KR840002302B1 - Process for preparing alkancarboxylic acid derivative - Google Patents

Abstract

Title compds. of formula (I) are prepd. by reacting benzotriazine derivs. of formula (IX) with compds. of formula (X). In the formulas, X is O; A, B, D and E are H, C1-6 alkyl, C1-6 haloalkyl, or C1-6 alkoxy; U anv V are H or halogen; R1 is H or C1-6 alkyl; R2 is H, C1-6 alkyl, or C2-6 alkoxyalkyl; R3 is H; W is -COG; G is C1-10 alkoxy; k,l, and m are 0 or 1, k+l+m being 0, 1 or 2; and n is 0, 1, or 2.

Description

Method for preparing alkancarboxylic acid derivative

The present invention relates to a method for producing an organic compound having biological activity, in particular an organic compound having herbicidal properties, and relates to useful intermediates produced during manufacture, compositions for herbicidal action, processes for utilizing these compounds, and the like.

The inventors have discovered a new class of benzotriazines which exhibit biological action, in particular herbicidal action.

Accordingly, the present invention provides methods for preparing compounds of formula I or their salts.

In the structure, A, B, C, D, E, U and V are hydrogen, halogen, nitro, cyano, thiocyano, amino, C ₁ -C ₆ alkylamino, di (C ₁ -C ₆ alkyl) amino , C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl, C ₂ -C ₆ alkenyl, C ₃ -C ₇ cycloalkyl, C ₁ -C ₆ alkoxy, C ₁ -C ₆ haloalkoxy, C _1- C ₆ alkylthio, C ₁ -C ₆ alkylsulfinyl, C ₁ -C ₆ alkylsulfonyl, C ₁ -C ₆ haloalkylsulfinyl, C ₁ -C ₆ haloalkylsulfonyl, sulfo, C ₁ -C ₆ Alkoxysulfonyl, sulfadoyl, N- (C ₁ -C ₆ alkyl) sulfamoyl, N, N-di (C ₁ -C ₆ alkyl) sulfamoyl, carboxy, (C ₁ -C ₆ alkoxy) -carbonyl , Carbamoyl, N- (C ₁ -C ₆ alkyl) carbamoyl, N, N-di (C ₁ -C ₆ alkyl) carbamoyl, phenyl, phenoxy, phenylthio and phenylcyclic halogen, C ₁ ~C ₆ alkyl, C ₁ ~C ₆ haloalkyl, C ₁ ~C ₆ alkoxy, nitro, cyano when phenyl, substituted phenoxy substituted with 1 to 3 minutes substituted selected from groups such as a furnace, substituted phenylthio Coming from each other Tube will be selected.

R ¹ is hydrogen, C ₁ -C ₆ alkyl, C ₂ -C ₁₀ alkenyl, C ₂ -C ₁₀ alkynyl, C ₂ -C ₁₀ alkoxyalkyl, cyanomethylene, (C ₁ -C ₆ ) alkoxy)- Carbonylmethylene, C ₁ -C ₁₀ haloalkyl, formyl, C ₂ -C ₁₀ haloalkyl, phenyl, benzyl, benzoyl and phenyl ring halogen, C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl, C ₁ -C ₆ alkoxy, nitro, cyano is selected from phenyl, benzyl, benzoyl group substituted with 1 to 3 minutes substituted selected from groups such as a furnace;

R ² is selected from hydrogen, C ₁ -C ₆ alkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ alkoxyalkyl, C ₁ -C ₆ haloalkyl, acetyl, propionyl and C ₂ -C ₆ alkoxycarbonyl groups will be ;

R ³ is selected from hydrogen, C ₁ -C ₆ alkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ alkoxyalkyl and C ₁ -C ₆ haloalkyl group, and R ² and R ³ together are methylene, ethylidene , Propylidene or isopropylidene group can be formed;

및 CH₂Z 등의 기중에서 선택된 것으로 :W is cyano, thiocarbamoyl,

And CH ₂ Z and the like selected from:

Wherein G is hydroxy, mercapto, C ₁ -C ₁₀ alkoxy, C ₁ -C ₁₀ haloalkoxy, C ₂ -C ₁₀ alkenyloxy, C ₂ -C ₁₀ alkynyloxy, C ₁ -C ₁₀ alkylthio, C ₂ -C ₁₀ alkenylthio, C ₂ -C ₁₀ alkynylthio, C ₃ -C ₇ cycloalkoxy, C ₃ -C ₇ cycloalkoxy, phenoxy, substituted with one or two C ₁ -C ₄ alkyl groups, Phenylthio, benzylthio, benzyloxy, or C ₁ -C ₆ alkoxy, amino, ammonio, cyano, N- (C ₁ -C ₆ alkyl) amino, N, N-di (C ₁ -C ₆ alkyl) C ₁ -C ₆ alkoxy or phenyl rings substituted with amino and N, N, N-tri (C ₁ -C ₆ alkyl) ammonia groups, such as halogen, nitro, cyano, C ₁ -C ₆ alkyl, OM, R, wherein phenoxy, phenylthio, benzyloxy and benzylthio, M are cations of an inorganic or organic base, substituted with 1-3 substituents selected from C ₁ -C ₆ haloalkyl, C ₁ -C ₆ alkoxy groups, and the like ⁴ is C ₁ -C ₁₀ alkyl and C ₁ -C ₁₀ -NHSO ₂ selected from a haloalkyl group R ^4, R ⁵ and R ⁶ are independently selected from hydrogen, C ₁ -C ₆ alkyl, C ₁ -C ₆ hydroxyalkyl, C ₁ -C ₆ haloalkyl, phenyl, benzyl groups or both R ⁵ and R ⁶ are hetero -NR ⁵ R ⁶ , R ¹⁰ selected from the ring is selected from such several groups as -ON = R ¹⁰ group, which is a C ₁ -C ₁₀ alkylidene group; Z is selected from halogen, hydroxy, mercapto, C ₁ -C ₁₀ alkoxy, C ₁ -C ₁₀ haloalkoxy, C ₁ -C ₁₀ alkylthio and NR ⁵ R ⁶ groups having R ⁵ and R ⁶ as defined above will be.

X is selected from oxygen and sulfur; k, l, m are each 0 or 1, provided that k + l + m is 0, 1 or 2; n is 0.1 or 2.

Compounds of formula I in which R ² and R ³ are not identical are optically active. The present invention therefore encompasses stereoisomeric mixtures which also contain racemic mixtures of the stereoisomers and stereoisomers of each of these compounds.

A, B, D, E, U and V include hydrogen, halogen, nitro, cyano, thiocyano, amino substituted with one or two C ₁ -C ₆ alkyl groups as needed, and one or more halogen atoms as required Substituted C ₁ -C ₆ alkyl, C ₂ -C ₆ alkenyl, C ₃ -C ₇ cycloalkyl, C ₁ -C ₆ alkoxy, C ₁ -C ₆ alkylthio, C ₁ -C ₆ alkylsulfinyl, C _1- C ₆ alkylsulfonyl, carbalcoxi where alkoxy is a C ₁ -C ₆ alkoxy group, phenyl ring halogen C ₁ -C ₆ haloalkyl, C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy, Phenyl, phenoxy, phenylthio groups, etc. substituted with 1-3 substitutions selected from nitro cyano groups etc. are suitable.

R ¹ includes hydrogen, C ₁ -C ₁₀ alkyl, C ₂ -C ₁₀ alkenyl, C ₂ -C ₁₀ alkoxyalkyl, C ₁ -C ₁₀ haloalkyl, formyl, C ₂ -C ₁₀ alkanoyl and a phenyl ring Phenyl, benzyl, benzoyl groups substituted with one or two substituents selected from halogen, nitro, cyano, C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl, C ₁ -C ₆ alkoxy groups, etc. Etc. are suitable.

R ² includes hydrogen, C ₁ -C ₆ alkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ alkoxyalkyl, C ₁ -C ₆ haloalkyl, acetyl, propionyl, C ₂ -C ₆ alkoxycarbonyl group, and the like. This is suitable.

R ³ is preferably hydrogen, C ₁ -C ₆ alkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ alkoxyalkyl and C ₁ -C ₆ haloalkyl group, and R ² and R ³ together are methylene and ethylidene. , Propylidene or isopropylidene group can be formed.

