Triazine derivatives, a process for preparing the derivatives, and herbicides containing the derivatives as the effective component

FIELD OF THE INVENTION
The present invention relates to novel triazine derivatives, a process for preparing the triazine derivatives, and herbicides containing the derivatives as the effective component.
BACKGROUND OF THE INVENTION
Various triazine-based herbicides have heretofore been known. For example, 2-methylthio-4,6-bis(alkylamino)-s-triazine derivatives are known to be effective herbicides having a high weed control activity. However, the effect of 2-methylthio-4,6-bis(ethylamino)-s-triazine, for example, greatly varies with conditions such as the type of soil and temperature. In more detail, when used in a mild district, it causes phytotoxicity (chemical damages) even in the commonly used amount, and in a cold district, its effect is exhibited only insufficiently. Thus 2-methylthio-4,6-bis(ethylamino)-s-triazine has a disadvantage in that it can be applied as a herbicide only in a limited district.
Under such circumstances, paddy herbicides prepared by the substitution of the alkylamino group of 2-chloro-4,6-bis(alkylamino)-s-triazine or 2-alkylthio-4,6-bis(alkylamino)-s-triazine derivatives with an .alpha.,.alpha.-dimethylbenzylamino group have been proposed (see, for example, Japanese Patent Publication Nos. 8261/74 and 8262/74). These compounds do not cause phytotoxicity to paddy rice plants and have herbicidal activity against annual weeds, but their effect against perennial weeds causing problems at present is undesirably low.
The present invention is intended to overcome the above problems and an object of the present invention is to provide a process for preparing a novel herbicide which can exhibit a nearly equal herbicidal effect under various soil and temperature conditions or irrespctive of the type of soil and temperature, does not cause phytotoxicity, and can effectively kill various weeds from annual to perennial weeds.
As a result of extensive investigations, it has been found that the above object can be attained by using specific triazine derivatives.
SUMMARY OF THE INVENTION
The present invention relates to a triazine derivative represented by the general formula (I): ##STR2## wherein R.sup.1 and R.sup.2 are each an alkyl group having 1 to 4 carbon atoms, and X.sup.1 and X.sup.2 are each a halogen atom, an alkyl group having 1 to 4 carbon atoms; an alkoxyl group having 1 to 4 carbon atoms, or an alkylthio group having 1 to 4 carbon atoms.
The present invention also relates to a process for preparing the triazine derivative represented by the general formula (I) which comprises the steps of:
reacting a benzylamine derivative represented by the general formula (II): ##STR3## (wherein X.sup.1, X.sup.2 and R.sup.1 are the same as defined above) with dihalogeno aminotriazine represented by the general formula (III): ##STR4## (wherein X.sup.3 and X.sup.4 are each a halogen atom) to form a benzylaminotriazine derivative represented by the general formula (IV): ##STR5## (wherein X.sup.1, X.sup.2, X.sup.3 and R.sup.1 are the same as defined above), and then
reacting the above benzylaminotriazine derivative with alkylmercaptan represented by the general formula:
R.sup.2 SH
(wherein R.sup.2 is the same as defined above), or alkylmercaptide represented by the general formula:
R.sup.2 SM
(wherein M is an alkali metal and R.sup.2 is the same as defined above).
The present invention further relates to a herbicide comprising (i) a herbicidal carrier, and (ii) an effective amount of a triazine derivative represented by the general formula (I).
DETAILED DESCRIPTION OF THE INVENTION
In the general formula (I), as described above, R.sup.1 and R.sup.2 are each an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a normal propyl group, an isopropyl group and a butyl group (n-, iso-, sec-, tert-butyl). X.sup.1 and X.sup.2 are each a halogen atom (such as a chlorine atom, a bromine atom, a fluorine atom and an iodine atom), an alkyl group having 1 to 4 carbon atoms (such as a methyl group, an ethyl group, a normal propyl group, isopropyl group and a butyl group), an alkoxy group having 1 to 4 carbon atoms (such as a methoxy group, an ethoxy group, a normal propoxy group, an isopropoxy group and a butoxy group), an an alkylthio group having 1 to 4 carbon atoms (such as methylthio group, an ethylthio group, a propylthio group and a butylthio group).
