NZ232518A - Substituted oxime derivatives and herbicidal compositions - Google Patents

Description

New Zealand Paient Spedficaiion for Paient Number £32518 232 5 1 8 Priority IX> COt#V>!rt*«> P .. .ill '■••.■ . '' . . c-,C,">712,J jW;vU;r, ^ ^ £0,.6<SJU* (P^XSjh'n;. fS'l M&J&; ..{J.& iV.;S.k?<.. .ftowv^L... '. ur.c: 2 5 .NOV. M P.O. J-viKo: -rr" Si* J .i new zealand patents act, 1953 No.: Date: complete specification • w ^ 1 ^ // ' V <5- *3 ■r$9n ~>J?J v E OXIME DERIVATIVES AND HERBICIDES CONTAINING THE SAME AS AN ACTIVE INGREDIENT \ ■X/We, TEIJIN LIMITED, a Japanese Body Corporate, of 6-7, Minarrrihommachi 1-chome, Chuo-ku, Osaka-shi, Osaka, Japan hereby declare the invention for which ){. / we pray that a patent may be granted to r£Jfe/us, and the method by which it is to be performed, to be particularly described in and by the following statement: - (followed by page - la -) 232518 - 1 a - SPECIFICATION Title of the Invention: OXIME DERIVATIVES AND HERBICIDES CONTAINING 5 THE SAME AS AN ACTIVE INGREDIENT "S Field of the Invention: The present invention relates to oxime derivatives and herbicidal compositions containing the same as an active 10 ingredient. Particularly, the present invention relates to a herbicide which shows excellent herbicidal activity against broad leaved weeds and narrow leaved weeds, and has selective herbicidal activity without any adverse effect on the growth of crop plants by selecting the application methods, 15 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-dichlorophenoxyacetic acid, 20 are known as selective herbicidally active compounds, the ■i, 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 25 that 2,4-dichlorophenoxyacetic acid has very little or no activity against narrow-leaved plants [see, for example, 'It 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 30 trifluoromethyl-substituted pyridyloxy group into the aromatic 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- * 232518 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-5 thylglycine derivatives as active ingredients are known and commercially available. These N-phosphonornethylglycine 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 10 Cyperaceae and against broad-leaved weeds such as Chenopodi-um album var, centrorubrum or Amaranthus retroflexas. Particularly, they hardly develop herbicidal activity against weeds in Convolvulaceae such as Ipomoea purpurea even 2 weeks after application. Further, the N-phosphonomethylgly-15 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 eradicated before sowing of a crop plant, but the slow acting may 20 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 25 herbicide quick-acting at a low application rate.

Herbicides containing some kinds of glufosinate compounds as a major active ingredient are known and commercially available. This type of herbicides also is basically non-selective, but has a disadvantage that a low application 30 rate reduces herbicidal activity against broad-leaved weeds such as Chenopodium album var. centrorubrum, Amaranthus retroflexas or Abutilon theophrasti. o The Objects and Summary of the Invention: 232 5 1 8 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 5 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 selectively eradicates broad-leaved weeds and narrow-leaved weeds substantially without chemical injury to useful crop plants, 10 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 15 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, accordingly can create a state vhere crop plants can easier grow than noxious weeds do in an area where both useful crops and 20 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 25 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 30 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 232 5 1 8 the novel oxime derivative according to the present inven-tion with known N-phosphonomethylglycine derivative and/or glufosinate derivative to utilize their herbicidal properties .

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) ^ w-cr1 =n-0-q-r2 (i) wherein X and Y are identical or different and each represents a hydrogen atom, a halogen atom, -CF^, or an alkyl group having 1 to 5 carbon atoms; Z is s=CH- or =N-; R1 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; R^ represents a group selected from the following 30 groups shown in a) to g): a) hydrogen atom: b) a saturated or unsaturated aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be optionally substituted by the following substituents: 232 5 18 - substituents: i) a halogen atom; ii) a hydroxyl group; iii) an alkoxy group having 1 to 5 carbon atoms; iv) -COR4; wherein R4 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-10 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 V in which and R6 are identical or different 20 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-25 tuted by a halogen atom, a hydroxyl group, -CF-j, -NC>2, -CN, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, -COR^ or -N/ V; vi) a phenoxy group; wherein the phenoxy group may be substituted by tha groups cited in 232518 v) or by phenyl, phenoxy or pyridyloxy groups (wherein the phenyl, phenoxy or pyridyloxy groups may be substituted by halogen atom or -CF3) vii ) R / -N \ 7 R' wherein R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or -COR4; 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 substituents 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^fc'll-owinc^ substituents: substituents: i) a halogen atom; ii) a hydroxyl group; iii) -CF^; iv) -N°2: v) -CN; vi) an alkyl group havin atoms; vii) an alkoxy group havijng 1 to 5 carbon atoms; viii)-COR4; 1 to 5 carbon 232 5 1 8 ix) R5 / -n ^ 7 R i x) -n+r5r6r8 Q wherein R is an alkyl group having 1 to 5 carbon atoms; xi) a phenyl group wherein the phenyl group may be substituted by the substituents v) in b); xii) a phenoxy group wherein the phenoxy group may be substituted by the substituents vi) in b); xiii)-CH2COR4; 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) R5 / -N V wherein is b), e) or f); R^ is a hydrogen atom ; or an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted by a halogen atom* a hydroxyl group, an alkoxy group, -COR^ or 0 0 II Jl f -CNH-P-QR Ad 1 1 wherein R1® and R1"1 are identical or different and represent a hydrogen atom, an alkyl group having 1 - c i L _/ ! 8 o to 5 carbon atoms, or a phenyl group; 0 S ll li Q represents a direct bond, -C-, or-C- wherein in case that Q is a direct bond, R2 is not c), d) or g); or their salts are provided.

The oxime derivatives according to the present invention have a wide range of herbicidal spectrum, exhibiting 10 excellent herbicidal activity against both broad-leaved weeds and narrow-leaved weeds. Further, the oxime derivatives according to the present invention can eradicate broad-leaved weeds and narrow-leaved weeds substantially without chemical injury to useful crops, especially soybeans "15 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 ana have quick-20 acting herbicidal activity.

The best embodiment of the invention: The present invention will be illustrated in detail as 25 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 ••« «» ,i? 23 2 5 1 £ preferably represents chlorine or trifluoromethy1.

In the formula (I), Z is =CH- or =N-.

In the formula (I), R1 represents a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 5 carbon atoms, 5 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-butoxy, n-pentoxy, etc.

R1 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 R1 .

The alkenyloxy group having 2 to 5 carbon atoms is, for 25 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 30 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 232 5 1 8 heterocyclic group having 3 to 20 carbon atoms, which con-/"■s 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 10 group and an aromatic hydrocarbon group. The concrete examples of the halogen atom, alkoxy group and -COR4 are the same as those cited in R2.

R is preferably methyl, ethyl, propyl, butyl or other aliphatic chained hydrocarbon groups having 1 to 5 carbon 15 atoms, <TH3 ?2H5 -ch2-cor4, -ch-cor4, -ch-cor4, H3 ( Cf2H5 particularly preferably -CH-COR4 , -CH-COR4 , wherein R4 20 represents a hydroxy, methoxy, ethoxy, propoxv or butoxy group. 0 5 M i| In the formula (I), Q is a direct bond, -C-, -C-, or 25 0 0 . " 1 „ w Jl w 0 S- , and preferably a direct bond or -C-. wherein, in case that Q is a direct bond, R2 is not an alkoxy group which may be substituted by c), a phenoxy group which may be substituted by d) or R~* / -N N 9 R .

Among the compounds of formula (I), the compounds selected from the following table have particularly 232 5 1 excellent herbicidal activity Q a direct bond 0 ii -C- X ci, cf3 ci. cf3 Y ci, cf3 Cl, CF3 R1 H H R2 e) An aromatic hydrocarbon a) groups other than group having 6-20 carbon H atom atoms which may be substituted f) An aromatic heterocyclic group having 3-20 carbon atoms which contains at least one N atom and may be substituted R3 5H* , ?2Hs -CHCOR4', -CHCOR4' Ch3 ^ C2H5 , -CHCOR4', -CHCOR4' Examples of the oxime derivatives of formula (I) are shown in the following table. - 12 y rs ,—( /—v R1 x-/ ^-£=N-0~r2 0-r3 ' .J 2325 1fc ^ No. X Y Z R1 R2 R3 (1B) -CF3 -CI -CH= -H -H ~C2H5 * (2B) -CF3 -CI -CH = ~H -H -CHCOOCH3 ch3 * (3B) -CF3 -CI -CH= -H -H -CHCOOC2H5 ch3 (4B) -CF3 -Cl -CH* -H -CH3 ~C2H5 * (5B) ~CF3 -CI -CH= -H -CH3 -CHCOOCH3 ch3 * (6B) -CF3 -CX -CH = -M "c2H5 -CHCOOCH3 CH3 * (7B) -CF3 -CI -CH= -H -nC3H? -CHCOOCH3 ch3 t * (8B) -CF3 -CI -CH= -H -lsoC3H7 -CHCOOCH3 ch3 * (9B) -CF3 -Cl -CH= -H -cyclohexyl -CBCOOCH3 ch3 ■k (10B) -CF3 -CI -CH= -H -CH2COOC2H5 -chcooch3 ch3 2325 1 8 No. X Y Z R1 R2 R3 1 5 ★ ( 1 1 B) -CF3 -Cl — C11 — -II -CII2-CII = CII2 -CHCOOCH J ch3 * (12B) -cf3 -cl -ch= -h -ch2-ch=ch-ch3 -chc00ci13 ch3 * (13B) -cf3 -cl -ch= -h -ch2-ch2-ch=ch3 -chcooch3 ch3 * (14B) -cf3 -cl -ch= -h -ch2-ch=ch2 -chcooc2h5 ch- 3 * (15B) -CF3 -Cl -CH= -H -CH2-CH=CH2 -CHCOOCH3 ci13 * (16B) -CF3 -Cl -CH= -CH3 -H -CHCOOCH3 CH3 * (17B) -CF3 -Cl -CH= -CH3 -CH3 -CHCOOCH3 ch3 * (18B) -CF3 -Cl — C11 = -H -benzyl -CIICOOCIl3 ch3 (19B) -CF3 -Cl -CH= -H -phenyl ~C2H5 * (20B) -CF3 -Cl -CH= -H -phenyl -CHCOOCH3 ch3 * (21B) -CF3 -Cl -CH= -H -4-fluorophenyl -CHCOOCH3 CH, pk £325 18 No. X Y Z R1 R2 R3 r*r (22B) -CF3 -Cl -CH= -H -2-fluorophenyl -chcooch3 CH3 * (23B) -CF3 -Cl -CH= -H -3-fluorophenyl -CHCOOCH3 ^ ch3 * (24B) -CF3 -Cl -CH= -H -4-chlorophenyl -CHC00CH3 CH3 * (25B) -CF3 -Cl -CH= -H -4-cyanophenyl -CHC00CH3 ch3 (26B) -CF3 -Cl -CH= -H -4-nitrophenyl -CHC00CH3 ch3 * {27B) -CF3 -Cl -CH= ~H -3-nitrophenyl -CHCOOCH3 ch3 * (28B) -CF3 -01 -CH= -H -3-trifluoro- -CHC00CH3 methylphenyl CH3 * (29B) -CF3 -Cl -CH= -H -3-methoxyphenyl -CHC00CH3 ch3 * {30B) -CF3 -Cl -CH= -H -4-methylphenyl -CHC00CH3 ch3 * (31B) -CF3 -Cl -CH= -H -4-phenylphenyl -CHC00CH3 ch3 * (32B) -CF3 -Cl -CH = -H -4-(4-trifluoro- -CHCOOCH3 methylphenoxy)- CH3 phenyl 2325 1 1 5 - No.

R' R" (33B) -CF3 -Cl -CH= -H - 3,4-dichloro- -CHCOOCH3 phenyl CH3 * {34B) -CF3 -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 1 5 phenyl CH3 ★ {37B) -CF3 -Cl -CH= -H - 3,5-dimethyl- -CHCOOCH3 phenyl d:H3 * (3 8 B) -Cl -Cl -CH* -H -phenyl -CHCOOCH CH3 3 (39B) -Cl -Cl -CH= -H -4-fluorophenyl -CHCOQCH3 ch3 * (4QB) -Cl -Cl -CH= -H -4-nitrophenyl -CHCOOCH3 ch3 * (41 B) -Cl -Cl -CH= -H -3-methoxyphenyl -CHCOOCH3 CH3 * (42B) -Cl -Cl -CH= -H -3-trifluoro- -CHCOOCH3 rnethylphenyl CH3 /•""N 232 5 1 £ No. X Y Z R1 R2 R3 * (43B) -Cl -Cl -CH= -H -4-methylphenyl -CHCOOCH-, _ I CH3 * (44B) -Cl -Cl -CH= -H -4-cyanophenyl -chcooch3 ^ CH3 * (45B) -Cl -Cl -CH= -H -2-chloro-4- -CHCOOCH-, 1 J trifluoromethyl- CH3 phenyl * (46B) -CF3 -H -CH = -H -phenyl -CHCOOCH3 CH3 * (47B) -CF3 -H -CH= -H -4-fluorophenyl -CHCOOCH3 ch3 * (48B) -CF3 -H -CH±« -H -4-chlorophenyl -CHCOOCH3 ch3 * (49B) -CF3 -H -CH= -H -3-trif luoro- -CHCOOCH-j methylphenyl CH^ * (SOB) -CF3 -Cl -CH= -H -2-pyridyl -CHCOOCH3 ch3 * (51B) -CF3 -Cl -CH= -h -6~methoxy-2- -CHCOOCH3 pyridyl CH3 . ) * (52B) -CF3 -Cl -CH= -H -3-chloro-2- -CHCOOCH3 pyridyl CH 3 * (53B) -CF3 -Cl -CH= -H -2-pyrazyl ~CHCOOCH3 CH-, 232 5 1 /"N NO. X Y Z R r' (54B) -CF3 -Cl -CH= -H -3, 6-dimethyl-5 2-pyrazyl ■chcooch3 ch3 (55B) -CF3 -Cl -CH- -H -2-quinolyl ( 56B) -CF-j -Cl -CH= -H -6-chloro-3-pyridazyl -chcooch3 ch3 * •chcooch-, 1 J ch, (57b) -cl -cl -ch= -h (58b) -cl -cl -ch = ~h -6-chloro-2-pyridyl -3,6-dimethyl-2-pyrazyl -chcooch-, i 3 ch-, -CHCOOCH 7 1 J CH -5 (59B) -CF, -H -CH= -H -6-chloro-2-pyridyl -chco0ch3 ch 3 (60b) -cf3 -cl -ch= -h (61b) -cl -cl -chs -h (63B) •CF3 -Cl -CH= -H -6-methoxy-2' pyridyl -3-chloro-2-pyridyl (62B) -Cl -H -CH= -H -phenyl -phenyl -chcooch, 1 ~> c«3 * -chcooch3 ch3 ■k -chcooch3 ch-3 -chcooh ch- (64B) -CF3 -Cl -CHa -H -phenyl -H 232 5 No. X Y Z R 1 8 r' R- {65B) -CF3 -Cl -N= -H -phenyl w (66B) (67B) ( 68b) ( 69b) 15 (70b) -CF3 -Cl -CH: -CF3 -Cl -CH: -CF3 -Cl -CH= -CF3 -Cl -CH: -CF3 -Cl -CH: -H ■H ■H •H -ch2-ch=ch2 -ch2-ch=ch2 -phenyl -phenyl ■H -CH2-CH=CH2 (71B) -CF3 -Cl -CH= -H -phenyl (720) *CF3 -Cl -CH- -H -phenyl (73B) -CF3 -Cl -CH= -H -H (74B) -CF3 -Cl -CH= -H -phenyl (75B) -CF3 -Cl -CH= -H -H (76B) -CF3 -Cl -CH= -H -phenyl -CHCOOCH-, t J CH -3 -CH2COOCH3 -ch2cooc2h5 -CH2COOCH3 -CH2COOC2H5 •CHCOOnC4H9 CH -j -chcooc2h5 ch -j -CHCOOnC3H7 iH3 -CHCOOCH3 c5h11 -CHCOO^Hg CH -5 -ch2cooch3 -CHC0nhisoc3h7 ch, 232 5 1 8 No. X Y Z R1 R2 r3 * (77B) -CF-, -Cl -CH= -H -H -CHCOOCH, c 1 J C2H5 * (78B) -Cl -Cl -CH* -H -H -CHCOOCH, I ^ CH3 k (79B) "CF3 ~C1 -CH= -CH3 -4-nltrophenyl -CHCOOCH3 ch3 * (80B) -CFo -Cl -CH= -H -4-ni trophenyl -CHCONHP( OCH,) ( ii 3 z CH3 0 1 5 *k (81B) -CF3 -Cl — CH = -H -phenyl -CHCOOH3 phenyl ★ (82B) -CF3 -Cl -CH= -H -4-chloro-2- -CHCOOCH3 nitrophenyl CH3 * (83B) -CF3 -Cl -CH= -H -2-nitropheny1 -CHCOOCH3 ch3 •k (S4B) -CF3 -Cl -CH- -H -2-methylthio- -CHCOOCH3 pyrimidine CH3 * (85B) -CF3 -Cl -CH= -H -4-nitrobenzyl -CHCOOCH3 CH- '3 * (86B) -CF3 -Cl -n= -H -4-nitrophenyl -CHCOOCH3 ch3 (87B) -CF3 -Cl -N= -H -4-fluorophenyl -CHCOOCH3 ' '3 CH- * 23 2 5 1 8 No. X Y Z R1 R2 R3 * (88B) -CF3 -Cl -N = -H -H -CHCOOCH3 CH3 * (89B) -CF3 -Cl -CH= -H -1-nitro-2-naphthyl -chcooch3 ^ ch3 * (90B) -CF3 -Cl -CH= -H -4-nitrophenyl -CHCONH2 ch3 * (91B) -CF3 -Cl -CH= -H -4-(2,2-dimethyl- -CHCOOCH3 ethyl)phenyl CHn * (92B) -CF3 -Cl -CH= -OCH3 -CH2COOCH2CH=CH2 -CHCOOCH3 ch3 * {93B) -CF3 -Cl -CH= -OCH3 -4-nitrophenyl -CHCOOCH3 CH3 * (94B) -CF3 -Cl -CH= -OCH3 -CK2COOC2H5 -CHCOOCH3 ch3 * (95B) -CF3 -Cl -CH= -H -4-methoxy- -CHCOOCH3 carbonylmethyl-2- CH nitrophenyl 1 U 3 * (96B) -CF3 -Cl -CH= -H -4-methoxy- -CHCOOCH3 carbonylphenyl <^H3 (97B) -CF3 -Cl ~CH- -H - 4-trif luoro- -CHCOOCH3 methylphenyl CH3 0* 232 5 1 21 - No. X Y Z R (98B) -CF3 -Cl -CH= -H -4-nitrophenyl -CH2COOCH3 (99B) -CF3 -Cl -CH= -H -4-nitrophenyl -CHCOOCH3 c2H5 (100B) -CF3 -Cl -CH= -H -4-nitrophenyl -CHCOOCH, np H 11 232 5 1 8 No. X Y Z R r' r- 'I ■ ' 'H (143b) -cf3 -cl -ch = (144b) -cf3 -cl -ch: (145b) -cf3 -cl -ch: ■h 6-chloro-2-quinoxalyl -H 4-acetylamino-phenyl -CH3 -H (155b) -cf3 -cl -ch= -oh -ch2c00c2h5 ■chcooch-j r J ch3 ■chcooch, i J ch, -CHCOOCH, t ■> CH, (146B) ~CF3 -Cl -CH= -H 4-nitrophenyl -H * (154B) ~CF3 -Cl -CH= -OH 4-nitrophenyl (156b) -cf3 -cl -ch= -oh -ch2cooch2ch=ch2 -chcooch3 chcooch3 ch, -chcooch, i J ch3 * chcooch- (157B) -CF3 -Cl -CH= -H -phenyl (158B) -cf3 -cl -ch= (159B) -CF-j -Cl -CH= (1 GOB) -CF3 -Cl -CH = -H -phenyl -H -phenyl -H -phenyl CH- -chc00isoc3h7 ch3 * -chconh^ CH- -CHCON(CH3)2 CH- -chcon(c2h5)2 ch, 232 5 1 r1 x-c y-0- $ v -c=n-0-q-r2 sjs? z » 0-r3 no. x y z r1 r2 r3 * (101B) -CF, -Cl -CH= -H -4-nitrophenyl -CHCOOCH, 0 ■j i J 11 CH3 -C- * (102B) -CF, -Cl -CH= -H -3,5-dinitro- -CHCOOCH, O J i J n phenyl CH3 -C- * (103B) -CF, -Cl -CH= -H -2,4-dinitro- -CHCOOCH, O J i J 11 phenyl CH3 -C- * (104B) -CF3 -Cl -CH= -H -4-fluorophenyl -CHCOOCH3 0 CH3 -C- * (105B) -CF3 -Cl -CH= -H -4-methoxy- -CHCOOCH3 0 carbonyl- CH3 -C- 2,3,5,6-tetra-25 chlorophenyl * (106B) -CF, -Cl -CH= -H 2-nitro-5-(2- -CHCOOCH, 0 , i il chloro-4- CH3 -C- trifluoromethyl-30 phenoxy)phenyl * J) (107B) -CF3 -Cl -CHs -H -4-pyridyl -CHCOOCH3 0 ch3 -c-* (10SB) -CF3 -Cl -CH= -CH3 -4-nitrophenyl -CHC00CH3 0 ch3 -c- 232 5 18 NO. X Y Z R r' R" (109B) -CF3 -Cl -CH= ~H (11 OB) -CF, -Cl -CH= -H (11 ib) -CF3 -Cl -CH= = -H -4-(N,N-dimethyl amino)phenyl -4-(N , N ,N-tri-methylammonium iodo)phenyl -4-trifluoro-methylphenyl (112B) -CF3 -Cl -CH= -H -4-cyanophenyl -chcooch-ch -j -chcooch3 ch3 -CHCOOCH-j ch3 -chcooch3 ch, 0 :i -c- o ll -c- 0 II -c- 0 ii -c- '■ -\ (113B) -CF3 -Cl -N= (114B) -CF3 -Cl ~CH= -H (115B) -CF3 -Cl -CH= -H ;116B) -CF3 -Cl -CH= -H (117B) -cf3 -cl -ch« - H -4-nitrophenyl -4-nitrophenyl -4-nitrophenyl -4-nitrophenyl -4-phenoxy -chcooch3 ch, -chcooch3 n cch 11 -CHCOOCH3 c2h5 0 11 -c- 0 11 -c- 0 II -c- -CH2COOCH3 0 -c- -CHCOOCH-CH, 0 ii -c- (118b) -cf3 -cl -ch= -h -3,4-dichloro-anilino -CHCOOCH-CH n 0 II -c- 232 5 18 No. x y z r R' R- (119B} -CF3 -Cl -CH= -H -4-chloro-5 anilino -CHCOOCH3 CH, -a. (120B) -cf3 -Cl -CH= -H -3-chloro- anilino (121B) -CF3 -Cl -CH= -H -4-fluoro- anilino (122B) -CF3 -Cl -CH= -H -4-nitroanili no (123B) -CF3 -Cl -CHs -H -4-chloroanilino -chcooch- ch3 * -chcooch- ch3 ★ -chcooch -ch, -chcooch-ch, -C- 0 11 -c- 0 II -c- s <1 -C- (124B) -CF3 -Cl -CH= -H -2,4-dichloro-20 phenyl -chcooch-ch, 0 11 -C- (125B) -CF3 -Cl -CH* -H -2,4-dichloro- phenoxymethyl -chcooch3 ch- 0 n -c- (1 26B) -CF3 -Cl -CH: ■H 1 4-(3-chloro-5-trifluoromethyl-2-pyridyloxy)phenoxy-ethyl -chcooch, I *3 ch, 0 11 -C- (1 27B) -CF3 -Cl -CH= -H -CH- -chcooch3 ch, 0 II -c- (128B) -CF3 -Cl -CH= -H 1 - [ 4- (5-tri- fluoromethyl-2-pyridyloxy)phenoxy-ethyl -CHCOOCH3 CH, 0 11 -c* A 26 - 1 5 232 5 1 no. x y z r1 r2 r3 q .-"-N _____ * (129b) -cf3 -cl -ch= -h -oc2h5 -chcooch3 0 ch3 -c- * (130b) -cf3 -cl -ch= -h -ncghig -chc00ch3 0 "~\ ch3 -c- * (131b) -cf3 -cl -ch= -h -cc12ch3 -chcooch3 0 ch3 -c-* (132b) -cf3 -cl -n= -h -ch3 -chcooch3 0 ch3 -c- * (133b) -cf3 -Cl -ch= -h -0ch2cc13 -chcoochj 0 ch3 -c-* (134B) -CF3 -Cl -CH= -H -NH- (CH2)3CH3 -CHCOOCH3 0 CH3 -C- ■k {135B) -CF, -Cl -CH= -H -3-aminophenyl -CHCOOCH, 0 j i j ii CH3 -C-* (136B) -CF, -Cl -CH = -H -3-(N,N-dimethyl- -CHCOOCH, 0 i -3 n carbainoylamino)- ch3 -c-phenyl * (137B) -CF, -Cl -CH= -H -4-ethoxycarbonyl- -CHCOOCH, 0 J i J 11 aminophenyl ch3 c- 232 5 18 No. r' R- Q ; 138B) -CF3 -Cl -CH= -H -phenyl •chcooch3 ch n 0 1 I -c- 139B) -CF3 -Cl -CH = -H -2,4,6-trimethyl- phenyl •chcooch3 CH-, 0 1 I -S- 11 0 {140B) -CF3 -Cl -CH= -H 4-tert butyl-phenyl -chcooch3 CH, 0 11 -c- (141b) -cf3 -cl -ch: -H 4-chloroacetyl- -CHCOOCH- i aminophenyl CH^ O n -C- (142b) -cf3 -cl -ch= •H 4-(1,1-dimethyl-propionylamino) • phenyl -chcooch3 ch3 o 11 -c- 232 5 18 28 R i CN i x-/ v -0- $ v -0-N-0-CH-W 0-R- NO. X Y Z R W (147B) -CF3 -Cl -CH= -H 1,1-dimethyl- propionylamino R- - CHCOOCH3 CH -i (148B) -CF3 -Cl -CH= -H 4-nitrophenyl -chcooch3 CH-, (149B) -CF3 -Cl -CH= -H 4-fluorobenzoyl- -CHCOOCH- amino CH-> (150B) -CF3 -Cl ~CH= -H ethenyl -CHCOOCH: CH -3 (151b) -cf3 -Cl -CH= -H ethoxycarbonyl- -CHC00CH- amino CH3 * (152B) -CF3 -Cl -CH* -H trichloroacetyl- -CHCOOCH- amino CH-> (153B) -CF3 -Cl -CH= -H 3-fluorobenzyl-30 amino -chcooch3 CH, 232 5 1 8 The compound of formula (I) can be produced, for example, by the processes shown by the following reaction schemes (i) and (ii). The processes are not limited only to them. method (i) Y Y 2325 18 method (ii) x 0- Z (xii) \\ 9 ? m-c-cl + h2n-o-q-r^ 0R- ?H -c=n-0-q-r2 ch2n2 9ch3 ( )>-c=n-0-q-r2 (xiv) or3 method (iii) y ~ ^ r9nco (vii) or3 (xv) or3 2325 1 8 31 method (iv) 0- z" (vii) R1 -C=N-0H r9n cs OR" wherein X, Y, Z, R1, R2, R3, R9 and Q are the same as in formula (I) and X' means a halogen atom or -0R4^; wherein R4^ is an alkylsulfonyl or an arylsulfonyl.