와 CH₂Z기등이 적당한데 ;W is cyano, thiocarbamoyl,

And CH ₂ Z groups are suitable;

In this equation, G is hydroxy, mercapto or halogen, hydroxy, C ₁ -C ₆ alkoxy group-substituted C ₁ -C ₁₀ alkoxy, or C ₁ -C ₁₀ alkylthio, C ₂ -C ₁₀ alkenyloxy, C ₂ -C ₁₀ alkynyloxy, C ₂ -C ₁₀ alkenylthio, C ₃ -C ₇ cycloalkoxy, substituted by 1 or 2 C ₁ -C ₄ alkyl groups, phenyl ring halogen, nitro, cyano, C ₁ Phenoxy, phenylthio, benzyloxy, benzylthio, M substituted with one or two substituents selected from -C ₆ alkyl, C ₁ -C ₆ haloalkyl, C ₁ -C ₆ alkoxy groups, etc. cations OM group, R ⁴ is C ₁ -C ₁₀ alkyl and C ₁ -C ₆ haloalkyl group in the selected de -NHSO ₂ R ⁴ group, R ⁵ and R ⁶ is hydrogen, C ₁ -C ₆ alkyl (halogen, hydroxy C ₁ -C ₁₀ alkoxy, C ₁ selected from hydroxy, phenyl, benzyl, or the like, or R ⁵ and R ⁶ together form a heterocycle, and Z is halogen, hydroxy, mercapto, or halogen. -C ₁₀ alkoxythio and It is appropriate that R ⁵ and R ⁶ are selected from the group —NR ⁵ R ⁶ as defined above. k, l and m are preferably 0 or 1, where k + 1 + m is 0 or 1.

Preferably A, B, D and E are hydrogen, halogen, nitro, cyano, amino, C ₁ -C ₆ alkylamino, di (C ₁ -C ₆ alkyl) amino, C ₁ -C ₆ alkyl, C ₁ -C Preferably ₆ haloalkyl, C ₂ -C ₆ alkenyl, C ₁ -C ₆ alkoxy, C ₁ -C ₆ haloalkoxy, C ₁ -C ₆ alkylthio, carboxy and (C ₁ -C ₆ alkoxy) carbonyl , U and V are preferably hydrogen, halogen, nitro, cyno, C ₁ -C ₆ alkyl and C ₁ -C ₆ haloalkyl.

In addition, R ¹ is composed of hydrogen, C ₁ -C ₆ alkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ alkynyl, benzyl, (C ₁ -C ₆ alkoxy) carbonylmethylene, cyanomethylene, etc. Preferably, R ² is preferably selected from hydrogen, C ₁ -C ₆ alkyl, C ₂ -C ₆ alkoxyalkyl and (C ₁ -C ₆ alkoxy) carbonyl and the like, and R ³ is preferably hydrogen and C ₁ -C ₆ alkyl It is good to be.

W should also be of the following groups:

기, 여기서 G는 히드록시, C₁-C₁₀알콕시, C₁-C₁₀할로알콕시, C₂-C₁₀알케닐옥시, C₂-C₁₀알키닐옥시, C₁-C₁₀알킬티오, C₂-C₁₀알케닐티오, C₂-C₁₀알키닐티오, 페녹시, 벤질옥시, 시클로헥실옥시, 또는 C₁-C₆알콕시, 아미노, N-(C₁-C₆알킬) 아미노, N, N-디(C₁-C₆알킬) 아미노와 N, N, N-트리(C₁-C₆)알킬 아미노기 등에서 선택한 치환분으로 치환된 C₁-C₁₀알콕시기, R⁵와 R⁶가 수소, C₁-C₆알킬, C₁-C₆히드록시알킬, C₁-C₆할로알킬, 페닐 등에서 서로 무관하게 선택된 NR⁵R⁶기, M이 알칼리금속이온이나 알칼리토금속이온, 암모늄이온 NH÷R⁷R⁸R⁹(R⁷, R⁸과 R⁹가 수소, C₁-C₆알킬, C₁-C₆히드록시알킬, 페닐과 벤질 등에서 임의로 선택된 것)인 OM기, R⁴가 C₁-C₆알킬인 -NHSO₂R⁴기, R¹⁰이 C₁-C₁₀알킬리덴인 -O-N=R¹⁰기 등 이러한 여러기에서 선택된 것이며 ;a)

Wherein G is hydroxy, C ₁ -C ₁₀ alkoxy, C ₁ -C ₁₀ haloalkoxy, C ₂ -C ₁₀ alkenyloxy, C ₂ -C ₁₀ alkynyloxy, C ₁ -C ₁₀ alkylthio, C ₂ -C ₁₀ alkenylthio, C ₂ -C ₁₀ alkynylthio, phenoxy, benzyloxy, cyclohexyloxy, or C ₁ -C ₆ alkoxy, amino, N- (C ₁ -C ₆ alkyl) amino, C ₁ -C ₁₀ alkoxy group substituted with a substituent selected from N, N-di (C ₁ -C ₆ alkyl) amino and N, N, N-tri (C ₁ -C ₆ ) alkyl amino group, R ⁵ and R ⁶ is hydrogen, C ₁ -C ₆ alkyl, C ₁ -C ₆ hydroxyalkyl, C ₁ -C ₆ haloalkyl, independently of each other selected from a phenyl group NR ⁵ R ^6, M is an alkali metal ion or alkaline earth metal ion, An OM group with ammonium ion NH ÷ R ⁷ R ⁸ R ⁹ (R ⁷ , R ⁸ and R ⁹ optionally selected from hydrogen, C ₁ -C ₆ alkyl, C ₁ -C ₆ hydroxyalkyl, phenyl and benzyl, etc.), -NHSO ₂ R ⁴ group wherein R ⁴ is C ₁ -C ₆ alkyl and -ON = R ¹⁰ group wherein R ¹⁰ is C ₁ -C ₁₀ alkylidene. Will;

b) a —CH ₂ Z group, where Z is halogen, hydroxy, mercapto C ₁ -C ₁₀ alkoxy and R ⁵ and R ⁶ are hydrogen, C ₁ -C ₆ alkyl, C ₁ -C ₆ hydroxyalkyl, C _And -NR ⁵ R ⁶ group optionally selected from ₁ -C ₆ haloalkyl and phenyl group. Preferably X is oxygen and n is 0 or 2. Even more preferred;

A, B, D and E are selected from hydrogen, halogen, C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy, C ₁ -C ₆ haloalkyl group, and the like, U and V are randomly selected from hydrogen and halogen, R ¹ is hydrogen, C ₁ -C ₆ alkyl, C ₂ -C ₆ alkynyl,

Benzyl, (C ₁ -C ₆ alkoxy) carbonylmethylene, cyanomethylene and the like.

R ² is preferably selected from hydrogen, C ₁ -C ₆ alkyl and C ₂ -C ₆ alkoxyalkyl group, and R ³ is selected from hydrogen and C ₁ -C ₆ alkyl group.

기로 된 것이 좋은데, 여기서 G는 히드록시, C₁-C₁₀알콕시, C₂-C₁₀알케닐옥시, C₂-C₁₀알키닐옥시, C₁-C₁₀알킬티오, C₁-C₁₀할로알콕시, 또는 아미노, N-(C₁-C₆알킬) 아미노, N, N-디(C₁-C₆알킬) 아미노와 N, N, N-트리(C₁-C₆알킬) 암모니오 등에서 선택한 치환분으로 치환된 C₁-C₆알콕시, M이 알칼리금속이온이거나 알칼리토금속이온인 OM기, R¹⁰이 C₁-C₆알킬리덴기인 -O-N=R¹⁰기, R⁵와 R⁶가 수소, C₁-C₆알킬, C₁-C₆히드록시알킬과 C₁-C₆할로알킬기 등에W is

Group is preferred, wherein G is hydroxy, C ₁ -C ₁₀ alkoxy, C ₂ -C ₁₀ alkenyloxy, C ₂ -C ₁₀ alkynyloxy, C ₁ -C ₁₀ alkylthio, C ₁ -C ₁₀ halo Alkoxy, or amino, N- (C ₁ -C ₆ alkyl) amino, N, N-di (C ₁ -C ₆ alkyl) amino and N, N, N-tri (C ₁ -C ₆ alkyl) ammonio C ₁ -C ₆ alkoxy substituted with the selected substituent, OM group in which M is an alkali metal or alkaline earth metal ion, -ON = R ¹⁰ group in which R ¹⁰ is a C ₁ -C ₆ alkylidene group, R ⁵ and R ⁶ are Hydrogen, C ₁ -C ₆ alkyl, C ₁ -C ₆ hydroxyalkyl and C ₁ -C ₆ haloalkyl groups, and the like.

Is selected from the group -NR ⁵ R ⁶ selected.

m is 0, k and l are selected from 0 and 1, k + l is 0 or 1 and n is 0.

Better compounds of formula I are compounds in which the phenyl ring therein is 1,4-substituted, ie, compounds of formula II.

Specific examples of the compounds according to the invention are listed in Tables 1, 2, 3 and 4 below.