Of these, each of R.sup.1 and R.sup.2 is preferably a methyl group, an ethyl group, a normal propyl group or an isopropyl group. X' is preferably a chlorine atom, a bromine atom, a fluorine atom, a methyl group, an ethyl group, an isopropyl group, a methoxy group, an ethoxy group, a normal propoxy group or an isopropoxy group. X.sup.2 is preferably a chlorine atom, a bromine atom, a fluorine atom, a methyl group, an ethyl group, a methoxy group; an ethoxy group, a normal propoxy group, an isopropoxy group, a normal butoxy group, a methylthio group or an ethylthio group.
Examples of the triazine derivatives of the general formula (I) include 2-methylthio-4-amino-6-(3'-chloro-4'-methoxy-.alpha.-methylbenzylamino)-s-triazine, 2-methylthio-4-amino-6-(3',4'-dimethoxy-.alpha.-methylbenzylamino)-s-triazine, 2-methylthio-4-amino-6-(3',4'-dimethyl-.alpha.-methylbenzylamino)-s-triazine, 2-methylthio-4-amino-6-(3',4'-dichloro-.alpha.-methylbenzylamino)-s-triazine, 2-methylthio-4-amino-6-(3'-methyl-4'-methoxy-.alpha.-methylbenzylamino)-s-triazine, 2-methylthio-4-amino-6-(3'-methyl-4'-chloro-.alpha.-ethylbenzylamino)-s-triazine, 2-ethylthio-4-amino-6-(3'-methyl-4'-methoxy-.alpha.-methylbenzylamino)-s-triazine, 2-methylthio-4-amino-6-(3'-methyl-4'-methoxy-.alpha.-ethylbenzylamino)-s-triazine, 2-methylthio-4-amino-6-(3'-methyl-4'-methoxy-.alpha.-isopropylbenzylamino)-s-triazine, 2-methylthio-4-amino-6-(3'-isopropyl-4'-methoxy-.alpha.-methylbenzylamino)-s-triazine, 2-methylthio-4-amino-6-(3'-methyl-4'-isopropoxy-.alpha.-methylbenzylamino)-s-triazine, 2-methylthio-4-amino-6-(3'-methyl-4'-methylthio-.alpha.-methylbenzylamino)-s-triazine, 2-methylthio-4-amino-6-(3'-chloro-4'-methyl-.alpha.-methylbenzylamino)-s-triazine, 2-methylthio-4-amino-6-(3'-methoxy-4' -methyl-.alpha.-methylbenzylamino)-s-triazine, 2-methylthio-4-amino-6-(3'-methyl-4'-ethoxy-.alpha.-methylbenzylamino)-s-triazine, 2-methylthio-4-amino-6-(3'-methyl-4'-normalpropoxy-.alpha.-methylbenzylamino)-s-triazine, 2-methylthio-4-amino-6-(3'-methyl-4'-tert-butoxy-.alpha.-methylbenzylamino)-s-triazine, 2-methylthio-4-amino-6-(3'-methyl-4'-normalbutoxy-.alpha.-methylbenzylamino)-s-triazine, 2-methylthio-4-amino-6-(3'-ethyl-4'-methoxy-.alpha.-methylbenzylamino)-s-triazine, 2-methylthio-4-amino-6-(3'-fluoro-4'-methoxy-.alpha.-methylbenzylamino)-s-triazine, 2-methylthio-4-amino-6-(3'-methyl-4'-ethylthio-.alpha.-methylbenzylamino)-s-triazine, 2-methylthio-4-amino-6-(3'-methyl-4'-normalpropylthio-.alpha.-methylbenzylamino)-s-triazine, 2-methylthio-4-amino-6-(3'-methyl-4'-isopropylthio-.alpha.-methylbenzylamino)-s-triazine, 2-methylthio-4-amino-6-(3'-chloro-4'-methylthio-.alpha.-methylbenzylamino)-s-triazine, 2-methylthio-4-amino-6-(3',4'-difluoro-.alpha.-methylbenzylamino)-s-triazine, 2-methylthio-4-amino-6-(3',4'-diethyl-.alpha.-methylbenzylamino)-s-triazine, 2-methylthio-4-amino-6-(3',4'-dibromo-.alpha.-methylbenzylamino)-s-triazine, 2-ethylthio-4-amino-6-(3'-methyl-4'-bromo-.alpha.-methylbenzylamino)-s-triazine, 2-methylthio-4-amino-6-(3' -methyl-4'-methoxy-.alpha.-normalpropylbenzylamino)-s-triazine, 2-methylthio-4-amino-6-(3',4'-diethoxy-.alpha.-methylbenzylamino)-s-triazine, 2-methylthio-4-amino-6-(3',4'-dinormalpropoxy-.alpha.-methylbenzylamino)-s-triazine, 2-methylthio-4-amino-6-(3'-methyl-4'-chloro-.alpha.-methylbenzylamino)-s-triazine, 2-methylthio-4-amino-6-(b 3'-ethyl-4'-chloro-.alpha.-methylbenzylamino)-s-triazine, 2-methylthio-4-amino-6-(3'-methyl-4'-bromo-.alpha.-methylbenzylamino)-s-triazine, 2-methylthio-4-amino-6-(3'-isopropyl-4'-chloro-.alpha.-methylbenzylamino)-s-triazine, 2-methylthio-4-amino-6-(3'-methyl-4'-fluoro-.alpha.-methylbenzylamino)-s-triazine.
