CA2168049A1 - Imidoylchloride derivatives and method of producing same - Google Patents

Abstract

The present invention concerns a imidoylchloride derivative represented by the general formula (II):

Description

This application is a division of the Canadian patent application n 2.108.757 filed on February 26, 1993.

N-ACYT.-N-PH~NYLTFTRAHYDROPHTHALAMIC ACID DERIVATIVES, M~THODS OF PRODUCING SAM~, A~D HERBICIDES
CONTAINING SAME AS EFFECTIVE COMPONENTS

Technological Field This invention relates to N-acyl-N-phenyltetrahydro-phthalamic acid derivatives which are novel compounds, tomethods of producing the same and to herbicides containing the same as the effective components, and to imidoylchloride derivatives as intermediate products and to methods of producing the same. N-acyl-N-phenyltetrahydrophthalamic acid derivatives of the present invention exhibit excellent herbicidal activity. The derivatives are useful as a herbicide which can be widely applied to upland, paddy field, orchard, pasture, turf, forest, non-crop land, etc. The derivatives are not harmful to crops BACKGROUND TECHNOLOGY

Hitherto, herbicidal activity of tetrahydro-phthalamic acid derivatives has been well known. For example, N-(4'-chlorophenyl)-3,4,5,6-tetrahydrophtalamic acid methyl ester is known, as is disclosed in JP-A (Patent) 48-44425.
However, the conventional tetrahydrophthalamic acid derivatives are not necessarily sufficient in herbicidal activity, or are substantially limited in herbicidal spectrum against weeds. Furthermore, these derivatives are insuf-ficient in selectivity between crops and weeds, thereby inducing problems of safety for crops.
It is an object of the present invention to solve the aforementioned problems, and to provide novel compounds which are excellent in herbicidal activity but not harmful to crops, methods of producing the same and herbicides containing q -the same as the effective components, and intermediate products and methods of producing the same.

DISCLOSURE OF THE INVENTION

The inventors have found and already proposed that novel tetrahydrophthalamic acid derivatives each having a specific substituent acyl group bonded to an amide nitrogen atom are very excellent in herbicidal activity, selectivity and herbicidal spectrum (International Application PCT/JP91/01109 which corresponds to European Patent Application serial No. 496 soO of August 05, 1992). In view of this, the inventors have intensely studied, and as a result have completed the present invention.
The present invention provides N-acyl-N-phenyl-tetrahydrophthalamic acid derivatives represented by the general formula (I), methods of producing the same, and herbicides containing the same as the effective components:

~ o,c-~2 O R1 o=c k3 wherein R1 represents a (C1-C4)-alkyl group, a (C2-C4)-alkenyl group, a (C2-C4)-alkynyl group, a (C1-C4)-alkoxy-(Cl-C4)-alkyl group, a halo-(C1-C4)-alkyl group, a halo-(C2-C4)-alkenyl group, a halo-(C2-C4)-alkynyl group or a cyano-(C1-C4)-alkyl group, R2 represents a (C1-C4)-alkyl group or a halogenated (C1-C4)-alkyl group, and R3 represents a (C1-C4)-alkoxy group, a (C2-C4)-alkenyloxy group, a (C2-C4)-alkynyloxy group, a (C1-C4)-alkoxy-(C1-C4)-alkoxy group, a benzyloxy group, a halo-(C1-C4)-alkyloxy group or a (C1-C4)-alkoxy-carbonyl-(C1-C4)-alkoxy group.
Furthermore, the present invention provides imidoylchloride derivatives represented by the general formula (II) and methods of producing the same:

~O~N=~ ( I I ) // `R

wherein R1 represents a (C1-C4)-alkyl group, a (C2-C4)-alkenyl group, a (C2-C4)-alkynyl group, a (C1-C4)-alkoxy-(C1-C4)-alkyl group, a halo-(C1-C4)-alkyl group, a halo-(C 2-C 4)-alkenyl group, a halo-(C2-C4)-alkynyl group or a cyano-(C1-C4)-alkyl group, R2 represents a (C1-C4)-alkyl group or a halogenated (C1-C4)-alkyl group.
N-acyl-N-phenyltetrahydrophthalamic acid derivatives (I) of the present invention can be produced, for example, as is shown by the following formula, by reacting imidoylchloride derivatives represented by the general formula (II) with carboxylic acids represented by the general formula (III):

