KR870001199B1 - Process for preparing 2-(2-imidazolin-2yl)quinolines - Google Patents

Abstract

Title compds. I [R1=C1-4 alkyl; R2=C1-4 alkyl, C3-6 cycloalkyl are prepd. Thus, 3.27g N-[1-(1-cyano-1,2-dimethyl propyl)-2,5-dioxo-3- pyrrolin-3-yl anthranilic acid in 20ml anhyd. acetic acid is reacted with 10ml triethyl amine and 0.122g dimethyl aminopyridine. After stirred at 25≰C under N-gas for 1 h, the reaction mixt. is added into cooled H2O. The resulting ppt. is dissolved in ether, filtered, and dried to give 2.54g 1, 3-dihydro-alpha- isopropyl-alpha -methyl-1,3- dioxo-2-H-pyrrolo [3,4-b -4-acetoxyquinolin-z-acetonitrile.

Description

Method for preparing 2- (2-imidazoline-2-yl) quinoline

The present invention relates to novel 2- (2-imidazoline-2-yl) quinoline compounds, to methods of preparing the quinoline compounds and to intermediates thereof, and also to controlling unnecessary annual and perennial plants with these compounds. It is about how to.

More specifically, the present invention relates to 2- (2-imidazoline-2-yl) quinoline compounds of the formula (I)

*

*

In the above formula,

R ₁ is C ₁ -C ₄ alkyl;

R ₂ is C ₁ -C ₄ alkyl or C ₃ -C ₆ cycloalkyl, when R ₁ and R ₂ are taken simultaneously they represent C ₃ -C ₆ cycloalkyl optionally substituted by methyl May or may not be;

A is COOR ₃ , CONHR ₆ , CHO, CH ₂ OH, COCH ₃ , COC ₆ H ₅ , CN, CH ₃ , CH = NOH, CH ₂ COOH, CONHOH, CHR ₈ OH, CH ₂ CH ₂ COOH,

R ₃ is (1) hydrogen,

(2) di-lower alkyl imino,

(3) C ₁ -C ₁₂ alkyl optionally substituted by any of the following groups: C ₁ -C ₃ alkoxy, halogen, hydroxyl, C ₃ -C ₆ cycloalkyl, benzyloxy, furyl, phenyl Halophenyl, lower alkylphenyl, lower alkoxyphenyl, nitrophenyl, carboxyl, lower alkoxycarbonyl, cyano, or tri-lower alkylammonium,

(4) C ₃ -C ₁₂ alkenyl optionally substituted by any of the following groups: C ₁ -C ₃ alkoxy, phenyl, halogen, or lower alkoxycarbonyl, or two C ₁ -C ₃ An alkoxy group, or two halogen groups,

(5) cycloalkyl of C ₃ -C ₆ optionally substituted by one or two C ₁ -C ₃ alkyl groups,

(6) alkynyl of C ₃ -C ₁₀ optionally substituted by one or two C ₁ -C ₃ alkyl groups,

(7) a cation selected from the group consisting of alkali metals, alkaline earth metals, manganese, copper, iron zinc, cobalt, lead, silver, nickel, ammonium and organic ammonium;

R ₆ is hydrogen, a hydroxyl group, C ₃ -alkenyl, C ₃ -alkynyl or an alkyl group of C ₁ -C ₄ optionally substituted by one hydroxyl group or one chlorine group;

B is H, COR ₄ , or SO ₂ R ₅ ; Provided that when B is COR ₄ or SO ₂ R ₅ , A is COOR ₃ (where R ₃ is not H), or a salt forming cation, CH ₃ or CN; W is O and R ₄ is C ₁ -C ₁₁ alkyl, chloromethyl or 1 chloro, 1 nitro, or phenyl optionally substituted by 1 methoxy group; R ₅ is C ₁ -C ₄ alkyl, or phenyl optionally substituted by one chloro, one methyl group;

W is O or S;

R ₈ is C ₁ -C ₄ alkyl or phenyl;

X is hydrogen, halogen, hydroxyl or methyl;

L, M, Q, R ₇ is hydrogen, halogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ alkylthio, C ₁ -C ₄ alkylsulfonyl, C ₁ —C ₄ haloalkyl, NO ₂ , CN, phenyl, phenoxy, amino, C ₁ -C ₄ alkylamino, di-lower alkylamino, chlorophenyl, methylphenyl or 1 Cl, CF ₃ or NO ₂ Or each selected from the group consisting of feoxy optionally substituted with a CH ₃ group; Wherein one of L, M, Q, and R ₇ may be a hydrogen, halogen, C ₁ -C ₄ alkyl or C ₁ -C ₄ non-alkoxy substituent; In addition, when W is O and A is CN, CH ₃ or COOR ₃ , R ₃ should not be unsaturated alkyl, and when R ₁ and R ₂ are not the same, they may be optical isomers thereof, and R It may be an acid addition salt thereof, except the _third one salt forming cation.

Among the 2- (2-imidazoline-2-yl) quinoline compounds of the formula (I), preferred as herbicides are R ₁ being methyl; R ₂ is methyl, ethyl, isopropyl or cyclopropyl; W is oxygen iso; B is CO-phenyl optionally substituted by hydrogen, CO-alkyl C ₁ -C ₆ or one chloro, nitro or methoxy group; A is R ₃ is a COOR, as defined in the formula _{(1) 3, CH 2 OH} , or CHO, and; X is hydrogen; L, M, Q and R ₇ consist of hydrogen, halogen, methoxy, nitro, C ₁ -C ₄ alkyl, CF ₃ , CN, N (CH ₃ ) ₂ , NH ₂ , SCH ₃ or SO ₂ CH ₃ Each selected from the group, wherein at least one of L, M, Q or R ₇ must be nitro, CF ₃ , CN, N (CH ₃ ) ₂ , NH ₂ , SCH ₃ or SO ₂ CH ₃ .

Among the 2- (2-imidazoline-2-yl) quinoline compounds of the formula (I), more preferably X, L and R ₇ are each hydrogen; R ₁ is methyl; R ₂ is methyl, ethyl, isopropyl or cyclopropyl, B is hydrogen or COCH ₃ ; A is R ₃ is the structural formula (I) as defined in the COOR _3, CH ₂ OH or CHO, and; W is hydrogen; M and Q are each selected from the group consisting of hydrogen, halogen, methyl, methoxy nitro, CF ₃ , CN, N (CH ₃ ) ₂ , NH ₂ , SCH ₃ or SO ₂ CH ₃ ; At least one of M and Q must be a substituent other than hydrogen, halogen, methyl or methoxy.

Even more preferred among the 2- (2-imidazoline-2-yl) quinoline compounds of the formula (1) is R ₁ being methyl; R ₂ is isopropyl; W is oxygen; B, X, L, M, Q and R ₇ are each hydrogen; A is COOR ₃ , wherein R ₃ is C ₁ -C ₈ alkyl, hydrogen, C ₃ -C ₈ alkenyl, C ₃ -C ₈ alkynyl, C ₃ -C ₆ cycloalkyl, or an alkali metal , Alkaline earth metal, manganese, copper, iron, zinc, cobalt, lead, silver, nickel, ammonium and aliphatic ammonium.