Triazine derivatives represented by the general formula (I) can be prepared by various procedures. In particular, the process of the present invention as described above permits efficient preparation of the triazine derivatives.
In accordance with the process of the present invention, benzylamine derivatives represented by the general formula (II) are first reacted with dihalogenated aminotriazines represented by the general formula (III) to prepare benzylaminotriazine derivatives represented by the general formula (IV), and then these benzylaminotriazine derivatives are reacted with alkylmercaptan represented by the general formula: R.sup.2 SH or alkylmercaptide represented by the general formula: R.sup.2 SM to prepare the desired triazine derivatives of the general formula (I).
As benzylamine derivatives, or 3,4-disubstituted-.alpha.-alkylbenzylamine of the general formula (II), various kinds of compounds can be used in the process of the present invention. In the general formula (II), R.sup.1 is preferably a methyl group, an ethyl group, a normal propyl group or an issopropyl group. X.sup.1 is preferably a chlorine atom, a bromine atom, a fluorine atom, a methyl group, an ethyl group, an isopropyl group, a methoxy group, an ethoxy group, or a normal propoxy group. X.sup.2 is preferably a chlorine atom, a bromine atom, a fluorine atom, a methyl group, an ethyl group, a methoxy group, an ethoxy group, a normal propoxy group, an isopropoxy group, a normal butoxy group, or a methylthio group.
Examples of the benzylamine derivatives represented by the general formula (II) include 3-chloro-4-methoxy-.alpha.-methylbenzylamine, 3,4-dimethoxy-.alpha.-methylbenzylamine, 3,4-dimethyl-.alpha.-methylbenzylamine, 3,4-dichloro-.alpha.-methylbenzylamine, 3-methyl-4-methoxy-.alpha.-methylbenzylamine, 3-methyl-4-chloro-.alpha.-ethylbenzylamine, 3-methyl-4-methoxy .alpha.-ethylbenzylamine, 3-methyl-4-methoxy-.alpha.-isopropylbenzylamine, 3-isopropyl-4-methoxy-.alpha.-methylbenzylamine, 3-methyl-4-isopropoxy-.alpha.-methylbenzylamine, 3-methyl-4-methylthio-.alpha.-methylbenzylamine, 3-chloro-4-methyl-.alpha.-methylbenzylamine, 3-methoxy-4-methyl-.alpha.-methylbenzylamine, 3-methyl-4-ethoxy-.alpha.-methylbenzylamine, 3-methyl-4-normalpropoxy-.alpha.-methylbenzylamine, 3-methyl-4-tert.-butoxy-.alpha.-methylbenzylamine, 3-methyl-4-normalbutoxy-.alpha.-methylbenzylamine, 3-ethyl-4-methoxy-.alpha.-methylbenzylamine, 3-fluoro-4-methoxy-.alpha.-methylbenzylamine, 3-methyl-4-ethylthio-.alpha.-methylbenzylamine, 3-methyl-4-normalpropylthio-.alpha.-methylbenzylamine, 3-methyl-4-isopropylthio-.alpha.-methylbenzylamine, 3-chloro-4-methylthio-.alpha.-methylbenzylamine, 3,4-difluoro-.alpha.-methylbenzylamine, 3,4-diethyl-.alpha.-methylbenzylamine, 3,4-dibromo-.alpha.-methylbenzylamine, 3-methyl-4-bromo-.alpha.-methylbenzylamine, 3-methyl-4-methoxy-.alpha.-normalpropylbenzylamine, 3,4-diethoxy-.alpha.-methylbenzylamine, 3,4-dinormalpropoxy-.alpha.-methylbenzylamine, 3-methyl-4-chloro-.alpha.-methylbenzylamine, 3-methyl-4-bromo-.alpha.-methylbenzylamine, 3-ethyl-4-chloro-.alpha.-methylbenzylamine, 3-isopropyl-4-chloro-.alpha.-methylbenzylamine, 3-methyl-4-fluoro-.alpha.-methylbenzylamine.