Additionally, optically active compounds of formula (I) (R enantiomer) can be obtained by appropriate selection of R3. For example, the compound R-enantiomer of (26B) is synthesized according to following reaction process (V) or (VI): * cl x'~chc00ch3 cl (v) cf3-<^-o-<^-cho ——cf3-(5-o~q-cho oh 0(j:hcooch3 ch3 h2n-0-q-,q2 cf3_^c_0„f^.ch=n_0„/^_n02 \ * ochcooch-CHo 232518 VI) CF-} - C \>-0-</ \)-CHO H°NH2 HC1^ CF,-/^-Q-(^>-CH.N-Q' OCHCOOCH, XOCHCOOCi ™3 m F-f \-N02 * OCHCOOCH-CH- '3 where, X' represents halogen atom or -OR4®, herein R4(^ is alkylsylfonyl or arylsulf onyl.

In the reaction processes (V) and (VI), X-CH-COOCH-> i should be employed in the form of its CH^ S-enantiomer in the preparation of the R.-enantiomer, because Walden inversion occurs in the asymmeric carbon during the reaction of the Compound with a prescribed hydroxy compound. In the same way, a prescribed S- enantiomer is used, instead of X'-CH-COOCH,, to effect the i J ch3 reaction with a prescribed hydroxy compound whereby a desired R-enantiomer is obtained. In addition, a variety of O-substituted hydroxylamines and a variety of halogen compounds relating to F-^^-NO^ (p-fluoronitrobenzene) can be suitably selected to obtain, the subject compounds of other types. 232518 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 5 aluminum trichloride or zinc chloride to produce a prescribed aldehyde derivative (see, for example, Organic Reactions, 9, 37 ( 1 957); Ber., 3_1_, 1 1 49 ( 1 898 ); Ber. , 32, 284 (1 899); Ann., .35, 31 3 ( 1 907); J. Am. Chem. Soc. , 45, 2373 (1932)], or the dichloromethyl alkyl ether method in 10 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., 9_3, 88 (1960); 15 Ann., 662, 105 (1963); Chem. Ber., 96, 308 (1963)], or the Reimer-Tiemann reaction in which a formylation reagent such as chloroform, bromoform, 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, 20 for example., Ber.,, Ji, 423 (1 876); J. Chem. Soc., 1 929 , 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 25 tetrachloride and the acetal produced is hydrolyzed to give a prescribed aldehyde (see, for example, Chem. Ber., 9_6, 308 (1963)], or the Duff method in which hexamethylenetetramine is allowed to react with in the presence of glycerol-boric acid or acetic acid-formic acid, and the Schiff base formed 30 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., 6_0, 1 1 9 (1 927)], or the 2325 18 dimethylformamide method in which dimethylformamide is used instead of the above-cited N-methylformanilide to introduce a formyl group [see, for example, J. Am. Chem. Soc., 7J5, 989 (1 953)) .

A benzaldehyde derivative of formula (II) Y ,1 W J W // wherein 1 O X, Y, Z, R , and RJ have the same meanings as in formula (I), wherein, in case that Z is =CH-, R1 is not an alkyl group having 1 to 5 carbon atoms, and R3 is not an aliphatic hydrocarbon group having 1 to 10 carbon 15 atoms which is substituted by -COR4, 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. 232 5 1 8 No. (1 A) (2A) (3A) 15 ( 4A) (5A) (6A) (7A) (8a) 25 (9a) (1 OA) (1 1a) (1 2A) (1 3 A) x-tf°-Q-cHo O-R3 X -CF: -CF: -Cl -Cl -cf- -cf; -cf. -cf- -CF3 -cf, -cf, -CF 3 -CF i -Cl -H -h -Cl -Cl -h -Cl -Cl -Cl -Cl -Cl -Cl -Cl -ch = -ch= -ch = -ch = -N= -N= -ch = -ch = -ch = ~ch = -ch= -ch = -ch= r- -h -h -h -h -h -H -ch- "C2H5 -ch2cooch3 -ch2cooc2h5 •chcooch3 ch3 -chcooc2h5 ch, -chcoonc^hg ch-, o v "j r, f. v a r> NO. (1 4a) ■cf3 -h -CH = r" -CHCOOCH-CH, (1 5 A) -Cl -H -CH = -CHCOOCH3 CH, (1 6 A) -Cl -Cl -CH= -CHCOOCH-CH-j (17A) -cf3 -Cl -N= -CHCOOCH, 1 -> CH-, ( 18A) -cf3 -H •N = -chcooch3 CH, C19A) (20A) •CF3 -Cl -CH= -cf3 -cl -CH* -chcooh ck-j -CHCOOCH3 c2h5 (21A) -CF3 -Cl -CH= - CHCOOCH-C5H1 1 (22a) -CF3 -Cl -CH= -CHCONHP ( OCH -j ) ? \ If * CH, O 232 5 1 8 The oxime derivatives of formula (I) according to the present invention have the property of affecting the metabolism of plants, for example, to inhibit the growth of a certain kind of plants, regulate the growth of a certain 5 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 10 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 15 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 be used in the racemic modification,, as well as in the form of R-enantiomers.

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, particularly preferably 0.01 to 5kg/ha.

The compounds according to the present invention can be 25 used in a usual formulation such as a solution, an emulsi-fiable concentrate, a suspension, a dust, a paste or granules .

Such formulations are prepared by using at least one agriculturally acceptable diluent. Examples include solid 30 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, dimethylformamide, N-methylpyrrolidone, dimethyl sulfoxide, 2 3 2 5 H cyclohexanone, methyl ethyl ketone, methyl isobutyl ketone; surfactant, emulsifiers or dispersants such as alkyl sulfate, alkylsulfonic acid salts, ligninsulfonic acid salts, polyoxyethylene glycol ethers, polyoxyethylene alkylaryl 5 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 10 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 15 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 eradicate hazardous plants, the compound according to the inven-20 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 eradicate the hazardous plants in a locus where useful plants or their seeds and hazardous plants or their seeds are present 25 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-30 ronment or do harm to it. Such hazardous plants are generally called weeds. Examples of the weeds are shown below. Amaranthaceae Amaranthus retroflexas Amaranthus lividus 39 - Convolvulaceae Ipomoea purpurea Cuscuta japonica Polygonaceae Polygonum convolvulus Polygonum hydropiper Polygonum lapathifolium Rumex obtusifolius 10 Rumex crispus Rumex bidens Chenopodiaceae Chenopodium album 15 Chenopodium album var. centrorubrum Chenopodium ficifolium Cruciferae Brassica kaber 20 Capsella bursa-pastoris Thlaspi arvense Raphanus raphanistrum Portulacaceae 25 POrtulaca oleracea Qeguminosae: Cassia obtusifolia Desmodium tortuosum 30 Sesbania exaltata Daubentonia texana Asclepiadaceae Asclepias syriaca 232 5 - 40 Labiatae .""■n Lamium amplexicaule Malvaceae 5 Abutilon theophrasti Sida spinosa ^J Solanaceae Solanum nigrum 10 Datula stramonium Solanum carolinense Plantaqinaceae Plantago lanceolata 15 Plantago major Plantago rugelii Compositae Erigeron annuus 20 Ambrosia artemisiaefolia var. elator Xanthium strumarium Cirsium arvense var. etosum Brdens pilosa Helianthus sp.

Sonchus oleraceus Matricaria chamomilla Taraxacum officinale Rubiaceae 30 Galium aparine Gramineae Sorghum halepense Avena fatua 23 2 5 1 1 41 Digitaria adscendens Setaria faberi Agropyron repens Panicum texanum 5 Echinochloa crus-galli Setaria viridis Poa annua Eleusine indica Axonopus affinis 10 Bachiaria platyphylla Bromus tectorum Cynodon dactylon Panicum dichotomiflorum Paspalum dilatatum 15 Echinochloa colona Panicum capillare Setaria faberi Alopecurus acqualis var. amurensis Dactylocteniura 20 Iraperata cylindrica Pennisetum alopecuroides Alopecurus myosuroides Bromus secalinus Agrostis alba 25 Apera spica-venti Avena ludoviciana Bromus sterilis Brachiaria eruciformis Cenchrus pauciflorus 30 Digitaria ischaemum Caryophyllaceae Stellaria media 23 2 5 1b Euphorbiaceae Euphorbia sp.

Scrophulariaceae 5 Veronica didytna Cyperaceae Cyperus rotundus Ceperus microiria 10 Cyperus serotinus Scirpus hotarui Eleocharis acicularis var. longiseta Alismataceae 15 Sagittaria pygmaea Ppntederiaceae 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 2325 18 43 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 compounds showing excellent herbicidal activity against 5 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 herbicidal 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 combination of the compound of formula (I) and an N-phosphonome-thylglycine derivative of formula (III) 1 5 0 it (III) wherein R2^ and R22 are identical or different and each represents a hydroxyl or -OR24, R23 represents a hydroxyl , -OR2^ or -NR2^R2(\ vherein R24 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; R2^ and R2^ are identical or different and each represents 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 232 5 1 8 R2-* and R2^, together with the nitrogen atom to which v, they are attached, may form a morpholino group, a piperidino group or a pyrrolidino group, and/or a glufosinate compound of formula (IV) 5 0 R31 CH-,-P-(-CH ■)-) 7-C-COR32 (IV) j l c z , ^ OH NH2 wherein R31 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R32 is -OH, -NH2/ -NHNH2, -NHCgH^ 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 foritmla (III), R21 and R22 are identical or different and each represents -OH, or -OR24, R23 represents -OH, -OR24 or -NR25R26, wherein R24 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 25 alkoxyalkoxyalkyl group (wherein each of the alkoxy, ..,s haloalkoxy, and alkyl groups has 1 to 5 carbon atoms), and a phenoxy group, R2~* and R2® are identical or different and each represents a hydrogen atom, an alkyl group having 1 to 5 30 carbon atoms, a hydroxyalkyl group having 1 to 5 carbon atoms, and an alkenyl group having 2 to 5 carbon atoms, or R2^ and R2^, together with the nitrogen atom to which they are attached, may form a morpholino group, a piperidino or a pyrrolidino group. 232 5 1 8 Examples of the alky] group for R ^ 4, R^~* and R^ may be the same as those given hereinabove with regard to X and V in formula (15.

Examples of the haloalkyl group having 1 to 5 carbon 5 atoms for R^4 include halomethyl, haloethyl, dihaloethyl, halopropyl, halobutyl, and ha 1openty1 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^4, and R^ include vinyl, propenyl, butenyl and penteny1 groups.

Examples of preferred alkoxyalkyl groups for R^ are methoxymethy1 and ethoxyethy1 groups. Examples of preferred haloalkoxyalkyl groups for are chlorethoxyethyl and chloromethoxyethyl groups.

Examples of preferred alkoxyalkoxyalkyl groups for R^4 are methoxyethoxyet hy i and et hoxyethoxyethy1 groups.

Examples of preferred hydroxyalkyl groups having 1 to 5 carbon atoms for R*J and R are hydroxymethy1, hydroxyethy1 and hydroxypenty1 qroups.

Compounds of formula (III) are disclosed in the Japa nese Patent Published Specification No.6401/{1981)(U.S.

Patent No. 7, 1 23,057 ) 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 25 the composition of this invent ion.

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 30 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, 232 5 1 1 trimethylsulfoxonium, triethylsulfoxonium, tripropyIsulfoxo-nium, when at least one of R , R and R represent -OH.

The alkali metal represents, for example, lithium, sodium and potassium, and the alkaline earth metal repre-5 sents, for example, magnesium and calcium.

