 51B 0-6-methoxypyrid-2-ylhydroxyl amine 52B 0-3-chloropyrid-2-ylhydroxyl amine

53B O-pyraz-2-ylhydroxylamine 54B 0-3,6-dimethylpyraz-2-ylhydroxy1 amine 55B 0-quinol-2-ylhydroxylamine 56B 0-5-chloro-pyridaz-2-ylhydroxyl amine 3.7 (56B)

Examples 57B, 58B and 61B Syntheses of compounds (57B), (58B), (61B)

Example 38B was repeated except that O-substituted hydroxylamines given in the following table 7B were used to give the products in yields shown in Table 7B, respectively. The IR and NMR data are given in Table 1B.

Table 7B Examples O-substituted hydroxylamines No.

57B 0-6-chloropyrid-2-ylhydroxylamine 58B 0-2,6-dimethylpyraz-2-ylhydroxyl amine 61B 0-3-chloropyrid-2-ylhydroxylamine

Examples 59B and 60B Syntheses of compounds (59B) and (60B)

Example 20B was repeated except that 2-(1-methoxy- carbonylethoxy)-4-(4-trifluoromethylphenoxy)benzaldehyde

(14A) (3.68 parts) was used instead of 2-(1-methoxycarbony¬ lethoxy)-4-(2-chloro-4-trifluoromethylphenoxy)-benzaldehyde (11A) (4.03 parts) and O-substituted hydroxylamines given in the following table 8B were used to give the products in yields shown in Table 8B, respectively. The IR and NMR spectral data are given in Table 1B.

Example 62B

Synthesis of 2-(1-methoxycarbonylethoxy)-4-(4-chlorophe¬ noxy)benzaldehyde O-phenyloxime (62B)

Example 20B was repeated except that 2-(1-methoxy¬ carbonylethoxy)-4-(4-chlorophenoxy)benzaldehyde (15A) (3.4 parts) was used instead of 2-(1-methoxycarbonylethoxy)- 4-(2-chloro-4-trifluoromethylphenoxy)benzaldehyde (11A) (4.03 parts) to give the subject product (3.8 parts). The IR and NMR spectral data are given in Table 1B.

Example 63B

Synthesis of 2-(1-carboxyethoxy)-4-(2-chloro-4-trifluoro¬ methylphenoxy)benzaldehyde O-phenyloxime (63B)

2-(1-Carboxyethoxy)-4-(2-chloro-4-trifluoromethyl- phenoxy)benzaldehyde (19A)(0.41 parts) was dissolved in tetrahydrof ran (30 parts), and combined with O-phenylhy- droxylamine hydrochloride (0.23 part), sodium carbonate (0.14 part), and water (2 parts by volume). The mixture was stirred at room temperature for about 3 hours. After comple- tion of the reaction, terahydrofuran was removed under reduced pressure, diluted with water, acidified with hydro¬ chloric acid, then extracted with ether. The organic layer was washed with water, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The crude product was purified by silica gel column chromatography to give the compound (63B) (0.3 part). The spectroscopic data is given in Table 1B.

Example 64B Synthesis of 2-hydroxy-4-(2-chloro-4-trifluoromethylphe¬ noxy)benzaldehyde O-phenyloxime (64B)

Example 20B was repeated except that 2-hydroxy-4-(2- chloro-4-trifluoromethylphenoxy)benzaldehyde (1A) (3.17 parts) was used instead of 2-(1-methoxycarbonylethox )-4-(2-

chloro-4-trifluoromethylphenoxy)benzaldehyde (11A) (4.03 parts) to give the subject compound (6 B) (2.90 parts). The IR and NMR spectral data are given in Table 1B.

Example 65B

Synthesis of 2-(1-methoxycarbonylethoxy)-4-(3-chloro-5- trifluoromethy1-2-pyridyloxy)benzaldehyde O-phenyloxime (65B)

Example 20B was repeated except that 2-(1-methoxycarbo- nylethoxy)-4-(3-chloro-5-trifluoromethylpyridyloxy)benzalde- hyde (17A) (4.03 parts) was used instead of 2-(1-methoxycar¬ bonylethoxy)-4-(2-chloro-4-trifluoromethylphenoxy)benzalde¬ hyde (11A) (4.03 parts) to give the subject product (3.90 parts). The IR and NMR data are given in Table IB.