Benzylamine derivatives of the general formula (II) can be prepared by various procedures. Usually they are prepared by the following method.
Di-substituted benzenes represented by the general formula (V): ##STR6## (wherein X.sup.1 and X.sup.2 are the same as defined above) are reacted with acyl halide represented by the general formula:
R.sup.1 COX
(wherein X is a halogen atom and R.sup.1 is the same as defined above) in the presence of e.g., a Lewis acid such as anhydrous aluminum chloride, anhydrous tin chloride, anhydrous zinc chloride and anhydrous iron chloride, sulfuric acid or polyphosphoric acid by the Friedel-Crafts reaction to prepare phenone derivatives represented by the general formula (VI): ##STR7## (wherein R.sup.1, X.sup.1 and X.sup.2 are the same as defined above), and then these phenone derivatives are reacted with ammonium formate or formamide and formic acid while heating at about 150.degree.-200.degree. C. to prepare N-formylbenzylamine derivatives represented by the general formula (VII): ##STR8## (wherein R.sup.1, X.sup.1 and X.sup.2 are the same as defined above). When these N-formylbenzylamine derivatives are hydrolyzed by heating in the presence of an acid such as concentrated hydrochloric acid, or a caustic alkali such as caustic soda, the benzylamine derivatives of the general formula (II) result.
The benzylamine derivatives of the general formula (II) can also be prepared by first reacting the phenone derivatives of the general formula (VI) with hydroxylamine in place of ammonium formate to prepare oximes (phenoneoxime derivatives) and then reducing the oximes with an alkali metal such as metallic sodium or subjecting them to catalytic reduction.
Moreover the benzylamine derivatives of the general formula (II) can be prepared by a method comprising the steps of reacting cyanobenzene derivatives of the general formula (VII): ##STR9## (wherein X.sup.1 and X.sup.2 are the same as defined above) with a Grignard reagent represented by the general formula: R.sup.1 MgX (wherein R.sup.1 and X are the same as defined above), hydrolyzing the reaction product as obtained above with hydrochloric acid, for example, to obtain the phenone derivatives of the general formula (VI), reacting the phenone derivatives with ammonium formate in the same manner as described above, and then hydrolyzing the N-formylbenzylamine derivatives thus obtained.
In accordance with the process of the present invention, the benzylamine derivatives of the general formula (II) as prepared above are reacted with the dihalogeno aminotriazines of the general formula (III), i.e., 2,6-dihalogeno-4-amino-s-triazine. The dihalogeno aminotriazine can be prepared by reacting cyanuric halide such as cyanuric chloride with ammonia.
In reacting the benzylamine derivative of the general formula (II) with the dihalogeno aminotriazine of the general formula (III), both compounds are used in a nearly equal molar ratio. Although a solvent is not always needed, alcohols such as methanol, ethanol and isopropanol, ketones such as acetone, methyl ethyl ketone and cyclohexanone, aliphatic hydrocarbons such as n-hexane and n-heptane, cyclic hydrocarbons such as benzene, decalin and alkylnaphthalene, chlorinated hydrocarbons such as carbon tetrachloride and ethylene tetrachloride, ethers such as tetrahydrofuran and dioxane, and the like can be used as the solvent. It is also effective to add a deacidification agent (de-hydrohalogenating agent) such as sodium hydrogencarbonate, sodium carbonate and triethylamine. The reaction temperature is not critical in the process of the present invention; the process of the present invention can be carried out over a wide temperature range, usually in the range of 10.degree. to 100.degree. C.