In the above structural formula (I), alkali metals include sodium, potassium and lithium, but sodium is generally preferred. In addition, the term "organic ammonium" refers to a reactor consisting of positively charged nitrogen atoms bonded to 1-4 aliphatic groups each containing 1-20 carbon atoms. Organic ammonium groups used to prepare the imidazolinyl quinoline acids and esters of formula (I) include monoalkylammonium, dialkylammonium, trialkylammonium, tetraalkylammonium, monoalkenylammonium, dialkylammonium, trialkenylammonium , Monoalkynyl ammonium, dialkyl ammonium, trialkynyl ammonium, monoalkanol ammonium, dialkanol ammonium, trialkanol ammonium, cycloalkylammonium of C ₅ -C ₆ , piperidinium, morpholinium, pyrroli Dinium, benzyl ammonium and the corresponding compounds and the like. Examples of halogens pointed out herein may include chlorine, fluoro, bromine and iodine, although chlorine and bromine are preferred.

As mentioned above, the present invention relates to 2- (2-imidazoline-2-yl) quinoline compounds and their use as herbicides. These novel quinoline compounds can be represented by formula (I).

Many of the processes as described below are used to prepare the quinoline derivatives of the present invention.

According to the present invention, R ₃ is a substituent other than hydrogen or a salt-forming cation, and R ₁ , R ₂ , X, L, M, Q, and R ₇ are 2- (2) of Structural Formula (V) as described below. To prepare the -imidazoline-2-yl) quinoline carbosylate ester, the dione of the structural formula (II) may be reacted with a suitable alcohol and an alkali metal alkoxide at a temperature of 20-50 ° C. In these reactions, Alcohols have two functions as reactants and solvents, so no separate solvent is required, but may be used if desired. A separate additional solvent may be used, for example, aprotic such as tetrahydrofuran or dioxane. Preference is given to using a solvent, these reactions can be represented as follows.

In which M is an alkali metal; X represents hydrogen, halogen, hydroxyl or methyl, provided that any one of L, M, Q, R ₇ is hydrogen, halogen, alkyl of C ₁ -C ₆ or other than alkoxy of C ₁ -C ₄ In the case of a substituent, X is hydrogen; L, MQ, R ₇ are each hydrogen, halogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ alkylthio, C ₁ -C ₄ alkylsulfonyl, C _1- Haloalkyl of C ₄ , NO ₂ , CN, phenyl, phenoxy, amino, alkylamino, di-lower alkylamino of C ₁ -C ₄ , chlorophenyl, methylphenyl, or one Cl, CF ₃ , NO ₂ , CH Selected from the group consisting of phenoxy substituted with ₃ groups, provided that only one of L, M, Q, R ₇ is hydrogen, halogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ other than alkoxy Or a substituent; R ₁ , R ₂ and R ₃ are as described above.

In order to obtain the 2- (2-imidazoline-2-yl) quinoline carboxylate ester of the formula (V), R ₁ , R ₂ , X, L, M, Q, R ₇ are as described above. The dioxopyrroloquinoline acetamide of (VI) is cyclo-linked with a strong base such as 1,5-diazabicyclo [5.4.0] undec-5-ene (DBU), for example, in the presence of an inert organic solvent such as xylene or toluene. To produce the coarse imidazopyrroloquinolinedione of formula (II). The reaction mixture is heated to a temperature of 100-150 ° C. and water is removed from the reaction mixture using a Dean-Starac water separator. Thereafter, alcohol R ₃ OH of formula (II), wherein R ₃ is as described above but is not hydrogen or a salt forming cation, is added to at least one equivalent of the reaction mixture, and the mixture thus formed is heated to reflux at a temperature of 100 to 150 ° C. The ester of (V) is obtained. This reaction can be expressed as follows.

Wherein R ₁ , R ₂ , R ₃ , X, L, M, Q and R ₇ are as described above.

The 2- (2-imidazoline-2-yl) quinoline carboxylate ester of formula (V) is a cyclocarbamoline of the carbamoyl quinoline carboxylate ester of formula (VIII) with contaminated phosphoric acid at a high temperature of 60-100 ° C. It can also be manufactured by chemistry. This reaction is generally carried out in an inert organic solvent such as toluene or benzene, by which the hydrochloride of 2- (2-imidazolin-2-yl) quinoline carboxylate ester of formula (V) Is generated. The hydrohalide salt thus formed is treated with a base such as, for example, sodium carbonate and potassium carbonate to give the 2- (2-imidazoline-2-yl) quinoline carboxylate ester of formula (V). The structure of the carbamoyl quinoline carboxylate ester of formula (VII) used in the reaction is as follows.

In the above formula, R ₃ is as described above, but is not hydrogen or a salt forming cation, and R ₁ , R ₂ , X, L, M, Q, and R ₇ are as described above.

The 2- (2-imidazoline-2-yl) quinoline carboxylate ester of formula (V) may also be prepared by cyclocyclizing the carbaoyl quinoline carboxylate ester of formula (VII), which also has the structure Can be.

In the above formula, R ₃ is as described above, but is not hydrogen or a salt forming cation, and R ₁ , R ₂ , X, L, M, Q, and R ₇ are as described above.

The carbamoyl quinoline carboxylate esters can be reacted with a mixture of contaminated phosphoric acid and oxyphosphoric acid chlorides to cyclocycle the esters. The reaction mixture is stirred at 15-35 ° C. for several hours and then POCL ₃ is removed in vacuo. The residue produced as a result of this treatment is dispersed in an organic solvent such as toluene. This solvent is removed from the resulting mixture and the residue is dispersed in hot water at 80-100 ° C. After cooling, sodium bicarbonate or potassium bicarbonate was added to adjust the pH of the liquid mixture to 5-6, and the product was extracted into methylene chloride to give 2- (2-imidazoline-2-yl) of formula (V). ) Quinoline carboxylate ester is obtained.

R ₃ is as described above, but not hydrogen or a salt forming cation, R ₁ , R ₂ , X, L, M, Q, R ₇ may contain at least one equivalent of a strong acid quinoline ester of formula (V). The reaction allows the ester to be converted to the corresponding acid addition salt. At this time, strong inorganic acids such as hydrochloric acid, sulfuric acid, bromic acid are used, but organic acids may be used. In practice, it has been found to be most satisfactory when the reaction proceeds in the presence of an inert organic solvent such as ether, chloroform, methylene, chloride or mixtures thereof. In this method, when a lower aliphatic alcohol is used instead of the solvent, a sulfate is prepared.

A is COOH, B is hydrogen, W is oxygen, and R ₁ , R ₂ , X, L, M, Q, R ₇ are as described above except that X, L, M, Q, R ₇ is halogen The 2- (2-imidazoline-2-yl) quinoline derivatives of formula (I), which are not nitro, can be selected from benzyl esters of 2- (2-imidazoline-2-yl) quinoline carboxylate of formula (V). It can be produced by hydrogenolysis. This reaction involves dispersing benzyl ester in an organic solvent and treating the reaction mixture thus formed with a hydrogen gas on a carbon carrier in the presence of a catalyst such as palladium or platinum. This hydrogenolysis is generally carried out at a temperature of 20-50 ° C.