F O

~ ~ cl O~C_R3 C-N o O R1 [II] [IIIl F O
deacidifier ~ ~_R2 ~C-N
[I] R3 8 ~
-wherein R1 represents a (C1-C4)-alkyl group, a (C2-C4)-alkenyl group, a (C2-C4)-alkynyl group, a (C1-C4)-alkoxy-(C1-C4)-alkyl group, a halo-(C1-C4)-alkyl group, a halo-(C2-C4)-alkenyl group, a halo-(C2-C4)-alkynyl group or a cyano-(C1-C4)-alkyl group, R2 represents a (C1-C4)-alkyl group or a halogenated (C1-C4)-alkyl group, and R3 represents a (C1-C4)-alkoxy group, a (C2-C4)-alkenyloxy group, a (C2-C4)-alkynyloxy group, a (C1-C4)-alkoxy-(C1-C4)-alkoxy group, a benzyloxy group, a halo-(C1-C4)-alkyloxy group or a (C1-C4)-alkoxycar-bonyl-(C1-C4)-alkoxy group.
The reaction can proceeds preferably in a suitable solvent such as benzene, toluene, zylene, methylene chloride, chloroform, ethyl acetate, dioxane, tetrahydrofuran, diethyl ether, dimethylformamide or dimethylsulfoxide, by adding a suitable deacidifying agent such as an organic base such as triethylamine or pyridine, or an inorganic base such as potassium hydroxide or sodium hydroxide.
The reaction temperature is not particularly limited, but is usually from 0C to 200C, and a preferred range is from 40C to 100C.
Furthermore, N-acyl-N-phenyltetrahydrophthalamic acid derivatives (I) of the present invention can be produced, as is shown by the following formula, by reacting imidoylchloride derivatives represented by the general formula (II) with alkali metal sal~s of carboxylic acids represented by the general formula (V), too.
F o ~2 ~,~,C-OM

~ C 1 ~c ~R 3 /C-N
O Rl [IIl [V]
F O
~< ,C-R2 O Rl O=C
~I] ~R3 CA21 ~04q wherein R1 represents a (C1-C4)-alkyl group, a (C2-C4)-alkenyl group, a (C2-C4)-alkynyl group, a (C1-C4)-alkoxy-(C1-C4)-alkyl group, a halo-(C1-C4)-alkyl group, a halo-(2C -4C )-alkenyl group, a halo-(C2-C4)-alkynyl group or a cyano-(C1-C4)-alkyl group, R2 represents a (C1-C4)-alkyl group or a halogenated (C1-C4)- alkyl group, and R3 represents a (C1-C4)-alkoxy group, a (C2-C4)-alkenyloxy group, a (C2-C4)-alkynyloxy group, a (C1-C4)-alkoxy-(C1-C4)-alkoxy group, a benzyloxy group, a halo-(C1-C4)-alkyloxy group or a (Cl-C4)-lo alkoxycarbonyl-(C1-C4)-alkoxy group, and M represents an alkali metal.
The reaction can proceeds in a suitable solvent such as benzene, toluene, xylene, methylene chloride, chloroform, ethyl acetate, dioxane, tetrahydrofuran, diethyl ether, dimethylformamide and dimethylsulfoxide or water, by adding, if necessary, a phase transfer catalyst such as a quaternary ammonium salt.
The reaction temperature is not particularly limited, but is usually from 0C to 200C, and a preferred range is from 0C to 100C.
Furthermore, imidoylchloride derivatives (II) which are necessary as a starting material to obtain N-acyl-N-phenyltetrahydrophthalamic acid derivatives (I) of the present invention can be produced, according to the following reaction, formula, by the reaction of anilide derivatives which are represented by the general formula (IV), using a dehydrochlorinating agent, in the presence of a reaction solvent or not:
F O~
~ ,C_R2 ( ~ ~H
C-N ( IV) o/' kl wherein R1 represents a (C1-C4)-alkyl group, a (C2-C4)-alkenyl - ~ A 21 ~

group, a (C2-C4)-alkynyl group, a (Cl-C4)-alkoxy-(C1-C4)-alkyl group, a halo-(C1-C4)-alkyl group, a halo-(C2-C4)-alkenyl group, a halo-(C2-C4)-alkynyl group or a cyano-(C1-C4)-alkyl group, and R2 represents a (C1-C4)-alkyl group or a halogenated (C1-C4~-alkyl group.

~ ,C R
( ~ H
// \ 1 o R
[IV] F
dehydrochlorinating agent ~ ~2 -~120 ~ ~ N=~
O kl [II]

wherein R1 represents a (C1-C4)-alkyl group, a (C2-C4)-alkenyl group, a (C2-C4)-alkynyl group, a (C1-C4)-alkoxy-(C1-C4)-alkyl group, a halo-(C1-C4)-alkyl group, a halo-(C2-C4)-alkenyl group, a halo-(C2-C4)-alkynyl group or a cyano-(C1-C4)-alkyl group, R represents a (C1-C4)-alkyl group or a halogenated (C1-C4)-alkyl group.
As preferable examples of the dehydrochlorinating agent used in the reaction, phosphorus pentachloride, phosphorus trichloride-chlorine, thionyl chloride, arylsulfo-nylchloride, phosgene, triphenylphosphine-carbon tetrachloride and polymer carried triphenylphosphinecarbon tetrachloride can be cited.
Furthermore, as preferable examples of the solvent used in the reaction, halogenated hydrocarbons such as dichloroethane, carbon tetrachloride, chloroform and methylene chloride, aromatic hydrocarbons such as benzene, toluene, xylene and chlorobenzene, polar solvents such as acetonitrile and dimethyl sulfoxide, etc. can be cited.
The reaction temperature is not particularly limited, but is preferably in the range from o to 100C.

T!~ B~ST MOD~ TO CARR.Y OUT T~ INVF~NTION

Hereinafter, the present invention will be described concretely with reference to Examples.