Example 66B Syntheses of compounds (26B), (34B), (50B) through (61B), (84B) and (143B)

Compounds (2B) obtained in Example 2B (4.18 parts) and 4-fluoronitrobenzene (1.55 part) were dissolved in N- methylpyrrolidone (20 parts) under stirring, then combined with 60% strength sodium hydride (0.42 part) at room temper¬ ature. Then, they were stirred at room temperature for additional 5 hours, the reaction mixture was poured into ice water, and extracted with diethyl ether. The organic layer was dried over anhydrous sodium sulfate, ether was removed under reduced pressure, and the residue was purified by silica-gel chromatography to give the compound (26B) (4.2 parts) . The same procedures were repeated except that alde- hyde oximes prescribed in the following Table 9B were used instead of the compound (2B) and halogen compounds pre¬ scribed in the following Table 9B were employed instead of 4-fluoronitrobenzene to give the subject compounds. The IR and NMR spectral data are given in Table 1B.

Table 9B

Compounds Aldehyde oxime Halogen compounds No. No.

4-fluoronitrobenzene

2,4-dinitrochlorobenzene

2-chloropyridine

2-chloro-6-methoxypyridine

2,3-dichloropyridine

2-chloropyrazine

2-chloro-3,6-dimethyl pyrazine 2-chloroquinoline 3,6-dichloropyridazine 2,6-dichloropyridine 2-chloro-3,6-dimethyl- pyrazine 2,6-dichloropyridine 2-chloro-6-methoxypyridine 2,3-dichloropyridine 4-chloro-2-methylthio- pyrimidine

(143B) (2B) 2,6-dichloroquinoxaline

through (100B), and (146B)

The reactions between the aldehydes and O-substituted hydroxylamine which are prescribed in the following Table 10B were carried out as in Example 6B to give the subject compounds in Table 10B. The IR and NMR spectral data are shown in Table 1B.

Table 1 OB

O-a1lylhydroxylamine

O-allylhydroxylamine

O-phenylhydroxylamine

O-phenylhydroxylamine

O-allylhydroxylamine

O-phenylhydroxylamine

O-4-nitrophenyl hydroxylamine O-4-nitrophenyl hydroxylamine 0-4-chloro-2-nitrophenyl hydroxylamine 0-2-nitrophenylhydrxylamine 0-4-nitrobenzylhydroxylamine 0-4-nitrophenylhydroxylamine 0-4-fluorophenylhydroxylamine 0-1-nitro-2-naphthyl hydroxylamine 0-4-(1,1-dimethylethyl)phenyl hydroxylamine 0-(4-m thoxycarbonylmethyl)-

2-nitrophenylhydroxylamine 0-4-methoxycarbonylpheny1 hydroxylamine 0-4-trifluoromethylpheny1

. hydroxylamine 0-4-nitrophenylhydroxylamine 0-4-nitrophenylhydroxylamine 0-4-nitrophenylhydroxylamine

(146B) (1A) 0-4-nitrophenylhydroxylamine (150B) (11A) 0-1-cyano-2-propenyl hydroxylamine

Example 68B

Syntheses of compounds (73B), (75B), (77B), (78B), (88B) and (145B)

Example 2B was repeated except that aldehydes pre- scribed in the following Table 11B were used instead of the compound (11A) to give the compounds given in Table 11B. The IR and NMR spectral data are shown in Table 1B.

Table 11B

Compounds No. Aldehyde derivatives

(73B) (21A)

(75B) ( 9A)

(77B) (20A) (78B) (16A)

(88B) (17A)

(145B) (24A)

Example 69B Synthesis of compound (90B)

Compound (146B) (0.24 part), α-bromopropionamide (0.09 part), and anhydrous potassium carbonate (0.15 part) were added to methyl ethyl ketone (20 parts by volume) and they were refluxed for 5 hours. The reaction mixture was fil- tered, the filtrate was concentrated, and the residue was purified by silica-gel chromatography to give the subject compound (90B) (0.05 part). The IR and NMR spectral data are shown in Table 1B.

Example 7OB Syntheses of compounds (92B) through (94B)

Compound (154B) (0.2 part) was dissolved in ether (4 parts by volume) , and a solution of diazomethane in ether was added in portions to the compound solution. After com¬ pletion of the reaction, ether was removed under reduced pressure, and the residue was purified by silica-gel chroma¬ tography to give the subject compound (93B) (0.16 part). The IR and NMR spectral data of the compound are given in Table 1B.