A is COOH, B is hydrogen, W is oxygen, and R ₁ , R ₂ , X, L, M, Q, R ₇ are 2- (2-imidazoline-) of formula (I) as described above. To prepare a 2-yl) quinoline derivative, R ₃ is as described above, but not hydrogen or a salt forming cation, and R ₁ , R ₂ , X, L, M, Q, R ₇ are as defined above The ester of may be reacted with at least one equivalent of a strongly basic aqueous solution such as, for example, an aqueous solution of alkali metal hydroxide at a temperature of 20-50 ° C. After cooling the mixture, the pH is adjusted to 6.5-7.5 with strong inorganic acids. This treatment results in the formation of the desired acid.

A is COOR ₃ , R ₃ is a salt forming cation, B is hydrogen, W is oxygen, and R ₁ , R ₂ , X, L, M, Q, R ₇ are of the formula (I) To prepare a 2- (2-imidazoline-2-yl) quinoline derivative, A is COOH, B is hydrogen, W is oxygen, and R ₁ , R ₂ , X, L, Q, R ₇ are described above. The acid of formula (I) as described above is dissolved in a suitable solvent, and the mixture is then reacted with at least one equivalent of salt forming cation.

The imidazoline quinoline carboxylic acid and its ester compound of formula (I), wherein B is hydrogen, may be a tautomer, but are conveniently represented by a single structure, such as formula (I). These compounds may exist in the following isomers.

Wherein A, W, X, L, M, Q, R ₇ , R ₁ , and R ₂ are as described above, and B is hydrogen.

Therefore, it is assumed that both isomers of the 2- (2-imidazoline-2-yl) quinoline compound are included in the structural formula (I).

In the 2- (2-imidazolin-2-yl) quinoline derivative of formula (I) and imidazopyrroloquinoline dione of formula (II), when R ₁ and R ₂ represent different substituents, R ₁ And the carbon to which R ₂ is attached becomes the asymmetric center, and the product (and its derivatives) is present in the form of d-, 1- and dl-.

Cyclolation of the imidazopyrroloquinoline acetamide of formula (VI) results in the intermediate product of the preparation of 2- (2-imidazolin-2-yl) quinoline carboxylic acid and its ester of formula (I). Tetracyclic imidazopyrroloquinolinedione of the phosphorus structural formulas (II) and (IIa).

The product of this reaction is mainly the desired imidazopyrroloquinolinedione and contains a small amount of the isomers of formula (IIa). Treatment of this isomeric mixture with an alkali metal alkoxide yields an almost pure quinoline carboxylate compound in terms of isomers.

Cyclolation reactions can be carried out at a temperature of 80-150 ° C., for example with a solvent which forms an equivalent mixture with water in the presence of a base such as sodium hydride or potassium hydride or in the presence of an acid such as aromatic sulfuric acid. It is preferably carried out while allowing it to be removed from the reaction mixture as soon as it is produced. Solvents that can be used at this time include toluene, benzene, xylene and cyclohexane. Bases that can be used include alkali metal hydroxides, alkali metal hydrides, alkali metal oxides, and diisopropylethylamine, 1,5-diazabicyclo [3.4] nonene-5,1,5-diazobicyclo [ 5.4.0] Same as undeck-5,1,4-diazabicyclo [2.2.2] octane tertiary amine, tetramethylguanidine, potassium fluoride, and quaternary ammonium hydroxides such as trimethylbenzyl ammonium hydroxide and There is a strong basic ion exchange resin.

Acidic reactants that can also be used include, for example, aromatic sulfuric acid such as p-toluene sulfate, β-naphthalene sulfate, and heavy sulfur naphthalene.

This reaction can be represented graphically as in the following flow diagram (I).

Flow diagram (I)

Various methods are used to prepare the pyrroloquinoline acetamide of formula VI. Preferably, a strong acid such as sulfuric acid is used to hydrate the pyrroloquinoline acetonitrile of formula (VIII). This reaction forms the pyrroloquinoline acetamide of formula VI. The addition of an inert solvent such as methylene chloride, chloroform and the like is not essential for the performance of the reaction, but it is generally preferred to add such solvent to the reaction mixture. This reaction is carried out mainly at temperatures of 10-70 ° C.

Another method of preparing pyrroloquinoline acetamide of formula (VI) is to conduct a cyclo addition reaction by Diels Alder method between substituted anthranyl of formula (IX) and dioxopyrroline acetamide of formula (X). will be. The temperature range required for this reaction is wide. That is, at 130 ° C., a significant amount of aldehyde, which is an intermediate product of formula (XI), is obtained, whereas at 130-200 ° C., pyrroloquinoline acetamide of formula (VI) is formed. Isolation of the intermediate product aldehyde of formula (XI) and cyclolation with reflux of xylene in the presence of an acid catalyst such as p-toluene, for example, affords the desired pyrroloquinoline acetamide of formula (VI). This reaction can be represented graphically as in the following flow diagram (II).

Flow diagram (II)

There are various methods for preparing pyrroloquinoline acetonitrile of formula (VIII), depending on the nature of the L, M, Q, R ₇ substituents.

Pyrroloquinoline acetonitrile of formula (VIII) is reacted with an appropriately substituted anhydride of formula (XII) with an α-aminocarbonitrile of formula (XIV) to form an acid of formula (XIIIa) and (XIIIb) It can be prepared by producing a mixture of monoamides.

This reaction is carried out at a temperature of 20-70 ° C., preferably 35-40 ° C., in an inert solvent such as, for example, tetrahydrofuran, methylene chloride, ether, chloroform, toluene and the like. The acid thus formed is then cyclocyclized to the corresponding pyrroloquinoline acetonitrile of formula (VIII) when the excess acetic anhydride is heated together at a temperature of 75-150 ° C. in the presence of a catalytic amount of sodium acetate or potassium acetate.

The reaction is usually carried out by treating the reaction mixture with acetic anhydride, acetyl chloride, thionyl chloride and the like and heating the reaction mixture to a temperature of 20-100 ° C. This reaction can be represented schematically as flow diagram (III) below, where R ₁ , R ₂ , X, L, M, Q, R ₇ are as described above.

Flow diagram (III)

A preferred method of preparing pyrroloquinoline acetonitrile of formula (VIII) is to react Dielsaldehyde heated cyclo addition with an appropriately substituted maleimide of formula (XV). X must be hydrogen.

The product of this reaction depends on the reaction temperature. At temperatures below 55 ° C., the intermediate product of formula (XVI) is obtained. Further heating of the reaction mixture to 55-130 ° C. yields the intermediate product aldehyde of formula (XI). If the reaction is carried out in an aprotic solvent such as 0-dichlorobenzene and the reaction mixture is heated to 140-200 ° C., this reaction yields pyrroloquinoline acetonitrile of formula (VIII).

This reaction can be expressed as shown in the following flow diagram (IV).

Flow diagram (IV)

The method is particularly effective when L, M, Q, R ₇ are each negatively charged, for example halogen, nitro, CF ₃ , SO ₃ , CH ₃ , CN.

As a method modified from the above method, maleimide or dioxopyrrole of formula (XIX) in which 0-aminoacetal of formula (XVII) is appropriately substituted at a temperature of 50-130 ° C. in the presence of an aprotic solvent such as xylene or toluene. There is a method of reacting with acetamide. These reactions can be represented schematically as follows.

As a further modification useful in the synthesis from aniline in which the positions of L, M, Q, R ₇ are substituted with electron donors or with one halogen or CF ₃ functional group, 0-alkyl or arylthio of the formula (XVIII) There is a method of reacting methylaniline with bromo maleide of formula (XXX) to form maleide of formula (XIX), and then oxidizing it to produce maleimide of formula (XXI). Cyclolation of the maleimide of formula (XXI) under an acid catalyst results in the pyrroloquinoline acetonitrile of formula (VIII). These reactions can be represented schematically as follows. At this time, R ₁ , R ₂ , L, M, Q, R ₇ are as described above.