EXAMPLE

Sy~thesis of N-(7-fluoro-4-pro~rgyl-2~-1,4-ben7ox~;ne-3~4H)-10 one-6-yl)-2-chloroacet;m;doylchloride (A compound which is represented by N 2 in Table 1 and by the general formula (II) First, l.oo g of N-(7-fluoro-4-propargyl-2H-1,4-benzoxazine-3(4H)-one-6-yl)-2-chloroacetamide, 2.25 g of triphenylphosphine polymer bound and 4 ml of carbon tetrachloride were dissolved in 35 ml of 1,2-dichloroethane, and then the reflux under heat was continued for 2 hr. After letting the solution stand to cool the same, the solid was filtered out, and then the solvent was distilled out under 20 reduced pressure to quantitatively obtain N-(7-fluoro-4-propargyl-2H-1,4-benzoxazine-3(4H)-one-6-yl)-2-chloroacetimidoylchloride.

Synthesis of N-(2-chloroacetyl)-N-(7-fluoro-4-propargyl-2H-1,4-benzoxa7;ne-3(4H)-one-6-yl)-3,4,5,6-tetrahydrophthalamic acid methyl ester (A compound which isrepresented by N 5 in Table 3 and by the general formula (I) First, 1.06 g of N-(7-fluoro-4-propargyl-2H-1,4-benzoxazine-3(4H)-one-6-yl)-2-chloroacetimidylchloride and 0.62 g of 3,4,5,6-tetrahydrophthalamic acid monomethyl ester were dissolved in 50 ml of benzene, and 0.38 g of triethylamine was added to the solution at room temperature.
After that the stirring was continued for 2 hr at 60C. After ~ A ~ 4 ~

letting the reaction liquid stand to cool the same, it was poured into cool water, and then the organic layer was separated therefrom. The organic layer was washed first with water and then whith saturated brine, and then dried by using anhydrous magnesium sulfate. The solvent was concentrate, and then methanol was added to the residue. The produced crystals were filtered out, then washed with methanol, and then dried to obtain 1.0 g of N-(2-chloroacetyl)-N-(7-fluoro-4-propargyl-2H-1,4-benzoxazine-3(4H)-one-6-yl)-3,4,5,6-tetrahydro-10 phthalamic acid methyl ester. The melting point was 156-158C.

Synthesis of N-(7-fluoro-4-propargyl-2H-1,4-benzoxazine-3(4H)-one-6-yl)-acetimidoylchloride (A compound which is represented by N 3 in Table 1 and by the general formula (II) First, 10 ml of benzene and 0.4 g of phosphorus pentachloride were added to 0.5 g of N-(7-fluoro-4-propargyl-2H-1,4-benzoxazine-3(4H)-one-6-yl)-acetamide, and the stirring was continued for l.o hr at 60C. After letting the mixture stand to cool the same, the produced phosphorus oxychloride and benzene were distilled out under reduced pressure to quantitatively obtain N-(7-fluoro-4-propargyl-2H-1,4-benzoxazine-3(4H)-one-6-yl)-acetimidoylchloride.

Synthes;s of N-acetyl-N-(7-fluoro-4-pro~ar~yl-2H-1,4-benzoxazine-3(4H)-one-6-yl)-3,4,5,6-tetrahydrophthalamic acid methyl ester (A compound wh;ch ;s represented by N 14 in Table 3 and by the general formula (I) First, 0.44 g of N-(7-fluoro-4-propargyl-2H-1,4-benzoxazine-3(4H)-one-6-yl)-acetimidoylchloride and 0.29 g of CA21~8~

3,4,5,6-tetrahydrophthalamic acid monomethyl ester were dissolved in 15 ml of benzene, and 0.17 g of triethylamine was added to the solution at room temperature. After that the stirring was continued for 2 hr at 60C. After letting the reaction liquid stand to cool the same, it was poured into cool water, and then the organic layer was separated therefrom. The organic layer was washed first with water and then with saturated brine, and then dried by using anhydrous magnesium sulfate. The solvent was concentrated, and then the lo residue was treated by silica gel column chromatography (development solvent: ethyl acetate/n-hexane) to obtain N-acetyl-N-(7-fluoro-4-propargyl-2H-1,4-benzoxazine-3(4H)-one-6-yl)-3,4,5,6-tetrahydrophthalamic acid methyl ester. The melting point was 153-154C.
Table 3 shows N-acyl-N-phenyltetrahydrophthalamic acid derivatives (I) of the present invention, each of which was obtained by a process analogous to the processes of the foregoing examples, and Table 4 shows 1H-NMR absorption spectrum values thereof. Table l shows imidoylchloride 20 derivatives (II), and Table 2 shows 1H-NMR absorption spectrum values thereof. However, the compounds of the present invention are not limited to those shown in Tables 1 to 4.
The compound Ns in Tables 1 to 4 will be employed in the following examples and experiments.