Compounds (155B) and (156B) were used instead of com¬ pound (154B) to repeat the above reaction whereby the sub¬ ject compounds (94B) and (92B) were obtained. The IR and NMR spectral data of these compounds are shown in Table 1B.

Example 71B

Syntheses of compounds (101B) through (109B), (111B) through (117B) , (124B) through (133B) and (135B) through (142B) Compound (2B) obtained according to Example 2B (4.18 parts) and triethylamine (1.11 part) were dissolved in tetrahydrofuran (40 parts), and stirred in an ice bath. A solution of 4-nitrobenzoyl chloride (1.94 part) in tetrahy¬ drofuran (5 parts) was added dropwise, stirred at room temperature for 1 hour, then tetrahydrofuran was removed under reduced pressure. Then, the residue was combined with water (20 parts), extracted with diethyl ether. The organic layer was.dried over anhydrous sodium sulfate, ether was removed, and the residue was purified by silica-gel column chromatography to give compound (101B) (4.3 parts). The same procedures were repeated except that aldehyde oximes listed in the following Table 12B were used instead of compound (2B) and acid chlorides in Table 12B were used instead of 4-nitrobenzoyl chloride to give the objective compounds. The

and NMR spectral data are showing in Table 1B.

Table 12B

Compounds Aldehyde oxime Acid chlorides No. No.

4-nitrobenzoyl chloride 3,5-dinitrobenzoyl chloride 2,4-dinitrobenzoyl chloride

4-fluorobenzoyl chloride 4-methoxycarbonyl-2,3,5,6- tetrachlorobenzoyl chloride (106B) (2B) 2-nitro-5-(2-chloro-4-tri- fluoromethylphenoxy)- benzoyl chloride (107B) (2B) isonicotinoyl chloride (108B) (145B) 4-nitromethylbenzoyl chloride (109B) (2B) 4-N,N-dimethylaminobenzoyl , chloride

(111B) (2B) 4-trifluoromethylbenzoyl chloride 4-cyanobenzoyl chloride 4-nitrobenzoyl chloride 4-nitrobenzoyl chloride

4-nitrobenzoyl chloride 4-nitrobenzoyl chloride phenyl chloroformate 2,4-dichlorobenzoyl chloride 2,4-dichlorophenoxyacetyl chloride (126B) (2B) 1-[4-(3-chloro-5-trifluoro- methyl-2-pyridyloxy)phenoxy- propionyl chloride

acetyl chloride

1-[4_(5-trifluoromethyl-2- pyridyloxy)phenoxypropionyl chloride ethyl chloroformate n-capryl chloride 1 ,1-dichloropropionyl chloride acetyl chloride 2,2,2-trichloroethyl chloroformate

3-aminobenzoyl chloride 3-(N,N-dimethylcarbamoyl- amino)benzoyl chloride (137B) (2B) 4-ethoxycarbonylaminobenzoyl chloride benzoyl chloride 2,4,6-trimethylbenzoyl chloride 4-(1 ,1-dimethylethyl)benzoyl chloride

4-chloroacetylaminobenzoyl chloride 4-(1 ,1-dimethylpropionyl- amino)benzoyl chloride

Example 72B Synthesis of compound (11OB)

Compound (109B) was dissolved in diethyl ether (50 parts), combined with methyl iodide (4.3 parts), and stirred at room temperature for 1 week. The crystals formed were filtered and rinsed with diethyl ether (50 parts) to give compound (110B) (3.2 parts). The IR and NMR spectral data are shown in Table 1B.

Example 73B Syntheses of compounds (118B) through (123B), and (134B) The reaction was carried out at room temperature by 5 adding 3,4-dichlorophenyl isocyanate (0.19 part) and trieth- ylamine (0.01 part) to a solution of compound (2B) (0.42 part) prepared in Example 2B in ether (5 parts by volume). After completion of the reaction, ether was removed under reduced pressure, and the crude product was purified by

10 silica-gel column chromatography to give the compound

(118B). The IR and NMR spectral data are given in Table 1B. The reaction was repeated except that corresponding isocyanates were employed, instead of 3,4-dichlorophenyl isocyanate, respectively, to give compounds (119B) through

15 (123B), and (134B). The IR and NMR spectral data of these compounds were shown in Table 1B, respectively.