TABLE 1

TABLE 2

TABLE 3

TABLE 4

Chart A

The present invention provides a process for the preparation of compounds of formula (I) which can be prepared by various methods.

임, 단 G는 히드록시가 아님) 화합물은 구조식 Ib(I식에서 W가 -CO₂H임)의 산으로부터 제조할 수 있는데, 예를 들면, 산성염을 생성하기 위해 염기로 산을 중화하거나, 산에스테르를 생성하기 위해 알코올, 티올, 페놀 또는 티오페놀 등으로 산을 에스테르화하거나, 아미드를 생성하기 위해 산(또는 산할로겐화물유도체)과 아민을 반응시키는 것이다 (도표 A). 산성염, 산에스테르, 산할로겐화물과 산아미드를 제조하는 기술에 있어서 공지된 방법을 적당히 실험상으로 적용시켜 본 발명에 의한 구조식 Ib의 화합물로부터 구조식 Ia의 화합물을 제조할 수 있다.Structural formula Ia, where W is

Provided that G is not hydroxy) The compound may be prepared from an acid of formula Ib (W in formula I is —CO ₂ H), for example, by neutralizing the acid with a base to produce an acid salt, or Acids are esterified with alcohols, thiols, phenols or thiophenols to produce esters, or acids (or acid halide derivatives) react with amines to produce amides (Figure A). In the art for producing acid salts, acid esters, acid halides and acid amides, known methods can be suitably applied experimentally to prepare compounds of formula Ia from the compounds of formula Ib according to the invention.

The nitrile of formula Ic in which W is -C = N in formula I can be prepared from the acid amide of cast Id (W in formula I is -CONH ₂ ).

Chart B

임, 단 G는 OH기 또는 O-알킬기)의 산 또는 산에스테를 환원시켜 제조할 수 있다 (도표 C). 예를 들어서 수소화 알루미늄리튬을 사용하여 환원시키는 것처럼 산 또는 산에스테르를 알코올로 환원시키는 기술에 있어서 공지된 방법을 적당히 실험상으로 적용시켜 본 발명에 의한 구조식 If의 에스테르로부터 구조식 Ie의 알코올을 제조할 수 있다.The alcohol of formula Ie (W in formula I is —CO ₂ OH) according to the present invention has the structure If (W in formula I

Provided that G can be prepared by reducing the acid or acid ester of an OH group or an O-alkyl group) (Table C). For example, in the technique of reducing acid or acid ester to alcohol, such as reducing with lithium aluminum hydride, a known method may be appropriately applied experimentally to prepare an alcohol of formula Ie from the ester of formula If according to the present invention. Can be.

Alkylhalides of formula Ig (W in formula I is —CH ₂ -halogen) according to the present invention may be prepared by halogenating an alcohol of formula Ie (W in formula I is —CH ₂ OH). For example, in the technique for converting an alcohol to an alkyl halide, such as by halogenating with a reagent such as thionyl chloride, a known method is appropriately applied experimentally to obtain an alkyl halide of formula Ig from an alcohol of formula Ie according to the present invention. It can manufacture.

The ether of formula Ih (W in formula I is —CO ₂ OR) according to the present invention is formula Ie (W in formula I is —CH ₂ −

Chart C

OH) alcohol can be prepared by alkylation. In the technique for converting alcohols into ethers, such as by reaction with alkylhalides by Williamson ether synthesis and alkylation, suitable methods are experimentally applied to determine the structure of the formula Ih from the alcohol of formula Ie according to the present invention. Teher can be prepared.

In addition, the ether (thioether) of the structural formula Ih (wherein W is -CH ₂ OR (-CH ₂ SR) in the formula I) is an alkyl halide of the formula Ig (W is -CH ₂ -halogen in the formula I). It can be prepared by alkoxylation (thioalkylation). Alkyl halides of the structural formula Ig according to the present invention are suitably applied in a known manner in the technique for converting alkyn halides to ethers (thioethers) as if they are alkoxylated by reaction with an alcohol (thiol) by the Williamson ether synthesis method. It is possible to prepare ethers (thioethers) of the formula Ih (Ii) from the cargo.

)의 아미드를 환원시켜 제조할 수 있다. 아민과 반응시켜 알킨할로겐화물을 아민으로 전환시키거나, 수소화 알루미늄리튬같은 시약을 사용하여 아미드를 아민으로 환원시키는 기술에 있어서 공지된 방법을 적당히 실험상에 적용시켜 본 발명에 의한 구조식 Ig의 알킬할로겐화물로부터 구조식 Ij의 아민을 제조하거나, 구조식 Ik의 아미드로부터 아민을 제조할 수 있다.The amine of formula Ij (W in formula I is —CH ₂ NR ⁴ R ⁵ ) according to the present invention may be aminated to alkyn halides of formula Ig (wherein W is —CH ₂ —halogen) or W

Can be prepared by reducing the amide of Alkyl halides of the formula Ig according to the present invention may be suitably applied in a known manner in the technique of reacting with an amine to convert an alkyn halide to an amine or to reduce the amide to an amine using a reagent such as lithium aluminum hydride. The amines of formula Ij can be prepared from the cargo, or the amines can be prepared from amides of formula Ik.

N-oxides of formula (I) according to the invention wherein one or more of k, l each m is 1 can be prepared by oxidizing a compound of formula (I) wherein one or more of k, l, m is O. In the technique of oxidizing benzotriazine to benzotriazine N-oxide using persulfate, peroxide, peracid, or perester, a well-known method is appropriately applied experimentally and the new N- Oxides can be prepared.

R ¹ a compound of formula I according to the invention is different from hydrogen can be prepared by R ¹ is the alkylation of a compound of the formula I hydrogen or acylated. In the technique for preparing derivatives of secondary amines by alkylating with alkyl halides or acylating with acyl halides, known methods can be suitably applied experimentally to produce novel compounds according to the invention wherein R ¹ is not hydrogen. .

Compounds of formula I wherein A, B, D, E, U, V, X, R ¹ , R ² , R ³ , W, k, l, m and n are defined above are preferred as shown in Table D. In the following, the compound of formula (VII) may be prepared by condensation reaction with a phenol or thiophenol of formula (VII) in the presence of an alkaline substance, wherein hal in formula (VII) is chlorine, bromine or iodine.

Chart D

The compound of formula I can also be prepared by the following method;

Chart E

a) a process of condensation of a suitable benzotriazine derivative of formula V with a suitable aniline of formula VI according to table E, in which L is a leaving group (e.g. alkylsulfonyl, chlorine, bromine or iodine) ; or

b) the method of successive steps:

(i) condensing a suitable benzotriazine derivative of formula (V) with a suitable aniline of formula (V) to form a compound of formula (V) where L is a leaving group, e.g. alkylsulfonyl, chlorine, bromine or iodine Q in Ⅶ and 를 represents hydroxy, mercapto, C ₁ -C ₆ alkoxy or C ₁ -C ₆ alkylthio);

(ii) dealkylation of the compound of formula VII prepared in step (i) to form a compound of formula VII (wherein Q is C ₁ -C ₆ alkoxy or C ₁ -C ₆ alkylthio); And

(iii) a method of condensing the product of formula (VII) obtained in step (i) or (ii) with a compound of formula (VII) according to the method described in Table D above (steps (i) and (ii) are shown in Table F) have) ; or

c) the method of successive steps:

(i) condensation of a suitable benzotriazine derivative of formula XI with a suitable benzene derivative of formula XII to form a compound of formula VII (wherein L in formula XII represents alkylsulfonyl, chlorine, bromine or iodine as leaving group and And in XIII Q is hydroxy, mercapto, C ₁ -C ₆ alkoxy or C ₁ -C ₆ alkylthio);

(ii) according to the method described in step (i) of Table F above, dealkylation of the compound of formula (VII) prepared in step (i) yields a compound of formula (V) wherein Q is C ₁ -C ₆ alkoxy or C ₁ -C ₆ alkylthio); And

(iii) a method of condensing the product of formula (VII) obtained in step (i) or (ii) with a compound of formula (VII) according to the method described in table D above (step (i) is shown in table G).

Chart G

The condensation reaction described in Table D and described above is preferably carried out in the presence of an alkaline substance and a solvent. Suitable alkaline materials include hydroxides and carbonates of alkali and alkaline earth metals such as sodium hydroxide, potassium hydroxide or sodium carbonate and potassium carbonate. Suitable solvents include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and dipolar aprotic such as dimethylformamide, dimethylacetamide, dimethyl sulfoxide, N-methylpyrrolidone, hexamethylphosphoramide, and sulfolane. Solvent and the like.