To prepare compounds of formula (VIII) in which the positions of L, M, Q, R ₇ are substituted with electron donors such as alkyl, alkoxy, alkylthio, dialkylamino, hydroxy, one halogen, for example, XXII) reacts with 0-aminobenzyl alcohol or atlanal acid of formula (XXIII) with boromo (or chloro) maleide of formula (XIX).

This reaction is carried out at a temperature of 0-30 ° C. in the presence of a protonic solvent such as isopropyl, or t-butyl alcohol, for example, hydroxymethylanilino maleimide of formula (XXIV) or dioxide of formula (XXV), respectively. To produce sopyrrolinyl anthranilic acid. Various base acceptors can be used in this reaction, for example alkaline earth metal hydroxides such as Ba (OH) ₂ , BaO, or sodium acetate. In many cases, however, this reaction proceeds satisfactorily even without a base acceptor.

The alcohol of formula (XXIV) can be oxidized to the aldehyde of formula (XI) by using various oxidizing agents, such as pyridinium chlorochromate in methylene chloride or active magnesium dioxide in t-butanol, for example. . Aldehydes of the formula (XI) are pyrroloquinoline acetonitrile cyclolated to formula (VIII) by any one of the above-mentioned methods, such as heating the aldehyde to 140-200 ° C. in the presence of an aprotic solvent. Can be.

The 0-anilinocarboxylic acid of formula (XXV) may be cyclocyclized to acetoxyquinoline of formula (XXVI) with acetic anhydride, triethylamine and 4-dimethylaminopyridine at room temperature. At this time, excessive reduction reduces pyrroquiquinoline acetonitrile of the formula (VIII). Hydrolysis in lukewarm aqueous acetic acid solution yields a compound of formula (VIII) which is X〓OH, and further reaction with POCl ₃ and pyridine yields a compound wherein X is chlorine. These reactions can be represented as in the following flow diagram (V).

Flow diagram (V)

Another method for preparing the 2- (2-amidazolin-2-yl) quinoline compound of formula (I), which is particularly suitable for synthesizing analogous compounds with different A, is 2- (2-imidazoline) of formula (XXVIII). There is a method of using 2-yl) quinoline. This intermediate product converts the quinoline carboxylic acid of formula (X XVII) to chloric anhydride or chloric acid, and then reacts it with the appropriately substituted α-aminocarbonitrile of formula (XIV) to give a nitrile of formula (XXIX). Or by reacting with an aminoamide of formula (XXX) to produce a carboxyamidoamide of formula (XXXI). The carboxyamidoamide is cyclocyclized by the method as described above, wherein it is preferred to cyclocyclize with sodium hydride in the presence of xylene. Treatment of the 2- (2-imidazoline-2-yl) quinoline of formula (XXVIII) with metallization reagents can introduce various types of A groups. While most organometallic agents are effective when two molecules form diions, their yields and reaction compounds are organometallization reagents, reaction solvents, reaction temperatures, and electrophiles used at the end of the reaction. It depends on the nature of the. In practice, organometallization reagents such as alkyllithium are preferred, and anions are formed by methyl, n-butyl, secondary butyl and tertiary butyl lithium. Phenyllithium and lithium diisopropylamide can also be used. The solvent must be aprotic and diethyl ether is preferred. The reaction temperature for forming the double anion is -78 ° C to 0 ° C, preferably in the range of -30 ° C to -10 ° C. When terminating the reaction as an electrolytic agent, a temperature of -78 ° C to + 20 ° C is common. If necessary, it may then be treated with acid. All reactions are carried out under inert ambient conditions. Examples of reactive electrophiles include CO ₂ , C ₁ CO ₂ CH ₃ , (CH ₃ ) ₂ NCHO, CH ₃ CHO, C ₆ H ₅ CHO, CH ₃ I. At this time, the value corresponding to A of Structural Formula (IIa) is COOH, COOCH ₃ , CHO, CH (OH) CH ₃ , CH (OH) C ₆ H ₅ , CH ₃ . It is also possible to modify the product at this time after the reaction has been terminated intimately. In other words, when aldehyde (A = CHO) obtained by terminating with DMF is reacted with hydroxylamine, oxime is produced. This method is useful when synthesizing compounds where A = COOH by treating double anions with carbon dioxide.

X, L, M, Q and R ₇ are not all suitable for the organometallization method. That is, when the reactors are Br, I or fluorine the suitability of these groups is lost and the 3-proton of quinoline is substituted. However, chlorine is suitable for this method. When L, M, Q, R ₇ is methoxy, a suitable cation is formed at the ortho position of the methoxy group.

The reactions can be represented graphically as in the following flow diagram (VI).

Flow Diagram (VI)

According to another method, various kinds of functional group A can be manufactured. In other words, reacting the imidasorirololoquinoline dione of formula (II) with R ₃ OM + yields the 2- (2-imidazol-2-yl) quinoline ester of formula (V). When A is CONHCH ₂ CH ₂ OH in the compound of formula (I), the group of A can be cyclocyclized with an oxazoline group by reacting the compound with triethyl phosphite while refluxing xylene.

In a derivative of formula (I) in which A is -CONH ₂ , the -CONH ₂ group can be converted to the corresponding cyano derivative, ie A = CN, while dehydrating the -CONH ₂ group.

Most compounds containing L, M, Q, R ₇ groups can be prepared by the methods described above, but amino, alkylamino, dialkylamano compounds may be prepared by the appropriate nitrosubstituents of L, M, Q or R ₇ . It is convenient to prepare by alkylation in position. Alkylsulfonyl compounds can be easily prepared by using an m-chloro perbenzoic acid to oxidize the alkylsulfonyl group without excessive oxidation at the position of L, M, Q or R ₇ at a temperature of 0-20 ° C. N-oxidation of quinoline nitrogen is minimal.

For example, N-protection of the imidazoline ring is preferentially performed with a COCH ₃ group or the like, and then N-oxidation at high temperature with peracetic acid or trifluor peracetic acid can be oxidized to N-oxide if necessary. .

2- (2-imidazoline-2-yl) quinoline compounds of formula (I) of the present invention, and imidazopyrrolo quinolinedione of formula (II) are an exceptionally broad variety of weeds and woody annuals, perennials. It is extremely effective as a herbicide useful for controlling monocotyledonous or dicotyledonous plants. These compounds are also very effective in controlling weeds that inherently grow in dry and wet soil areas. They are also useful as aquatic herbicides and contain about 0.016-4.0 kg / in water containing the leaves, soil, or propagation parts or seeds, such as tuber rhizome or rhizome. When applied at a rate of ha, preferably at a rate of about 0.032-2.0 kg / ha, the plants can be effectively and excellently controlled.

Of course, herbicides may be added at a rate of 4.0 kg / ha or more to kill unnecessary plant seeds. However, adding excessive amounts of such toxic compounds may not only be expensive but also have no effective function for the environment. Use of herbicides in excess of the amount necessary to avoid them should be avoided.