Example 74B Syntheses of compounds (147B), (149B) and (151B) through

12. (153B)

4-Fluorobenzoylaminoacetonitrile (0.59 part) was dis¬ solved in ethyl acetate (35 parts by volume), and bromine (0.58 part) was added dropwise to the solution, as they are cooled to 0°C (after several drops of bromine were added, a

25 solution of hydrogen bromide in acetic acid was added sever¬ al drops, then remaining bromine was added) . After comple¬ tion of addition, the reaction mixture was cooled down- to. -25°C, then a solution of the compound (2B) (1.5 part) prepared in Example 2B in ethyl acetate (7 parts by volume)

30 and triethylamine (0.73 part) were added dropwise, simulta¬ neously, thereto. After addition, stirring was continued at 0°C for 15 minutes, then the reaction mixture was filtered with suction, the filtrate was concentrated, and purified by silica gel column chromatography to give the objective

compound (149B). The IR and NMR spectral data are shown in Table 1B. Corresponding acetonitrile derivatives were used instead of 4-fluorobenzoylaminoacetonitrile to carry out similar reactions whereby compounds (147B), (151B) through (153B) were obtained. The IR and NMR spectral data of these compounds are given in Table 1B.

Example 75B Synthesis of compound (148B) Compound (2B) (4.18 parts) , 1-bromo-1-(4-nitrophenyl)- acetonitrile (2.41 parts), anhydrous potassium carbonate (1.39 part) and acetonitrile (40 parts) were mixed, stirred at 100°C for 5 hours, then, acetonitrile was removed under reduced pressure, combined with water, and extracted with ethyl ether. The organic layer was dried over anhydrous sodium sulfate, ether was removed, and the residue was purified by silica-gel column chromatography to give the compound (148B) (3.2 parts). The IR and NMR spectral data are given in Table 1B.

Example 76B Syntheses of compounds (154B) through (156B)

Methyl 2-[2-carboxy-5-(2-chloro-4-trifluoromethyl¬ phenoxy) ]phenoxypropionate (1.9 part) was combined with thionyl chloride (1.07 part) and heated at 60 to 70°C for 2 hours. After completion of the reaction, the excessive thionyl chloride was removed under reduced pressure, and the resulting solution of the crude product in benzene (5 parts by volume) was combined with a solution of 0-4- nitrophenylhydroxylamine (0.83 part) in benzene (10 parts by volume) at room temperature. After completion of the reac¬ tion, water was added to the reaction mixture to separate the organic layer, which was dried over anhydrous sodium sulfate. The solvent was removed under reduced pressure, and

the crude product was purified by silica-gel column chroma¬ tography to give the compound (154B) (2.5 parts). The IR and NMR spectral data of the compound are shown in Table 1B. O- ethoxycarbonylmethylhydroxylamine and 0-2-propenyloxycarbo- nylmethylhydroxylamine were used instead of 0-4-nitrophe¬ nylhydroxylamine, to carry out similar reactions, respec¬ tively whereby compounds (155B) and (156B) were obtained. The IR and NMR spectral data are shown in Table 1B.

Table 1B

Table 1B (continued)

Table IB (continued)

Table 1B (continued)

Table IB (continued)

Table IB (continued)

Table lB (continued)

Table 1 B (continued)

Compounds IR Spectra NMR spectra (in CDCI3) No. (cm ^"1 ) δ (ppm)

(36B) 1750 1590 1.67(3H), 3.70(3H), 1320 1130 3.77(6H), 4.73(1H) , 1080 6.00-6.67(5H), 7.03(1H), 7.50(1H) , 7.73(1H) , 7.93(1H), 8.77(1H)

(37B) 1755 1590 1.63(3H), 2.33(6H) , 1320 1130 3.72(3H), 4.72(1H), 1080 6.40-7.20(6H), 7.50(1H),

7.73(1H), 7.93(1H),

8.77(1H)

(38B) 1755 1605 1.63(3H), 3.70(3H), 1270 1090 4.70(1H), 6.33-6.63(2H), 7.00-7.53(8H), 7.93(1H), 8.78(1H)

(39B) 1750 1605 1.63(3H), 1.73(3H), 1270 1225 4.73(1H), 6.33-6.63(2H), 1235 1090 6.80-7.57(7H), 7.90(1H), 8.77(1H)