The condensation reaction described above and described in Tables E and F is preferably carried out in the presence of a solvent. In order for the condensation of Tables D, E, F and G described above to be an effective reaction, the reaction conditions vary depending on the nature of the reactants and the solvent used. In general, the reaction is accelerated by heating, which is better to react for 30 minutes to 20 hours at a temperature of 40 ℃ -150 ℃. However, if necessary, the reaction temperature can be raised or lowered and the reaction time can be further reduced or extended.

The dealkylation reactions described in steps (ii) of step b) and (ii) of step c) and shown in Tables F and G can be enhanced using various reagents known in the art. For example, sodium thioethoxide dissolved in pyridine hydrochloride, hydroiodic acid, hydrobromic acid, dimethylformamide, acetyl P-toluesulfonic acid, potassium iodide or sodium iodide dissolved in formic acid or acetic acid, 2, 4, 6- Reagents such as lithium iodide and boron tribromide dissolved in collidine may be used to cleave the atyl-alkylether bond. Reaction time and reaction conditions vary widely depending on the dealkylation reagent used and the ether cleaved.

In general, the reaction conditions when using the above "ether-cut" reagent are known to those skilled in the art, and the method is suitably applied experimentally to steps (ii) and (ii) of (b) above. The "ether-cut" reactions described in the steps and shown in Tables F and G can be effectively carried out.

Compounds of formula (VII), which are useful intermediates produced during the preparation of compounds of formula (I), are new.

Accordingly, embodiments of the present invention also provide a process for the preparation of the compounds of formula V wherein A, B, D, E, k, l, m, R ¹ , U, V and Q are defined above.

The compound of formula I is effective as a herbicide and further the present invention provides a method of severely damaging or killing weeds by administering an effective amount of the compound of formula I as described above to a crop or growth medium of the crop.

In general, compounds of formula I are effective for herbicidal action on many types of work. However, some compounds according to the present invention are selectively effective against monocotyledonous plants and the dicotyledonous plants are hardly affected by the extent of administration of the compounds according to the invention, which causes severe damage or lethality in other plant species.

In addition, some of the compounds of formula I are optionally effective in the monocotyledonous plants and thus can be used in sufficient proportion to kill or severely damage the monocotyledonous weeds present in the monocotyledon crops.

Therefore, in another aspect, the present invention provides a sufficient amount of the compound of formula I as defined above to kill or severely damage the weeds and to substantially inhibit the growth of weeds present in the crops by substantially adding to the growth medium of the crops. Provide a method.

The compounds of formula I can be used either by direct administration to plants (administration after germination) or by addition to the soil before the plants germinate (administration before germination). In general, however, these compounds are more effective when administered after the plants have received them.

The compounds of formula I may be used alone to kill or severely damage weeds and inhibit their growth, but preferably are used in the form of a composition comprising a compound of the invention in a mixture with a carrier containing a solid or liquid diluent. good. Therefore, in another aspect, the present invention provides a composition containing the compound of formula I as defined above and an inert carrier, as a composition for inhibiting weed growth, damaging and killing weeds.

The composition according to the present invention may be a composition which is diluted to be used directly, or a concentrated composition which should be diluted with water before use. Preferably these compositions contain 0.01-90% by weight of the active ingredients of the present invention, but in the case of dilutable compositions which can be used directly, they contain 0.01-2% of the active ingredient and 20-90 for the concentrated composition. It contains 20% of active ingredient, preferably 20-70%.

The solid composition may be in the form of a granule or a dispersant in which solid diluents such as kaolin, bentonite, diatomaceous earth, dolomite, calcium carbonate, talc, powdered magnesia, poppo and gypsum are mixed with an active ingredient. They may also be in the form of powders or particles containing a humectant to facilitate the dispersion of the powders or particles in the liquid. Solid compositions in powder form are used as foliar powders.

The liquid composition optionally contains a surfactant and consists of a solution or dispersion in which the active ingredient is dissolved in water. They may also consist of solutions or dispersions in which the active ingredient is dissolved in an organic solvent that does not mix with water dispersed as water droplets.

The surfactant can be cationic, anionic or nonionic. Cationic surfactants include quaternary ammonium compounds such as cetyltrimethylammonium bromide. Suitable anionic surfactants include aliphatic monoester salts of sulfuric acid such as sodium lauryl sulfate and sodium dodecylbenzenesulfonate, sodium lignosulfonate, calcium lignosulfonate, ammonium lignosulfonate, butylnaphthalene sulfonate and diisopropyl. And salts of sulfonated aromatic compounds such as sodium salt mixtures of triisopropyl naphthalenesulfonic acid and the like. Suitable nonionic surfactants include condensation products in which fatty alcohols such as oleyl alcohol and cetyl alcohol or alkylphenols such as octyl-, nonyl-phenol and octyl-cresol are reacted with ethylene oxide. Other nonionic surfactants include partially esterified and hexitol anhydrides derived from long chain fatty acids. For example, sorbitan monolaurinate and lecithin are partial esters that are condensation products with ethylene oxide.

Aqueous solutions or dispersions can be prepared by dissolving an effective component in an organic solvent or water that optionally contains a wetting agent or a dispersing agent, and in the case of using an organic solvent, the resulting mixture is prepared by adding a wetting agent or a dispersing agent to water optionally. . Suitable organic solvents include ethylene dichloride, isopropyl alcohol, propylene glycol, diacetone alcohol, toluene, petroleum, methylnaphthalene, xylene and trichloroethylene.

Compositions used in the form of aqueous solutions or dispersions are generally supplied as concentrates containing high concentrations of the active ingredient, so the concentrate is diluted with water before use. Concentrates should be prepared to withstand long term storage, so that aqueous formulations prepared by dilution with water after long term storage should be made homogeneous for sufficient time to be used by conventional injectors. . Concentrates usually contain 20-90%, preferably 20-70%, by weight of the active ingredient. The ready-to-use diluted formulation forms contain different amounts of active ingredients depending on the intended and intended purpose, and are usually used in an amount of 0.01-10.0% by weight, preferably 0.1-2% by weight.

A more preferred form of the concentrated composition consists of the finely divided active ingredient dispersed in water in the presence of a surfactant or suspending agent. Suitable suspension agents include hydrophilic colloids such as polyvinylpyrrolidone and sodium carboxymethylcellulose and vegetable rubbers such as gum arabic and tragacanth. More preferred suspension agents are hydrous colloidal silicate minerals that give thixotropic properties to the concentrate and increase their viscosity. For example, montmorillonite, Weidelite, nontronite, hectorite, sandpaper. Knight, sorbite and the like, with bentonite being particularly preferred. Other suspension agents include cellulose derivatives and polyvinyl alcohol. The amount of use of the compound according to the invention is due to various factors, for example, depending on the kind of compound to be used, the kind of plant to inhibit growth, the type of formulation to be used and whether the compound to be used is foliar absorption or root absorption. However, as a general guideline, it is appropriate to administer about 0.005-20 kg per hectare and about 0.01-5 kg / ha.

The composition according to the present invention may contain one or more compounds having biological activities not according to the present invention in addition to one or more compounds prepared by the present invention. As noted above, the compounds according to the invention are substantially more effective on monocotyledonous plants or narrow leaf herbaceous plants than on dicotyledonous or broadleaf plants.

In conclusion, in some applications, the compounds according to the invention may be used alone for herbicidal purposes to provide sufficient protection of the crops.

Thus, in further embodying the present invention, the present invention provides a herbicidal composition consisting of a mixture comprising not only at least one herbicidal compound of formula I as defined above, but also at least one other herbicide.

Another herbicide is a herbicide that does not have structure I and is generally a supplement. Most preferred is a mixture of herbicides that act on herbicides, followed by mixtures containing contact herbicides.

Examples of useful supplements include the following.