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

Examples of the organic amine include alkylamines, alkylenepolyamines, and alkanolamines, such as methylamine, 10 ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, secondary butylamine, n-amylamine, isoamyla-mine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, undecylamine, dodecylamine, tridecylamine, tetradecylamine, pentadecylamine, hexadecylamine, heptadecy-15 lamine, octadecylamine, methylethylamine, methylisopropyla-mine, methylhexylamine, methylnonylamine, methylpentadecyla-mine, methyloctadecylamine, ethylbutylamine, ethylheptyla-mine, ethyloctylamine, hexylheptylamine, hexyloctylamine, dimethylamine, diethylamine, di-n-propylamine, diisopropyla-20 mine, di-n-amylamine, 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, 25 diethanolamine, N,N-diethylethanolamine, N-ethylethanol-amine, N-butylethanolamine, allylamine, n-butenyl-2-amine, n-pentenyl-2-amine, 2,3-dimethylbutenyl-2-amine, di-butenyl-2- amine, n-hexenyl-2-aniine, and propylenedia-mine, primary arylamines, such as aniline, methoxyaniline, 30 ethoxyaniline, 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 232 5 1 8 - 47 w* one or two of R21 , R22, and R23 are -OH, -OH salt or -OR24, and the remainder of R21 , R22 and R23 is -OH or its salt. There can also be cited compounds of formula (III) in which one or two of R ,21 21 R22 and R23 are salts of -OH, and 1 5 the remainder of R^1, R22 and R23 is -OH. Examples of the salts of -OH are ammonium or organic ammonium salts in which the organic ammonium group is selected from monoalkylammoni-um, dialkylammonium, trialkylammonium, monoalkenylammonium, dialkenylammonium, trialkenylammonium, rnonoalkynylammonium, dialkynylammoniurn, trialkynylammonium, 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 the:ir acid addition salts or their salts with bases are shown below. 101 1 02 i 03 104 105 106 107 108 109 II 0 11 1 I 1 2 ii 3 11 4 115 116 N-phosphonomethylglycine. N-phosphonodimethylglycine sodium salt. N-phosphonomethylglycine ammonium salt. N-phosphonomethylglycine calcium salt monohydrate, N-phosphonomethylglycine magnesium salt. N-phosphonomethylglycine potassium salt. N-phosphonomethylglycine dimethylartimonium salt. N-phosphonomethylglycine copper salt. N-phosphonomethylglycine zinc salt. N-phosphonomethylglycinamide. methyl N-phosphonomethylglycinate. ethyl N-phosphonomethylglycinate. n-propyl N-phosphonomethylglycinate. n-butyl N-phosphonCmethylglycinate. cyclohexyl N-phosphonomethylglycinate. chloroethyl N-phosphonomethylglycinate. 232 5 1 1 (117) N-phosphonomethylglycine isopropylammonium salt. (118) N-phosphonomethylglycine methylammonium salt. (119) N-phosphonomethylglycine diisopropylammonium salt. (120) N-phosphonomethylglycine pyridinium salt. 5 (121) N-phosphonomethylglycine anilinium salt. (122) N-phosphonomethylglycine trimethylsulfonium salt. (123) N-phosphonomethylglycine trimethylsulfoxonium salt.

In the formula (IV), R31 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R3^ is -OH, -NH2, -NHNHj, -NHCgH^ or an alkoxy group having 1 to 12 carbon atoms which may be substituted by -OH. *3 1 Examples of the alkyl group for R 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 R32 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-undecanoxy, and dodecanoxy groups. 20 These alkoxy groups may be substituted by -OH, thus, for Example, r3^ 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 30 addition salts of the compound of formula (IV). It is believed 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 232 5 1 3 - 4 9 - (III) .

In the formula (IV), R31 is preferably a hydrogen atom and R3^ is preferably -OH, -N^, -NHNh^, an alkoxy group having 1 to 4 carbon atoms, and a hydroxyalkoxy group having 5 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-alklvlamine having 1 to 4 carbon atoms in each alkyl moiety, or aniline, acid adducts with acids such as hydrochloric 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 15 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)-propyl~1 ]-methyl-phosphinic acid (501) ((3~amino-3-carboxy)-propyl-1 J-methyl-phosphinic acid monosodium salt. (502) t(3-amino-3-carbqxy)-propyl-1 ]-methyl-phosphinic acid monopotassium salt. (503) [(3-amino-3-carboxy)-propyl-1 j-methyl-phosphinic acid monoammonium salt. (504) [(3-amino-3-carboxy)-propyl-1 J-methyl-phosphinic acid diammonium salt. (505) [(3-amino-3-carboxy)-propyl-1 ]-methyl-phosphinic acid magnesium salt. (506) [(3-amino-3-carboxy)-propyl-1 ]-methyl-phosphinic acid monQpropylammonium salt. (50?) [ (3-amino-3-,-carboxy) -propyl-1 ]-methyl-phosphinic acid mono(diisopropylammonium) salt. 23 2 5 11 (508) ((3-amino-3-carbomethoxy)-propyl-1]-methyl-phosphinic acid. (509) I(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 10 acid sodium salt. (513) f(3-amino-3-carbamido)-propyl-1J-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-1]-methyl-phosphinic acid monoammonium salt.

Bialaphos also may be used as a similar compound of formula (IV) for mixing with the compound of formula (X).

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 fL_ •' 232 5 18 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 5 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 combination with a carrier and/or a surfactant.

The composition of this invention can be prepared, for 15 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 preparing a composition comprising the compound (I) and another composition comprising the other herbicidal compositions, 20 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 (1) and the other herbici-25 dal compounds, simultaneously or successively, to a locus where weeds are growing in an amount effective for eradicate ing the weeds.

In this method, the compound of formula (I) and the other herbicidal compounds may be applied simultaneously to 30 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 2325 18 the composition of the other herbicidal compounds, separately prepared, may be applied to the aforesaid locus successively .

The sequence of application of the composition of the 5 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 compounds still remain on the foliage of the weeds. Usually, 10 after one of the composition is applied, the other may preferably be applied immediately or within 2 to 3 days, although 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 15 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-20 mined suitably as a measure of the amount of these compounds described in the compositions.

Advantageously, according to the method of this invention, both broad-leaved weeds and narrow-leaved weeds can be eradicated at a low application rate. 2 5 Moreover, the compounds of formula (1) 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 include organophosphate insecticipdes such as parathion, 30 fenitrothion, diazinon, or fenthion; carbamate insecticides such as carbaryl, dioxacarb, carbanolate; pyrethroid insecticides such as permethrin, allethrin, fenvalerate, cyperme-thrin, bifenthrin, flucythrinate, cyhalothrin or tefluthrin; diphenyl insecticides such as DDT, methoxychlor, dicofol, 23 2 5 1 chlorobenzilate, or bromopropylate; additionally, cyhexatin, lindane, dinochlor, chlordane and others.

In addition to triazine herbicides, glyphosate and glufosinate aforementioned, following herbicides also can be 5 combined: cyclohexadione herbicides such as alloxydim, sethoxy-dim, cloproxydim or cycloxydim; phenoxyacetic acid herbicides such as fluazifop, dichlofop, guinofop, poppenate, trifopsime, haloxyfop, chlorazifop, fenoxaprop, fenthiaprop, 10 2,4-D or MCP; benzoic acid herbicides such as 2,3,6-TBA, dinoben, Chloramben, dicamba, or chlorthal; carbamate herbicides such as chlorpropham, phenmedipham, asulam, molinate, benthiocarb, or ethiolate; amide herbicides such as propa-nil, naptalam, allidochlor, metolachlor, alachlor or buta-15 chlor; nitrile herbicides such as bromofenoxim, ioxynil or dichlobenil; urea herbicides such as diuron, linuron, fenu-ron or benzthiazuron; diphertyl ether herbicides such as nitrofen, acifluorfen or chlomethoxynil; further diquat, praq.uat, 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-25 ed on a scale of 6 degrees. In other words, 0 means the state where the plants are as sound as before the application 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 30 enfeebled state of the plants between 0 and 5. 232 5 1 Example 1A Synthesis of 2-Hydroxy-4-(2-chloro-4-trifluoromethylphenoxy )benzaldehyde (1 A) 3-( 2-Chloro-4-trifluoromethylphenoxy)phenol (52 parts) 5 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-10 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-15 gel chromatography to give the subject compound (1A) (42 parts).. The product melted at 37 to 40bC. The IR and NMR spectra data are given in Table 1A.

Examples 2A through 5A 20 Syntheses of compounds (2A) through (5A) Instead of 3-(2~chloro-4-trifluoromethylphenoxy)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 25 the IR and NMR spectral data are shown in Table 1A.

Table 2A Example Phenol derivative Compound Yield No. No. (parts) 2A 3-(4-Trifluoromethylphenoxy)phenol (2A) 3 A 3-(4-Chlorophenoxy)phenol (3A) 32 4A 3 -(2,4-Dichlorophenoxy)phenol (4A) 40 5A 3~(3-Chloro-5-trifluoromethyl-2-pyridyloxy)phenol ( 5A) 232 5 1 Example 6A Synthesis of 2-ethoxy-4-(2-chloro-4-trifluoromethylphenoxy )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 10 over anhydrous sodium sulfate, and concentrated under reduced 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. 1 5 Example 7A Synthesis of 2-rnethoxycarbonylmethQxy-4-(2-chloro-4-trifluoromethylphenoxy)benzaldehyde (9A) The compound obtained in Example 1A (1.5 part) was mixed with methyl a-bromoacetate (0.73 part), anhydrous 20 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 filtrate was washed with water, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The crude 25 product was purified on silica gel chromatography to give the subject compound (9A) (1.6 part). The IR and NMR spectral data are shown in Table 1A.

Example 8A Synthesis of 2-ethoxycarbonylmethoxy-4-(2-chloro-4-trifluoromethylphenoxy)benzaldehyde (1 OA) Example 7A was repeated except that ethyl a-bromoacetate (0.79 part) was used instead of methyl a-bromoacetate. The yield of the compound (10A) was 1.7 part. The IR and NMR ■r> i~ ! O /-"•s spectral data are shown in Table 1A.

Example 9A Synthesis of 2-(1-methoxycarbonylethoxy)-4-(2-chloro-4-5 trifluoromethvlphenoxv)benzaldehvde (11 A) The compound obtained in Example 1A (8.2 part) was mixed with methyl a-bromopropionate (5.2 part), anhydrous potassium carbonate (7.2 part), and methyl ethyl ketone (tOOparts by volume), and the mixture was refluxed for about 10 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 (11 A) (9.5 part). The melting point of the product was 77 to 79°C and the IR and NMR spectral data 15 are shown in Table 1A.

Example 1 OA Sv.nthesis of 2-(1 methoxycarbonylethoxv )-4-( 2-chloro-4-trifluoromethylphenoxy)benzaldehvde (12A) Example 9A was repeated except that ethyl a-bromopropi onate (5.6 parts) was used instead of methyl a-bromopropionate. The yield of the compound (12A) was 9.6 parts. The IR and NMR spectral data are shown in Table 1A. 2 5 Example 11 A Synthesis of 2-(1 -n-butoxycarbonvlethoxv)-4-(2-chloro-4-trif luoromethylphenoxy ) benzaldehvde (1,3A ) Example 9A was repeated except that n-butyl a-bromopropionate (6.5 parts) was used instead of methyl a-bromo-30 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 (14A) through (17A) 232 5 1 Example 9A was repeated except that aldehyde derivatives 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 5 yields are shown in Table 3A. The IR and NMR spectral data are given in Table 1A.

Table 3A Examples No.

Aldehyde derivatives Compounds NO.

Yield (parts) 1 2A (2A) (14A) 8.8 1 3A (3A) (1 5A) 7.9 1 4A ( 4 A) (1 6 A) 8.5 1 5A (5A) (17A) 9.4 Example 16A Synthesis of 2-(1-carboxyethoxy)-4-(2-chloro-4-trifluoro-tnethylphenoxy)benzaldehyde (1 9A) The compound (11 A) 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 1A.

Example 17A Synthesis of compound (5A) 2,3-Dichloro-5-trifluoromethylpyridine (2.16 parts)t 2,4-dihydroxybenzaldehyde (1.41 part), and dimethylsulfoxide 232 5 U (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 a-bromopropionate in Example 9A. The IR and NMR spectral data of these products are given in Table 1A.

Example 21A Preparation of the R-enantiomer of compound (11 A) A solution of p-toluenesulfonyl chloride (38.2 parts) was added to a solution of methyl (s)-(-)-lactate (20.8 parts) and triethylamine (24.3 parts) in benzene (80 parts), and stirring was additionally continued at room temperature for 18 hours. It was worked up to obtain methyl 0-(p-toluenesulfonyl)-(S)-(-)-lactate.

A mixture of (1A) (31.7 parts), methyl 0-(p-toluenesulfonyl)-(S)-(-)-lactate (25.8 parts) and anhydrous potassium carbonate (28.0 parts) in dry acetonitrile (300 parts) was stirred under reflux for 6 hours. Upon work-up and purification and column chromatography (silica gel, benzene), R-enantiomer of (11a) was obtained, + 14.T (C2H5OH, c=0.347).

The IR and NMR spectral data are shown in Table 1A. 232 5 - 59 -Table 1 A Compounds No.

IR Spectra (cm-1) NMR Spectra (in CDCl-j) 6 (ppm) (1a) o (2a) (3a) (4A) 3100 1 630 1 495 3100 1 630 1 495 31 00 1 640 1 490 3100 1 640 1 490 1650 1600 1650 1605 1650 1620 1650 1620 6.40(1h) , 7.23(1h) , 7.47-7.70(2H), 9 . 78(1H), 6.45-6.67(2H), 7.07-7.20(2H), 7.40-7.70(3H), 11 .40 C1H) 6.37-6.63(2H), 6.90-7.05(2H), 7.23-7.50(3H), 11.33(1h) 6.35-6.73(2H), 7.06-7.70(4H), 1 1 . 3 5 (1 H) 6.57(1H), 7.77(1 H) 11.37(1H) 9. 73(1 H) , 9.72(1h), 9.73(1h), (5A) 3100 1620 1650 6.73-7.00(2H), 7.57(1 H), 8 . 28(1h), 11.27(1h) 8 . 00(1h) , 9 . 80(1H) , (8A) 1 690 1 320 1590 1.47(3H), 6.30-6.55(2H), 4.07(3h) , 7 .1 2 (1 h ) , 7.43-7.72(3H), 10.2 2(1H) 2325 1 Compounds No.

Table 1A (continued) IR Spectra (cm"1 ) NMR Spectra (in CDCl-j) 6 (ppm) o (9A) (1 oa) (1 1a) (1 2 A) (1 3 a) 1750 1670 1590 1320 1 750 1590 1 750 1 590 1 740 1590 1740 1590 1 670 1 320 1 670 1 325 1 680 1320 1 680 1 320 3.78(2H } , 4 . 70{2H), 6.45-6.60(2H), 7.13(1H), 7 . 55(1H), 7.73-7.90(2H), 10.40(1H) 1.28(3h), 4.70(2h), 7 .1 7 (1 H ) , 4 . 27(2H), 6.47-6.63(2H), 7.57(1h), 7.77-7.93(2H) , 10.43OH) 1.68(3H), 3 .73(3H), 4.83(1H), 6.45-6.61(2H), 7 .1 7(1H) , 7.57(1 H) , 7 . 73-7. 87 ( 2H ) , 10.40(1H) 1.22(3h), 1.68(3h), 4 . 1 7(2H), 4.75(1H), 6.37-6.57(2H) , 7.10(1H), 7.53(1H) , 7 . 68-7. 87 (2H) , 1 0.37(1h) 0.77-1 .83(7H ) , 1 .67(3H), 4.13(2H), 4 .80(1H), 6 . 43-6 . 63 ( 2H) , 7.13(1H), 7.57(1H), 7.77-7.93(2H) 232 5 1 Table 1A (continued) Compounds No.

IR Spectra (cm-1) NMR Spectra (in CDC13) & (ppm) (1 4A) J (15A) (16A) (17A) (1 9A) 1750 1680 1590 1325 1 750 1 580 1750 1 580 1750 1590 1675 1250 1675 1250 1675 2700-3500 (broad) 1720 1670 1 590 1 .6 5(3H ) , 4 . 73(1H) , 7 . 07(2H), 1 0.27(1h) 1.65(3H), 4.77(1h ) , 6.97(2h), 7.77(1h) , 3.73(3h)f 6.37-6.63(2H) ; 7.53-7.77(4H) 3.70(3H), 6 . 35-6.62(2H), 7 . 33(2H), 10.37(1h) 1.67(3h), 4 . 7 7 (T H) ( 7.07-7.47(3H), 10.40(1H) 3.73(3H), 6.30-6.73(2H), 7.80(1h), 1 .67(3H), 4.78C1H), 7 . 5 9 (1 H ) , 1 0 . 4 0 (1 H ) 3.73(3h), 6 . 74-7.02(2H), 7 . 90-8.28(2H) , 1-72(3H), 6.45-6.63(2H), 7 .1 7 (1 H) , 7.73-7.90(2H), 10.33(1h) 4 . 85(1H), 7.57(1h), 8 .1 8 (1 h) , ?32 5 r^i - 62 -Table 1 A (continued) G Compounds IR Spectra NMR Spectra (in CDCI3) No. (cm 6 (ppm) ( 20A) 1750 1 680 1 .1 3(3H), 2.06(2H), 1590 1 485 3.70(3H), 4.55(1H), 1460 1 430 6 . 30(1H), 6.50(1H), 1 400 1 320 7 .1 0(1H), 7.50(1H), 1260 7 . 70(1H), 7.75(1H), 1 0.33(1H) (21 A) 1 750 1 680 0.7-1 .1{3H) , 3.67(3H), - 1595 1 485 1.1-1 . 7 (6H) , 4. 60(1H) , 1 5 1 460 1 435 1.7-2.3{2H), 6 . 30(1H) , 1 400 1 320 6. 50(1H) , 7 .1 0 {1 H) , 1260 7 . 5 0 (1 H) , 7 . 7 0 C1 H) , 7 . 75(1 H) , 1 0 . 3 3 (1 H) ( 22A) 1700 1 590 1 - 63(3H) , 3.77(6H), 1 490 1 435 4.75(1HJ , 6-50(1H)f 1 400 1 330 6 . 60(1 H ) , 7.10(2H), 1 250 7. 53(1 H) , 7.70(2H)f (11A/R- 1 750 1 670 1 . 6 8 ( 3 H ) , 3.73(3 H), enantiomer) 1 590 1 325 4.83(1H), 6.45 -6.61(2H), 7 . 1 7 (1 H) , 7.57(1H), 7.73-7.87(2H), .40(1H) t. * 232 5 1 1 _ 63 - Example 1B Synthesis of 2-ethoxy-4-(2-chloro-4-trifluoromethylphenoxy )benzaldehyde oxime (IB) A solution of hydroxylamine hydrochloride (0.7 part) in 5 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 carbonate (0.76 part ) was added to the solution with stirring at room temperature, and stirring was additionally continued at 10 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 anhydrous sodium sulfate, then ether was removed. The residue was purified by silica-gel chromatography to give compound 15 (1B) (3.2 parts). The IR and NMR spectral data of the compound are shown in Table 1B.

Example 2B Synthesis of 2-(1-methoxycarbonylethoxy)-4-(2-chloro-20 4-trifluoromethylphenoxy)benzaldehyde oxime (2B) '•"'S Example IB was repeated except that 2-(1-methoxycarbo- nylethoxy)-4 -(2-chloro-4-trifluoromethylphenoxy)benzaldehyde (11A) (4.03 parts) was used instead of 2-ethoxy-4-(2-chloro-4-trifluoro-methylphenoxy)benzaldehyde (8A) (3.45 parts). 25 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-c.hloro-4-30 trifluoromethylphenoxy)benzaldehyde oxime (3B) Example IB was repeated except that 2-(1-ethoxy-carbo-nylethoxy)-4-(1-chloro-4-trifluoromethylphenoxy)benzaldehyde (12A) (4.16 parts) was used instead of 2-ethoxy-4-(2-Chloro-4-trifluoromethylphenoxy(benzaldehyde (8A) (3.45 /»' ,r i 23 2 5 1 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 hydroxylamine hydrochloride (0.7 part) to produce the subject 10 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-4-15 trifluoromethylphenoxy)benzaldehyde O-methyloxime (5B) Example 2B was repeated except that O-methylhydroxyl-amine hydrochloride (0.84 part) was used instead of hydroxylamine hydrochloride (0.7 part) to produce the subject compound (3.85 parts) (5B). The IR and NMR spectral data of 20 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-25 4-trifluoromethylphenoxy)benzaldehyde (11 A) (4.03 parts) in ^ tetrahydrofuran (20 parts) is combined with an aqueous solution containing an equimolar amount of 0-substituted hydroxylamine given in Table IB and the mixture was stirred at room temperature for additional 1 hour. Then, tetrahy-30 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 23 2 5 1 Table 2B. The IR and NMR spectral data of the compounds are given in Table 1B.

Table 2B Examples O-substituted hydroxylamine Yield Compounds No. (parts) No. 6B h2n-och2ch3 3.66 (6B) 7B H2N-OCH2CH2CH3 3.72 (7B) 8B CHn / J H-jN-OCH ch3 4. 05 (8B) 9B H2N-O-<V> 4.00 (9B) 1 OB h2n-o-ch2cooc2h5 3.78 (1 0B) 11B h2n-o-ch2ch=ch2 3.89 (11 B) 12B h2n-o-ch2ch=ch-ch3 3.75 (12B) 13B h2n-o-(ch2)2ch=ch2 3.93 (1 3B) Example 14B Synthesis of 2-(1-ethoxycarbonylethoxy)-4~(2-chloro-4-trifluoromethylphenoxy)benzaldehyde O-allyloxime (14B) Example 11B was repeated except that 2-{1-ethoxycarbo-25 nylethoxy)-4-(2-chloro-4-trifluoromethylphenoxy)benzaldehyde (12A) (4.16 parts) was used instead of 2-(1-methoxycarbonylethoxy )-4-(2-chloro-4-trifluoromethylphenoxy)benzaldehyde (11 A) {4-03 parts) to produce the subject compound (14B) (3-90 parts). The IR and NMR spectral data of the 30 compound are given in Table 1B.