The weeds that can be removed with the compounds of the present invention include E. larine triandra, porphyria pigmea, sydpus hotarui, ciperus serotonin, eclipta alba, ciperus deformis, rotala indica, Lindernia pyridoria, Echinocchia crousgali, Digitarian sanduillis, Setaria viridis, Scitus tubundus, Convolbours Arvensis, Agrophyton Refens, Darrastramonium, Allopecurus Myosuroides, Ipomea sapiens, Cedarspinoza, Ambrosia Artemisiapolia, Akkothnia Kracifes, Xantium Pennsylvania, Cesvania Exaltara, Avena Patua, Aburillon Teoplasti, Bromus Tektorium, Sorgum Haleppesse, Ralium Sapiens, Panicum dicholomilolium, Matracaria cypiens, Amitantus Tetroflexus, Kitsium Arvense and Lumex japonicus.

Surprisingly, some of the compounds of formulas (I) and (II) of the present invention may be added to the leaves or soil of plants at relatively low rates, i.e. at a rate of about 0.016-2.0 kg / ha. And it has been found that can selectively produce effects depending on the type of crop to be treated.

The 2- (2-imidazolin-2-yl) quinoline compounds of formula (I) are also generally selective compounds and are particularly effective at removing weeds that coexist with crops such as soybeans. However, certain types of compounds of formula (I) are less selective than the other compounds described herein.

Several types of 2- (2-imidazolin-2-yl) quinoline compounds of formula (I) were found to be effective as leaf growth inhibitors when added to cotton at a rate of about 0.016-4.0 kg / ha. It has also been found that adding a quinoline compound of formula (I) at a rate of 0.01 kg / ha or less is also effective in increasing grain yields by increasing the branches of the passing crops.

Pyrroloquinoline acetonitrile of formula (VIII) and pyruloquinoline acetamide of formula (VI) are imides of the 2- (2-imidazolin-2-yl) quinoline compound of formula (I), Structural Formula (II) It is useful as an intermediate product for preparing herbicides such as quinolol with quinolinedione.

Since R ₃ is a salt forming cation, the imidazolinyl quinoline compounds of formula (I) are water soluble, so these compounds are readily dispersed in water, thus diluting sprays on the leaves of the plant, It can be added to the soil it contains. These salts may also be prepared in the form of flowable concentrates.

The 2- (2-imidazoline-2-yl) quinoline compound of formula (I) and the imidazopyrroloquinolindi temperature of formula (II) are also wettable powders, flowable concentrates, emulsifiable concentrates, and granular ) Can be manufactured into processed products and the like.

The wettable powder may be, for example, about 20-45% of fine powder carriers such as kaolin, bentonite, diatomaceous earth, etherpulgite, etc., 45-80% by weight of active compound, 2-5% by weight of dispersant such as sulfonate with sodium league. %, And 2-5% by weight of nonionic surfactants such as, for example, octylphenoxy polyethoxy ethanol nonylphenoxy polyethoxy ethanol and the like.

The flowable liquid is prepared by mixing about 40% by weight of the active ingredient with about 2% by weight of a gelling agent such as bentonite, for example 3% by weight of a dispersant such as sodium lignosulfate, 1% by weight of polyethylene alcohol, and 54% by weight of water. Is representative.

The emulsifiable concentrate dissolves about 5-25% by weight of the active ingredient in about 65-90% by weight of N-methylpyrrolidone, isophorone, butylselsolve, methyl acetate, and the like, for example, with alkylphenoxy polyethoxyalcohol. Typically, about 5-10% by weight of the same nonionic surfactant is prepared by dispersing it in the solution. When using this concentrate, it is dispersed in water to form a spray solution.

When the compound of the present invention is to be used as a herbicide containing a soil treating agent, the compound may be prepared as a granular processing agent. In order to prepare such a granular processing agent, the active ingredient is dissolved in a solvent such as methylene chloride, N-methylpyrrolidone, and the like, and the solution thus formed is granular carrier such as corn flour, sand, ether pearlite, kaolin, or the like. What is necessary is just to spray.

Granular workpieces thus prepared generally contain about 3-20% by weight of active ingredient and about 97-80% by weight of granular carrier.

The present invention will be further described through the following examples. These examples are intended to illustrate the present invention more specifically, but the present invention is not limited thereto.

In these examples, all parts are by weight unless otherwise indicated.

Example 1

Preparation of 1,3-dihydro-α-isopropyl-α-methyl-1,3-dioxo-2-H-pyrrolo [3,4-b] quinoline-2-acetonitrile

A method

Anthranil (59.6 g, 0.5 mole) was added to the α-isopropyl-α-methyl-2,5-dioxo-3-pyrroline-1-acetonitrile reflux solution (450 mL) in 0-dichlorobenze under nitrogen for 45 minutes. Stirred dropwise over. After 18 hours the reaction mixture was cooled and methylene chloride was added. This solution was eluted with methylene chloride and passed through a 3 inch silica gel column. The eluate was concentrated to 500 ml and hexanes were added. The precipitate formed was filtered off and dried in air to afford 110.6 g (75%) of a light brown solid. Crystallization with ethyl acetate-hexane affords the target compound as a pale yellow crystal having a melting point of 195 to 196 ° C. Calcd for C ₁₇ H ₁₅ N ₃ O ₂ ; C = 69,61; H = 5.15; N = 14.33 found; C = 69.37; H = 5.15; N = 14.43.

The compounds of the following Table I were prepared under the conditions as described above.

B way

N- (1-cyano-1,2-dimethylpropyl) -2- (0-formylanilino) maleimide (7.19 g,) in xylene (300 ml) containing p-toluene sulfate (0.3 g 0.0016 mol) 0.23 mole) of the dissolved solution was heated for 4 hours while refluxing in a Dean-Starark water separator to remove water. The reaction was cooled and then evaporated under reduced pressure, dissolved in hot ethyl acetate and passed through a 3 inch silica gel column. When the eluted ethyl acetate portion was combined, 1,3-dihydro-α-isopropyl-α-methyl-1,3-dioxo-2-H-pyrrolo [3,4-b] having a melting point of 195-195.5 占 폚. 5.51 g (81%) of quinoline-2-acetonitrile solid is obtained.

Other compounds prepared by this method are listed in Table I.

Example 2

C method

Preparation of 1,3-dihydro-α-isopropyl-α-methyl-1,3-dioxo-2-H-pyrrolo [3,4-b] -4-acetoxyquinoline-2-acetonitrile

N- [1- (1-cyano-1,2-dimethylpropyl) -2,5-dioxo-3-pyrroline-3-yl] antranylic acid (3.27 g, 0.01 mol) acetic anhydride (20 ml) The solution dissolved in was treated with triethyl amine (10 ml) and dimethylaminopyridine (0.122 g, 0.001 mol) all at once. After stirring for 1 hour at 25 ° C. in the presence of nitrogen, the reaction was poured into ice water. The solid formed was filtered off. Purification by resuspension in ether, filtration and drying.

인 목적 화합물 2.54g(72%)가 얻어졌다.Melting point is 145-151 ℃

2.54 g (72%) of the target compound was obtained.