In the process of the present invention, the benzylaminotriazine derivatives, e.g., 2-halogeno-4-amino-6-(3',4'-di-substituted-.alpha.-alkylbenzylamino)-s-traizines, of the general formula (VI) as prepared above are further reacted with alkylmercaptan represented by the general formula: R.sup.2 SH or alkylmercaptide represented by the general formula: R.sup.2 SM.
Examples of the alkylmercaptan used herein include methylmercaptan, ethylmercaptan, and propylmercaptan. Examples of the alkylmercaptide used herein include sodium methylmercaptide (CH.sub.3 SNa), potassium methylmercaptide (CH.sub.3 SK), sodium ethylmercaptide (C.sub.2 H.sub.5 SNa), potassium ethylmercaptide (C.sub.2 H.sub.5 SK), sodium propylmercaptide (C.sub.3 H.sub.7 SNa), and potassium propylmercaptide (C.sub.3 H.sub.7 SK).
The ratio of the benzylaminotriazine derivatives of the general formula (IV) to alkylmercaptan or alkylmercaptide is not critical; for example, they are used in an equimolar ratio. The reaction can be carried out in the absence or presence of a solvent, e.g., isopropyl alcohol, dimethylformamide, toluene, xylene and benzene. The reaction temperature is not critical; the reaction can be carried out over a wide temperature range, particularly in a range of 10.degree. to 150.degree. C.
When alkylmercaptan is used, the reaction is carried out in the presence of caustic alkali such as sodium hydroxide and potassium hydroxide.
After completion of the reaction, the product is isolated and washed, whereupon the triazine derivatives of the general formula (I) can be obtained in a high purity and a high yield.
The triazine derivatives prepared according to the process of the present invention are novel compounds.
The triazine derivatives represented by the general formula (I) are useful as herbicides, since they inhibit the budding and growth of weeds with high selectivity. Moreover the triazine derivatives are excellent in the effect of killing not only broadleaf weeds such as Rotala indica(Willd.)Koehne var. uligirosa(Miq.)Koehne., Lindernia pyxidaria L. and Monochoria vaginalis Presl var. plantaginea(Roxb.)Solms-Laub., species of Cyperaceae such as Cyperus difformis L., and Graminceae such as Echinochloa crus-galli L., but also perennial weeds such as Scirpus juncoides Roxb. var. Hotarui Ohwi, Cyperus serotinus Rottb. and Sagittaria pygmaea Miq. which are now considered to be difficult to control, without causing phytotoxicity onto paddy rice plants. Herbicides of the present invention comprises (i) a herbicidal carrier, and (ii) an effective amount of the triazine derivative of the general formula (I).
The herbicides of the present invention can be applied in the form of compositions such as a wettable powder, an emulsifiable concentrate, dust, granules and the like. Such compositions are prepared by mixing the triazine derivative of the general formula (I) as the effective component with a liquid carrier such as an organic solvent and the like or a solid carrier such as a mineral powder and the like. Addition of a surfactant is preferred to impart the properties of ready emulsifying, dispersing, spreading and the like to the preparations.
When the herbicides of this invention are applied in the form of wettable powder, the herbicides usually comprise 10-55 parts by weight of the triazine derivative as the effective component, 40-88 parts by weight of a solid carrier and 2-5 parts by weight of a surfactant. When the herbicides are applied in the form of dust, the herbicides usually comprise 1-15 parts by weight of the triazine derivative as the effective component, 80-97 parts by weight of a solid carrier and 2-5 parts by weight of a surfactant. When the herbicides are applied in the form of granules, the herbicides usually comprise 0.1-10 parts by weight of the triazine derivative as the effective component, 85-97.9 parts by weight of a solid carrier and 2-5 parts by weight of a surfactant. When the herbicides are applied in the form of emulsifiable concentrate, the herbicides usually comprise 20-50 parts by weight of the triazine derivative as the effective component, 35-75 parts by weight of a solvent and 5-15 parts by weight of a surfactant.