TABLE
CompoundN Rl R2 16 CH(CH3)2 CH3 ~9 CH2CH=CH2 CH3 CH(CH3)C CH CH3 CA~ 1 ~8~9 Compound lH-NMR Absorption Spectrum Values (~) N (in CDCl3) 1 4.53(s,2H),4.7(s,2H),4.75(m,2H),6.89(d,J=loHz, lH),6.91(d,J=7Hz,lH) 2 2.3(t,J=2Hz,lH),4.5(s,2H),4.65(s,2H),4.7(m,2H) ,6.84(d,J=lOHz,lH),6.86(d,J=7Hz,lH) 3 2.3(t,J=2Hz,lH),2.63(s,3H),4.65(s,4H),6.71(d,J
=7Hz,lH),6.80(d,J=lOHz,lH) 1.29(t,J=7Hz,3H),2.65(s,3H),3.9(q,J=7Hz,2H),4.
62(s,2H),6.73(d,J=7Hz,lH),6.96(d,J=lOHz,lH) 16 1.5(d,J=7Hz,6H),2.6(s,3H),4.48(s,2H),4.5~5.0(m ,lH),6.69(d,J-7Hz,lH),6.79(d,J=lOHz,lH) 10 17 2.6(s,3H),3.9~4.1(m,1H),4.15~4.25(m,2H),4.61(s ,2H),4.8~5.0(m,1H),6.71(d,J=7Hz,lH),6.8(d,J=10 Hz,lH) 18 2.62(s,3H),3.35(s,3H),3.5~3.7(m,2H),3.9~4.1(m, 2H),4.61(s,2H),6.7(d,J=7Hz,lH),6.73(d,J=lOHz,l H) 19 2.56(s,3H),4.4~4.6(m,2H),4.57(s,2H),5.0~5.4(m, 2H),5.6~6.0(m,1H),6.5(d,J=7Hz,lH),6,75(d,J=lOH
z,lH) 1.6(d,J=7Hz,3H),2.13(s,1H),2.16(s,3H),4.55(s,2 H),4.85~5.2(m,1H),6.27(d,J=7Hz,lH),6.77(d,J=10 Hz,lH) TABLE 3(1) TABLE 3(1) Compound Rl R2 R3 m.p. (C) 4 CH2CN CH2ClOCH3 181~183 CH2C-CH CH2ClOCH3 156~158 6 CH2C-CH CH2ClOCH2C--CH 142~143 7 CH2C--CH CH2ClOCH2(CH2)2cH3110~111 8 CH2C-CH CH2ClOCH2 ~ 166.5~167.5 9 CH2C-CH CH2ClOCH2CH3 154.5~155.5 CH C-CH CH2ClOCH2C02cH2cH3138~139 11 CH2C-CH CH2ClOCH2CH=CH2127.5~128.5 12 CH2C-CH CH2ClOCH2CH20CH3 96~98 13 CH C-CH CH2Cl. OCH(cH3)2 84~86 14 CH C-CH CH3OCH3 153~154 21 CH2C--CH CH3OCH2(CH2)2cH3 90~91 22 CH2C--CH CH3OCH2 ~ 155~156 23 CH C-CH CH3OCH2CH20CH3 90~91 24 CH2C-CH CH3OCH(cH3)2 oil-like substance CH C-CH CH3CH(cH3)cH2cH3115~116 26 CH2CH3 CH3OCH3 oil-like substance 27 CH2CH3 CH3OCH(CH3)2 114~115 CA21 6804~

TABLE 3(2) Compound R1 R2 R3 m.p. (C) N
28 CH(CH3~2 CH3OCH3 oil-like substance 29CH(CH3)2 CH3 OCH(CH3)CH20CH3 oil like substance 30 CH2CH2F CH3OCH3 141~142 31 CH2CH2F CH3OCH2CH20CH3oil-like substance 32CH2CH2OCH3 CH3OCH3 92~93 33CH2CH2OCH3 CH3OCH2CH20CH3oil-like substance 34CH2CH=CH2 CH3OCH2CH20CH3oil-like substance 35CHtCH3)C--CH CH3OCH2CH20CH3oil-like substance - C~2 1 6~049 TABLE 4(1) Compound lH-NMR Absorption Spectrum Values (~) N (in CDCl3) 4 1.4~1.7(m,4H),2.15~2.45(m,4H),3.8(s,3H),4,6(s, 2H),4.78(s,2H),4.8(m,2H),6.95(d,J=lOHz,lH),7.3 8(d,J=7Hz,lH) 1.4~1.7(m,4H),2.15~2.45(m,5H),3.79(s,3H),4.57( s,2H),4.65(m,2H),4.73(s,2H),6.9(d,J=lOHz,7.33( d,J=7Hz,lH) 6 1.4~1.7(m,4H),2.15~2.45(m,5H),2.52(t,J=2Hz,lH) ,4.56(s,2H),4.64(m,2H),4.7(m,2H),4.77(d,J=2Hz, 2H),6.87(d,J=lOHz,lH),7.28(d,J=7Hz,lH) 7 0.92(t,J=7Hz,3H),1.2~1.7(m,8H),2.15~2.45(m,5H) ,4.14(t,J=7Hz,2H),4.53(s,2H),4.6(m,2H),4.68(s, 2H),6.86(d,J=lOHz,lH),7.3(d,J=7Hz,lH) 8 1.4~1.7(m,4H),2.18(t,J=2Hz,lH),2.15~2.45(m,4H) ,4.42(bs,2H),4.56(m,2H),4.69(s,2H),5.2(s,2H),6 .86(d,J=lOHz,lH),7.25(d,J=7Hz,lH),7.35(s,5H) 9 1.3(t,J=7Hz,3H),1.4~1.7(m,4H),2.15~2.45(m,5H), 4.23(q,J=7Hz,2H),4.56(s,2H),4.67(m,2H),4.71(s, 2H),6.88(d,J=lOHz,lH),7.32(d,J=7Hz,lH) 1.29(t,J=7Hz,3H),1.4~1.7(m,4H),2.25(t,J=2Hz,lH
,2.15~2.45(m,4H) ,4.24(q,J=7Hz,2H) ,4.56(bs,2H), 4.64(m,2H),4.7(s,4H),6.87(d,J=lOHz,lH),7.34(d, J=7Hz,lH) 11 1.4~1.7(m,4H),2.15~2.45(m,5H),4.57(s,2H),4.65( bs,2H),4.71(s,4H),5.16~5.48(m,2H),5.75~6.2(m,1 H),6.89(d,J=lOHz,lH),7.29(d,J=7Hz,lH) 12 1.4~1.7(m,4H),2.15~2.45(m,5H),3.36(s,3H),3.64( t,J=6Hz,2H),4.33(t,J=6Hz,2H),4.64(m,2H),4.69(s ,2H),4.71(s,2H),6.88(d,J=lOHz,lH),7.34(d,J=7Hz ,lH) 13 1.28(d,J=6Hz,6H),1.4~1.7(m,4H),2.15~2.45(m,5H) ,4.54(s,2H),4.63(bs,2H),4.71(s,2H),5.08(m,1H,6 .88(d,J=lOHz,lH),7.36(d,J=7Hz,lH) - ~A~ 1 6~o~