A. benzo-2, 1, 3-thiadiazin-4-one, such as 3-isopropylbenzo-2, 1, 3-thiadiazin-4-one-2, 2-dioxide (common name, bentazone) -2, 2-oxide

B. Hormone herbicides and in particular 4-chloro-2-methylphenoxy acetic acid (Gen. MCPA), 2- (2,4-dichlorophenoxy) propionic acid (Gen., dichloroprop), 2, 4, 5-trichlorophenoxy Citric acid (genus name, 2, 4, 5-T), 4- (4-chloro-2-methylphenoxy) butyric acid (genus name, MCPB), 2, 4-dichlorophenoxy acetic acid (genus name, 2, 4-D ), 4- (2, 4-dichlorophenoxy) butyric acid (genus, 2, 4-DB), 2- (4-chloro-2-methyl-phenoxy) propionic acid (genus, mepprop) and derivatives thereof ( Phenoxy alkanoic acid such as salts, esters, amides, etc.);

C. 3- [4- (4-halophenoxy) phenyl] -1, 1-di such as 3- [4- (4-chlorophenoxy) phenyl] -1, 1-dimethylurea (genus name, chlorocuron) Alkyl element;

D. dinitrophenol and 2-methyl-4, 6-dinitrophenol (Gen. DNOC), 2-3 tert-butyl-4, 6-dinitrophenol (Gen. dinolove), 2-tert-butyl-4 Derivatives of dinitrophenol (acetate), such as 6-dinitrophenol (genus name, dinoceb) and ester dinoceb acetate thereof;

E. N ', N'-diethyl-2, 6-dinitro-4-trifluoromethyl-m-phenylenediamine (common name, dinitramine), 2, 6-dinitro-N, N dipropyl Dinitroaniline herbicides such as -4-trifluoromethylaniline (Gen. triflulatin), 4-methylsulfonyl-2, 6-dinitro-N, N-dipropylaniline (Gen. nitrilin);

F. N '-(3,4-dichloro-phenyl) -N, N-dimethylurea (genus name, diuron) and N, N-dimethylurea (genus name, diuron) and N, N-dimethyl-N'- Phenylurea herbicides such as [3-trifluoromethyl) phenyl] urea (genus name, fluoromethuron);

G. 3-[(methoxycarbonyl) amino] phenyl (3-methylphenyl) -carbamate (general name, phenmedipham) and 3-[(ethoxy-carbonyl) amino] phenyl phenylcarbamate (genus name Phenylcarbamoyloxyphenylcarbamate such as desmedipham);

H. 2-phenylpyridazin-3-ones such as 5-amino-4-chloro-2-phenylpyridazin-3-one (common name, pyrazone);

I. 3-cyclohexyl-5, 6-trimethyleneuracil (generic name, lenacil), 5-bromo-3-secondary butyl-6-methyluracil (generic name, bromacil) and tert-butyl-5 Uracil herbicides, such as -chloro-6-methyluracil (genus name and turbasil);

J. 2-Chloro-4-ethylamino-6- (iso-propylamino) -1, 3, 5-triazine (general name atrazine), 2-chloro-4, 6-di (ethylamino) -1, Triazines such as 3, 5-triazine (Gen. Sima) and 2-azido-4- (iso-propylamino) -6-methylthio-1, 3, 5-triazine (Gen. Azinprotrin) Herbicide;

K. 3- (3,4-Dichlorophenyl) -1-methoxy-1-methylurea (general name, linuron), 3- (4-chlorophenyl-1-methoxy-1-methylurea (genus, mono Linuron) and 1-alkoxy-1-alkyl-3-phenylurea herbicides such as 3- (4-bromo-4-chlorophenyl) -1-methoxy-1-petylurea (general name, chlorobromuron);

Thiocarbamate herbicides such as L. S-propyldipropyl-thiocarbamate (general name, verotate);

M. 4-Amino-4, 5-dihydro-3-methyl-6-phenyl-1, 2, 4-triazine-5-one (common name, metamitrone) and 4-amino-6-tert-butyl 1, 2, 4-triazine-5-one herbicides such as -4, 5-dihydro-3-methylthio-1, 2, 4-triazine-5-one (common name, metrizin);

N. 2, 3, 6-trichloro-benzoic acid (Gen. 2, 3, 6-TBA), 3, 6-dichloro-2-methoxybenzoic acid (Gen. Dicamba) and 3-amino-2, 5- Benzoic acid herbicides such as dichlorobenzoic acid (genus name, chlorambene);

O. N-Butoxymethyl-α-chloro-2 ', 6'-diethylacetanilide (genus name, butacrol), corresponding N-methoxy compound (genus name, arachrol), and corresponding N-iso Anilide herbicides such as -propyl compound (genus name, propacrol) and 3 ', 4'-dichloro-propionanilide (genus name, propanyl);

P. 2, 6-dichlorobenzonitrile (general name, dichlorobenyl), 3, 5-dibrobo-4-hydroxybenzonitrile (general name, bromoxynil) and 3, 5-diiodo-4-hydride Dihalobenzonitrile herbicides such as oxybenzonitrile (genus name, Ioxynyl);

Q. 2, haloalkanoic acid herbicides such as 2-dichloro-propionic acid (genus name, Darapon), trichloroacetic acid (genus name, TCA) and salts thereof;

R. 4-nitrophenyl 2-nitro-4-trifluoromethylphenylether (general name, fluorodiphene), 5- (2,4-dichlorophenoxy) -2-methyl nitrobenzoate (genus name, biphenox), 2 -Nitro-5- (2-chloro-4-trifluoromethylphenoxy) benzoic acid, 2-chloro-4-trifluoromethylphenyl 3-ethoxy-4-nitro-phenylether and EP 3,416 Diphenyl ether herbicides such as compounds;

S. N, N-dimethyl-diphenylacetamide (genus name, diphenamide), N- (1-naphthyl) phthalate monoamide (genus name, naphtharam) and 3-amino-1, 2, 4-triazole, etc. Mixed herbicides;

T. BP with an active ingredient of 1, 1'-dimethyl-4, 4'-dipyridyrium ion (general name, paraquat) and 1, 1'-ethylene-2, 2'-dipyridyrium ion (genus name, diquat) Lidrium herbicides;

U. organic arsenic-containing herbicides such as monosodium methane arsenate (genus MSMA);

V. amino acid herbicides such as N- (phosphonomethyl) -glycine (Gen. Glyphosate) and salts and esters thereof;

The invention is illustrated by the following examples. However, these do not limit the present invention.

Example 1

2- {4- [N-methyl-N- (7-chloro-1-oxide-1, 2, 4-benzotriazin-3-yl) amino] methyl phenoxy propionate (1)

a) a mixture of 3, 7-dichloro-1, 2, 4-benzotriazine 1-oxide ^* (3.5 g), 4- (N-methylamino) phenol sulfate (5.6 g) and ethanol solution (50 ml) Heated under reflux for 18 hours. The solvent was partially removed by evaporation and the red solid precipitate (3.0 g) was collected by filtration. The chromatography developed on silica gel (80 g) using chloroform as eluent gave 4- [methyl (7-chloro-1-oxide-1, 2, 4-benzotriazin-3-yl) amino as a red solid. ] Phenol (2.1 g) was calculated.

Mass spectrometry: M ⁺ (molecular ion) was detected at m / e302: C ₁₄ H ₁₁ ClN ₄ O ₂ is seen at m / e302.

b) 4- [methyl (7-chloro-1-oxide-1, 2, 4-benzotriazin-3-yl) amino] phenol (2.1 g), methyl 2-bromopropionate (1.9 g) A mixture of potassium (1.6 g) and methyl ethyl ketone (30 ml) was heated to reflux for 20 hours.

The reaction mixture was filtered and the solvent was distilled off under reduced pressure and an orange solid (3.0 g) was collected. Chromatography developed on silica gel (70 g) using chloroform / methanol as eluent gave an orange solid of 2- {4- [methyl (7-chloro-1-oxide-1, 2, 4-benzotriazine-3 -Yl) 2.7 g of amino phenoxy} propionate was produced.

Vaginal spectroscopy: M ⁺ (molecular ion) was detected at m / e386

C ₁₈ H ₁₇ ClN ₄ O ₄ is found at m / e386.

* J. Jui and G.P. It was prepared by the manufacturing process of Mueller. (J. Org. Chem., 24, 813-818) (1959).

F.J. Wolf, R.M. Wilson, K.P. See also the manufacture of Fister and M. Tishler. (J. Amer, Chem. Soc., 76, 4611-4613) (1954).

Example 2

2- {4- [N-methyl-N- (7-chloro-1-oxide-1, 2, 4-benzotriazin-3-yl) amino] phenoxy} methyl propionate (1)

a) 3, 7-dichloro-1, 2, 4-benzotriazine 1-oxide (30.0 g), 4- (N-methylamino) phenol sulfate (48.0 g), water (400 ml) and acetonitrile (400 ml ) Was heated at reflux for 24 h with stirring.

The solution was concentrated and cooled to give red crystals. The product was recrystallized in acetonitrile-water solution to give 4- [N-methyl-N- (7-chloro-1-oxide-1, 2, 4-benzo) as a red crystalline solid with a melting point of 228-230 ° C. Triazin-3-yl) amino] phenol (36.5%) was produced.

b) 4- [N-methyl-N- (7-chloro-1-oxide-1, 2, 4-benzotriazin-3-yl) amino] phenol (20.8 g), 2-bromopropionate ( 13.8 g), a mixture of anhydrous potassium carbonate (11.4 g) and anhydrous dimethylformamide (100 ml) was heated at 100 ° C. for 2 hours with stirring. After cooling the solution and adding dichloromethane, the mixture was washed repeatedly with water. The obtained organic phase was dried over anhydrous magnesium sulfate, and distilled off under reduced pressure with a solvent.