Example 15B Synthesis of 2-(1-methoxycarbonylethoxy)-4-(2-chloro-4-trifluoromethylphenoxy)benzaldehyde O-propargyloxime (15B) 232 5 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 5 1 B.

Example 1 6B Synthesis of 2-(1-methoxycarbonylethoxy)-4-(2-chloro-4-trifluoromethylphenoxy)acetophenone oxime (16B) Example 1B was repeated except that 2-(1-methoxycarbonylethoxy )-4-(2-chloro-4-trifluoromethylphenoxy)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 IB.

Example 17B Synthesis of 2-(1-methoxycarbonylethoxy)-4-(2-chloro-4-trifluoromethylphenoxy)acetophenone Q-methyloxime (17B) Example 16B was repeated except that Q-methylhydroxyl-amine hydrochloride (0.84 part) was used instead of hydroxylamine 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-30 tion of 2-(1-methoxycarbonylethoxy)-4-(2-chloro-4-trifluoromethylphenoxy ) benzaldehyde (11 A) 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 1 5 2325 1 the subject compound (18B) (4.67 parts). The IR and NMR spectral data of the compound are given in Table IB.

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-trifluoromethylphenoxyJbenzaldehyde (8A) (3.45 parts) was used instead of 2-(1-methoxycarbonylethoxy}-10 4-(2-chloro-4-trifluoromethylphenoxy)benzaldehyde (11 A) (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. 1 5 Examples 20B through 37B Syntheses of compounds (20B) through (37B) 2-(1-Methoxycarbonylethoxy)-4-(2-chloro-4-trifluoromethylphenoxy )benzaldehyde (11 A) (4.03 parts) was dissolved 20 .in tetrahydrof uran (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 25 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. 2325 1 rs "-s .twsn - 68 -Table 3B Examples O-substituted hydroxylamines Yields Compounds No. (parts) No. 20B O-phenylhydroxylamine 4.4 (20B) 21B 0-4-fluorophenylhydroxylamine 4.3 (21B) 22B 0-2-fluorophenylhydroxylamine 4.2 (22B) 23B 0-3-fluorophenylhydroxylamine 4.3 (23B) 24B 0-4-chlorophenylhydroxylamine 4.7 (24B) 25B 0-4-cyanophenylhydroxylamine 4.6 (25B) 26B 0-4-nitrophenylhydroxylamine 4.8 (26B) 27B 0-3-nitrophenylhydroxylamine 4.7 (27B) 28B 0-3-trifluoromethylphenylhydroxyl amine 5.0 (28B) 29B 0-3-methoxyphenylhydroxylamine 4.7 (29B) 30B 0-4-methylphenylhydroxylamine 4.1 (30B) 31B 0-4-phenylphenylhydroxylamine 4.5 (31B) 32B 0-4-(4-trifluoromethylphenoxy)- phenylhydroxylamine 5.0 (32B) 33B 0-3,4-dichlorophenylhydroxyl amine 5.0 (33B) 34B 0-2,4-dinitrophenylhydroxylamine 5.0 (34B) 35B 0-2-chlorb-4-trifluoromethyl phenylhydroxylamine 5.3 (35B) 36B 0-3,5-dimethoxyphenylhydroxyl amine 4.9 (36B) 37B 0-3,5-dimethylphenylhydroxyl amine 4.2 (37B) Examples 38B through 45B Syntheses of compounds (38B) through (45B) Example 20B was repeated except that 2-(1-methoxycarbonylethoxy )-4 -(2,4-dichlorophenoxy)benzaldehyde (16A) (3.70 parts) was used instead of 2-(1-methoxycarbony- a ' 2325 18 lethoxy)-4-(2-chloro-4-trifluoromethylphenoxy)benzaldehyde (VIA) (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 5 spectral data are given in Table IB.

Table 4B Examples O-substituted hydroxylamines Yields Compoounds No. (parts) No. 1 0 38B O-phenylhydroxylamine 4 . 1 (38B) 39B O-4-fluorophenylhydroxylamine 4.0 (39B) 40B O-4-nitrophenylhydroxylamine 4.5 ( 40B) 41 B 0-3-methoxyphenylhydroxylamine 4.4 ( 41 B) 42B 0-3-trifluoromethylphenyl hydroxylamine 4.5 (42B) 43B O-4-methylphehylhydroxyamine 4.0 (43B) 44 B 0-4'-cy a nopheny lhydroxylamine 4.2 (44B) 45B 0-2-chloro-4-trifluoromethyl phenylhydroxylamine ,0 (45B) i; Examples 4 6B through 4 9B Syntheses of compounds (46B) through (49B) Example 20B was repeated except that 2-(1-methoxycar-25 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 (11 A) (4.03 parts) and O-substituted hydroxylamines given in the following table 5B were used to give the 30 products in yields shown in Table 5B, respectively. The IR and NMR spectral data are given in Table 1B. 23 2 5 1 8 Table 5B Examples 0- •substituted hydroxylamines Yields Compounds No. (parts) No. 46B 0- phenylhydroxylamine 4.1 ( 46B) 47B 0- 4-fluorophenylhydroxylamine 4.0 ( 47B) 48B 0- 4-chlorophenylhydroxylamine 4.2 ( 48B) 49B 0- ■3-trifluoromethylphenyl hydroxylamine 4.5 (49B) 1 0 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 15 give the products in yields shown in Table 6B, respectively. The IR and NMR spectral data are given in Table IB.

Table 6IB Examples No.

Q-Substituted hydroxylamines Yields (parts) Compounds No.

SOB O- pyrid-2-ylhydroxylamine 3.5 (50B) 51 B O- 6-methoxypyrid-2-ylhydroxyl amine 3.8 (51 B) 52B 0- 3-chloropyrid-2-ylhydroxyl amine 3.7 (52B) 53B 0- ■pyraz-2-ylhydroxylamine 3.4 (53B) 54B 0- •3,6-dimethylpyraz-2-ylhydroxyl amine 3.7 ( 54B) 55B 0- •quinol-2-ylhydroxylamine 3.8 ( 55B) 56B 0- •5-chloro-pyridaz-2-ylhydroxyl amine 3.7 ( 56B) 2325 1 1 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 5 give the products in yields shown in Table 7B, respectively. The IR and NMR data are given in Table IB, t Table 7B Examples 0-substituted hydroxylamines Yields Compounds No. (parts) No. 57B 0- ■6-chloropyrid-2-ylhydroxylamine 3.5 (57B) 58B 0- ■2,6-dimethylpyraz-2-ylhydroxyl amine 3.4 (58B) 61 B 0- 3-chloropyrid-2-ylhydroxylamine 3.2 (61 B) Examples 59B and BOB Syntheses of compounds (59B) and (60B) Example 20B was repeated except that 2-(1-methoxy-20 car,bonylethoxy)-4-(4-trifluoromethylphenoxy)benzaldehyde •""S (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 25 yields shown in Table 8B, respectively. The IR and NMR ":"h spectral data are given in Table 1B. w Table 8B Examples 0- -substituted hydroxylamines Yields Compounds No- (parts) No. 59B 0-6- -chloropyrid-2-ylhydroxylamine 3-4 (59B) 60B 0-6- -methoxypyrid-2-ylhydroxyl amine 3.2 (60B) f ' 23 2 5 1 1 Example 62B Synthesis of 2-(1-methoxycarbonylethoxy)-4-(4-chlorophe-noxy(benzaldehyde O-phenyloxime (62B) Example 20B was repeated except that 2-(1-methoxy-5 carbonylethoxy)-4-(4-chlorophenoxy)benzaldehyde (15A) (3.4 parts) was used instead of 2-(1-methoxycarbonylethoxy)-4-(2-chloro-4-trifluoromethylphenoxy)benzaldehyde (11 A) (4.03 parts) to give the subject product (3.8 parts). The IR and NMR spectral data are given in Table IB. 1 0 Example 63B Synthesis of 2-(1-carboxyethoxy)-4-(2-chloro-4-trifluoromethylphenoxy )benzaldehyde O-phenyloxime (63B) 2-(1-Carboxyethoxy) ~4 - (2-chloro-4-trifluoromethyl -15 phenoxy)benzaldehyde (19A)(0.41 parts) was dissolved in tetrahydrofuran (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-20 tion of the reaction, terahydrofuran was removed under reduced pressure, diluted with water, acidified with hydrochloric 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 25 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-trif luoromethylphenoxy )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-methoxycarbonylethoxy)-4-(2- f ■ 2325 chloro-4-trifluoromethylphenoxy(benzaldehyde (11 A) {4.03 ' . parts) to give the subject compound (64B) (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~ trifluoromethyl-2-pyridyloxy)benzaldehyde O-phenyloxime (65B) Example 20B was repeated except that 2-(1-methoxycarbo-1 0 nylethoxy)-4-(3-chloro-5-trifluoromethylpyridyloxy)benzaldehyde (17A) (4.03 parts) was used instead of 2-(1-methoxycarbonylethoxy )-4-(2-chloro-4-trifluoromethylphenoxy)benzaldehyde (11A) (4.03 parts) to give the subject product (3.90 parts). The IR and NMR data are given in Table IB. 1 5 Example 66B Syntheses of compounds (26B), (34B), (50B) through (61B), (84B) and (143B) Compounds (2B) obtained in Example 2B (4.18 parts) and 20 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 temperature. Then, they were stirred at room temperature for additional 5 hours, the reaction mixture was poured into ice 25 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-30 hyde oximes prescribed in the following Table 9B were used instead of the compound (2B) and halogen compounds prescribed 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. /"""s t ■ 2325 1 8 Table 9B 1 5 Compounds No. (26B) ( 34B) (50B) (51 B) (52B) ( 5 3 B) (54B) ( 5 5 B) ( 56B) ( 57B) (58B) (59B) (60B) (61B) (84B) (143B] Aldehyde oxime No.

Halogen compounds (2B) (2B) (2b) (2B) (2b) (2b) (2B) (2b) (2B) (78B) (78B) (2b) (2B) (78B) (2B) ( 2B) 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 2, 6-dichloroquinoxaline Example 67B Syntheses of (66B) through (70B), (74B), (79B), (80B), (82B), (83B), (85B) through (87B), (89B), (91B), (95B) through (10QB), and (146B) The reactions between the aldehydes and O-substituted 30 hydroxylamine which are prescribed in the following TablG 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. f J 232 5 1 •-—\ G - 75 -Table 10B Compounds Aldehyde O-substituted hydroxylamine derivatives No. No. (66B) (9A) O-allylhydroxylamine ■""•n (67B) (10A) O-allylhydroxylamine (68B) {9A) O-phenylhydroxylamine (69B) {10A) O-phenylhydroxylamine (70B) (13A) O-allylhydroxylamine (74B) (13A) O-phenylhydroxylamine (79B) (24A) O-4-nitrophenyl hydroxylamine (80B) (22A) O-4-nitrophenyl hydroxylamine (82B) (11A) 0-4-chloro-2-nitrophenyl hydroxylamine (83B) (11 A) O-2-nitrophenylhydrxylamine (85B) (11 A) 0-4-nitrobenzylhydroxylamine (86B) (17 A) 0-4-nitrophenylhydroxylamine (87B) (17A) 0-4-f luorophenylhydroxylamine (89B) (11A) 0-1-nitro-2-naphthyl hydroxylamine (91B) (11A) 0-4-(1,1-dimethylethyl)phenyl hydroxylamine (95B) (1U) 0-(4-methoxycarbonylmethyl)- 2-nitrophenylhydroxylamine (96B) (11 A) 0-4-methoxycarbonylphenyl hydroxylamine (97B) (11 A) 0-4-trifluoromethylpheny1 hydroxylamine (98B) (9A) 0-4-nitrophenylhydroxylamine (99B) (20A) 0-4-nitrophenylhydroxylamine (100B) (21 A) 0-4-nitrophenylhydroxylamine f ■ 23 2 5 U (146B) (1A) 0-4-nitrophenylhydroxylamine (150B) (11 A) 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-10 scribed in the following Table 11B were used instead of the compound (11 A) to give the compounds given in Table 11B. The IR and NMR spectral data are shown in Table 1B.

Table 1 1B Compounds No.

Aldehyde derivatives (73B) (21A) (75B) ( 9A) ( 7 7 B) (20A) (78B) (16A) ( 8 8 B) (17A) (145B) ( 2 4 A) Example 69B 25 Synthesis of compound (90B) Compound (146B) (0.24 part), -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-30 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. 232 5 - 77 Example 70B 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 5 was added in portions to the compound solution. After completion of the reaction, ether was removed under reduced pressure, and the residue was purified by silica-gel chromatography to give the subject compound (93B) (0.16 part). The IR and NMR spectral data of the compound are given in Table 10 1 b.

Compounds (155B) and (156B) were used instead of compound (154B) to repeat the above reaction whereby the subject compounds (94B) and (92B) were obtained. The IR and NMR spectral data of these compounds are shown in Table 1B. 1 5 Example 71B Syntheses of compounds (101B) through (109B), (11 IB) 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 tetrahydrof uran (5 parts) was added dropwise, stirred at room 25 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 30 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 tl ' 232 5 1 8 - 78 IR and NMR spectral data are showing in Table 1B, Table 12B Compounds Aldehyde oxime No. No.

Acid chlorides 1 0 1 5 (1 01B) (102B) (103B) (104B) (105B) (106B) (1 0 7 B) (108B) (1 0 9 B) (11tb) (112B) (113B) (114B) (11SB) (116b) (11 7B) (124B) (125B) (126B) (2b) (2B) (2B) (2B) (2B) (2B) (2B) (1 45B! (2B) (2B) (2B) (88B) (73B) (77B) ( 7 5 B) (2B) (2B) ( 2B) (2B) 4-nitroben2oyl chloride 3,5-dinitrobenzoyl chloride 2,4-dinitrobenzoyl chloride 4-fluorobenzoyl chloride 4-methoxycarbonyl-2,3,5,6- tetrachlorobenzoy1 chloride 2-nitro-5-(2-chloro-4-tri-fluoromethylphenoxy)- benzoyl chloride iSonicotinoyl chloride 4-nitro.methylbenzoyl chloride 4-N,N-dimethylaminobenzoy1 chloride 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 1 -[4 -(3-chloro-5-trifluoromethyl -2-pyridyloxy)phenoxy-propionyl chloride r * i ' % •-—' 232 5 U 79 {127B) (2B) acetyl chloride (128B) (2B) 1-[4-(5-trifluoromethyl-2- pyridyloxy)phenoxypropionyl chloride (129B) (2B) ethyl chloroformate (130B) (2B) n-capryl chloride (131B) (2B) 1 ,1 -dichloropropionyl chloride (132B) (88B) acetyl chloride (133B) (2B) 2,2,2-trichloroethyl chloroformate (135B) (2B) 3-aminobenzoyl chloride (136B) (2B) 3 -(N,N-dimethy1carbamoyl- amino)benzoyl chloride (137B) (2B) 4-ethoxycarbonylaminobenzoyl chloride (138B) (2B) benzoyl chloride (13 9 B) (2b) 2,4,6-trimethylbenzoyl chloride (HOB) (2B) 4-(1,1-dimethylethyl)benzoyl chloride (141B) (2B) 4-chloroacetylaminobenzoyl chloride (142B) (2B) 4-(1,1-dimethylpropionyl- amino)benzoyl Chloride Example 72B Synthesis of compound (1.1 OB) Compound (109B) was dissolved in diethyl ether (50 30 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 (11 OB) (3.2 parts). The IR and NMR spectral data are shown in Table 1B. f • 232 5 18 Example 73B Syntheses of compounds (118B) through (123B), and (134B) The reaction was carried out at room temperature by 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 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 (123B), and (134B). The ir and nmr spectral data of these compounds were shown in Table 1B, respectively.

Example 7 4B Syntheses of compounds (147B), (149B) and (151B) through 20 (1.53B) 4-Fluorobenzoylaminoacetonitrile (0-59 part) was dissolved 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 several drops, then remaining bromine was added). After completion 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, simultaneously, thereto. After addition, stirring was continued at 0°G 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 10 81 - 23 2 5 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 15 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-trifluoromethylphenoxy )]phenoxypropionate (1.9 part) was combined with 25 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 0-4-30 nitrophenylhydroxylamine (0.83 part) in benzene (10 parts by volume) at room temperature. After completion of the reaction, 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 ? 3 2 5 i 8 82 o 10 1 5 20 25 the crude product was purified by silica-gel column chromatography 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 O-2-propenyloxycarbo-nylmethylhydroxylamine were used instead of 0-4-nitrophenylhydroxylamine, to carry out similar reactions, respectively whereby compounds (155B) and (156B) were obtained. The IR and NMR spectral data are shown in Table 1B.

Example 77B Preparation of the R-enantiomer of compound (26B) The R-enantiomer of compound (11A) (12.1 parts) was dissolved in tetrahydrofuran (60 parts). Then, an equimolar amount of 0-4-nitrophenylhydroxylamine and a drop of concentrated hydrochloric acid were added to the solution, and they were stirred at room temperature for 20 minutes.

Tetrahydrofuran was evaporated under reduced pressure, the residue was re-crystallized from ethanol to give the product, m.p. 92-93.5°C [ce]^5 - 1.0° (C2H5OH, c=1.0).

The IR and NMR spectral data are shown in Table 1B.

Example 78B Preparation of the R-enantiomer of compound (2B) The R-enantiomer of compound (11 A) (12.1 parts) was dissolved in benzene (100 parts). A solution of hydroxylamine hydrochloride (2.5 parts in water (50 parts) was added to the solution, and stirred vigorously. Then, sodium carbonate (1.91 part) was added, and stirring was continued at 70°C for 7 hours.

Organic layer was separated, concentrated under reduced pressure, and purified by silica gel column chromatography to give compound (162B), +■ 3.5° (THF, c = 0'.74).

The IR and NMR spectral data are shown in Table 1B. f ' /""n Compounds No.

Table 1B 2325 18 IR Spectra (cm-1 ) NMR Spectra (in CDC13) 6 (ppm) (IB) (2B) 3250 1075 3300 I 595 II 20 1 595 1 755 1 320 1 080 1.43(3H), 4.03(2H), 6.40-6.67(2H) , 7.07(1H), 7.50(1H), 7.67-7.83(2H), 8.33(1h), 10.80(1h) 1.62{3h), 3.70(3h), 4.72(1H), 6.40-6.63(2H) , 7.00(1h), 7.47(1h) , 7.63-7.80(2H) , 8.50(1H) , 8.93(1h) f^ (3B) (4B) (5b) 3350 1590 11 20 1595 11 20 1755 1320 1 05O 1 740 1320 1 080 1320 1 050 1595 11 25 1.20(3H), 1.62(3H), 4 .13(2H), 4.67(1H), 6.37-6.60(2H) , 6.97(1H), 74 3 (1 H) , 7.63 ~7.77(2H) , 8. 47(1H ) 1.42(3H), 3 . 87(3H) , 3.97(2H), 6.35-6.50(2H), 6.97(1h) , 7.43(1 h) , 7 . 67-7.80(2H ) , 8.23(1H) 1.62(3h), 3.97(3h), 7 . 47(1H) , 8 . 4 3 (1 H) 3.70(3H), 4.68(1h) , 7 . 67-7.87(2H) , f ' 232 5 18 ■84 ■ Table IB (continued) Compounds No.