TABLE 4(2) Compound lH-NMR Absorption Spectrum Values (~) N (in CDC13) 14 1.4~1.7(m,4H),2.15~2.45(m,5H),2.2(s,3H),3,78(s ,3H),4.73tm,4H),6.94(d,J=lOHz,lH),7.41(d,J=7Hz ,lH) 21 0.92(t,J=6Hz,3H),1.5~1.8(m,8H),2.1~2.4(m,5H),2 .25(s,3H),4.14(t,J=6Hz,2H),4.5~4.7(m,2H),4.68( s,2H),6.85(d,J=lOHz,lH),7.39(d,J=7Hz,lH) 22 1.6~1.8(m,4H),2.18(s,3H),2.3~2.5(m,5H),4.6~4.7 5(m,2H),4.68(s,2H),5.2(s,2H),6.85(d,J=lOHz,lH) ,7.33(d,J=7Hz,lH),7.33(s,5H) 23 1.45~1.7(m,4H),2.1~2.45(m,5H),2.31(s,3H),3.35( s,3H),3.6(m,2H),4.3(m,2H),4.5~4.7(m,2H),4.69(s ,2H),6.85(d,J=lOHz,lH),7.42(d,J=7Hz,lH) 24 1.21(d,J=7Hz,6H),1.4~1.75(m,4H),2.05~2.45(m,5H
),2.2(s,3H),4.45~4.8(m,2H),4.64(s,2H),4.85~5.2 (m,lH),6.81(d,J=lOHz,lH),7.38(d,J=7Hz,lH) 10 25 1.24(d,J=6Hz,3H),1.45~1.75(m,4H),2.05~2.45(m,5 H),2.28(s,3H),3.32(s,3H),3.35~3.5(m,2H),4.5~4.
75(m,2H),4.67(s,2H),4.9~5.3(m,1H),6.84(d,J=lOH
z,lH),7.44(d,J=7Hz,lH) 26 1.26(t,J=7Hz,3H),1.5~1.75(m,4H),2.1~2.4(m,4H), 2.24(s,3H),3.74(s,3H),4.0(q,J=7Hz,2H),4.65(s,2 H),6.85(d,J=lOHz,lH),7.27(d,J=7Hz,lH) 27 1.24(t,J=7Hz,3H),1.26(d,J=6Hz,6H),1.55~1.75(m, 4H),2.1~2.4(m,4H),2.25(s,3H),3.94(q,J=7Hz,2H), 4.65(s,2H),4.48~5.15(m,1H),6.8(d,J=lOHz,lH),7.
34(d,J=7Hz,lH) 28 1.58(d,J=7Hz,6H),1.45~1.8(m,4H),2.2(s,3H),2.15 ~2.4(m,4H),3.72(s,3H),4.56(s,2H),4.6~5.0(m,1H) ,6.86(d,J=lOHz,lH),7.52(d,J=7Hz,lH) 29 1.25(d,J=7Hz,3H),1.49(d,J=7Hz,6H),1.45~1.75(m, 4H),2.2(s,3H),2.1~2.5(m,4H),3.34(s,3H),3.36~3.
48(m,2H),4.56(s,2H),4.6~5.15(m,2H),6.85(d,J=10 Hz,lH),7.6(d,J=7Hz,lH) TABLE 4(3) Compound lH-NMR Absorption Spectrum Values t~) N (in CDCl3) 1.5~1.7(m,4H),2.1~2.4(m,4H),2.25(s,3H),3,73(s, 3H),4.05(m,1H),4.36(m,2H),4.68(s,2H),4.94(m,1H
),6.85(d,J=lOHz,lH),7.33(d,J=7Hz,lH) 31 1.45~1.7(m,4H),2.1~2.4(m,4H),2.29(s,3H),3.36(s ,3H),3.61(m,2H),4.08(m,1H),4.16~4.4(m,4H),4.68 (s,2H),4.92(m,1H),6.85(d,J=lOHz,lH),7.39(d,J=7 Hz,lH) 32 1.5~1.8(m,4H),2.15~2.45(m,4H),2.22(s,3H),3.32( s,3H),3.62(m,2H),3.74(s,3H),4.07(m,2H),4.67(s, 2H),6.84(d,J=lOHz,lH),7.39(d,J=7Hz,lH) 33 1.45~1.75(m,4H),2.1~2.4(m,4H),2.27(s,3H),3.33( s,3H),3.38(s,3H),3.45~3.65(m,4H),3.9~4.1(m,2H) ,4.15~4.3(m,2H),4.68(s,2H),6.85(d,J=lOHz,lH),7 .44(d,J=7Hz,lH) 34 1.45~1.8(m,4H),2.15~2.45(m,4H),2.22(s,3H),3.36 (s,3H),3.6(m,2H),4.27(m,2H),4.4~4.6(m,2H),4.69 (s,2H),5.0~5.3(m,2H),5.75~6.0(m,1H),6.85(d,J=
lOHz,lH),7.26(d,J=7Hz,lH), 1.55(d,J=7Hz,3H),1.4~1.75(m,4H),2.18(s,3H),2.1 ~2.45(m,5H),3.37(s,3H),3.62(m,2H),4.32(m,2H),4 .7(s,2H),4.9~5.2(m,1H),6.92(d,J=lOHz,lH),7.12( d,J=7Hz,lH) CA 21~804 9 A herbicide of the present invention containing N-acyl-N-phenyltetrahydrophthalamic acid derivatives (I) of the present invention as the effective component has a superior herbicidal activity against various weeds causing problems upon the submerged soil treatment in paddy fields, such as gramineous weeds such as nobie (barnyardgrass, Echinochloa spp.), broad-leaved weeds such as azena (flase pimpernel, Lindernia pyxidaria), kikashigusa (toothcup, Rotala indica), mizohakobe (waterwort, Elatine triandra), cyperaceous weeds such as tamagayatsuri (small-flowered umbrellaplant, Cyperus difformis) and hotarui (bulrush, Scirpus juncoides), and weeds such as konagi (Monochoria vaginalis). Furthermore, the herbicide has a superior herbicidal activity against various weeds causin problems upon the foliage treatment and the soil treatment in uplands, such