The product was recrystallized in methanol to give the title compound (16.8 g) with a melting point of 132 DEG C and orange crystals. The defined structure was confirmed by proton magnetic resonance spectroscopy and mass spectrometry.

Example 3

Compounds 13, 14, 15, 16, 17, 18, 19, 22 and 62 listed in Table 1 were prepared in the same order as described in Examples 1 and 2, 1, 2, 4-benzotriazine, 4 It was prepared from a mixed mixture of-(N-methylamino) phenol sulfate and the appropriate 2-halopropionate analkyl. The structure determined for each compound was confirmed by proton resonance spectroscopy and mass spectrometry. Specific physical constants are shown in Table 24 in Example 24.

Example 4

2- {4- [N- (7-chloro-1-oxide-1, 2, 4-benzotriazin-3-yl) amino] phenoxy} methyl propionate (2)

a) heating a mixture of 3, 7-dichloro-1, 2, 4-benzotriazine 1-oxide ^* (3.5 g), 4-aminophenol (3.53 g) and ethanol solution (30 ml) under reflux for 18 hours It was. The solvent was distilled off under reduced pressure to yield 4-[(7-chloro-1-oxide-1, 2, 4-benzotriazin-3-yl) amino] phenol (4.0 g).

b) 4-[(7-chloro-1-oxide-1, 2, 4-benzotriazin-3-yl) amino] phenol (4.0 g) produced in a), methyl 2-bromopropionate (3.7 g), potassium carbonate (3.0 g) and methyl ethyl ketone (40 ml) were heated at reflux for 18 hours. The solvent was distilled off under reduced pressure and the residue was separated into water and chloroform. The chloroform layer was evaporated to dryness to yield a crimson solid (3.0 g). This solid was washed with boiling methanol to give the red solid 2- {4-[(7-chloro-1-oxide-1,2,4-benzotriazin-3-yl) amino] phenoxy}. Methyl propionate (2.0 g) was obtained.

Vaginal spectroscopy: M ⁺ (molecular ion) was detected at m / e374

C ^I ₇ H ₁₅ ClN ₄ O ₄ is found at m / e374.

Example 5

Compounds 12, 54, 56, 65, 67, 74 and 85 described in Tables 1, 2 and 3 were prepared in the same order as described in Example 4 in the appropriate 1, 2, 4-benzotriazine, 4-amino Prepared from a mixture of phenol and the appropriate alkyl 2-halopropionate. The structure determined for each compound was confirmed by proton magnetic resonance spectroscopy and mass spectrometry. Specific physical constants were recorded in Example 24 in Table 5.

Example 6

2- {4- [N-methyl-N- (7-chloro-1, 2, 4-benzotriazin-3-yl) aminophenoxy} methyl propionate (3)

a) 4- [N-methyl-N- (7-chloro-1-oxide-1,2,4-benzotriazin-3-yl) amino] phenol (10.0 g) and zinc powder obtained from Example 1 (4.3 g) was added to a mixture of acetic acid (100 ml) and water (10 ml). The mixture was heated at 100 ° C. for 30 minutes with vigorous stirring. Additional zinc powder (4.3 g) was added followed by heating with continued stirring for 30 minutes. After cooling the mixture, it was filtered and the filtrate was added to a solution mixed with water (100 ml) and 30% V / V hydrogen peroxide solution (5 ml). The mixture solution was stirred at room temperature for 1 hour and filtered to give a solid. The solid was washed with water and dried to give 4- [N-methyl-N- (7-chloro-1, 2,4-benzotriazin-3-yl) amino] phenol, which has a melting point of 224-226 ° C and a red crystalline solid. (8.2 g) was produced.

b) 4- [N-methyl-N- (7-chloro-1, 2, 4-benzotriazin-3-yl) amino] phenol is prepared in the same sequence as described in b) of example 1 Reaction with methyl bromomorphionate gave the title compound having a melting point of 120 ° C. The structure determined by proton magnetic resonance spectroscopy and mass spectrometry was confirmed.

Example 7

Compounds 20, 21, 23, 27, 29, 48, and 63 described in Table 1 were prepared in the same order as described in Example 6 in the appropriate 4- [N-methyl-N- (1-oxide-1, 2,4-benzotriazin-3-yl) amino] phenol and reduced 4- [N-methyl-N- (1,2,4-benzotriazin-3-yl) amino] phenol in a subsequent reaction Was prepared by reacting with an appropriate 2-halopropionate. The structure determined for each compound was confirmed by proton magnetic resonance spectroscopy and mass spectrometry, and the specific physical constants were recorded in Example 24 in Table 5.

Example 8

2- {4- [N-ethyl-N- (7-chloro-1-oxide-1, 2, 4-benzotriazin-3-yl) amino] phenoxy} ethyl propionate (58)

2- {4- [N- (7-chloro-1-oxide-1,2,4-benzotriazin-3-yl) amino] phenoxy} ethyl propionate (1.5 g, compound 85 shown in Example 5) ) And sodium hydride (0.19 g), ethyl iodide (0.60 g) and dimethylformamide dispersed 50% in mineral oil were stirred at room temperature for 15 minutes. The mixture was poured into dichloromethane and washed repeatedly with water. The organic phase was dried over anhydrous magnesium sulfate and the solvent was distilled off under reduced pressure to give a red oil. The crude product was purified by chromatography on silica gel using dichloromethanol as eluent to yield the title compound as a red oil. The structure determined by proton magnetic resonance spectroscopy and mass spectrometry was confirmed.

pmr spectrum (δ ppm in CDCl ₃ ): 1. 30, t, 3H; 1.65, d, 3 H; 4.20, m, 4 H; 4.80, q, 1 H; 7.20, m, 4 H; 7.60, d, 2 H; 8.20, S, 1 H.

Example 9

Structural formulas wherein R ¹ is hydrogen according to the same order as described in Example 8 for compounds 24, 25, 26, 30, 31, 32, 55, 57, 68, 73 and 75 described in Tables 1, 2 and 3 Was prepared by alkylation with a suitable alkyl halide (compound 65 was used to prepare compounds 24, 25, 26, 30, 31 and 32 and compounds 54, 56, 67, 85 and 74 were compounds 55). , 57, 68, 73 and 75, respectively). The structure determined for each compound was confirmed by proton magnetic resonance spectroscopy and mass spectrometry. Specific physical constants were recorded in Example 24 in Table 5.

Example 10

2- {4- [N-methyl-N- (7-chloro-1, 2, 4-benzotriazin-3-yl) amino] phenoxy} propionic acid (28)

Ethyl phenoxypropionate (5.0 g) isopropyl 2-4- [N-methyl-N- (7-chloro-1,2,4-benzotriazin-3-yl) amino] amino After dispersing in propyl alcohol (25 ml), a solution of sodium hydroxide (0.56 g) in water (25 ml) was slowly added for 45 minutes. Isopropyl alcohol (30 ml) was further added to the mixture, followed by stirring at room temperature for 48 hours. The alcohol was distilled off under reduced pressure and the residue was taken up in water. 2M hydrochloric acid was added to this solution to acidify to pH4. The precipitate was collected by filtration and dried to give the title compound having a melting point of 125 ° C. The defined structure was confirmed by proton magnetic resonance spectroscopy and mass spectrometry.

Example 11

Compounds 44, 69 and 82 described in Tables 1 and 4 were prepared by hydrolyzing the corresponding esters 18, 59 and 84, respectively, in the same order as described in Example 10. The structure determined from each compound was confirmed by proton magnetic resonance spectroscopy and mass spectrometry, and the specific physical constants were recorded in Example 24 in Table 5.

Example 12

n-propyl 2- {4- [N-methyl-N- (7-chloro-1, 2, 4-benzotriazin-3-yl) amino] phenoxy} propionate (36)

2- {4- [N-methyl-N- (7-chloro-1, 2, 4-benzotriazin-3-yl) amino] phenoxy} ethyl propionate (80 g) as compound No. 21 in Example 7 A mixture of n-propanol (800 ml) and concentrated sulfuric acid (3 ml) was heated under reflux for 6 h.

A small amount of water was added and the mixture was concentrated. Dichloromethanol was added to this concentrate, and the mixture was washed first with dilute potassium carbonate solution and then again with water.

The organic phase was dried over anhydrous magnesium sulfate and the solvent was distilled off under reduced pressure to give the title compound (80 g) as a red oil. The defined structure was confirmed by proton magnetic resonance spectroscopy and mass spectrometry.