IR Spectra (cm-1) NMR Spectra (in CDCl-j) 6 (ppra) (6B) 1755 1595 1320 1125 1050 1.30(3H), 3.70(3h), 4 - 70 <1H), 7.00(1h), 1 .62(3H), 4.20(2h), 6.40-6.63(2H), 7 . 47(1H), 7.70-7.90(2H), 8.47(1H) (7B) 1 5 1755 1 320 1050 I 595 II 25 0.98(3h), 1 .47-2.05(2H), 4 .1 2(2H), 6.40-6.67(2H), 1.62(3h), 3.72(3h), 4.72(IH), 7.00(1h), 7 . 48(1H ) , 8.48(1h) 7.70-7.90(2H), (8B) (9B) 1 750 1 320 1 750 1 320 1595 11 20 1 595 1125 1 . 2 7 (3 H), 3.67(3h), 4.63(1h), 6.53(1H), 7.43(1h), 8.27(1h ) 1 . 6 2 ( 3 H ) , 4 . 3 2 (1 H ) , 6.3 3(2h) , 6 . 9 7 (1 H ) , 67-7.87(2H), 1.60(3H), 1.23-2.23(10H), 3 . 67(3H), 3.87-4.37(1 H), 4.68(1H), 6.37-6.63(2H), 6.97(1H) , 7.47(1 H ) , 7- 67 — 7.93(2H), 8 - 4 5(1H) (1 ob) 1 750 I 595 II 20 1740 1320 1.27(3h), 3.67(3H) , 4.63(1H), 6.40(1h), 7.00(1h) , 7.67-7.80(2H), 1 .62(3H) , 4 . 23(2H), 4.70(1h), 6.67(1 h) , 7 - 4 7 (1 H) , 8 . 5 2 (1 H) , 232 5 1 •85- Table IB (continued) Compounds No. 'w' IR Spectra (cm-1) NMR Spectra (in CDCl^) 6 (ppm) (1 1B) 1755 1595 1 .60(3H), 3. 60(3H), 1320 1 125 4 . 47-4 . 80 (3H) , 6. 33(1H) , - 03-5.37(2H) , 6. 50(1H), .67-6.27(1H), 6. 97(1H) , 7 .67-7.83(2H) , 7. 43(1H) , 8 .33(1H) (1 2B) 1 755 1 595 1 .53-1 .80(6H) , 3 . 70(3H) , 1320 1 1 25 4 .50-4.87(2H}, 6. 40(1H), 6 .70(1H)# 6. 97(1H), 7 .4 7(1H), 7.67 -7. 87(2H), 8 -47(1 H)- (13B) 1750 1595 1 . 6 0(3 H), 2.30 -2. 6 3(2H), 1 320 11 25 3 .67(3H), 4 . 1 7 ( 2H) , - 4 .6 7(1H), 4.93 -5. 23(2H), .43-6.23(1H), 6. 93(1H), 6 .33-6.60(2H), 7. 4 3(2H ) , 7 .67-7.83(2H), 8. 40(1H) (14B) 1 750 1 595 1 .23(3H), 1 . 60(3H ), 1 320 11 25 4 .13 ( 2H), 4.43 -4 . 70(2H), .7 0-6.27(1 H), 7. 4 0 (1 H ) , 6 .33-6.70(2H), 7 .63-7.83(2H) (1 5B) 3300 1 750 1 . 60(3H) , 2. 33(1H), 95 1 320 3 . 6 3(3 H), 4.47 -4. 80(3H), 11 25 6 .33(1H), 6. 50(1H), 6 .97(1H), 7. 4 3(1H), 7 .67-7.87(2H), 8. 3 3 (1 H) 232 5 1 8 ■86- Table IB (continued) Compounds No.

IR Spectra (cm-1) NMR Spectra (in CDCI2) 6 (ppm) (16B) 1 5 (17B) (18B) 3250 1 595 1 1 30 1 755 1 320 1 750 1 320 1750 1 320 1 595 1130 1595 1125 1 .60(3H), 3.67(3h), 6.37-6.57(2H), 7,20-7.67(4H) 2.27(3H), 4 . 70(1H), 6 . 97(IH), 1 .60(3H), 3.70(3h) , 4.73(1h), 6.97(1h ) , 2 . 27(3H) , 3 .97(3H), 6 . 40-6.63(2H), 7 . 23-7 .73(3H) 1.60(3h), 4 .7 3 (1 H ) , 6 . 40-6.70(2H) 7.27-7.60(6H) 7.77-7.97(2H) 3 • 7 0(3H), 5 . 2 3 ( 2 H) , 7 - 03(1H), 8.63(1h) , (1 9B) 1590 11 25 1320 1080 1.40(3H), 6.27-6.63(2H), 6.77-7•47(7H), 7 . 63-7.98(2H), 3. 9 5 (2 H ), 8. 68(1 H ) (20B) 1 750 1 320 1080 I 590 II 25 1.67(3h), 3.73(3h), 4.78(1H), 6.47-6.73(2H), 7.03-7.63(7H), 7.82(1H), 8 . 03(1H), 8.90(1H ) r ■ 232 5 1 8 Tabie 1B (continued) o Compounds No.

IR Spectra (cm-1 ) NMR Spectra (in CDCI3) 6 (ppm) (21 B) 1750 1590 1 . 63(3H ) , 3 . 67(3H), 1320 11 25 4. 70(1H), 6.33 -6 . 60(2H), 1080 6. 73-7.23(5H}, 7 .27(1H ) , 7. 67(1H), 7 .87(1H ) , 8. 70(1H) (22B) 1750 1590 1 . 65(3H), 3 .67(3H), 1320 11 25 4 . 70(1H), 6.37 -6 .63(2H) , 1080 6. 83-7.60(6H), 7 .70(1H), 1 5 7. 87 (IH)., 8 .83(3H) (23B) 1755 1 595 1 .. 63(3H), 3 .67(3H), 1 320 1 120 4 . 70(1H), 6. 37 -7 .23(7H), 1 080 7. 43 (IH) , 7 . 6 7 (1 H ) , 7. 87(1H), 8 . 72(1H) ( 2 4 B) 1750 1 590 1 . 63(3H), 3 .67(3H), 1320 1 125 4. 70(1H), 6.33 -6 .60(2H), 1 080 6. 90-7.23(5H), 7 .43(1H), 7. 67(1H), 7 CO 8. 73(1H) (25B) 221 0 1 750 1 . 6 7 ( 3 H ) , 3 - 7 0 ( 3 H) , 1 595 1320 4. 73(1H), 6.37 -6 . 63(2H), 11 25 1080 6. 93-7.67(7H), 7 .85(1H ) , 8. 73(1H) 23 2 5 1 8 Table IB (continued) Compounds IR Spectra NMR Spectra (in CDCI3) No. ( cm"1 ) 6 (pprn ) (26B) 1 750 1 590 1 . 65(3H), 3. 68(3H), 1510 1 320 4 . 7 3 (1 H ) , 6.37 -6. 63(2H), 1 1 25 1080 6 . 97-7 . 70(5H), 7 .78-8.18(3H), 8. 78(1H) (27B) 1750 1 595 1 .67(3H), 3. 70(3H), 1 525 1320 4 .73(1H), 6. 37 -6. 63(2H), 11 30 1080 7 .00(1H), 7.33 -8. 03(7H), 8 .75(1H) (28B) 1 755 1595 1 .65(3H), 3. 6 7 ( 3 H •) , 1 320 11 25 4 . 72 (1 H) , 6.37 -6. 63(2H), 1 080 7 .00(1H), 7.1 7 -7. 52(5H), - 7 . 6 7 (1 H) , 8 . 77(1H) (29B) 1 750 1595 1 .65(3H), 3. 68(3H), 1320 11 30 3 .77(3H), 4 . 7 2 (1 H) , 1080 6 .30-7.53(8H), 7. 02(1H), 7 . 90 (1H) , 8. 73(1H) ( 30B) 1750 1595 1 . 63(3H), 2. 27(3H), 1320 1 130 3 . 67(3H), 4. 70{1H), 1080 6 .3 5-6. 63(2H), 7. 68(1H), 6 .90-7.53(6H), 7. 88(1H), 8 . 70(1H) /-s r 232 5 1 8 r-n Compounds No.

Table 1B (continued) IR Spectra (cm-1) NMR Spectra (in CDC13) 6 (ppm) (31 b> 1750 1590 1320 1120 1 080 1.63(3H), 3.67(3H ) , 4 . 70(1H), 6.33-8.1 3(15H), 8 . 7 7 (1 H ) (32B) 1 750 1 320 1 080 1595 11 20 1 .67(3h), 3.70(3h) , 4.72(1H), 6.37-6.63(2H) , 6.83-7.60(1 OH), 7.70(1H), 7 . 87(1H), 8.73(1H) (33B) 1 755 1320 1080 1 590 1 120 1.63(3h), 3.68(3h), 4.72(1H), 6.35-6.63(2H), 6.85-7.50(5»), 7.7 0(1H), 7.85(1H), 8 . 7 2 (1 H ) (3 4 B) (35B) 1750 1525 11 30 1755 1 320 1 080 1 600 1 320 1 080 1 595 1 1 20 1.70(3H), 3.70(3H), 4-77(IH), 6.37-6.63(2H), 7.08(1H), 7.50(1H), 7.70-7.97(3h), 8.37(1h), 8.73(1h), 8.92(1h) 1.68(3H), 4.77(1H), 7.07(1h), 7.73(1h), 8.92(1h) 3 . 70(3H), 6.40-6.67(2H), 7 . 40-7.63( 4H), 7 . 93(1 H ) , 23 2 5 1 1 ■"n Compounds No. (36B) Table 1B (continued) IR Spectra (cm"1 ) 1 750 1 590 1 320 1 1 30 1080 NMR spectra (in CDCI3) 6 (ppm) 1 .67(3H), 3 . 77(6H), 6.00-6.67(5H), 7 . 50 (1 H) , 7.93(1H), 3.70(3h), 4 .7 3 (1 H) , 7.03(1h), 7 . 73(1H), 8.77(1h) (37B) 1 755 1 320 1 080 I 590 II 30 1 .63(3H), 3.72(3H) , 6 . 40-7.20(6H), 7 . 73(1H), 8. 77(1 H) 2.33(6H), 4.72(1H), 7 . 50(1H), 7.93(1h}, 3 ( 3 8 B) (39B) 1755 1 270 1 750 1 270 1 235 1605 1090 1 605 1 225 1090 1 . 63(3H), 3.70(3H), 4 . 70(1 H), 6.33-6.63(2H), 7 . 00-7 . 53 ( 8H) , 7.930H), 8 . 7 8 (1 H} 1 .63(3H), 1 .7 3(3H ) , 4 . 73(1H), 6.33-6.63(2H), 6.80-7.57(7H), 7.90(1h), 8.77(1h) ( 4 0 B) 1 750 1510 1 235 1 605 1 270 1090 1.67(3H ), 1 .7 3(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), t < 232 5 1 Compounds No.

Table IB (continued) IR Spectra (cm-1) NMR spectra (in CDC13; 6 (ppm) (41B) 1 5 •J (42B) ( 43B) (44B) (45B) 1750 1 270 1090 1755 1325 1090 1 750 1 270 1 090 1080 1 600 1 225 1 605 1 1 25 1 605 1 220 2210 1 750 1600 1270 1230 1090 1750 1605 1320 1120 1 .6 5(3h), 3 . 73(3H), 6.33-6.63(3H), 6.73-7.57(6H), 3.70(1h), 4.70(1h), 7.93(1h)i 8.78(1h) 1.67(3H ), 3.73(3H), 4 . 74{1H), 6.37-6.67(2H), 7.03-7.53(7H ) , 7.93(1H), 8.83(1h) 1 .67(3h), 3.72(3h), 6. 33-6.67(2H ) , 6.87-7.60(7H), 8.80(1h) 2 . 3 0 ( 3 H) , 4 - 73(1H), 7.9311H) , 1.67(3h), 3.7 3(3h), 4.75(1H), 6.37-6.67(2H), 7.03-7.67(7tt), 7.90{1H) 8.83(1h) 1.67(3h), 3.70(3h), 4.73(1H), 6.33-6.62(2H), 7.00-7.70(6H), 7.87(1H), 8 . 88(1h) f r*> 232 5 1 6 -""•n Compounds No.

Table 1B (continued) IH Spectra (cm-1) NMR spectra (in CDCl^) 6 (ppm) (46B) 1755 1595 1320 1120 1080 1.63(3h), 4 . 70(1H), 6.60(1h), 7.57(2H), 8 . 7 7 (1 H) 3.67(3h), 6.40(1h), 6.97-7.30(7H), 7.93(2h), 1 5 (47B) 1740 1 320 I 595 II 20 1.67(3H), 4.75(1h), 6.67(1h), 7.63(2H), 8.80(1h) 3 - 7 2(3H), 6 . 4 5 (1 H) , 7.00-7.3 3(6h), 7 . 95(1H), ( 48B) 1740 T 595 1 . 67(3H), 3. 70(3H), 1 325 1 120 4. 75 (1H), 6, 45(IH), 6. 6 7 (1 H ) , 7. 00 -7. 33(6H), 7. 63(2H)r 7. 95(1H), 8. 82(1H) (49B) 1755 1 595 1 . 67(3H), 3. 70(3H), 1325 1 1 20 4. 73(1H ), 6. 4 5 (1 H) , 6. 65(1H), 7 ♦ 00 -7. 70(8H), 7. 97(1H ) , 8. 83 (1H) (50B) 1 730 1 580 1 . 65(3H), 3. 63(3H), 1 320 1 1 60 4. 63(1tf ) , 6. 23(1H), 11 20 6. 50(1H) , 6. 70 -7. (2H), 7. 1 5 (1 H ) , 7 . -7. 60(2H), 7. 70(1H), 7. 90 (1H) , 8. 1 0(1H) , 8. 70(1H) r ' 232518 •93- Table IB (continued) Compounds No.

IR Spectra (cm-1 ) NMR spectra (in CDCI3) 6 (ppm) ( 51 b) . j 1760 1600 1570 1320 1160 1 . 65(3H), 3.85(3h), 6.20-6.30(2h), 6.80(1h), 7.30-7.60(2H), 7.90(1h), 3 . 65(3H), 4.70(1h), 6.55(1h), 7.05(1h), 7.65(1h) , 8 . 1 0 (1 h) 1 5 (52B) 1750 1 590 1170 1 640 1 320 1 1 20 1.65(3h), 3.70(3h), 4.70(1H), 6.30-6.60(2H), 6.90-7.10(2H), 8.00(1H), 7-40-7.80(3H), 8.10(1H), 8.90(1h) , " "Hi (53B) 2s ( 54B) 1750 1 320 1125 1740 1320 1120 I 590 II 70 I 595 II 60 1 . 65(3H), 4.73(1h), 7 .1 0 (1 H) , 7 . 7 0 (1 H) , 8 .10-8.30(2H), 8.90(1H) 3 .70(3H), 6.30-6.70(2h), 7.50(1h), 7 . 90(1H), 8 . 60(1h), 1.70(3H), 2.55(3H), 4.75(1h), 7.00(1h), 7.70(1h)f 8. 90(1h ) 2 . 55{3H), 3 . 70(3H), 6.40-6.70(2H), 7 . 5 0 (1 H) , 8 . 00(1h), (55B) 1740 I 320 II 25 1 590 1 1 70 1.63(3h), 4.65{1H), 6.50(1h), 7.00-7.90(7H), 8.75(1h) 3.65I3H), 6 . 3 0 (1 h) , 6.90(1h), 7 . 9 5 (2 H ) , f : 232 5 1 8 Table 1B (continued) Compounds No.

IR Spectra (cm-1) NMR spectra (in CDCI3 6 (ppm) (56B) 1 740 1 590 1 . 65(3H), 3. 70(3H), 1 325 1 1 60 4. 73(1H), 6.30 -6. 70(2H), 1110 7. 05(1H ) , 7. 30 -7. 70(4H), 7. 90(1H), 8. 93(1 H) (57B) 1 750 1 600 1 . 65(3H), 3. 70(3H), 1 570 11 60 4. 65(1H), 6. (1 H), 1 1 25 6. 56(1H) , 6. 90 -7. 80(6H), 7. 90 <1M), 8. 76(1H) (50B) 1 740 1600 1 . 66(3H ) / 2. 50(3H), 1570 11 60 2. 53(3H), 3. 73(3H), 1120 4. 75(1H), 6. (1H ), 6. 56(1H), 7. 00(IH), 7. -7.50(1H), 8. 00(2H ) , 8. 90(1H) (59B) 1745 1590 1 . 67(3H), 3. 70(3H), 1320 11 60 4. 73(1H), 6. (1H ) , 11 20 6. 66(1H) , 6. 90 -7. (4H) , 7. 50-7.70(3H ) , 7. 90(1H), 8. 80(1H) (60B) 1730 1 580 1 . 65(3H), 3. 70(3H) , 1320 11 60 3. 90(3H), 4. 70(1H) , 11 20 6. -6.50(2H), 6. 66(1H) , 6. , 70-7.20(3H), 7. 90(1H), 7. , 30-7.70(3H), 8. 80(1H) 2325 U •95- Compounds No.

Table IB (continued ) IR Spectra (cm"1) NMR spectra (in CDCl^) 6 (ppm) (61 B) 1740 1600 1580 1160 11 20 1.66(3H) , 4.66(IH) , 6.60(1h ) , 6.90-7.20(2H) , 3 . 70(3H ) , 6 - 30(1H), 7 .00(1H), 7 . 40(1H), 7 . 6 5 (1 H) , 8. 80(IH) 8.00-8.20(2h), (62B) 1 5 1750 1605 1270 1215 1 090 1.60(3H), 4 . 6 7 (1 H ) , 6 . 5 5 (1 H) , 7.88(1H), 3 . 67(3H), 6.35(1h) , 6. 80-7. 67(9H) , 8.78(1h) (63B) (64B) 3300 1 720 1 320 3200 1 320 1080 2400 1 590 1080 1590 11 25 1.67(3h), 6.45-6.73(2H), 6.83-7.53(8H), 8.75(1H) 6.43-6 . 60(2h), 6.87-7.60(8H), 9.90(1h) 4 . 7 8 (1 H) , 7 . 70(1H), 7.87(1h), 7.72(1h ) , 8. 43(1H ) , (65B) 1750 1590 1320 1130 1125 1090 30 1.67(3h), 3.73(3h), 4.78(1H), 6.70-7.67(6H), 7.93-8.30(4B), 8.83(1H) /> 232 5 1 Table 1B (continued) Compounds No.

IR Spectra (cm-1) NMR spectra (in 6 (ppm) CDCI3) (66B) 1 760 1 590 3.75(3H), 4 . 58(2H), 1 490 1210 4.65(2H), 5.10- .43(2H >, .73-6.30(1H), 7.00(1H), 6.42-6.63(2H), 7 . 47(1 H) , 1 0 7.70-7.87(2H ) , 8 . 48(1H ) (67B) 1 755 1 590 1.23(3H), 4.20(2H ) , 1 490 1 210 4.57(2H), 5.08- .43(2H ) , 4.62{2H), 5.73- 6.27(1H), 6.40-6.63(2H), 7 . 00(1 H ) , 7.4 7(1H), 7.67- 7.85(2H) , 8. 4 7 (1 H) (68B) 1750 1590 3.75(3H) , 4.60(2H), 1 480 1 210 6 - 45-6 . 67(2H), 7 . 7 3 (1 H ) , 6.97-7.57(7H), 7.93(1H ) , 8.80(1H) (69B) 1750 1 590 1.25(3H), 4 . 23(2H ) , 1 490 1 210 4.5812H), 6.45- 6.67(2H), 7.. 96-7 . 57 ( 7H) , 7 .7 3 (1 H ) , 7.95(1H), 8 . 80(1H) (70B) 1740 1580 0.7-1.0(3H), 1 .0 '-1 .7(4H) , 1 490 1 240 1.60(3H), 4 .10(2H), 4.5-4.9(3H), 5.1 -5.5(2H), .7-6.3(1H), 6.45(1H), e.sooHj, 6.95(1H) , 7.45(1H), 7.70(1H) , 7 . 76(1H), 8.50(1H) ■97- Table 1B (continued) Compounds No.