as broad-leaved weeds such as karashina (indian mustard, Brassica Juncea), aobiyu (slender amaranth, Amaranthus viridis), hakobe (chickweed, Stellaria media), shiroza (common lambsquarters, Chenopodium album), onamomi (heartleaf cocklebur, Xanthium strumarium), maruba-asagao (tall morningglory, Ipomoea purpurea), yaemugura (catchweed bedstraw, Galium aparine), suberihiyu (common purslane, Portulaca oleracea), ichibi (velvetleaf, Abutilon theophrasti), amerika-tsunokusanemu (hemp sesbania, Sesbania exaltata), ebisugusa (sicklepod, Cassia obtusifolia), inuhouzuki (black nightshade, Solanum nigrum), spedwells, smart weeds, violets, tade (Persicaria longiseta) and its relatives, and sumire (Viola mandshurica) and its relatives, gramineous weeds such as inubie (barnyardgrass, Echinochloa crus-galli), enokorogusa (green foxtail, Setaria viridis), karasumugi (wild oat, Avena fatua), mehishiba (henry crabgrass, Digitaria ciliaris), seibanmorokoshi (johnsongrass, Sorghum halepense) and enbaku (oat, Avena sativa), cyperaceous weeds such as kogomegayatsuri (rice flatsedge, Cyperus iria) and hamasuge (nut grass, Cyperus rotundus), an commelinaceous weeds such as tsuyukusa (dayflower, Commelina communis). The herbicide of the present invention hardly injures major crops such as rice, wheat, corn and soybean.
Therefore, the herbicide of the present invention can be applied to upland, paddy field, orchard, pasture, turf, forest and non-crop land.
It is possible to process the herbicide of the present invention containing N-acyl-N-phenyltetrahydro-phthalamic acid derivatives (I) as the effective component into an arbitrary form such as wettable powder, emulsion, granules, powder or flowable by using a pesticide adjuvant which is generally used in this field, such as an inactive solid carrier or liquid carrier and/or an emulsifying and dispersing agent and the like. As the inactive carriers, for example, talc, clay, bentonite, kaolin, diatomaceous earth, calcium carbonate, wood flour, starch, gum arabic, water, alcohol, kerosene, benzene, xylene, n-hexane, acetone, dimethylformamide, glycol ether, N-methylpyrrolidone can be cited.
Besides, it is possible to adequately incorporate auxiliary agents for formulation, such as spreader, diluent, surfactant and solvent.
Upon using N-acyl-N-phenyltetrahydrophthalamic acid derivatives (I)of the present invention as a herbicide, a suitable application dosage is variable according to related factors such as manner of application, object of application, time of application and occurrence condition of weeds, but in general the application dosage, as expressed as the amount of the effective component, is preferably from 0.1 to 300 g, and particularly preferably from 1 to 300 g, per lo ares.
Furthermore, to use the herbicide containing N-acyl-N-phenyltetrahydrophthalamic acid derivatives (I) of the present invention, it may be mixed with other herbicides, plant growth regulators, fungicides, insecticides, other pesticides, fertilizers and soil conditioners.
The following are Examples of herbicides according to the present invention, though compounds, carriers, adjuvants and the proportions of the ingredients are not limited to those in these examples. In these examples the amount of each component is indicated by parts by weight.