A mineral powder can be used as the solid carrier described above. The mineral powder includes oxide such as diatomaceous earth and slaked lime, phosphate such as apatite, sulfate such as gypsum, and silicate such as talc, pyrophyllite, clay, kaolin, bentonite, acid clay, white carbon, quartz powder and silica powder. An organic solvent can be used as the solvent described above. The organic solvent includes an aromatic hydrocarbon such as xylene, toluene and benzene, a chlorinated hydrocarbon such as o-chlorotoluene, trichloromethane and trichloroethylene, an alcohol such as cyclohexanol, amylalcohol and ethylene glycol, a ketone such as isophorone, cyclohexane and cyclohexenylcyclohexanone, an ether such as butylcellosolve, dimethylether and methylethylether, an ester such as isopropyl acetate, benzyl acetate and methyl phthalate, an amide such as dimethylformamide, and a mixture thereof. The above surfactant includes various kinds of surfactant, that is anion type, cation type, nonion type and amphoteric ion type (e.g. amino acid and betaine).
The novel triazine derivatives of the general formula (I) prepared by the process of the present invention are quite useful as herbicides which exhibit a high herbicidal activity to not only annual weeds but also perennial weeds, do not cause phytotoxicity to paddy rice plants, and is of high selectivity.
The herbicides of the present invention may contain as effective components other herbicidal materials in combination with the triazine derivatives of the general formula (I). As these herbicidal materials, various commercially available herbicides can be used, including phenoxy-, diphenyl ether-, triazine-, urea-, carbamate-, thiolcarbamate-, anilide-, pyrazole-, phosphoric acid-, and oxadiazone-based herbicides.
The herbicides of the present invention can be used in combination with an insectcide, a fungicide, a plant growth regulator agent, a fertilizer and the like if necessary.
The herbicides of the present invention are greatly effective compared with conventional herbicides for paddy rice plants, cause less phytotoxicity, and further have a broad herbicidal spectra width. In more detail, the herbicide of the present invention is greatly effective not only in killing Echinochloa crus-galli L. and broadleaf weeds, but also in killing perennial weeds such as Sagittaria pygmaea Miq., Scirpus juncoides Roxb. var. Hotarui Ohwi and Cyperus serotinus Rottb.

The present invention is described below in greater detail by reference to the following examples although it is not intended to be limited thereto.
PREPARATION EXAMPLE 1
Preparation of Benzylamine Derivative
A mixture of 30 grams (210 millimoles) of orthochloroanisole and 19.8 grams (252 millimoles) of acetyl chloride was dissolved in 400 milliliters of methylene chloride, and then 33.6 grams (252 millimoles) of anhydrous aluminum chloride was gradually added thereto while cooling with ice and stirring. The resulting mixture was further stirred for 3 hours while cooling with ice. The reaction mixture was allowed to stand to room temperature and stirred for 2 hours at room temperature. Then the reaction mixture was added to 1,200 milliliters of 5% hydrochloric acid, which was then allowed to separate into aqueous and organic layers. The organic layer thus obtained was washed with a 5% aqueous solution of sodium carbonate and dried over anhydrous sodium sulfate and, thereafter, the methylene chloride was distilled away under reduced pressure. Thus, as a product, 37.4 grams (202 millimoles) of 3-chloro-4-methoxyacetophenone was obtained (yield, 97%).
This 3-chloro-4-methoxyacetophenone in the amount of 32.4 grams (176 millimoles) was mixed with 35.4 grams (562 millimoles) of ammonium formate and then stirred at 180.degree. C. for 5 hours. The reaction mixture was dissolved in 200 milliliters of benzene, washed with water and dried over anhydrous sodium sulfate, and thereafter the benzene was distilled away under reduced pressure. To the product as obtained after distillation of the benzene was added 60 milliliters of 35% hydrochloric acid, and the resulting mixture was refluxed with heating for one hour and a half. The mixture was cooled, and then 100 milliliters of ethyl acetate was added thereto and the resulting aqueous layer was separated. This aqueous layer was made alkaline by adding an aqueous solution of sodium hydroxide, whereupon a free oil layer was obtained.
This oil layer was subjected to vacuum distillation under conditions of 130.degree. C. and 4 millimeter mercury (mm Hg) to yield 19.2 grams (10.3 millimoles) of a benzylamine derivative, 3-chloro-4-methoxy-.alpha.-methylbenzylamine (yield, 51%).