(40B) 1.67(3H), 1.73(3H), 4.77(1H), 6.37-6.67(2H), 7.03-7.47(6H), 7.93(1H), 8.10-8.27(2H) , 8.83(1H),

Table 1B ( continued )

Table 1B (continued)

Table IB (continued)

Table IB (continued)

Table 1B (continued)

Table 1B (continued)

Compounds IR Spectra NMR spectra (in CDCI3 ) No. (cm ^"1 ) δ (ppm)

(66B) 1760 1590 3.75(3H), 4.58(2H), 1490 1210 4.65(2H), 5.10-5.43(2H) , 5.73-6.30(1H) , 7.00(1H), 6.42-6.63(2H), 7.47(1H), 7.70-7.87(2H), 8.48(1H)

(67B) 1755 1590 1.23(3H), 4.20(2H), 1490 1210 4.57(2H), 5.08-5.43(2H), 4.62(2H), 5.73-6.27(1H) , 6.40-6.63(2H), 7.00(1H), 7.47(1H), 7.67-7.85(2H), 8.47(1H)

(68B) 1750 1590 3.75(3H), 4.60(2H), 1480 1210 6.45-6.67(2H), 7.73(1H), 6.97-7.57(7H), 7.93(1H), 8.80(1H)

(69B) 1750 1590 1.25(3H), 4.23(2H), 1490 1210 4.58(2H), 6.45-6.67(2H) , 7.96-7.57(7H), 7.73(1H), 7.95(1H), 8.80(1H)

(70B) 1740 1580 0.7-1.0(3H), 1.0-1.7(4H) 1490 1240 1.60(3H) 4.10(2H)

4.5-4.9(3H), 5.1-5.5(2H),

5.7-6.3(1H), 6.45(1H), 6.50(1H), 6.95(1H) , 7.45(1H), 7.70(1H), 7.76(1H), 8.50(1H)

Table 1B (continued )

Table 1B (continued)

Table 1B (continued)

Table 1B (continued)

Table IB (continued)

Table 1B continued

Table 1 B ( continued )

Table 1B (continued)

Table 1B (continued)

Table 1B (continued)

Compounds IR Spectra NMR spectra (in CDCI3) No. (cm" ¹ ) δ (ppm)

(114B) 3000 1755 0.7-1.9(9H) , 3.73(3H), 1600 1530 1.9-2.3(2H), 4.73(1H) , 1495 1430 6.50(1H), 6.60(1H) , 1410 1320 7.20(1H), 7.55(1H), 1260 7.76(1H), 8.05(1H),

8.30(4H), 9.00(1H)

(115B) 1.13(3H), 2.10(2H), 3.73(3H), 4.70(1H) , 6.50(1H), 6.60(1H) , 7.15(1H), 7.50(1H) , 7.73(1H), 8.00(1H), 8.30(4H), 8.95(1H)

(116B) 2900 1765 3.80(3H), 4.70(2H), 1600 1530 6.53(1H), 6.60(1H), 1495 1460 7.15(1H), 7.55(1H), 1330 1260 7.75(1H), 8.05(1H) , 8.30(4H), 9.00(1H)

(117B) 1.63(3H), 3.70(3H), 4.73(1H), 6.45(1H) , 6.50(1H), 6.7-7.6(7H), 7.70(2H), 8.55(1H)

Table 1B (continued)

Table 1 B (continued)

Table IB (continued)

Table 1B (continued)

Table 1 B ( continued )

Table IB (continued)

Table 1B (continued)

Compounds IR Spectra NMR spectra (in CDCI3) No. (cm ^-1 ) δ (ppm)

(150B) 3350 2200 1.60(3H), 3.70(3H), 1755 1600 4.6-5.0{3H), 5.3-5.6(1H), 1490 6.3-6.7(3H), 7.00(1H),

7.50(1H), 7.70(1H),

7.75(1H), 8.80(1H)

(151B) 3350 1750 1.27(3H), 1.63(3H), 1735 1600 3.73(3H), 4.22(2H), 1490 1320 4.75(1H), 6.27-6.77(4H) , 7.07(113), 7.53(1H),

7.73-7.91 (2H), 8.57(1H)

(152B) 3350 2250 1.63(3H), 3.73(3H), 1750 1730 4.76(1H), 6.40-6.63(3H), 1600 1490 7.43(1H), 7.57(1H), 1320 7.73-8.33(3H), 8.63(1H)