EXAMPT~ 5(Wettable Powder) Compound No. 5 10 parts Sodium lignin sulfonate 1.5 parts Polyoxyethylene alkylaryl ether1.5 parts Clay 87 parts These materials were mixed together until a uniform mixture was obtained, and the mixture was pulverized to obtain a wettable powder.

EXAMPLE 6 (Granules) Compound No. 5 7 parts Bentonite 30 parts Sodium alkylsulfonate 2 parts Clay 61 parts These materials were mixed together and kneaded until a uniform mixture was obtained, and the mixture was granulated by an ordinary granulation method thereby to obtain granules.

EXAMPLE 7 (Emulsion) Compound No. 5 5 parts N-methylpyrrolidone 44 parts Solpol 7065 43 parts (product of Toho Kagaku Kogyo co., Ltd.) Solpol 355 8 parts (product of Toho Kagaku Kogyo co., Ltd.) These materials were mixed together until a uniform mixture was obtained, thereby to obtain an emulsion.
The following experiments are illustrative of the herbicidal effects of N-acyl-N-phenyltetrahydrophthalamic derivatives (I) of the present invention.

-CA21 ~8~
EXPERIMENT 1 (flooded Soil Treatment) Paddy soil (clay loam) was put into a pot so as to have a surface area of 1/15500 ares. Uniformly mixed seeds of several kinds of weeds, viz., nobie (barnyardgrass, Echinochloa spp.), broad-leaved weeds, hotarui (bulrush, Scirpus juncoides) and tamagayatsuri (small-flowered umbrellaplant, Cyperus difformis), were sown in the surface layer of the soil in each pot, and then paddy rice seedlings at the two- or three-leaved stage were transplanted into each pot to a depth of 2 cm, and water was fed into each pot so as to provide a 3 cm deep water layer on the soil surface. After 3 days, in other words at the initial stage of germination of nobie (barnyardgrass, Echinochloa spp.), a predetermined amount of a selected compound in the form of diluted aqueous solution was dropped into the water layer in each pot. After that, the pots were kept in a glass chamber to allow the paddy rice and the weeds to grow, and after the lapse of 4 weeks from the treatment with the selected compounds, the herbicidal effects and the degree of injury to the paddy rice were evaluated. The results are shown in Table 5. In the table, the herbicidal effects and the degree of injury to the paddy rice are indicated by numerical values, which have the following meaning.
5: completely killed 4: seriously injured 3: considerably injured 2: somewhat injured 1: slightly injured 0: not injured (normally grown) EXPERIMENT 2 (Foliage Treatment) Upon seedling stage (two- or three-leaved stage) of rice, cockspur (Panicum crus-galli), garden radish, aobiyu (slender amaranth, Amaranthus viridis) and mehishiba (henry crabgrass, Digitaria cliaris) which were grown on a cultivated soil put in pots of 1/15500 ares, a selected compound in - C~2l68049 suspended wettable powder was sprayed to each plant. After that, the pots were kept in a glass chamber to allow each plant to grow, and after the lapse of 4 weeks from the treatment with the selected compounds the herbicidal effects were evaluated. The results are shown in Table 7. The evaluation of the herbicidal effects was similarly conducted as to that of Experiment 1.

EXPERIMENT 3 (Foliage Treatment) Upon seedling stage (two- or three-leaved stage) of ichibi (velvetleaf, Abutilon theophrasti), onamomi (heartleaf cocklebur, Xanthium strumarium) (4L stage), noasagao (blue morningglory, Ipomoea indica) and ooinutade (pale smartweed, Persicaria lapathifolia) which were grown on a cultivated soil put in pots of 1/8850 ares, a selected compound in suspended wettable powder was sprayed to each plant. After that, the pots were kept in a glass chamber to allow each plant to grow, and after the lapse of 4 weeks from the treatment with the selected compounds the herbicidal effects were evaluated. The results are shown in Table 7. The evaluation of the herbicidal effects was similarly conducted as to that of Experiment 1.