IR Spectra (cm-1) NMR spectra (in CDCl^) 6 (ppm) (73B) 3300 1595 11 20 1 760 1 320 1080 0.7-1 .0(3 h) 3.70(3h), 6.45(1h), 7.00(1h), 7 . 70(1h), 8 . 53(1h ) , 1 . 0-2.3(8h ) , 4 . 65(1h), 6 . 50(1h), 7.50(1h) , 7 . 75(1h), 9.30(1h) (74B) (75b) 1740 1 490 3300 1590 11 20 1 590 1 21 5 0.7-1.0(3h), 1.0-1.7(4h), 1760 1325 1080 1.65(3h), 4.73(3h), 6.50(1h), 6.9-7.4(5h), 7 . 7 0 (1 h) , 8.80(1h) 3.70(3h ) , 6.45(1h), 7 . 00(1h) , 7.6-7.9(2h), 8.70(1h) 4.10(2h), 6 . 4 5 (1 h) , 7 . 00(1h), 7 . 45(1h), 7 . 9 3 (1 h) , 4.6 0(2H ) , 6 . 5 0 (1 h) , 7 . 50(1h ) , 8.50(1h), (77b) 3300 1590 11 20 1 760 1 320 1075 1.05(3h), 3 .70(3h), 6 . 4 5 (1 h) , 7.00(1h), 7 . 70(1h), 8.55(1h), 2.00(2h), 4.60{1 h) , 6.50(1h) , 7.45(1h), 7 . 75(1h), 9 . 40(1 h} f ' 232518 Table IB (continued) Compounds IR Spectra NMR spectra (in CDCl^) No. (cm" 1) 6 (ppm) (78b) 3300 1760 1.65(3h), 3 . 70(3h), 1 600 1 320 4.75(1h), 6.35 -6.73(2h) , 11 20 1080 7.05-7.70(4h), 8.55(1h), 9 . 3 ( 1 h ) (79b) 1 740 1600 1 .65(3h) , 2 . 50(3h), 1 580 11 65 3.70(3h), 4.76(1h), 11 25 6.40(1h), 6 . 55(1h), 7 -1 0 (1 h ) , 7 . 26(2h), 7 - 33(1h), 7 . 53(1h), 7, 7 5 (1 h) , 8.15(2h) (8 ob) 3100 1710 1 .66(3h), 3.70(6h ) , 1585 1505 4 . 7 5 (1 h ) , 6 - 52(1h ) , 1 480 1460 6.60(1h), 7.10(1h ) , 7.20(1h), 7. 26(2h), 7.55{1h) , 7 . 7 5 (1 h) , 8.20(2h), 8 . 60(1h), 8.80(1h) (81b) 1750 1600 3.7 0(3h), 4 . 82(1h), 1 495 1320 6 . 4 5 (1 h) , 6.55(1h) , 7.10(1h), 7.4 -8.0(12h) , 7.88(1h) , 8.90(1h), (82b) 1730 1 600 1 . 65(3h), 3 . 7 0(3h), 1 530 1 330 4.75(1h), 6.45(1h) , 6.55(1h), 7 .1 0 (1 h) , 7.4-8.0(6h), 8 . 9 3 (1 h) 232 5 1 8 Table IB (continued) Compounds No.

IR Spectra (cm"1) NMR spectra (in CDCl^) 6 (ppm) (83B) 1755 1 600 1 . 70(3H), 3.73I3H), 1525 1 490 4. 76(1H) , 6. 43-6.70(2H), 1 325 7. 00-7.80(6H) , 7 . 93{2H), 8. 95(1H) (84B) 1 760 1 730 1 . 65(3H), 2.50(3H), 1 600 1 560 3. 70(3H), 4 . 70(1H), 1 530 6. 4 3 ( 1 H ) , 6.60(1H), 6. -6.7(1H), 7 . 1 5 (1 H) , 7. 3-7.8(2H), 7.80(1H), 7. 97(1H ) , 8.90(1H) <85B) 1755 1600 1 . 63(3H), 3.70(3H), 1 490 1325 4 . 73 (IH), - 27(2H ) , 6. 38-6.63(2H) , 7.02(1H), 7. 38-7.83(5H) , 8.20(2H ) , 8. 57(1H) (86B) 1755 1585 1 . 67(3H), 3.75(3H), 1510 1 480 4. 80(1H) , 6 . 7 0 (1 H) , 1 4 60 6 . 83 (1 H) , 7.30(2H ) , 7. 97 (1H) , 8.03(1H ) , 8. (2H) , 8.25(1H) , 8. 90 (1 H ) (87B) 1 755 1 590 1 . 62(3H}, 3.70(3H), 1 495 1 4 60 4 . 76(1H), 6.6-7.3(6H) , 7. 95(1H), 8 . 1 0(1 H) , 8. (1H), 8•80(1H) 2325 1 8 -1 00- Compounds No.

Table IB (continued) IR Spectra (cm"1) NMR spectra (in CDCl^) 6 (ppm) (88B) 3300 I 595 II 20 1760 1320 1080 1 . 60(3h), 4 - 75(1 H) , 6 .75(1h), 7.95(1h), 8.45(1h), 3 - 70(3H), 6. 60(1h), 7 . 80(1H), 8 . 25(1H), 8.52(1h), (89B) 1 745 1 490 1 600 1 325 1.67(3h), 3.72(3h), 4.75(1H), 6.40-6.67(2H), 7.07(1H), 7.23-8.03(9H), 8.87(1H) (90B) 3300 1675 1500 1460 3200 1585 1 480 1 .53(3H), 6 . 67(1H), 7.2-7.7(4h) , 7.8-8.0(2H) , 8. 96(1H) 4.80(1h), 6.75(1h), 7 . 4 0 ( 2 H) , 8.25(2h); (91 B) 1755 1 490 1595 1230 1 .33 ( 9H) , 1.63(3H), 4.73(1H), 6. 40-6. 67 (2H), 6. 96-7.57 ( 6H), 7 - 75(1H) , 7-95(1H), 8.80(1H) (92B) 1 760 1 490 1 600 1 325 1.67(3h), 3.83(3H), 4.70(2h), 5.10-5.43(2H) 5.67-6.20(1H) 6.40-6.63(2H) 7.77(1H) 3.73(3h), 4.63(2H), 4.77(1h), 7.07(1h), 7.37(1h), 7.53(1h) , r) 232 5 1 Table IB (continued) Compounds No.

IR Spectra (cm"1) NMR spectra (in CDCl-j) 6 (ppm) , J (93B) (94B) (956) ( 9 6 B') ( 97B) 1735 1600 1510 1 325 1755 1 490 1750 1 590 1 490 1750 1 600 1 460 1 640 1590 1 490 1 600 1325 1735 1510 1 320 1710 1 500 1760 1615 1600 1495 1 460 1 . 63(3H), 3.88(3h), 6.40-6.6 3(2H), 7.00-7.73(6H), 3.70(3h), 4.77(1h), 8.13(2h) 1 . 25(3H) 3 . 6 8 ( 3 H) 4 . 20(2H) 4 . 70 (1 H) 7.03(1h) 7.50(1h) 1.27(3h) 3.80(3h) 4.5 5(2h) 6.35-6.62(2H) 7.33(IH) 7 . 7 2(1H) 1 . 6 8 ( 3 H ) 3 .72(6H) 6 . 40-6.70(2H) , 7.00-8.00(9H), 1 . 6 2 c 3 h ) 3 . 80(3h) 6.32(1h) 6 . 9 8 (1 h ) 7 . 43(1h) 7.87(3h) 1.65(3h) 4.70(1h) 6. 56 (1H) 7.20(2h) 7.70(1h) 8 . 73(1h) 3.67(2h), 4 .78(1H), 8.93(IH) 3 . 63(3H), 4.65(1h), 6 . 53(1H) , 7 .1 3 ( 2 H) , 7.70(1H), 8 . 7 0 (1 H) 3.70(3h), 6 . 3 3 (1 H ) , 7.03(1H), 7 • 5 0 ( 3 H) , 7.90(1H), 232 5 1 •3 Table IB (continued) Compounds No.

IR Spectra (cm-1 ) NMR spectra 6 (ppm) (in CDC13) (98B) 1 750 1 620 3.78(3H), 4.63(2H), 1600 1 500 6 . 4 5 (1 H) , 6 . 57(1 H) , 1 460 7 .1 0 (1 H ) , 7.23(2H), 7.50(1H), 7.75(1H), 7.88(1H), 8 .13(2H), 8.76(1H) (99 B) 1 760 1 61 0 1 .1 3(3H), 2.05(2H), 1 600 1 520 3.70(3H), 4.55(114), 1 500 6.35(1H), 6 . 56 (1 H) 7 . 1 0 (1 H ) , 7 . 2 3 { 2 H) , 7.50(1H ) , 7.73(1H), 7 . 87(1H ) , 8.12(2H), 8. 76 (1 H) (100B) 1740 1 600 0.7-1.2(3 H), 1.2-1 .7(6H) , 1 520 1 495 1 .7-2.3(2H), 3.70(3H), 1 460 4 . 57(1H ) , 6 . 33(1H), 7 . 07(1H), 7.25(1H), 7.50(1H), 7.73UH) , 7 . 90(1 H ) , 8.12(2H), 8.76 (1 H) (101B) 3200 1760 1.70(3H), 3.73(3H) , 1 600 1 540 4.86(1H), 6 . 5 0 (1 H) , 1 495 1 350 6 . 57(1H ) , 7.1 3(1H) , 1 320 1 255 7.53(1H), 7 . 7 5 (1 H) , 8.03(1H ) , 8 . 30(4H), 8.97(1H) ¥. ri 232 5 1 8 Compounds No. -1 03- Table 1B (continued) IR Spectra (cm-1) NMR spectra (in CDCI3) 6 (ppm) (102B) 3200 1 600 1 490 1 320 1765 1540 1350 1255 1-70(3H), 4.80(1h), 6.57(1h), 7.53(1 h) , 8 . 02(1h) 3.73(3h), 6.47(1h) , 7 .1 3 (1 H) , 7.75(1h), (103B) 1 5 3200 1 600 1 490 1320 1 760 1 540 1 350 1 260 1.65(3H), 4.75(1 h) , 6. 53(1H), 7. 4-7.8(3H), 8. 5 3 (1 H ), 8.85(1h ) 3.70(3h) , 6.46(1h ) , 7 . 1 0 (1 H) , 7.95(1h ) , 8 . 8 0 (1 h) , (1 0 4 B) (105B) 3200 1600 1320 3200 1 600 1 325 1 750 1 495 1250 1755 1495 1260 1 . 6 3 ( 3 H ) 4.80(1h) 6.58(1H) 7.10(2H) 7.73(1H) 8.20(1H) 1 .6 7(3h) 4.00(3H) 6 . 4 5 (1 H ) 7 .1 0 ( 1 H) 7.75(1h) 8.85(1H) 3.70(3h), 6.48(1h), 7.05(1h), 7.53(1H); 8 .10(2H), 8 . 95 (1 H) 3.75(3h), 4.80(1h), 6.53(1h), 7.50(1h), 7.95(1h), 232 5 1 8 Table 1B (continued) Compounds No.

IR Spectra (cm-1) NMR spectra (in CDCl^) 6 (ppm) (106B) o 3200 1 600 1 320 1 760 1590 1260 1 .63(3h ) , 4 . 7 5 (1 h) , 6.53(1h ) , 7 . 95(1h) , 8.80(1H) 3.73(3h), 6.40{1h), 7.0-8.0(8h), 8 .1 0 (1 h) , (107b) 1 5 (1088) (109B) 3050 1 600 1 430 1 320 3000 1600 1 495 1260 3000 1600 1 490 1 260 1755 1 590 1410 1260 1 750 1 525 1 320 1755 1 530 1 320 1 . 67(3h) 4.80(1h) 6.55(1h) 7.57(1h) 7.95(2h ) 8.85(2h) 1 .63(3h) 3.65(3h) 6 . 4 6 (1 h) 7 . 00(1h) 7.70(1h) 1 . 7 5 ( 3 h) 3 . 7 0 ( 3 h ) 6 . 43(1 h) 6.60(1h) 7.50(1h) 7.95(1h) 8 . 9 0 (1 h) 3.75(3h), 6.45(1h), 7 .1 0 (1 h ) , 7.77(1h), 8.05(1h), 8.97(1h) 2 - 60(3h), 4 . 80(1h) , 6 . 5 3 (1 h) , 7.4 5(2h), 8.25(4h) 3.05(6h), 4.77(1h), 6 . 5 0 (1 h) , 7.07(1h), 7 . 7 3 (1 h) , 8 .10(2h), 2325 1 8 -1 05- Table IB (continued) Compounds No.

IR Spectra (cm-1) NMR spectra (in CDCI3) (ppm) (110B) (111B) (112B) ! (113B) 3000 1 600 1 410 1 260 3020 1 600 1 430 1 320 3020 1750 1 490 1 405 1 260 3050 1 600 1 495 1 250 1 755 1 495 1 325 1 750 1 490 1 405 1 260 2220 1600 1 430 1320 1 750 1520 1 320 1 .75(3H) , 3.70(3H ) , 6.6-6.9(4H), 7.7-8.1(5H), 1 . 67(3H) 4.80(1H) 6 . 60(1H) 7.55(1H) 7.75(1H) 8.23(2H) 1 . 7 0 {3 H) 4.80(1H) 6 . 57(1H) 7.5Q(1H) 7 . 7 3 (2 H) 8.20(2H) 1 - 7 0 (3 H) 4 . 88(1H) 6.86(1H) 8 . 0 5 (1 H ) 8.30(4H) 3.1 -3.4(9H), 5.20(1H), 7 . 30(1H), 8.90(1H) 3.70(3H), 6.50(1H), 7.1 0 (1 H) , 7.70(2H), 8.05(1H), 8 . 9 5 (1H) 3 . 7 3{3H ) , 6 . 50(1H), 7 .1 0 (1 H ) , 7 .7 0 (1 H) , 8.03(1H), 8 . 9 5 (1 H) 3 . 77(3H) , 6.77(1H), 8.00(1H) , 8.25(1H ) , 9.00(1H) 2325 1 6 Table IB (continued) Compounds IR Spectra NMR spectra (in CDCI3) No. (cm" ') 6 (ppm) (1 1 4B) 3000 1 755 0.7-1.9(9H), 3.73(3H), 1 600 1 530 1.9-2.3(2H), 4 . 73(1H), 1 495 1 430 6.50(1H), 6.60(1H), 1410 1 320 7 . 2 0 (1 H) , 7.55(1 H) , 1 260 7.76(1H), 8.05(1H ), 8.30(4H), 9 . 00(1H) (115B) 3000 1 755 1.13(3H), 2 .1 0(2H), 1 600 1 530 3.73(3H), 4.70(1H ) , 1 495 1 430 6.50(1 H), 6.60(1H), 1 410 1 320 7 .1 5 (1 H) , 7 . 5 0 (1 H) , 1 260 7.73(1H), 8 . 0 0 (1 H) , 8 . 3 0 ( 4 H ), 8.95(1H) (116B) 2900 1765 3.80(3H), 4.70(2H) , 1600 1 530 6 . 5 3 (1 H ) , 6.60(1H), 1 495 1 460 7 .1 5 (1 H ) , 7 . 55(1H) , 1330 1 260 7 . 7 5 (1 H ) , 8.05(1H), 8 . 30(4H ) , 9 . 0 0 (1 H) (117B) 3050 1755 1 . 63(3H ), 3 . 70(3H), 1600 1 590 4.73(1H), 6 . 4 5 (1 H) , 1 430 1410 6 . 50(1H), 6.7-7 - 6(7H), 13 20 1260 7.70(2H), 8.55(1H) 232 5 1 8 -1 07- Compounds No.

Table IB (continued) IR Spectra (cm-1 ) NMR spectra (in CDCl^) 6 (ppm) (118B) •""N i (119B) {120B) (1 21B) (122B) (123B) 3300 1 600 1 490 3350 1 600 1 490 3350 1 600 1490 3400 1 600 1 4 90 3350 1 600 1 490 3350 1 600 1 490 1 740 1510 1 320 1 750 1510 1 320 1750 1510 1 320 1 740 1 510 1 320 1 740 1510 1 320 1 750 1510 1 320 1 .63(3H), 3.7 3(3H), 4.80(1H), 6.43-6.67(2H), 7.03-7.90(7H), 8.20(1H), 8.73(1H) 1.63(3H), 3.70(3H) , 4.77(1H), 6.43-6.67(2H), 7.03-7.90(8H), 8.17(1H), 8.77(1H) 1 . 65(3H) , 3.70(3H), 4.77(1H), 6.43-6.67(2H), 7.00-7.90{8H), 8.22(1H), 8 . 7 7 (1 H) 1 . 65(3H), 3.72(3H) , 4.77(1H), 6.42-6.65(2H), 6.83-7.92(8H), 8.18(1H), 8.77(1H) 1 . 67(3H), 3 . 73(3H), 4.82(1H), 6.47-6.67(2H), 7.05-8.27(8H), 8.63(1H), 8.77(1H) 1.67(3H), 3.70(3H), 4.77(1H), 6.40-6.67(2H), 7.03-7.90(8H), 8.13(1H), 8.77(1H) 232 5 1 8 Compounds No.

Table 1B (continued) IR Spectra (cm"1) NMR spectra (in CDCly 6 (ppm) (124B) 3100 1 680 1 320 1 260 1 760 1 600 1 490 1 . 6 3 ( 3 H) , 4.70(1H), 6 . 55(1H), 7 . 2-7.5(3H), 7.75(1H), 8.80(1H) 3 . 70(3H), 6.50(1H ) , 7 .1 0 (1 H) , 7.53(1H) , 7.95(1H), (125B) (12 6B) 3100 1 600 1 460 1310 31 00 1 600 1 460 1 320 1 750 1 500 1 400 1 260 1 760 1 500 1 4 00 1 260 1.63(3H) 4.73(1H) 6.47(1H) 6.90(1H) 7.53(1H) 7 . 95(1H) 1.65(3H) 3 . 73(3H) 4.93(1H) 6 . 53(1H) 7 . 1 0 ( 4 H) 7.86(1H) 8 . 0 0 (1 H) 8.83(1H) 3 . 70(3H), 4 . 80(2H), 6.55(1H) , 7.0-7.5(3H) , 7 . 7 7 (1 H) , 8 . 8 0 (1 H) 1 .77(3H) , 4.78(1H), 6.45(1H) , 6.93(1H), 7.56(1H), 7 . 9 5 (1 H) , 8.25(1H), (1 27B) 3000 1 600 1 430 1 260 1760 1 490 1 320 1 . 63(3H), 3.70(3H) , 6 . 4 6 (1H ) , 7 .1 0 (1 H) , 7 . 73(1H), 8 . 7 3 (1 H ) 2 . 20(3H), 4 • 76(1H), 6.53(1H), 7.50(1H), 7.95(1H), 2325 1 8 r*\ Compounds No. -1 09- Table IB (continued) IR Spectra (cm-1 ) NMR spectra (in CDCl^) 6 (ppm) (1 28B) j 3000 1 600 1485 1260 1760 1505 1 325 1 . 63(3H), 3 . 70(3H), 4.85(1H), 6.53(1H), 7 .1 0 (1 H) , 7.50(1H), 7 . 97(1H), 8.80(1H) 1.75(3H ) , 4.70(1H ) , 6 . 4 5 (1 H ) , 7 . 00(4H), , 9-7.5(2H), 7 . 80(1H), 8.40(1 H) , (129B) (130B) 3000 1760 1 495 1320 2900 1600 1 430 1 260 1 780 1600 1 430 1 260 1 760 1 490 1 320 W 1 . 37(3H) 3.70(3H) 4 . 75(1H) 6 . 5 3 (1 H) 7 . 50(1H) 7.95(IH) 0.6-1 .8(17H), 2 . 4 5 ( 2 H) , 4.75(1H ) , 6.53(1H), 7.50(1H), 7.95(1H), 1.63(3H) 4.30(2H) 6 . 45(1H) 7 ,1 0 (1H) 7.75(1H) 8 . 7 5 (1 H) 1.63 < 3H) 3.67(3H) 6.45(1H) 7 . 1 0 (1 H) 7.73(1H) 8.73(1H) (1 31 B) 3000 1 600 1440 1 260 1 760 1 500 1 320 1.63(3H), 3 . 70(3H), 6 . 3 0 (1 H) , 7 .1 0 (1 H) , 7 . 7 5 (1 H ) , 8.90(1H) 2.40(3H), 4 , 75(1H), 6.53(1H), 7.53(1H), 7.98(1H), 2325 18 -1 10- Compounds No.

Table 1B (continued) IR Spectra (cm-1) NMR spectra (in CDCl-j) 6 (ppm) (132B) 1 0 {133B) 1 5 (134B) 3100 1 760 1 600 1 460 1 270 3100 1 600 1 420 1 260 3350 1600 1490 2955 1 755 1 500 1320 1 760 1 500 1 320 1740 1510 1 320 1 .67(3H) 3.73(3H) 6.73(1H) 7.97(1H) 8.25(1H) 1.63(3H) 4.10(2H) 6.45(1H) 7 . 1 0 (1 H ) 7 . 73(2H) 1.03(3H) 1.65(3H) 3.73(3H) 6.07-6. 40(1'H) 6.43-6.68(2H) 7.76-7.90(2H) 2.20(3H), 4 .8 0 (1 H) , 6.80(1H), 8.03(1H) , 8.80(1H) 3.70(3H), 4.70(1H), 6.53(1H), 7 . 5 0 (1 H) , 8 - 5 0 (1 H) 1.23-1.70(4H), 3 . 3 6 ( 2 H)., 4 . 75(1 H) , 7 .1 0 (1 H) , 7 . 57(1H), 8.75(1H) (135B) ' S 3I 3400 1 600 1 320 1740 1 490 1.67(3H), 3.17-4.43(2H), 6.37-6.63(2H) , 6.77-7.70(7H), 3.70(3H), 4.73(1H), 8 . 03(1H), 8. 85(1H) f*y 232518 Compounds No.