Pmr spectrum (δ ppm in CDCl ₃ ): 0.90, t, 3H; 1.65, m, 5 H; 3.65, S, 3 H; 4.20, t, 2H: 4.80, q, 1H; 7. 20, m, 4H; 7.65, S, 2 H; 8.25, S, 1 H.

Example 13

Chemicals 33, 34, 35, 40, 41, 42, 43 and 78 described in Tables 1 and 4 were prepared by transesterification of the corresponding ethyl esters in the same order as described in Example 12. (Compounds 33, 34 and 35 were prepared from compound 21, compounds 40, 41, 42 and 43 were prepared from compound 18 and compound 78 was prepared from compound 76). The structure determined for each compound was confirmed by proton magnetic resonance spectroscopy and mass spectrometry, and the specific physical constants were recorded in Example 24 in Table 5.

Example 14

2- {4- [N-methyl-N- (7-chloro-1, 2, 4-benzotriazin-3-yl) amino] phenoxy} sodium propionate (37) having a melting point of 178 ° C and a melting point of 184 Sodium propionate (45) is 2- [4- [N-methyl-N- (7-chloro-1-oxide-1,2,4-benzotriazin-3-yl) amino] phenoxy} 45 ° C. Sodium was prepared by neutralizing the corresponding acids (compound No. 28 in Example 10 and compound 44 in Example 11), respectively, and removing the solvent under reduced pressure.

Example 15

2- {4- [N-methyl-N- (7-chloro-oxide-1, 2, 4-benzotriazin-3-yl) amino] phenoxy} propionic acid 2- (dimethylamino) ethyl (51)

a) 2- {4- [N-methyl-N- (7-chloro-2-oxide-1, 2, 4-benzotriazin-3-yl) amino] phenoxy}, compound 44 of Example 11} A mixture of propionic acid (1.5 g) and excess thionyl chloride was heated at reflux for 5 hours.

Excess thionyl chloride was distilled off under reduced pressure to remove 2- {4- [N-methyl-N- (7-chloro-1-oxide-1, 2, 4-benzotriazin-3-yl) amino] Phenoxy} propionyl chloride.

b) A mixture of the acid chloride, 2- (dimethylamino) ethanol (0.41 g) and dichloromethane (20 ml) prepared in step a) was stirred overnight at room temperature. The solvent was distilled off under reduced pressure to give a red oil. The crude product was purified by chromatography on silica gel using dichloromethane as eluent to yield the title compound (1.0 g) as a red oil. The defined structure was confirmed by proton magnetic resonance spectroscopy and mass spectrometry.

Pmr spectrum (δ ppm in CDCl ₃ ): 1.65, d, 3H; 2.00, S, 6 H; 2.40, t, t, 2H; 3.65, S, S, 3 H: 4.15, t, 2 H; 4.80, q, 1 H; 7.20, m, 4 H; 7.60, S, 2 H; 8.20, S, 1 H.

Example 16

Compounds 38, 39, 49, 50, 53, 60, 70, 71, 72 and 83 described in Tables 1 and 4 were prepared after the corresponding gods were prepared with acid chlorides in the same order as described in Example 15. did. Compounds 38, 39 and 71 were prepared from acidic compound 28 of Example 10, compounds 49, 50, 52, 53, 60 and 72 were prepared from acidic compound 44 of Example 11, and compound 70 was Example 11 Was prepared from acidic compound No. 69, and compound 83 was prepared from acidic compound No. 82 of Example 11. The structure determined for each compound was confirmed by proton magnetic resonance spectroscopy and mass spectrometry, and the specific physical constants were recorded in Example 24 in Table 5.

Example 17

2- {4- [N-methyl-N- (7-chloro-1-oxide-1, 2, 4-benzotriazin-3-yl) amino] phenoxy} propanoic acid propargyl (47)

Example 44 compound 2-4- [N-methyl-N- (7-chloro-1-oxide-1,2,4-benzotriazin-3-yl) amino] phenoxy} propionic acid (2.1 g), a mixture of P-toluenesulfonic acid (0.5 g) and excess propargyl alcohol was stirred at 100 ° C. for 4 hours.

After cooling the solution, it was poured into ethyl acetate and the mixture was washed with water. The organic phase was dried over anhydrous magnesium sulfate and the solvent was distilled off under reduced pressure to yield an oil. The crude product was purified by chromatography on silica gel using dichloromethane as the eluent to give the title compound (1.26 g), which had a melting point of 101 ° C. and was an orange crystalline solid. The defined structure was confirmed by proton magnetic resonance spectroscopy and mass spectrometry.

Example 18

2- {4- [N-methyl-N- (7-chloro-1-oxide-1, 2, 4-benzotriazin-3-yl) amino according to the same sequence as described in Example 17 Phenoxy} allyl propionate (46) to 2- {4- [N-methyl-N- (7-chloro-1-oxide-1, 2, 4-benzotriazin-3-yl) amino] phenoxy } Prepared from propionic acid and allyl alcohol, 2- {4- [N-methyl-N- (7-chloro-2-oxide-1, 2, 4-benzotriazin-3-yl) amino] phenoxy} Propionic acid n-propyl (66) 2- {4- [N-methyl-N- (7-chloro-2-oxide-1,2,4-benzotriazin-3-yl) amino] phenoxy} propionic acid Prepared from n-propanol. The structure determined for each compound was confirmed by proton magnetic resonance spectroscopy and mass spectrometry, and the specific physical constants were recorded in Example 24 in Table 5.

Example 19

2- {4- [N-methyl-N- (7-chloro-1, 2, 4-benzotriazin-3-yl) amino] phenoxy} -2-methylpropioate (81)

Example 6 a) 4- [N-methyl-N- (7-chloro-1, 2, 4-benzotriazin-3-yl) amino] phenol (1.5 g), 2-bromo-2 A mixture of ethyl methyl propionate (1.23 g), anhydrous potassium carbonate (0.87 g) and dimethylformamide (15 ml) was heated at 100 ° C. for 3 days with stirring. The inner ear solution was cooled and poured into dichloromethane and the mixture was washed with water. The aqueous phase was dried over anhydrous sulfuric acid magnesium and the solvent was distilled off under reduced pressure to give an oil. The crude product was purified by chromatography on silica gel using dichloromethane as eluent to give the title compound (0.9 g) as a red oil. The defined structure was confirmed by proton magnetic resonance spectroscopy and mass spectrometry.

Pmr spectrum (δ ppm in CDCl ₃ ): 1.30, t, 3H; 1.70, S, 6 H; 3.65, S, 3 H; 4.30, q, 2 H: 7.20, m, 4 H; 7.60, S, 2 H; 8.20, S, 1 H.

Example 20

Compounds 76, 77, 79, 80 and 84 in the appropriate order as described in Example 19 in the appropriate 4- [N-methyl-N- (1, 2, 4-benzotriazin-3-yl) amino] Prepared from phenol and the appropriate 2-haloalkane-carboxylic acid alkyl. The structure determined for each compound was confirmed by proton magnetic resonance spectroscopy and mass spectrometry and the specific physical constants were recorded in Example 24 as Table 5.

Example 21

2- {4- [N-methyl-N- (7-chloro-2-oxide-1, 2, 4-benzotriazin-3-yl) amino] phenoxy} methyl propionate (59)

2- {4- [N-methyl-N- (7-chloro-2-oxide-1,2,4-benzotriazin-3-yl) amino] phenoxy} methyl propionate as compound 3 of Example 6 (6.1 g) and a mixture of acetic acid (110 ml) and hydrogen peroxide 30% V / V solution (44 ml) were stirred at room temperature for 5 days. The precipitated yellow solid was collected by filtration and recrystallized from acetic acid to yield the title compound (5.0 g) having a melting point of 130 DEG C and a yellow crystalline solid. The defined structure was confirmed by proton magnetic resonance spectroscopy and mass spectrometry.

Example 22

2- {4- [N- (7-chloro-2-oxide-1,2,4-benzotriazin-3-yl) amino] phenoxy} ethyl propionate (64) was prepared as described in Example 21. Prepared by oxidizing the compound No. 65 of Example 5 2- {4- [N- (7-chloro-1, 2,4-benzotriazin-3-yl) amino] phenoxy} ethyl propionate by the same procedure It was. The defined structure was confirmed by proton magnetic resonance spectroscopy and mass spectrometry, and the specific physical constants were recorded in Example 24 as Table 5.