-TABLE 5(1) ~ 9 Com- Quan- InjuryHerbicidal Effect pound tity of of No. com- Paddy poundnob1e broad- hota- tama-g/lOa leaved rui gayat-weed suri 6.25 0.5 4.5 5 2 5 4 3.13 0.5 4.5 4.5 1 3 6.25 1 5 5 4.5 5 3.13 1 5 5 4.5 5 6.25 1 5 5 5 5 6 3.13 0.5 5 5 4.5 5 6.25 2 5 5 4.5 5 7 3.13 1 5 5 4 5 8 6.25 0.5 5 5 3 5 3.13 0.5 5 4.5 2 5 9 6.25 3 5 5 4 5 3.13 2 5 5 3 5 6.25 3 5 5 4 5 3.13 1 5 5 3 5 6.25 2 5 5 4.5 5 11 3.13 0.5 5 5 4 5 1 6.25 2 5 5 5 5 2 3.13 2 5 5 5 5 3 6.25 4 5 5 5 5 1 3.13 3 5 5 5 5 6.25 2 5 5 4.5 5 14 3.13 1 5 5 4 5 21 6.25 2 5 5 4.5 5 3.13 1 5 5 4.5 5 22 6.25 1 5 5 4 5 3.13 1 5 5 3 5 6.25 3 5 5 4.5 5 23 3.13 1 5 5 4 5 -TABLE 5(2) Com- Quan- Injury . ~ - Herbicldal Effect poun~ y Ol Ol No. com- Paddy pound noble broad- hota- tama-g/lOa leaved rui gayat-weed suri 24 6.25 3 5 5 5 5 3.13 1 5 5 4.5 5 6.25 1 4 5 4 5 3.13 1 3 4.5 3 5 6.25 1 5 5 5 5 26 3.13 1 5 5 4 5 27 6.25 4 5 5 5 5 3.13 1 5 5 5 5 28 3 13 O 4.5 5 4.5 5 6 25 2 5 5 4.5 5 29 3 13 1 4 5 4.5 5 6.25 3 5 5 5 5 3.13 1 5 5 4.5 5 1 6.25 2 5 5 4 5 3 3.13 1 5 5 4 5 32 6.25 1 5 5 4.5 5 3.13 1 5 5 4 5 33 6.25 1 5 5 4.5 5 3.13 1 5 5 4.5 5 6.25 3 5 5 5 5 34 3.13 1 5 5 4.5 5 3 13 1 3 4.5 3 5 TABLE 6(1) Com- Quan-No. com- Rice cockspur gaaddesh aobiyu mehishiba pound g/lOa 4 40 0.5 0 5 5 0 4 4.5 5 5 4.5 4 4.5 5 5 4.5 4.5 4.5 5 5 5 3 4.5 5 5 5 TABLE 6(2) CA 2l6 804 9 Com- Quan-pound tity of d No. pound Rice cockspur gradiseh aobiyu mehishiba g/lOa Com- Quantity C A 2 1 ~ 8 0 4 9 pound compound ichibi onamomi noasagao ooinutade 0. g/loa 4 5 4 4.5 5 4 4.5 3 4 5 INDUSTRIAL APPLICABILITY

N-acyl-N-phenyltetrahydrophthalamic acid derivatives of the present invention, which are novel compounds exhibit excellent herbicidal activity, and are useful as a herbicide which can be widely applied to upland, paddy field, orchard, turf, forest, non-crop land, etc., and which is not hamful to crops.

Claims (3)

1. An imidoylchloride derivatives represented by the general formula (II):

(II) wherein R1 represents a (C1-C4)-alkyl group, a (C2-C4)-alkenyl group, a (C2-C4)-alkynyl group, a (C1-C4)-alkoxy-(C1-C4)-alkyl group, a halo-(C1-C4)-alkyl group, a (C2-C4)-haloalkenyl group, a halo-(C2-C4)-alkynyl group or a cyano-(C1-C4)-alkyl group, R2 represents a (C1-C4)-alkyl group or a halogenated (C1-C4)-alkyl group.

2. A method of producing an imidoylchloride derivative represented by the general formula (II):

(II) wherein R1 represents a (C1-C4)-alkyl group, a (C2-C4)-alkenyl group, a (C2-C4)-alkynyl group, a (C1-C4)-alkoxy-(C1-C4)-alkyl group, a halo-(C1-C4)-alkyl group, a (C2-C4)-haloalkenyl group, a halo-(C2-C4)-alkynyl group or a cyano-(C1-C4)-alkyl group, R2 represents a (C1-C4)-alkyl group or a halogenated (C1-C4)-alkyl group, said method being characterized in that an anilide derivative represented by the general formula (IV):

( IV) wherein R1 represents a (C1-C4)-alkyl group, a (C2-C4)-alkenyl group, a (C2-C4)-alkynyl group, a (C1-C4)-alkoxy-(C1-C4)-alkyl group, a halo-(C1-C4)-alkyl group, a halo-(C2-C4)-alkenyl group, a halo-(C2-C4)-alkynyl group or a cyano-(C1-C4)-alkyl group, and R2 represents a (C1-C4)-alkyl group or a halogenated (C1-C4)-alkyl group, is reacted with a dehydrochlorinating agent.

3. A method of producing an imidoylchloride derivative according to claim 2, said method being characterized in that said dehydrochlorinating agent is selected from the group consisting of phosphorus pentachloride, phosphorus trichloride-chlorine, thionyl chloride, arylsulfonyl chloride, phosgene, triphenyl-phosphine-carbon tetrachloride and polymer-carrier triphenylphosphine-carbon tetrachloride.