Table IB (continued) IR Spectra (cm-1) NMR spectra (in CDCI3) 6 (ppm) (136B) (137B) 3350 1 660 1 490 3350 1 600 1 320 1 740 1 590 1 320 1750 1 490 1 .67{3H), 3.72(3H), 6.40-6.65(2H), 7.17-8.12(8H), 3.03(6H ) , 4.77(1H), 6.93(1H), 8.92(1H) 1 5 1.28(3H), 1.68(3H), 3.70(3H), 4.20(2H), 4 . 73(1H), 6.40-6 . 62( 2H), 6 - 97-7 - 70(6H), 7 .95-8.10(3H), 8.87(1H) (1 3813) 1 755 1 490 1 600 1 320 t . 65(3H), 4 . 7 5 (1 H) , 6.63(1H ) , 7.3-7.7(4H), 8.07(1H ) , 8.85 (IH) 3 . 7 0 ( 3 H) , 6.32(1H), 7 .1 0 (1 H') , 7.75(1 H) , 8. 10(2H), (139B) 1760 1 490 1 590 1 460 1.60(3H), 2.53(3H), 4 . 72 (1H) , 6.50(1H), 7.02(2H), 7.70(1H), 8.73(1H) 2 . 30(6H ) , 3.70(3H ) , 6 . 40 (1 H ) , 6 . 95(1 H) , 7.55(1H ) , 7 .8 0 (1 H ) , 232 5 1 8 -11 2- Table IB (continued) Compounds No.

IR Spectra (cm-1) NMR spectra (in CDCI3) 6 (ppm) (140B) 1 750 1610 1730 1 490 1.3 3(9H), 3.70(3H), 6.40-6.67(2H); 7.38-7.57(3H), 7.95-8.13(3H), 1.65(3H), 4.75(1H), 7.07(1H), 7.71(1H), 8. 90(1H) (1 41B) 3300 1 730 1 600 1760 1675 1.68(3H), 4.18(2H) , 6.40-6.63(2H), 7.25-8.17(7H), 8.90(1H) 3.71(3H), 4.76(1H), 7.08(1H ) , 8 . 60(1H), (1 4 2 S) 3350 1 740 1 595 1750 1 690 1.33(9H ), 3.71<3H), 6.40-6.63(2H), 7.25-7.73(5H), 8.95-8.13(39), 1.67(3H) , 4 . 7 6 (1 H ) , 7.08(1H) , 8.93(1H) (143B) 1760 1 490 1 600 1.65(3H), 4 . 7 5 (1 H) , 6.55(1H), 7.4-7.8(4H), 8 . 00(1H) , 8 . 9 5 (1 H) 3 . 70(3H), 6 . 45(1H), 7 .1 0 (1 H) , 7 . 95(1H) , 8.90(1H) , 2325 1 8 -11 3- Table IB (continued) Compounds No.

IR Spectra (cm"1 ) NMR spectra 6 (ppm) (in CDC13) (1 45B) 3300 1 740 1 . 60(3H ) , 2.30(3H), 1600 1 580 3.70(3H), 4.70(1 H) , 1 1 65 11 20 6. 4 5 (1 H ) , 6.50(1H) , 7 . 0 0 {1 H) , 7.40(1H), 7.45(1H), 7.70(1 H ) , 9.80(1H) (146B) 3300 1600 6.5-6.7(2H), 7. 1 -7.4(4H) , 1 580 1510 7.50(1H) , 7 . 75( 1 H ) , 1 480 8 . 22(2H) , 8. 53 (1 H ) , 9.40(1H) (147B) 3350 2250 1 .23(9H), 1.62(3H) , 1 750 1 690 3 . 70(3H), 4 . 75(1 H), 6.40-6.71(3H ) , 7-33-7.63(2H), 7. 08 (1 H ) , 7.70-7.90(2H), 8. 55 (1 H ) (1 48B) 2220 1750 1.65(3H), 3•70(3H), 1 600 1520 . 50(1H ) , 4.80(1H ) , 1 490 6 . 45 (1 H ) , 6.50(1H) , 7 .1 0 (1 H ) , 7. 3-7.7(4H), 8. 00(1H ) , 8.16(2H) 8. 93 (1 H) (149B) 3350 1 750 1 .60(3H), 3 .6 7(3H), 1680 1 600 4.68(1H), 6 .37 -6.55{2H) , 6.68-8.02CI0H) , 8 . 4 5 (1H ) 232518 -114.

Compounds No.

Table IB (continued) IR Spectra (cm-1) NMR spectra (in CDCl^) 6 (ppm) (150B) 3350 2200 1755 1600 1 490 1.60(3H), 3.70(3H), 4 . 6-5.0(3H), 5.3-5.6(1H), 6.3-6.7(3H), 7.00(1H), 7.50(1H) , 7.70(1H), 7.75(1H) , 8.80(1H) (1 51 B) 3350 1 735 1 490 1 750 1 600 1 320 1 .27(3H), 3.73(3H), 4 . 75(1H), 7.07(1H) , 1.63(3H), 4 . 22(2H), 6 . 27-6 . 77 ( 4H ) , 7.53(1H), 7.73-7.91(2H), 8.57(1H) (152B) 3350 1 750 1 600 1 320 2250 1730. 1 490 1 .63{3H) , 3.73(3H), 4.76(1H) , 6.40-6 . 63(3H), 7.43(1H) , 7.57(1H), 7.73-8.33(3H), 8.63(1H) (153B) (154B) 3350 1690 3350 1670 1320 17 50 1 600 1740 1 590 1.60(3H), 4 . 7 3 (1 H ) , 6.83(1H) , 8.37(1H) , 3.70(3H), 6.40-6.60(2H), 7.00-7.86(8H), 8. 53(1H) 1 . 73 (3H) , 3. 77 ( 3H) , .00(1H), 6.50-6.70(2H), 7.03-7.33(4H), 7.60(1H), 7.7 6(1H), 8.03-8.23(3H), 11 .53{1 H) 232 5 1 8 -1 15- Table IB (continued) Compounds IR Spectra NMR spectra (in CDCI3) No. (cm-1) 6 (ppm) (155B) 3350 1 670 1 320 1 750 1 600 1.30{3H), 3.80(3H), 4.60(2H), 6.53(1H), 7. 1 0 (1 H) , 7.75(1H) , 11 .03(1H) 1.77(3H), 4.25(2H), 4 . 95(IH), 6.60(IH) , 7.57(1H), 8. 1 3 (1 H ) , (156B) 3350 1670 1 490 1750 1600 1320 1.75(3H), 4.60(2H), 4 . 93(1H), 5.67-6.27(1 H), 6.55(1H), 7-53(1H), 8 .1 0 (1 H ) , 3.80(3H), 4.70(2H), 5. 10-5.40(2H), 6. 50{1H), 7.08(TH), 7 . 7 2'(1 H) , 11.00(1H) (26B/R-enantiomer) 1750 1510 11 25 1590 1320 1080 1.65(3H), 3.68(3H) , 4.73(1H), 6.37-6.63(2H), 6.97-7.70(5H), 7.78-8.18(3H), 8.78(1H) (2B/R-enantiomer) 3300 I 595 II 20 1 755 1 320 1 080 1.62(3H), 3.70(3H), 4.72(1H), 6.40-6.63(2H), 7.00(1H ), 7.4 7(1H), 7.63-7.80(2H), 8.50(1H), 8 . 93(1H ) 1 f 232 5 1 8 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 5 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 1 C. seeds of plants were sown in the soil, and after germination, cultivated for 2 to 3 weeks.

The prepared solution was applied to these plants at the rate of application indicated in Table 1C. Thereafter, w' the plants were continued to be cultivated for 3 weeks without applying the above solution. The results are given in Table 1 C. ""t TEST EXAMPLE 2C Seeds of plants to be tested were sown in the soilf and on the second day after sowing, were treated as follows and the growth of the plants was obseirved 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 2325 1 8 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 2325 Ii Compound Table 1C Rate of Application Plants No. (kg/ha) a b c d e f g h i j k (1 B) 0.5 2 1 1 2 1 1 4 1 1 0 (2B) 0.5 4 2 2 3 0 0.1 25 3 1 1 2 4 3 4 3 1 0 (3B) 0.5 2 2 2 3 3 1 0.1 25 2 2 2 2 3 1 0 C5B) 0.5 3 2 3 4 2 3 0 (6B) 0.5 2 1 1 4 4 3 3 1 (7B) 0.5 2 2 1 2 3 3 3 0 (8B) 0.5 2 1 1 3 3 4 2 1 1 5 (1 1B) 0.5 3 3 4 1 0.1 25 2 2 2 4 3 3 0 (12B) 0.5 4 3 3 4 4 0 0.125 1 1 1 3 2 3 4 3 0 (13B) 0.5 2 1 1 4 2 2 3 0 0.125 1 1 1 2 2 1 3 1 3 0 (1 4B) 0.5 4- 3 4 4 4 1 0.125 3 2 3 4 3 1 (15B) 0.5 3 1 2 4 4 3 2 0 0.125 1 1 1 4 3 4 3 2 1 0 (1 6B) 0.5 1 1 1 4 3 3 2 4 1 0.125 1 1 1 2 2 3 2 2 1 0 (1 7B) 0.5 2 1 1 4 3 3 3 2 0 (18B) 0.5 1 1 1 2 1 2 4 3 3 2 0 (19B) 0.5 4 4 4 4 3 3 2 0.125 3 2 3 4 3 2 3 3 1 (20B) 0.5 0.125 4 4 3 0. 031 4 1 3 4 4 2 (21 B) 0.5 0.125 4 4 2 0. 031 3 2 3 3 4 1 2325 1 8 Table 1C (continued) Rate of Compound Application Plants No. (kg/ha) a b c d e f g h i j k (22B) 0.5 4 0.1 25 3 4 '5 4 0.031 3 1 1 4 3 2 (23B) 0.5 4 0.1 25 4 2 4 4 3 0.031 2 1 1 4 4 2 1 (24B) 0.5 0.125 4 4 3 0.031 2 1 2 4 2 (25B) 0.5 0.125 3 4 0.031 2 1 1 3 3 4 3 2 (26B) 0.5 0.125 0.031 -3 2 4 4 4 (26B/R- 0.125 enantiomer) 0.04 4 ( 2 7 B) 0.5 0.125 2 4 0.031 3 1 3 4 3 4 3 (28B) 0.5 0.125 2 3 4 4 3 0.031 2 2 2 1 3 3 3 1 (29B) 0.5 0.125 2 4 2 0.031 2 1 1 3 3 2 4 1 (30B) 0.5 4 0.125 4 2 3 4 3 0.031 3 1 2 4 4 1 (31 B) 0.5 0.125 4 2 4 4 k 3 2 1 3 1 0 4 3 0 2 0 0 2 2 1 0 0 0 0 0 3 0 3 0 2 0 3 0 232 5 1 8 •1 20- Table 1C (continued) Compound Rate of Application Plants No. (kg/ha) a b c d e f g h i j ( 32B) 0.5 0.1 25 4 3 4 0.031 3 1 3 2 4 3 4 (33B) 0.5 4 0.1 25 4 2 3 4 4 0.031 2 1 1 4 4 2 (34B) 0.5 4 0.1 25 4 2 4 4 0.031 3 1 2 4 3 4 (35B) 0.5 4 0.125 3 1 4 4 4 0.031 1 1 1 2 3 4 3 (36B) 0.5 0.125 4 3 4 4 0. 031 1 1 3 2 4 4 (37B) 0.5 - 0.125 2 0. 031 3 1 3 ( 38 B) 0.5 0 0 0 1 1 1 3 2 1 {39B) 0.5 0 0 0 1 1 1 3 1 1 (4 OB) 0.5 0 0 0 1 1 1 3 1 ( 41 B) 0.5 0 0 0 1 1 1 1 1 (43B) 0.5 1 0 0 1 1 1 3 1 1 ( 46B) 0.5 2 3 3 4 2 3 0.125 1 1 2 1 1 1 1 2 3 (47B) 0.5 3 1 2 3 2 3 3 0.125 1 1 1 1 2 2 1 1 2 (48B) 0.5 2 1 1 2 3 3 0.1 25 1 1 1 1 1 1 4 3 1 1 (49B) 0.5 2 2 2 2 2 2 3 0.1 25 1 1 1 1 1 1 4 3 1 1 1 0 2325 18 -1 21 - Table 1C (continued) ""•n Compound Rate of Application Plants No. (kg/ha) a b c d e f 9 h i j k (SOB) 0.5 0. 1 25 4 4 3 0.031 3 1 3 4 4 3 (51 B) 0.5 3 3 4 3 0.125 2 3 4 1 0. 031 2 1 1 4 3 3 » 1 0 ( 52B) 0.5 0.125 4 4 3 0. 031 3 2 4 3 4 3 2 1 5 (53B) 0.5 4 0.125 4 4 4 4 4 2 0-031 3 1 3 3 4 3 0 (54B) 0.5 4 0.1 25 1 3 4 4 2 0.031 3 1 3 4 4 1 (55B) 0.5 4 4 0.1 25 3 4 2 0.031 3 1 2 3 4 4 4 0 (56B) 0.5 4 4 2 0.1 25 4 2 3 4 2 •0.031 3 1 1 4 4 3 0 (59B) 0-5 2 1 1 3 1 3 4 3 0 0.125 1 1 1 2 1 1 1 1 2 0 (60B) 0.5 2 1 1 1 3 3 4 1 3 1 0.125 1 1 1 1 1 1 1 1 1 0 (61 B) 0.5 0 0 0 1 1 1 4 1 1 0 (63B) 0.5 3 4 3 0.125 2 1 2 1 0.031 1 1 1 4 4 4 4 0 (65B) 0.5 3 4 3 4 0 0.1 25 2 2 1 1 1 2 3 0 232 5 1 8 N Table 1C (continued) ■> Compound Rate of Application Plants No. (kg/ha) a b c d e f g h i j k (66B) 0.5 3 1 3 1 4 0 0.1 25 2 1 1 2 1 2 3 0 0.031 1 1 1 1 1 4 1 3 1 0 (67B) 0.5 3 1 1 1 3 1 0 0.125 1 1 1 3 2 1 2 1 0 ( 68B) 0.5 4 3 4 1 0.1 25 3 1 1 4 2 3 1 0.031 2 1 1 4 1 2 2 0 (69B) 0.5 3 4 4 4 0 0.1 25 3 1 3 2 2 4 0 0.031 1 1 1 2 2 1 3 0 (70B) 0.5 4 4 4 0 0.125 2 1 1 2 1 0 (74B) 0,5 4 4 1 2 0 0.125 3 1 2 1 0.031 1- 1 1 2 1 1 1 2 1 (79B) 0.5 0 0 0 1 1 1 4 1 1 0 (BOB) 0-5 3 3 3 3 1 0.1 25 2 0 0 1 4 0 0.031 0 0 0 1 1 3 1 2 0 (81 B) 0.5 1 1 1 1 1 3 3 0 0.125 0 0 0 1 4 0 2 3 0 (82B) 0.125 (83B) 0.125 4 (84B) 0.5 3 4 1 (&5B) 0.5 2 0 2 2 3 4 2 1 0 (86B) 0.5 4 1 0.125 4 4 4 4 1 0 1 4 2 2 0 0 0 3 0 0 1 1 1 1 4 1 2 1 0 1 0 3 1 232 5 -1 23- Table 1C (continued) Compound Rate of Application Plants No. (kg/ha) a b c d e f g h i (87B) 0.5 0.1 25 4 4 (88B) 0.1 25 1 0 0 0 0 0 1 1 (89B) 0.125 4 3 4 OOB) 0.125 3 3 2 (91 B) 0.125 3 3 1 0.031 4 3 3 1 4 ( 92B) 1 . 0 0 0 0 1 0 1 3 2 0 (93B) 1 .0 0 0 0 2 2 2 (94B) 1 .0 0 0 0 0 0 1 3 1 1 (95B) 0.5 0.125 4 3 0.031 2 1 1 3 3 (96B) 0.062 3 4 0.01 6 3 3 4 1 3 4 ( 97B) 0.062 - 3 2 2 0.01 6 3 2 1 1 3 3 (98B) 0.5 4 (99B) 0.5 (1OOB) 0.5 3 1 1 (101 B) 0.125 4 2 4" 4 0.031 2 2 2 1 (102B) 0.5 4 0.125 4 3 3 4 (103B) 0.5 4 0.1 25 3 3 3 4 0.031 1 0 1 4 0 3 (104B) 0.5 0.125 3 0.031 4 1 1 1 3 1 0 1 5 2 0 232518 -1 24- Table 1C (continued) Rate of Plants No. (kg/ha) a b c d e f g h i j k (1 0 5 B) 0.5 4 0.1 25 4 4 3 0.031 1 0 2 3 4 3 4 1 (1 0 6 B) 0.125 3 2 1 1 1 1 0 0.031 2 1 1 1 4 3 1 (107B) 0.125 4 2 3 4 1 0.031 2 1 2 3 0 4 3 3 1 (108B) 0.125 2 1 1 2 0 1 2 0 1 0 (1 09B) 0.125 3 1 1 5 (11 OB) 0.1 25 4 4 3 0.031 4 3 3 4 4 3 (1 1 IB) 0.125 2 2 2 4 1 0.031 1 0 1 1 1 1 0 (112B) 0.125 2 0.031 2 2 1 2 4 2 3 2 (113B) 0.125 4- 4 2 1 3 4 4 1 0.031 3 3 1 3 1 2 3 2 3 1 (114B) 0.1 25 1 0 0 3 1 3 3 3 1 (115B) 0.125 3 4 4 0. 031 2 0 2 3 2 1 (11 6B) 0.1 25 2 2 3 3 4 (117B) 0-5 1 0 0 1 4 1 0.031 0 0 0 2 0 2 3 2 0 0 0 (118B) 0.5 3 1 0.1 25 3 1 4 4 0 0.062 1 1 4 2 4 4 2 1 (119B) 0.5 3 1 0.125 3 4 0 (12 OB) 0.5 3 3 4 2 0.125 4 1 2 1 2325 1 8 -1 25- Table 1C (continued) •'-H. J Compound Rate of Application Plants NO. (kg/ha) a b c d e f g h i j k (121B) 0.5 3 0 0.1 25 2 0 (122B) 0.5 4 3 0.125 3 2 (123B) 0.5 4 2 0.125 2 2 3 1 (124B) 0.062 4 4 4 3 1 (125B) 0.5 3 3 0.125 4 1 4 0 (126B) 0.5 4 0.125 4 3 3 4 3 3 0.031 3 1 2 2 3 1 C127B) 0.5 4 3 0.1 25 4 4 2 0.031 1 0 1 1 4 2 4 1 (128B) 0.1 25 - 1 2 1 4 4 1 0.031 3 1 1 3 0 3 1 4 1 (129B) 0.1 25 2 3 4 1 0.031 3 0 1 0 4 4 T (130B) 0.125 4 2 4 1 (131B) 0.1 25 3 2 0.031 3 0 1 3 1 3 3 0 (13 2B 0.125 3 4 3 3 0 1 3 3 3 2 (133B) 0.5 0 0 2 2 1 0 0.031 0 0 0 0 0 1 2 3 0 0 0 (134B) 0.5 4 4 0.1 25 2 2 2 (135B) 0.5 0.1 25 4 3 3 0.031 2 2 2 4 0 2325 18 -1 26- Table 1C (continued) •"~s ■ -"i k1f -M."' Compound Rate of Application Plants No. (kg/ha) a b c d e f g h i 3 k (136B) 0.1 25 3 3 2 0.031 1 2 3 1 4 2 (137B) 0.1 25 3 4 0.031 3 2 3 1 4 4 2 (138B) 0.1 25 4 2 4 2 (139B) 0.5 4 0.1 25 3 3 1 (140B) 0.1 25 4 4 0.031 4 3 4 4 3 {141B) 0.1 25 4 4 4 3 0.031 3 2 3 4 3 4 3 (142B) 0.1 25 4 1 0.031 4 3 3 2 4 3 0 H43B) 0.5 . 0.1 25 2 3 4 (1 47B.) 0.125 2- 1 2 3 1 4 4 1 0.031 1 1 1 2 1 3 2 0 (148B) 0.1 25 3 2 3 4 4 4 0.031 1 0 0 1 4 4 0 (149B) 0.5 2 2 2 4 0 0.1 25 1 1 1 1 3 1 3 0 0.031 1 0 0 1 2 4 4 0 0 0 (150B) 0.1 25 1 0 1 3 4 2 1 (1 51B) 0.1 25 2 1 1 4 1 4 1 3 0 0.031 1 1 1 2 1 3 1 0 0 (152B) 0.1 25 1 1 1 3 1 3 1 2 0 0.031 1 0 1 3 1 3 3 1 1 0 (153B) 0 .1 25 2 1 2 2 1 4 2 0 0.031 1 0 0 3 1 2 4 1 1 0 2325 Ii -1 27- Table 2C .""*N 1 , „,/J .