TABLE I

Example 3

Preparation of 1,3-dihydro-α-isopropyl-α-methyl-1,3-dioxo-2-pyrrolo [3,4-b] quinoline-2-acetoamino

1,3-dihydro-α-isopropyl-α-methyl-1,3-dioxo-2-H-pyrrolo [3,4-b] quinoline-2-acetonitrile (0.44 g; 0.0015 mol) It was dissolved in concentrated sulfuric acid (5 mL) at room temperature and stirred overnight. The reaction mixture was poured into crushed ice (50 mL), and the white precipitate formed was filtered off, washed with water, sodium bicarbonate solution, and then dried in vacuo. At this time, 0.34 g (74%) of the title compound having a melting point of 237-239 ° C was obtained. Calcd for C ₁₇ H ₁₇ N ₃ O ₃ ; C = 65.58; H = 5.50; N = 13.50. Found value; C = 65.03; H = 5.63; N = 13.19.

The following compounds were also prepared in the same manner as above.

TABLE II

Example 4

Preparation of 2- (5-isopropyl-5-methyl-4oxo-2-imidazoline-2-yl) -3-quinoline carboxylic acid

A method

1,3-dihydro-α-isopropyl-α-methyl-1,3-dioxo-2-H-pyrrolo [3,4-b] quinoline-2-acetamide (5.67 g, 0.0185 mol) A 50% oily suspension of sodium hydride (1.33 g, 0.0278 mol) was added to the slurry dissolved in dry xylene (600 mL), and the mixture was heated to reflux to make the reaction mixture homogeneous. After refluxing for 3 hours, the reaction mixture was left at room temperature overnight, methane (15 mL) containing sodium methoxide (0.1 g) was added slowly and then heated to reflux for 1 hour. Filtration of the hot reaction mixture as is to remove the organic solvent yields a fund and a solid. A mixture of methylene chloride and water was added together with the residue to shake the residue. The aqueous layer (200 ml) was separated and acidified slowly with acetic acid (5 ml). When the precipitate of the target compound formed, it was collected by filtration to obtain 3.91 g (72%) of the target compound having a melting point of 219-224 占 폚. Recrystallization with hexane-ethyl acetate gives a compound having a melting point of 219-222 占 폚 (decomposition). Calcd for C ₁₇ H ₁₇ N ₃ O ₃ ; C = 65.58; H = 5.50; N = 13.50. Found value; C = 65.09; H = 5.50; N = 13.59.

This Example is used to prepare the compound of the Example. However, to prevent the formation of esters, instead of filtering out the insoluble components and removing the xylenes, only methanol and water are added to the xylene layer in order (hydrogen must be released).

TABLE III

Example 5

Preparation of ethyl-2- (5-isopropyl-5-methyl-4-oxo-2-imidazoline-2-yl) -3-quinoline carboxylic acid

2-isopropyl-2-methyl-5H-imidazo [1 ', 2': 1,2] pyrazolo [3,4-b] quinoline-3H (2H), 5 in anhydrous ethanol (40 mL) in the presence of nitrogen -50% sodium hydride (0.34 g, 0.00716 mol) is added to dione (2 g, 0.0068 mol) by ice-cooling. Gas evolution is observed. After 10 minutes the reaction is neutralized with ammonium chloride aqueous solution, stripped and partitioned between water and ethyl acetate. The organic layer was separated, dried over anhydrous magnesium sulfate, filtered and stripped, and the residue crystallized from ethyl hexane to yield 1.38 g (60%) white solid, mp 146-147.5 ° C.

In a similar manner, the esters of Table IV below can be prepared by Process A.

Example 6

Preparation of Methyl-2- (5-isopropyl-5-methyl-4-oxo-2-imidazoline-2-yl) -3-quinoline carboxylic acid

Fair B

50% sodium hydride oil dispersion (1.4 g, 0.0292 mol) was dried 1,3-dihydro-α-isopropyl-α-methyl-1,3-dioxo-2-H-pyrrolo [3,4. -B] quinoline-2-acetamide (6 g, 0.0191 mol) is added in the presence of nitrogen. The mixture is heated and stirred under reflux for 6 hours, cooled and slowly cooled with a solution of sodium methoxide (0.1 g) in methanol (20 mL). After 3 hours of heating at 60 ° C., the mixture is filtered and the stripped filtrate gives a white solid which is soluble in the methylene chloride-water mixture.

Organic layer separation and stripping give 0.48 g of solid, which is purified by passing through silica gel pede with ethyl acetate as solvent. After removal of the solvent, the solid residue was crystallized from ethyl acetate-hexane to give 0.4 g of required ether of white needles and mp 145-154 ° C.

Calculated analysis of C ₁₈ H ₁₉ N ₃ O ₃ ; C66.44; H5.89; N12.92.

Found value; C66.35; H5.93; N12.83.

TABLE IV

Example 7

Acid addition salts of quinoline carboxylic acid esters:

Preparation of Hydrochloride of Methyl-2- (5-isopropyl-5-methyl-4oxo-2-imidazoline-2-yl) -3-quinoline carboxylic acid

The ester solution was dissolved in ethyl-methylene chloride solution and dried hydrogen chloride was passed through the solution until all solid hydrochloride was formed, filtered and washed with ether and vacuum dried to obtain mp 226-270 ° C. In a similar manner the following salts can be prepared by replacing the appropriate acid HX and using ethyl acetate as the preferred solvent for acid addition salts.

Table V

Example 8

Preparation of Sodium 2- (5-isopropyl-5-methyl-4-oxo-2-imidazoline-2-yl) -3-quinoline carboxylic acid

Sodium hydroxide (0.3 g, 0.0075 mol) of 2- (5-isopropyl-5-methyl-4-oxo-2-imidazoline-2-yl) -3-quinoline carboxylic acid (2.33 g, 0.0075 mol) The aqueous solution containing (22 ml) was stirred at room temperature overnight, washed with methylene chloride, the aqueous layer was separated and evaporated to give an orange solid, washed with ether and dried with air. The product is obtained as a creamy solid dihydrate, mp 235-250 ° C. (decomposition).

Calcd. Analysis for C ₁₇ H ₁₆ N ₃ O ₃ Na.2H ₂ O; C55.27; H5.45; N11.37; Na6.22

Found value; C55.56; H5.31; N11.35; Na6.30.

The following salts are prepared by replacing sodium hydroxide in a similar manner. Compounds prepared in this manner are shown in Table VI.

Table VI

Example 9

2-isopropyl-2-methyl-5-imidazo [1 ', 2': 1,2] pyrazolo [3,4-b] quinoline 3 (2H), 5-dione, 2-isopropyl- Preparation of 2-methyl

Process A

Dicyclohexylcarbodiimide (3.47 g, 0.0168 mol) in methylene chloride in the presence of nitrogen was added with 2- (5-isopropyl-5-methyl-4-oxo-2-imidazoline-2-yl) in methylene chloride. To a stirred suspension of 3-quinoline carboxylic acid (5.24 g, 0.0168 mol) is added overnight at room temperature. The reaction is incomplete and further 0.3 g of dicyclohexylcarbodiimide is added and the mixture is stirred for 48 hours. The reaction mixture is evaporated to a yellow solid and purified by chromatography on a silica gel column. The product is eluted with acetonitrile-methylene chloride to give a white solid which is crystallized from toluene to mp 225-227 ° C.

Calculated analysis for C ₁₇ H ₁₅ N ₃ O ₃ ; C69.61; H5.15; N14.33.

Found value; C69.76; H5.31; N14.13.