(153B) 3350 1750 1.60(3H), 3.70(3H) , 1690 1600 4.73(1H), 6.40-6.60(2H) , 6.83(1H), 7.00-7.86(8H), 8.37(1H), 8.53(1H)

(154B) 3350 1740 1.73(3H), 3.77(3H), 1670 1590 5.00(1H), 6.50-6.70(2H), 1320 7.03-7.33(4H), 7.60(1H), 7.76(1H), 8.03-8.23(3H) , 11.53(1H)

Table 1B (continued)

FORMULATION EXAMPLE 1C One part of the active compound of this invention was added to 5000 parts of a mixture of acetone and water (1 : 1 by volume), and 2.6 parts of a nonionic surfactant (Sorpol 2680, tradename) was added to form a solution.

FORMULATION EXAMPLE 2C One part of the active compound of this invention, 8.7 parts of a mixture of equal amounts of talc and bentonite, and 0.3 part of a mixture of equal amounts of Sorpol 5060

(tradename) and Sorpol 800A (tradename) were well pulverized and mixed to form a wettable powder.

TEST EXAMPLE 1C A solution of the active compound of the invention was prepared in accordance with the above Formulation Example 1C.

Seeds of plants were sown in the soil, and after germi¬ nation, cultivated for 2 to 3 weeks. The prepared solution was applied to these plants at the rate of application indicated in Table 1C. Thereafter, the plants were continued to be cultivated for 3 weeks without applying the above solution. The results are given in Table 1C.

TEST EXAMPLE 2C Seeds of plants to be tested were sown in the soil, and on the second day after sowing, were treated as follows and the growth of the plants was observed for 3 weeks. A wettable powder containing each of the active com¬ pounds of this invention which was prepared in accordance with Formulation Example 2 was suspended in 150 cc/m of water so that the total amount of the active compounds became 0.1 g/m . The suspension was uniformly applied to the

surface of the soil after the sowing. Thereafter, without further applying the test chemical, the plants were grown. The results are shown in Table 2C.

The alphabet characters in the plant column of Tables 1C and 2C symbolize the following plants: a: Digitaria adscendens b: Setaria viridis c: Sorghum halepense d: Chenopodium album var. centrorubrum e: Amaranthus mangostanus f: Astragalus sinicus g: Abutilon theophrosti h: Solanum nigrum i: Xanthium strumarium j: Soybean; Glycine max k: Corn; Zea mays

Table 1C (continued)

Table 1C (continued)

Table 1C (continued)

Table 1C (continued)

Table 1 C continued )

Table 1C (continued)

Table 1C (continued)

Table 1C (continued

TEST EXAMPLES 3C - 6C AND TEST COMPARATIVE EXAMPLES 1C - 2C

In each run, each of the oxime derivatives shown in Table 3C alone or with each of the N-phosphonomethylglycine derivatives shown in Table 3C (in the indicated mixing ratios) was dissolved in 16 parts by volume of a mixture of water and acetone (1 : 1 by volume; containing 0.05 % of a nonionic surfactant, Sorpol-2680) to prepare a spray solu¬ tion. The amounts of the herbicidal compounds were such that the rates of application were as shown in Table 3C. The plants tested were grown in vinyl resin pots

(diameter 10 cm) filled with soil in a green house for 2 to 3 weeks after germination from seeds or tubers.

The spray solution was applied to the plants so that the total volume sprayed became 4 cc/100 cm ² , and the herbi- cidal activity was examined.

The results are shown in Table 3C.

The alphabetical symbols in the Table represent the following plants, respectively:

1: Ipomoea hederacea m: Cossia obtusifolia n: Sida spinosa o: Ambrosia artemisiaefolia var. elator p: Datula stramonium q: Avena fatua r: Agropyron repens s: Amaranthus lividus t: Panicum texanum

cn cπ

Table 3C (continued)

I cn M

TEST EXAMPLES 7C - 14C AND TEST COMPARATIVE EXAMPLES 3C - 4C

In each run, each of the oxime derivative shown in Table 4C alone or with each of the N-phosphonomethylglycine derivatives shown in Table 4C (in the indicated mixing ratios) was dissolved in 16 parts by volume of a mixture of water and acetone (1 : 1 by volume; containing 0.05 % of a nonionic surfactant, Sorpol-2680) to prepare a spray solu¬ tion. The amounts of the herbicidal compounds were such that the rates of application were as shown in Table 4C. The plants tested were grown in vinyl resin pots

(diameter 10 cm) filled with soil in a green house for 2 to 3 weeks after germination from seeds or tubers.