Rate of Compound application Plants NO. (kg/ha) a b c e f g h i j k (2B) 2.0 4 3 2 4 4 0 0 0.5 3 1 2 4 2 1 0 0 (1 IB) 2.0 0 0 0.5 4 3 3 2 1 0 0 (20B) 2.0 4 0 0 0.5 4 3 3 4 2 0 0 (21 B) 2.0 0 0 0.5 4 0 0 (26B) 2.0 0 0 0.5 4 0 0 2325 1 8 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 5 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. 10 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-15 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 20 m: Cossia obtusifolia ' '*") n: Sida spinosa o: Ambrosia artemisiaefolia var. elator p: Datula stramonium q: Avena fatua 25 r: Agropyron repens s: Amaranthus lividus t: Panicum texanum G O o o -1 29- Table 3C Rate of Compound Days After Plants No. (kg/ha) Treatment 1 m n o P q r s t Test 3 0 0 0 0 0 0 0 0 0 comparative (117) 0.5 7 0 0 0 0 0 i 2 3 2 example 1C 1 4 1 1 1 0 0 2 3 3 4 Test 3 0 0 0 0 0 0 0 0 0 comparative (117) 0.375 7 0 0 0 0 0 1 1 2 1 example 2C 1 4 1 1 0 0 0 1 2 2 3 Test (117) 0-375 3 4 2 4 4 4 2 1 3 2 example 3C 7 4 3 4 4 3 3 4 3 (1TB) 0.125 1 4 4 4 3 4 4 Test 3 3 1 3 3 3 1 1 2 1 example 4C (11 B ) 0.1 25 7 3 2 4 4 4 1 1 3 1 1 4 4 2 1 1 3 1 Test (117) 0.375 3 4 4 4 3 3 4 4 example 5C 7 4 ( 20B) 0.1 25 1 4 OJ rv> (jn CO 0 -1 30- Table 3C (continued) Rate of Days Compound Application After Plants no. (kg/ha) Treatment lmnopqrst Test 3 423442333 example 6C (20B) 0.125 7 554553354 14 555554354 I ro CM ro arc CO 2325 1 8 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 5 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 4C. 10 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-15 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 20 two types o.f herbicidal compounds indicated above exhibit herbicidal activity earlier and thus have better quick-acting efficacy than the N-phosphonomethylglycine derivatives alone.

In contrast, the compositions of this invention, for 25 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-phosphonomethylglycine derivative, the herbicidal composition of this invention surprisingly showed increased quick-acting effica-30 cy and a broadened herbicidal spectrum at low application rate as the synergistic effect of the combined use. -1 32- Table 4C Compound Rate of Days Application After Plants No. (kg/ha) Treatment a b c d e f 9 h i Test 3 0 0 0 0 0 0 0 0 0 comparative (117) 0.5 7 1 0 1 1 0 1 0 0 1 example 3C 1 4 4 4 4 4 2 4 1 1 4 Test 3 0 0 0 0 0 0 0 0 0 comparative (117) 0.375 7 1 0 1 0 0 1 0 0 1 example 4C ■ 1 4 3 4 4 0 2 4 1 1 4 Test (117) 0.375 3 4 2 4 4 3 3 4 4 4 example 7C 7 4 4 (1 01 B) 0.1 25 1 4 4 Test 3 3 2 4 4 3 2 4 4 4 example 8C (1 01B) 0.1 25 7 4 3 4 3 3 1 4 4 3 4 4 Test (117) 0. 375 3 4 2 4 4 2 3 4 4 4 example 9C 7 4 3 4 2 3 (127B) 0.125 1 4 4 ro 04 ro en oo -1 33- Table 4C (continued) Compound No.

Test example 1OC Test example 11C Test example 12C Test example 1 3C Test example 1 4C Rate of Application (kg/ha) Days After Treatment Plants f 9 (1 27B) (117) (129B) (129B) (117) (26B) ( 26B) 0.125 0 . 375 0.125 0.125 0.375 0.125 0.1 25 3 7 1 4 3 7 1 4 3 7 1 4 3 7 1 4 3 7 1 4 3 2 3 4 3 4 4 3 4 4 3 4 4 3 5 4 5 4 2 3 4 3 4 4 3 4 4 4 4 5 4 4 4 3 3 4 4 4 4 4 5 4 5 4 5 4 5 4 5 4 5 1 1 4 1 1 4 5 4 4 4 4 3 4 4 2 2 4 2 2 4 4 5 3 4 4 5 4 5 4 5 4 5 3 5 5 4 5 4 5 4 5 4 5 4 5 4 5 4 5 4 5 4 5 4 5 ro CM ro CJl 2325 1 8 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 5 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 cmand the herbi-15 cidal activity was examined.

The results 3 weeks after treatment are shown in Table 5C. 232518 -1 35- Table 5C Rate of Compound Application Plants No. (kg/ha) abcdefghi Test ^ comparative Atrazine 0.5 100105551 w' example 5C 1 0 Test comparative Atrazine 0.25 000001050 example 6C Test Atrazine 0.5 555555555 example 15C (26B) 0.125 Test Atrazine 0.25 555555555 example 16C (26B) 0.125 232 5 1 8 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 cm2, and the herbicidal activity was examined.

The results are shown in Table 6C.

Test compartive example 7C Test compartive example 8C Test example 17C Test example 18C Rate of Compound Application No. (kg/ha) (500) (500) (500) (26B) (500) ( 26B) 0. 25 0.125 0.25 0.125 0.125 G. 1 25 O O 3 Table 6C Days After Plants Treatment abcdefghi 3 1 1 1 1 0 1 0 0 0 7 3 3 2 3 1 4 2 2 2 1 4 4 4 2 3 1 2 4 4 3 1 1 1 1 0 1 0 0 0 7 3 3 2 1 1 4 2 2 2 1 4 4 4 2 1 1 4 2 3 3 3 7 1 4 4 5 2 4 4 5 4 5 3 4 3 5 5 4 5 4 5 4 5 3 7 1 4 4 3 4 4 3 5 4 5 4 5 3 4 3 5 5 4 4 4 5 5 4 5 ro 04 ro cn CO 2325 1 8 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 5 N-phosphonomethylglycine derivatives alone.

The N-phosphonomethylglycine derivatives, used alone, part icularly 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 10 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 15 applying a combination of the oxime derivative and N-phosphonomethylglycine derivative, the herbicidal composition of this invention surprisingly showed increased quick-acting efficacy and a broadened herbicidal spectrum at low application rate as the synergistic effect of the combined use. 2.0 When Compound (500) was used alone, the herbicidal activity of the compound was low against broad-leaved weeds y Such as Chenopodium album vars centrorubrum, Amaranthus viridis or Abutilon theophrasti in low application rates, as shown in Table 6C. On the contrary, the herbicidal composi-25 tion of this invention overcomes these defects and has "*'■> sufficient herbicidal activity.

L.J 232 5 1 8 o

Claims (14)

WHAT WE CLAIM IS:
1. ' 1. Oxime derivatives of formula (I) Y 5 x-^~^-q-^~^-cr1 =n-q-q-r2 (i) or3 wherein X and Y are identical or different and each represents a hydrogen atom, a halogen atom, -CFg, or an alkyl 10 group having 1 to 5 carbon atoms; Z is =CH- or =N-; R1 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; 15 R2 represents a group selected from the following groups shown in a) to g): a) hydrogen atom: b) a saturated or unsaturated aliphatic hydrocarbon group having 1 to ~10 carbon atoms which may be 20 optionally substituted by the following substituents: J slabstituents: i) a halogen atom; ii) a hydroxyl group; iii) an alkoxy group having 1 to 5 25 carbon atoms; iv) -COR4; * wherein R^ is a hydroxyl group, an alkyl group having 1 to 5 carbon atoms which may be substituted by a halogen 30 atom, a phenyl group which may be substituted by a halogen atom, an alkoxy group having 1 to 5 carbon atoms, a alkenyloxy group having 1 to 5 carbon atoms or a group of the ■iC. . 15 8 - 1 40 -formula / ; "N ^ fi R in which 5 and R^ are identical or different and each represents a hydrogen atom or an alkyl group having 1 to 5 carbon ,^5 atoms; v-) a phenyl group; 10 wherein the phenyl group may be substi tuted by a halogen atom, a hydroxyl group, -CF^, -NO2, -CN, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, -COR^ 15 or R5 / "N\ 6 tu ; JR vi) a phenoxy group..wherein-R^ and Rfi-nro ac rlrfinrrt nhnvrii wherein the phenoxy group may be substituted by the groups cited in v) or by phenyl, phenoxy or pyridyloxy .groups (wherein the phenyl, phenoxy or pyridyloxy groups may be substituted by halogen atom or -CF^) W 25 vii) ^R5 -N V wherein is as defined above and R? is a hydrogen atom, an alkyl group having 1 to 5 carbon 30 atoms or -COR^ wherein R^is as defined above; or viii) -CN; c) an alkoxy group which may be substituted by the following substituents: substituents: i) a halogen atom; or ii) a phenyl group (wherein the j^hepyl % v T* /<■ \s r f) ft .. t'< ' O O 7 r; 1 q /jijio - 141 - 10 -15 20 25 30 group may be substituted by substituents 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; iii) -CF^; iv) v) vi) -no2 -CN; an alkyl group having 1 to 5 carbon atoms; vii) an alkoxy group having 1 to 5 carbon atoms; viii) -COR wherein R4 is as defined above* n5 IX -N ✓- r7 wherein R5 and R'7 are as defined above x) -N+R5R6R8 wherein R^ and R6 are as defined above and R8 is an alkyl group having 1 to 5 carbon atoms; xi) a phenyl group wherein the phenyl group may be substituted by the substituents v) in b); xii) a phenoxy group wherein the phenoxy group may be substituted by the substituents vi) in b) ; or xiii) -CH2COR4 wherein R4 is as defined above; f) an aromatic heterocyclic group containing^. St" least one nitrogen atom having 3 to 20 carbon atoms -;1,, t3 OCT V792 Q 732518 - 142 - o which may be substituted by the following substituents: substituents: the same substituents as shown in e) ; and 10 1 5 20 g) r- -n / \ r" wherein R^is as defined above and R9 is b), e) or f); RJ is a hydrogen atom ; or an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted by a halogen atom, a hydroxyl group, an alkoxy group, -COR4 or 0 n 0 ii -CNH-P-OR 10 I OR 11 wherein R10 and R11 are identical or different and represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a phenyl group; and Q represents a direct bond, 0 S n it -C —, or -C- 25 wherein in case that Q is a direct bond, R^ is not c), d) or g ) ; and their salts. .q;"v. 'I Vi i : 113 OCT 1992 ' | f ■ _JX_ tfi -'V'l I ■' ?325 i 8 1 43
2. A herbicidal composition comprising a herbicidally effective amount of compound of claim 1 and at least one 10 component selected from the group composed of additives, carriers, and pesticides and other herbicidal agents.
3. 3. A herbicidal composition comprising a herbicidally effective amount of a compound of claim 1 as an active *15 ingredient, and a carrier and/or a surfactant.
4. 4. A process for producing a herbicidal composition characterized in that a compound of claim 1 is mixed with at 20 least one component selected from the group composed of additives, carriers, and pesticides and other herbicidal agents
5. 5. A herbicidal composition comprising as a herbicidal ingredient a combination of herbicidally effective amounts 25 of a compound of claim 1 and an N-phosphonomethylglycine derivative of formula (III) O r21 -P-CH2-NHCH2-COR 23 (III) 30 wherein R2^ and R22 are identical or different, and each represents a hydroxyl group or -OR24 and R23 is a hydroxyl group, -OR24 or /r25 -N o ?3251 - 144 - '~N wherein . R24 represents an alkyl group having 1 to 5 carbon atoms, a cyclohexyl group, a haloalkyl group having 1 5 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon-atoms or an alkoxyalkyl, haloalkoxyalkyl or alkoxyalkoxyalkyl group (herein each of the alkoxy, haloalkoxy and alkyl groups has 1 to 5 carbon atoms) or a phenoxy group; and 10 R2-* and R2^ 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 or, an alkenyl group having 2 to 5 carbon atoms, or R2^ and R2^, together with the nitrogen atom to which "15 they are attached, can form a morpholino group, a piperidino group or a pyrrolidino group, and/or a glufosinate compound of formula (IV) 0 R31 CH3-P-(-CH2-)2-C-COR32 (IV) 20 OH NH2 wherein R3"1 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and •R32 represents -OH, -NH2, -NHNH2/ -NHCgH^ or an alkoxy 25 group having 1 to 12 carbon atoms which may be substi- tuted by -OH, or an acid addition salt or a salt with a base, and a carrier and/or a surfactant. /'J? *"r 0%. J " > O "2 1 SEP 1992 v - 1 45 - Process for preparing oxime derivatives represented by the following formula (I) Y X »-CR1 =N-0-Q-R2 (I) wherein X and Y are identical or different and each represents a hydrogen atom, a halogen atom, -CF-j, or an alkyl group having 1 to 5 carbon atoms; Z is =CH- or =N-; 1 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; R2 represents a group selected from the following groups shown in a) to g): ' a) hydrogen atom: b) a saturated or unsaturated aliphatic hydrocarbon 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) -COR4; 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 substituted by a halogen atom, an alkoxy group having 1 to 5 carbon atoms, a alkenyloxy group having 1 to 5 carbon atoms or a group of^the/ .. ?325i 8 - 14 6 - formula R-* _ / -N j \ c. R° in which R** and R® are identical or different 5 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- 10 tuted by a halogen atom, a hydroxyl group, -CF^, -N°2' -CN, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, -COR^ or R5 / 15 -N N R6 ; vi) a phenoxy group; wherein the phenoxy group may be substituted by the groups cited in 20 v) or by phenyl, phenoxy or pyridyloxy groups (wherein the phenyl, phenoxy or pyridyloxy groups may be substituted by halogen atom or -CF^) vii) R5 / ■ 25 -N \ 7 £&% R' wherein R7 is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or -COR4; or 30 viii) -CN; c) an alkoxy group which may be substituted by the following substituents: substituents: i) a halogen atom; or ii) a phenyl group (wherein the phenyl 232518 - 147 10 group may be substituted by substituents 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; iii) -CF2 iv) v) vi) -no2 -cn; 15 an alkyl group having 1 to 5 carbon atoms; vii) an alkoxy group having 1 to 5 carbon atoms; viii)-COR4; 20 ix) x) ~n r
6. 7 . -N+R5R6R8 ,8 25 30 wherein R° is an alkyl group having 1 to 5 carbon atoms; xi) a phenyl group wherein the phenyl group may be substituted by the substituents v) in b); xii) a phenoxy group wherein the phenoxy group may be substituted by the substituents vi) b) ; or xiii)-CH2COR4; f) an aromatic heterocyclic group containing at least one nitrogen atom having 3 to 20 car m h 24 J.u "7 -148- which may be substituted by the following substituents: substituents: the same substituents as shown in e); and g) ^ R5 5 -N ^ 9 R wherein is b), e) or f); R3 is a hydrogen atom ; or an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substi-10 tuted by a halogen atom, a hydroxyl group, an alkoxy group, -COR4 or 0 0 -CNH-P-OR10 OR11 15 wherein R10 and R11 are identical or different and represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a phenyl group; and O S ii m Q represents a direct bond, -C-,or-C- 20 wherein in case that Q is a direct bond, R is not c) , d) or g); or their salts characterized by 25 (A) converting the compound of formula (V) into the compound of formula (X) according to the following reaction scheme: 232518 - 149 - (I) or (B) converting the compound of formula (V) into the compound of formula (I) according to the following reaction scheme: ?325)8 - 150 - (C) by starting with the reaction between the compounds of formula (VIII) and formula (IX) and converting the product of formula (X) into the compounds of formula (I) according to the following reaction scheme: (I) or (D) by starting with the reaction between the compounds of formula (VIII) and formula (IX) and converting the product of formula (X) into the compounds (I) according to the following reaction scheme: 232518 -151 - (I) or (EJ converting the compound of formula (X) into the desired compound of formula (I) according to the following scheme: 232518 - O - 152 - (F) by converting the compound of formula (XII) into the desired compound of formula (I) according to the following reaction scheme: y ^ x-/~^)-o-/~~\-£-ci + h2n-o-q-r2 2 V OR3 (XII) /f~A 7 CH2N2 X_f \> -C=N-0-Q-R^ ^=-Z (XIII) OR3 X-^-0-Q-6--NW2 OR3 is?,*S or ;xiv) (G) converting the compound of formula (VII) into the compound of formula (XV) according to the following reaction scheme: ?325i8 - 153 - (H) converting the compound of formula (VII) into the compound of formula (XVI) according to the following reaction scheme: Y (XVI) wherein X, Y, Z, R1 , R2, R3, R^ and Q are the same as in formula (I) and X' means a halogen atom or -OR4^, wherein R4^ is an alkylsulfonyl or arylsulfony1.
7. 7. A process for producing a herbicidal composition characterized in that a compound of cl"aim 1 is mixed with at least one component selected from the group composed of carriers and surfactants.
8. 8. A process for producing a herbicidal composition characterized in that a compound of claim 1 is mixed with at least one component selected from the group composed of an N-phosphonomethylglycine derivative of formula (III) R21 and R22 are identical or different, and eafah-repre- SH. 07ir ~ £ 5 1 54 sents a hydroxyl group or -OR24 and R23 is a hydroxyl group, -OR24 or ^R25 -N Vs, wherein ) 9 A 5 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, haloalkoxyalkyl or alkoxyalkoxyalkyl group (herein each of the alkoxy, haloalkoxy and alkyl groups has 1 to 5 carbon atoms) and a 10 phenoxy group; and R2^ and R2^ are identical or different and each represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a hydroxvalkyl group having 1 to 5 15 carbon atoms, a hvaroxyalkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or R2^ and R2^, together with the nitrogen atom to which they are attached, can form a morpholino group, a piperidino group or a pyrrolidino group, and/or a 20 glufosinate compound of formula (XV) ^31 L J N 0 IjJ- CH3-P-(-CH2-)2-C-COR32 (IV) 25 OH NH2 wherein R31 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R32 represents -OH, -NH2, -NHNH2, -NHCgH5 or an alkoxy group having 1 to 12 carbon atoms which may be substituted by -OH, or an acid addition salt or^a salt with a base, and a carrier and/or a surf ac tant^A ^>v J "2 1 SE? 1992 232518 - 155 -
9. 9. A method for controlling undesired weeds characterized by applying a compound of formula (1) according to claim 1 as such or in the form of a composition according to claim 3, 4 or 5 to the weeds and/or their seeds directly or to the 5 soil in an amount enough to satisfactorily inhibit their growth or eradicate them in the places where useful plants and/or their seeds coexist or possibly coexist with undesired weeds and/or their seeds.
10. 10. Oxime derivatives of formula (I) as defined in claim 1 or a salt thereof substantially as herein described with reference to any example thereof.
11. 11. A herbicidal composition as defined in any one of claims 3, 4 and 6 substantially as herein described with reference to any example thereof.
12. 12. A process as defined in any one of claims 5, 8 and 9 for producing a herbicial composition substantially as herein described with reference to any example thereof.
13. 13. A process as defined in claim 7 for preparing oxime derivatives or their salts substantially as herein described with reference to any example thereof.
14. 14. A method as defined in claim 10 for controlling undesired weeds substantially as herein described with reference to any example thereof. By j^Ttheir authorised Agenw.t A. J. PARK & SON. Per J) - "