Example 10

Fair B

Cis and trans 1,11b-dihydro-11b-hydroxy-3-isopropyl-3-methyl-5-H-imidazo [1 ', 2': 1,2] pyrrolo [3,4-b] Preparation of quinoline-2 (3H), 5-dione

1,3-dihydro-α-isopropyl-α-methyl-1,3-dioxo-2-H-pyrrolo [3,4-b] quinoline-2-acetamide (0.5 g, 0.0016 mol) Heated under reflux for 23 hours in xylene. Upon cooling, white solid 0.17 g, mp 191-192 ° C precipitated, and diluted the filtrate with hexane, 0.1 g, mp 187-189 ℃ further formed.

Calculated analysis for C ₁₇ H ₁₇ N ₃ O ₃ ; C 65.58; H5.50; N13.50.

Found value; C 66.08; H5.65; N13.00.

Other tricyclic compounds are obtained in a similar manner to Processes A and B.

Tricyclic example:

Example 11

Preparation of N- (1-cyano) -1,2-dimethylpropyl-2- (O-promilanilino) maleimide

Process A

A solution of anthranyl (3.55 g, 0.298 mol) and α-isopropyl-α-methyl-2,5-dioxo-3-pyrroline-1-acetonitrile (5.73 g, 0.0298 mol) in xylene (20 mL) Heat to reflux for 39 hours in the presence.

Upon cooling a yellow precipitate formed and was filtered to yield 2.78 g, 191-192 ° C. product.

Calculated analysis for C ₁₇ H ₁₇ N ₃ O ₃ ; C65.58; H5.50; N13.50.

Found value; C65.33; H5.44; N13.36.

Example 12

Preparation of N- (1-cyano-1,2-dimethylpropyl) -2- (2-formyl-5-chloroanilino) maleimide

Pyridinium chlorochromate (4.4 g, 0.204 mol) in methylene dichloride (20 mL) was rapidly added N- (1-cyano-1,2-dimethylpropyl) -2 (5-chloro-2-hydroxymethylanilino). It is added to a solution of Malay (4.75 g, 0.0136 mol). After 2 hours the dark reaction mixture was diluted with ether (20 mL) and the yellow precipitate was filtered off. This solid is redissolved in ethyl acetate: methylene chloride (1: 1) and passed through a silica gel column to yield 4.31 g (92%) mp 80 ° C. (decomposition) of a yellow solid.

The next aldehyde is prepared according to Process A or B as indicated in Table VII.

[Table VII]

Example 13

Preparation of N- (1-cyano-1,2-dimethylpropyl) -2- (2-hydroxymethylanilino) maleimide

3 g of 5A finely ground sieve in 0-aminobenzyl alcohol (2 g, 0.0125 mole) and 3-bromo isopropylmethyl-2,5-dioxo-3-pyrroline-1-acetonitrile (2.7 g, 0.01 mole) Anhydrous ethanol (100 ml) containing the same is added. The mixture is stirred at room temperature for 20 hours. The solvent is removed and the residue is purified by passing through a silica gel dry column with etel-hexane (2: 1) as eluent. Bromomalade is recovered first, followed by 1.89 g (60%) of light yellow solid, mp 39-45 ° C.

Calculated analysis for C ₁₇ H ₁₉ N ₂ O ₃ ; C65.16; H6.11; N13.41.

Found value; C65.94; H6.21; N12.87.

Other compounds are prepared by this method from variously substituted 0-anobenzyl alcohols. The use of i-propanol or t-butanol for ethanol generally improves the yield and may also use a base as an acid acceptor.

TABLE VIII

Example 14

Preparation of 3-bromo-α-isopropyl-α-methyl-2,5-dioxo-3-pyrroline-1-acetonitrile

Bromine (40.76 g, in acetic acid (80 ml) to α-isopropyl-methyl-2,5-dioxo-3-pyrroline-1-acetonitrile (50 g, 0.25 moles) in acetic acid (500 ml) heated to 75 ° C. 0.255 mol) is dripped while stirring. The reaction was kept at 85 ° C. overnight, evaporated to syrup, dissolved in methylene chloride (300 mL), cooled to 5 ° C. and triethylamine (34.78 mL) added. After stirring for 2 hours, the brown methylene chloride solution is diluted with ether, and a white precipitate is formed. It was extracted with water (400 ml) and the organic layer was dried over anhydrous magnesium sulfate and then passed through a 2-inch silica gel bed eluted with methylene chloride. Eluate is obtained as dark brown oil.

Calculated analysis of C ₁₀ H ₁₀ N ₂ O ₂ Br; C44.29; H4.09; N10.33.

Found value; C43.37; H 4.05; N 10.07.

Other bromomaleimides are prepared in a similar manner.

Example 15

Preparation of α-isopropyl-α-methyl-2,5-dioxo-3-pyrroline-1-acetonitrile

N- (1-cyano-1,2-dimethylpropyl) maleic acid (595 g, 2.83 mol) in acetic anhydride (3.96 liters) containing sodium acetate (13.72 g, 0.167 mol) was heated under reflux for 1 hour and cooled. To remove the solvent in vacuo. The product is distilled at 120-130 ° C./0.1 mm (pot temperature should not exceed 200 °) to yield 337 g (63%) of product.

Calculation analysis for C ₁₀ H ₁₂ N ₂ O ₂ ; C62.49; H6.29; N14.57.

Found value; C62.32; H6.36; N 14.59.

In a similar manner the following compounds are prepared.

Example 16

Preparation of N- [1- (1-cyano-1,2-dimethylpropyl) -2,5-dioxo-3-pyrroline-3-yl] anthranilic acid

Anthranilic acid (13.7 g, 0.1 mol), 3-bromo-α-isopropyl-α-methyl-2,5-dioxo-3-pyrroline-1-acetonitrile (27 g, 0.1 mol), isoprotanol (200 ml) and sodium acetate (8.2 g) are stirred at room temperature for 3 days and then heated to reflux for 1 hour. After cooling and adding ether, 31.6 g (97.7%) of a yellow solid was obtained. After recrystallization in acetic acid, mp was 262-266 ° C.

Calculated analysis of C ₁₇ H ₁₇ N ₃ O ₄ ; C62.37; H5.24; N12.84.

Found value; C62.24; H5.19; N 12.70.

Other maleimides can be prepared in a similar manner.

Example 17

Preparation of N- (1-carbamoyl-1,2-dimethylpropyl) -quinalamide

To a solution of quinal acid (20 g, 0.116 mol) in tetrahydrofuran (500 ml) cooled to -9 ° C, methyl chloroformate (8.92 ml, 0.116 mol) was added followed by triethylamine (18.4 ml, 0.139 mol).

After 20 minutes α-isopropyl-α-methyl-3-pyrroline-1-acetamide (15.1 g, 0.116 mol) is added and the mixture is stirred at rt overnight. Water is added and the solution is reduced to 200 ml on a rotary evaporator. The white precipitate is separated, filtered, washed with water and dried. Recrystallization from anhydrous ethanol affords the product mp 179-180 ° C., 26.86 g (87%).

Calculated analysis of C ₁₆ H ₁₉ N ₃ O ₂ ; C67.34; H6.73; N14.72.

Found value; C67.14; H6.17; N14.72.

Other quinoline carboxamides can be prepared in a similar manner.