The spray solution was applied to the plants so that the total volume sprayed became 4 cc/100 cm ² , and the herbi- cidal activity was examined.

The results are shown in Table 4C.

When the results of Test Examples 7C to 14C and Test Comparative Examples 3C to 4C are compared, it is found that the herbicidal compositions of this invention comprising the two types of herbicidal compounds indicated above exhibit herbicidal activity earlier and thus have better quick- acting efficacy than the N-phosphonomethylglycine deriva¬ tives alone.

In contrast, the compositions of this invention, for example that used in Test Example 13C, could kill all of the weeds shown in Table 4C within about 1 week. By applying a combination of the oxime derivative and the N-phosphonome¬ thylglycine derivative, the herbicidal composition of this invention surprisingly showed increased quick-acting effica- cy and a broadened herbicidal spectrum at low application rate as the synergistic effect of the combined use.

to co - ¹ o cn o cπ

(penuτ^uoo) ^s X ^c l^-I

TEST EXAMPLES 15C - 16C AND TEST COMPARATIVE EXAMPLES 5C - 6C

In each run, each of the oxime derivative shown in Table 5C and atrazine (in the indicated mixing ratios) was dissolved in 16 parts by volume of a mixture of water and acetone (1 : 1 by volume; containing 0.05 % of a nonionic surfactant, Sorpol-2680) to prepare a spray solution. The amounts of the herbicidal compounds were such that the rates of application were as shown in Table 5C. The plants tested were grown in vinyl resin pots

(diameter 10 cm) filled with soil in a green house for 2 to 3 weeks after germination from seeds or tubers.

The spray solution was applied to the plants so that the total volume sprayed became 4 cc/100 cm , and the herbi- cidal activity was examined.

The results 3 weeks after treatment are shown in Table 5C.

Table 5C

Rate of

Compound Application Plants No. (kg/ha) a b c d e f g h i

Test comparative Atrazine 0.5 1 0 0 1 0 5 5 5 1 example 5C

Test comparative Atrazine 0.25 0 0 0 0 0 1 0 5 0 example 6C

Test Atrazine 0.5 5 5 5 5 5 5 5 5 5 example 15C (26B) 0.125

Test Atrazine 0.25 5 5 5 5 5 5 5 5 5 example 16C (26B) 0.125

TEST EXAMPLES 17C - 18C AND TEST COMPARATIVE EXAMPLES 7C - 8C

In each run, the compound (26B) and compound (500) were dissolved in 16 parts by volume of a mixture of water and acetone (1 : 1 by volume; containing 0.05 % of a nonionic surfactant, Sorpol-2680) so that the mixing ratios and the application rates became prescribed values, respectively to prepare a spray solution.

The plants tested were grown in vinyl resin pots (diameter 10 cm) filled with soil in a green house for 2 to 3 weeks after germination from seeds or tubers.

The spray solution was applied to the plants so that the total volume sprayed became 4 cc/100 cm , and the herbi¬ cidal activity was examined. The results are shown in Table 6C.

When the results of Test Examples 3C to 14C and Test Comparative Examples 1C to 4C are compared, the herbicidal compositions of this invention exhibited herbicidal activity earlier and thus have better quick-acting efficacy than the N-phosphonomethylglycine derivatives alone.

The N-phosphonomethylglycine derivatives, used alone, particularly in low application rates, have lowered herbici¬ dal activity against broad-leaved weeds including Ipomoea hederacea, Sida spinosa and other weeds and 14 days after the treatment showed hardly any activity or showed only insufficient activity.

In contrast, the compositions of this invention, for example, the composition in Test Example 13C could kill all of the weeds shown in Table 4C within about 1 week. By applying a combination of the oxime derivative and N-phos¬ phonomethylglycine derivative, the herbicidal composition of this invention surprisingly showed increased quick-acting efficacy and a broadened herbicidal spectrum at low applica¬ tion rate as the synergistic effect of the combined use. When Compound (500) was used alone, the herbicidal activity of the compound was low against broad-leaved weeds such as Chenopodium album var. centrorubrum, Amaranthus viridis or Abutilon theophrasti in low application rates, as shown in Table 6C. On the contrary, the herbicidal σomposi- tion of this invention overcomes these defects and has sufficient herbicidal activity.