Example 23

2- {3-chloro-4- [N- (7-chloro-1-oxide-1, 2, 4-benzotriazin-3-yl) amino] phenoxy} ethyl propioate (61)

2- {4- [N- (7-chloro-1-oxide-1, 2, 4-benzotriazin-3-yl) amino] phenoxy} ethyl propionate (1.5 g) as compound 85 of Example 5 , A mixture of N-chlorosuccinamide (0.57 g) and dichloromethane (20 ml) was stirred at room temperature for 3 days. The mixture was washed with water, dried over anhydrous magnesium sulfate and the solvent was distilled off under reduced pressure to give a red oil. The crude product was purified by chromatography on silica gel using dichloromethane as eluent to collect the title compound (0.81 g) as an orange crystalline solid with a melting point of 169 ° C. The defined structure was confirmed by proton magnetic resonance spectroscopy and mass spectrometry.

Example 24

Many of the compounds according to the invention described in Tables 1 and 4 are solid and can be identified by melting point. Melting points are listed in Table 5a below for convenience.

In addition, many of the compounds according to the invention described in Tables 1 and 4 are oils, which can be identified and identified by proton magnetic resonance (Pmr) spectra. For convenience, Pmr spectroscopy data are reported in Table 5b below.

TABLE 5a

TABLE 5b

Example 25

Concentrated formulations of the compounds according to the invention were prepared as follows:

a) For solids such as oil and lead, 7% V / V of "Teric" Nl3 ("Teric" is a trademark and the ethoxylation product of nonylphenol is "Teric" Nl3 available from ICI Australia Limited) and 3 Dissolving the compound in toluene containing "Kemmat" SC15B ("Kemmat" is a trademark and "Kemmat" SC15B is a formulation of calcium dodecylbenzel calcium sulfonate) in% V / V; or

b) In the case of crystalline solids, the compound and "Dyapol TP (Dyapol" are trademarks and "Dyapol" PT is an anionic suspension agent) contain "Teric" N8 (containing 0.25% V / V of the ethoxylation product of nonylphenol) The mixture was added to an aqueous solution but added in a weight ratio of 5: 1: 94 and ball-milled to the mixture to make a stable suspension.

The resulting emulsified concentrate and suspension were diluted with water to produce an aqueous composition of the concentrate required for use in assessing herbicidal activity before and after germination of the compounds according to the invention.

Example 26

Compounds according to the invention formulated as described in Example 25 were administered prior to germination and herbicidal activity was investigated by the following procedure. The seeds of the species to be tested were sown side by side in a soiled seed box about 2 cm deep. The monocotyledonous plant and the dicotyledonous plant were sprayed by separating the boxes and spraying the two boxes with the required amount of the composition according to the present invention after the seeding.

Two working boxes without spraying the composition according to the present invention were identically made in the same manner and used for comparison purposes. All the boxes were placed in a greenhouse and watered little by little with a watering can to promote germination. Then, sub-irrigation was done to help the crops to best grow. Three weeks later, these boxes were removed from the greenhouse and the results of the visual evaluation of the treatments are listed in Table 6. In Table 6, the degree of damage to the crop is set at 0-3, where 0 represents 0-25% damage, 3 represents 77-99% damage, and 3+ represents 100% damage.

The names of the crops tested were:

Wh Wheat P Bean

Ot Oat Ip Sweet Potato

Rg Tarantula Ms Mustard

Jm Japanese Millet Sf Sunflower

TABLE 6

Example 27

Compounds according to the invention formulated as described in Example 25 were administered after germination and herbicidal activity was investigated by the following procedure. The seeds of the species to be tested were sown side by side in a soiled seed box about 2 cm deep. The monocotyledonous plant and the dicotyledonous plant were sprinkled separately in the same box made in the same way, and the four seed boxes were placed in the greenhouse. Then watering was sprinkled with watering cans to promote germination and underground watering was used to help the crops grow most appropriately. When the crops grew about 20-12.5 cm, each seed box of the monocotyledonous plant and the dicotyledonous plant was moved one by one in the greenhouse, and the composition according to the present invention was sprayed as needed. After the spraying was finished, the box was returned to the greenhouse and left for three more weeks. After 3 weeks, the treatment effect was visually evaluated in comparison with the standard crop not treated with the compound and the results are shown in Table 7.

In Table 7, the degree of damage to the crop is set at a 0-3 rating, where 0 represents 0-25% damage, 3 represents 75-99% damage, and 3+ represents 100% damage.

The names of the experimental crops are as follows:

Wh Wheat Rg Tarantula

Ot Oat Ip Sweet Potato

Jm Nippon Badge Ms Mustard

P Bean Sf Sunflower

TABLE 7

Example 28

The compounds according to the invention were formulated as follows for use in experiments. 160 ml of solution containing "Span" 80. 21.8 g / I and "Tween" 20. 78.2 g / I is diluted to 500 ml in methylcyclohexanone, and 5 ml of the emulsion is added to the appropriate amount of the compound according to the present invention. Mixed.

"Span" 80 is a trademark for surfactants containing sorbitan monolaurate and "Tween" 20 is a trademark for surfactants containing concentrate of sorbitan monolaurate concentrated with 20 moles of ethylene oxide. to be. 5 ml of each emulsion containing the test compound was added to water and diluted to 40 ml. This dilution was then sprayed onto the young plant complexes of the species described in Table 8 and below (experiment after germination). After 14 days, the extent of damage to the experimental crops was evaluated and divided into 0-5 grades and recorded in Table 8.

In Table 8, 0 indicates 0-20% damage and 5 indicates 100% damage completely. When herbicides were administered prior to germination to investigate their activity, the seeds of the experimental crops were placed alongside a thin line in the soil contained in a fiberboard box. Then, the surface was evened out, sprayed with diluent, and a thin layer of new soil was sprayed onto the sprayed soil. After 21 days, damage by herbicides was assessed by dividing them into grades 0-5, as tested after germination. In both cases, the extent of damage by herbicides was assessed in comparison to standard crops not treated with the compound. The results are reported in Table 8 below, and the symbol "-" in the table means that it has not been tested.

The name of the experimental crop is as follows.

Sb beet Xa Xanthium pensylvanicum

RP Rapeseed Ab Abutilon thcophrasti

Ct Cotton Cv Convolvulus arvensis

Sy Bean Co Cassia obtusifolia

Mz corn Av Avena fatua

Mw Fall Wheat Dg Digitaria sanguinalis

Rc paddy Pu Poa annua

Sn Senecio vulgaris Al Alopecurus myosuroides

Ip Ipomea purpurea St Setaria viridis

Am Amaranthus retroflexus Ec Echinochloa crus-galli

Pi Polygonum aviculare Sh Sorghum halepense

Ca Chenopodium album Ag Agropyron repens

Po Portulaca oleracea Cn Cyperus rotundas

Ga Galium aparine

Table 8-A

Table 8-B

Example 29

This example illustrates the selective herbicidal activity of the compounds when the compounds of the invention are administered to pastures. The test compound was formulated in the same order as described in Example 28. Seeds of the experimental crops were rooted using a Stanhay Precision Seeder on hills with flat ends spaced 1 meter apart, and sown two species on each hill. Flattened hills were separated within a subregion based on the dose of the chemical being tested.

Crop seeds were sown at different times and reached almost the same stage of growth at the same time. The Oxford Precision Sprayer with two No "O" T-outlets was fixed at the center of a hill with a width of 1.25m and the prepared experimental compound was sprayed with a width of 1m at this center. In the experiment before germination, the seed compound was sprayed into the hill after seeding. 14, 21, 35 and 63 days after spraying, the degree of damage to crops was visually assessed and the results are expressed in% of damage and reported in Table 9-A. In the experiment after germination, the test compound was sprayed to the hill after 2-3 leaves of the crop were sprouted. 7, 14, 28 and 56 days after the injection, the degree of damage was visually evaluated and the results are expressed in% of damage and recorded in Table 9-B.

The name of the experimental crop is as follows.

Sy Bean (Bethal) Dg Digitaria sanguinalis

Ct cotton (Delta Pine 16) Ec Echinochloa crus-galli

Pn Peanut (Red Spanish) Sg Goldrush

Ss Setaria anceps Sh Sorghum Halepense

Table 9-A

Table 9-B

Claims (1)

In the method for preparing a compound of formula (I), an optical isomer thereof and a salt thereof, the benzotriazine derivative of formula (X) is reacted with a compound of formula (X). Method for preparing the compound.

Wherein X is oxygen; A, B, D and E are each selected from hydrogen, halogen, C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl and C ₁ -C ₆ alkoxy; U and V are Each selected from hydrogen and halogen; R ¹ is selected from hydrogen and C ₁ -C ₆ alkyl; R ² is selected from hydrogen, C ₁ -C ₆ alkyl and C ₂ -C ₆ alkoxyalkyl; R ² is Hydrogen and W is a -COG group, G is C ₁ -C ₁₀ alkoxy; k and l are each 0 or 1 and k + l is 0 or 1; m + n is 0; hal is chlorine, bromine or iodine to be).