Example 18

Preparation of α-isopropyl-α-methyl-2,5-dioxo-3-pyrroline-1-acetamide

Α-isopropyl-α-methyl-2,5-dioxo-3-pyrroline-1-acetonitrile (2.0 g, 0.104 mol) in methylene chloride (30 mL) is added as a fine stream to concentrated sulfuric acid at room temperature. After stirring overnight at room temperature, the mixture is poured on ice containing sodium chloride and ethyl acetate for 16 hours.

The organic layer is washed with aqueous sodium bicarbonate solution and brine and dried.

Evaporation after washing with ether-pentane gave a solid (72%), mp 138.5-140 ° C.

Calculated analysis for C ₁₀ H ₁₄ N ₂ O ₃ ; C57.13; H6.71; N13.33.

Found value; C56.89; H6.64; N13.16.

In a similar manner, other imideamides are prepared.

Example 19

5-isopropyl-5-methyl-2- (2-quinolyl) -2-imidazoline-4-ones

Sodium hydride (2.7 g, 0.056 mol) in a slurry of N- (1-carbamoyl-1,2-dimethylpropyl) -2-quinoline carboxamide (16.04 g, 0.0562 mol) in xylene (610 ml) in the presence of nitrogen 50% oil dispersion is added at 20 ° C. Heated under reflux for 2 hours to cool and water (50 ml) is added. The aqueous layer is extracted with methylene chloride and the organic layers combined and evaporated to yield 17 g of yellow oil. Hexane-ethyl acetate was used as the solvent to purify through a silica gel column. A pale yellow solid is obtained and recrystallized from ethyl acetate to give 11.77 g (78%) of white product, mp 112-117 ° C.

Calcd. For C ₁₆ H ₁₇ N ₃ O; C71.88; H6.41; N15.72.

Found value; C71.91; H6.47; N15.70.

Other compounds prepared in a similar manner are shown in Table IX.

TABLE IX

Example 20

Preparation of 2- (5-isopropyl-5-methyl-4-oxo-2-imidazoline-2-yl) -3-quinoline carboxaldehyde

Tetramethyl ethylenediamine (3.4 g, 0.00225 mol) to 5-isopropyl-5-methyl-2- (2-quinolin) -2-imidazoline-4-one (3 g, 0.0112 mol) mixture in ether (150 ml) Add. N-butyllithium (17 ml, 0.027 mol) in hexane was added dropwise to the reaction mixture cooled to -63 占 폚.

Dark red occurred and after addition the mixture was maintained at -10 to -20 ° C for 2-0.5 hours. Dry DMF (5 mL) was added at -10 ° C and the mixture was left to stir overnight until room temperature. The mixture is diluted with water (75 mL) and neutralized with acetic acid.

2.57 g (78%) of a pale yellow solid were obtained, and the mp after crystallization from 95% ethanol was 226-227 ° C.

Calculated analysis for C ₁₇ H ₁₇ N ₃ O ₂ ; C69.13; H5.80; N14.23.

Found value; C68,98; H5.88; N14.25.

Dilution of 95% ethanol with 5-10 ml of water gives a new solid. Washing the solid with 95% ethanol removes the yellow color and gives a material of mp 168-169 ° C. Confirm that m + 1 / e is a tricyclic structure A or B.

In a similar manner, other A groups are prepared.

Example 21

Preparation of 2--3- (hydroxymethyl) -2-quinolin-5-isopropyl-5-methyl-2-imidazoline-4-one

Powdered sodium borohydride (0.5 g, 0.013 mol) was dissolved in ethanol (150 ml) in the presence of nitrogen in suspension 2- (5-isopropyl-5-methyl-4-oxo-2-imidazoline-2-yl) -3 Quinoline carboxaldehyde (0.78 g, 0.00264 mol) is added. A clear yellow solution is obtained. After 20 minutes the reaction is concentrated to 40 ml and diluted with water (75 ml). Ethylene chloride extraction and evaporation yielded crystals of pale yellow mp 138-149 ° C., M / e 298 from hexane-ethyl acetate.

Properly substituted quinoline-carboxaldehydes can be used to prepare other compounds by this method.

Such compounds are shown in Table X.

Example 22

Evaluation of herbicidal ability after expression of test compound

The herbicidal ability after expression of the compound of the present invention is demonstrated by the following experiments in which various monocotyledonous plants and dicotyledonous plants are treated with test compounds dispersed in a mixture of water and acetone.

Seed plants grow on the plate for two weeks in the experiment. The test compound was sprayed through a spray nozzle operated at 40 psi for a predetermined time in a 50/50 acetone / water mixture containing 0.5% TWEEN®20, a polyoxyethylene sorbitan monolaurate salt from Atlas Chemical Industries. When applied to plants, it is sufficiently dispersed to be equivalent to about 0.016 kg to 10 kg per hectare of active compound. After spraying, the plants are placed in greenhouse benches and kept in the usual way. Seed plants from 4 to 5 weeks after treatment are tested and evaluated according to the evaluation system provided below. The data obtained are reported in Table XI.

Most data are for a single experiment, but some are averages from more than one experiment.

Used Plant Species

Vanyard Grass (Echinochloa Crusgalli)

Foxtail (Setaria viridis)

Hyangbuja (Cyperus rotundus L.)

Wild Oats (Avena Fatua)

Wheat Flour (Agropyron repens)

Wildflower (Convolvulus arvensis l.)

Cocotail (Xanthium pensylvanicum)

Morning Glory (Ipomoea purpurea)

Urticaria (Ambrosia artemisiifolia)

Velvet Lihu (Abutilon Theophtrasti)

Barley (Hordeum vulgare)

Corn (Zea mays)

Rice (Oryza Sativa)

Beans (Glycine max)

Sunflower (Heliantus annus)

Wheat (Triticum aestivum)

Table ⅩⅠ

Table XII

Claims (1)

And reacting the compound of formula (II) alone or in the presence of a neutral solvent with an alcohol represented by at least one equivalent of R ₃ OH and an alkali metal alkoxide R ₃ O-M + at a temperature between about 20 ° C. to 50 ° C. A process for preparing a compound of formula (I) characterized by the above-mentioned.

In the above formula R ₁ is C ₁ -C ₄ alkyl; R ₂ is C ₁ -C ₄ alkyl or C ₃ -C ₆ cycloalkyl, and R ₁ and R ₂ together can represent C ₃ -C ₆ cycloalkyl optionally substituted with methyl; A is COOR ₃ ; R ₃ is C ₁ -C ₃ alkoxy, halogen, hydroxyl, C ₃ -C ₆ cycloalkyl, benzyloxy, furyl, phenyl, halophenyl, lower alkylphenyl, lower alkoxyphenyl, nitrophenyl, carboxyl, lower alkoxycar C ₃ -C ₁₂ alkenyl or cations optionally substituted with C ₁ -C ₁₂ alkyl C ₁ -C ₃ alkoxy, phenyl, halogen or lower alkoxy carbonyl, optionally substituted with carbonyl, cyano or trilower alkylammonium; B is H; W is O; X is hydrogen, halogen, hydroxyl or methyl; L, M, Q and R ₇ are each hydrogen, halogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ alkylthio, C ₁ -C ₄ alkylsulfonyl, C ₁ -C ₄ Haloalkyl, NO ₂ , CN, phenyl, phenoxy, amino, C ₁ -C ₄ alkylamino, lower alkylamino, chlorophenyl, methylphenyl, or phenoxy substituted with C 1, CF ₃ , NO ₂ or CH ₃ ; M + is an alkali metal.