______________________________________Elemental Analysis (%) Carbon Hydrogen Nitrogen Chlorine______________________________________Found 57.9 6.6 7.4 19.3Calculated 58.2 6.5 7.5 19.1______________________________________
The structure of the derivative is as follows: ##STR10##
PREPARATION EXAMPLE 2
Preparation of Benzylamine Derivative
Commercially available 3,4-dimethoxyacetophenone in the amount of 36.4 grams (202 millimoles) was mixed with 35.4 grams (562 millimoles) of ammonium formate, and then the resulting mixture was stirred at 180.degree. C. for 5 hours. Thereafter the same procedure as in Preparation Example 1 was performed to yield a free oil layer. This oil layer was separated and subjected to vacuum distillation to yield 13.5 grams (75 millimoles) of a benzylamine derivative, 3,4-di-methoxy-.alpha.-methylbenzylamine (yield, 37%).
______________________________________Elemental Analysis (%) Carbon Hydrogen Nitrogen______________________________________Found 66.5 8.2 7.6Calculated 66.3 8.3 7.7______________________________________
Refractive Index: n.sub.D.sup.20 =1.5564
The structure of the derivative is as follows: ##STR11##
PREPARATION EXAMPLE 3
Preparation of Benzylamine Derivative
Commercially available 3,4-dimethylacetophenone in the amount of 26.1 grams (176 millimoles) was mixed with 35.4 grams (562 millimoles) of ammonium formate, and the resulting mixture was stirred at 180.degree. C. for 5 hours. Thereafter the same procedure as in preparative example 1 was performed to yield a free oil layer.
This oil layer was separated and subjected to vacuum distillation under conditions of 68.5.degree. C. and 0.35 mmHg to yield 13.4 grams (89.8 millimoles) of a benzylamine derivative, 3,4-dimethyl-.alpha.-methylbenzylamine (yield, 51%).
______________________________________Elemental Analysis (%) Carbon Hydrogen Nitrogen______________________________________Found 80.6 9.9 9.5Calculated 80.5 10.1 9.4______________________________________
The structure of the derivative is as follows: ##STR12##
PREPARATION EXAMPLE 4
Preparation of Benzylamine Derivative
Commercially available 3,4-dichloroacetophenone in the amount of 33.3 grams (176 millimoles) was mixed with 35.4 grams (562 millimoles) of ammonium formate, and the resulting mixture was stirred at 180.degree. C. for 5 hours. Thereafter the same procedure as in preparation example 1 was performed to yield a free oil layer.
This oil layer was separated and subjected to vacuum distillation under conditions of 88.5.degree. C. and 0.3 mmHg to yield 20.1 grams (106 millimoles) of a benzylamine derivative, 3,4-dichloro-.alpha.-methylbenzylamine (yield, 60%).
______________________________________Elemental Analysis (%) Carbon Hydrogen Nitrogen Chlorine______________________________________Found 50.8 4.7 7.4 37.5Calculated 50.6 4.8 7.3 37.3______________________________________
The structure of the derivative is as follows: ##STR13##
PREPARATION EXAMPLE 5
Preparation of Benzylamine Derivative
A mixture of 25.7 grams (210 millimoles) of ortho-methyl anisole and 19.8 grams (252 millimoles) of acetyl chloride was dissolved in 400 milliliters of methylene chloride, and then 33.6 grams (252 millimoles) of anhydrous aluminum chloride was gradually added thereto while cooling with ice and stirring. The resulting mixture was further stirred for 3 hours while cooling with ice. The reaction mixture was allowed to stand to room temperature and stirred for 2 hours at room temperature. Then the reaction mixture was added to 1,200 milliliters of 5% hydrochloric acid, which was then allowed to separate into aqueous and organic layers. The organic layer thus obtained was washed with a 5% aqueous solution of sodium carbonate and dried over anhydrous sodium sulfate and, thereafter, the methylene chloride was distilled away under reduced pressure. Thus, as a product, 27.9 grams (170 millimoles) of 3-methyl-4-methoxyacetophenone was obtained (yield, 81%).
This 3-methyl-4-methoxyacetophenone in the amount of 28.9 grams (176 millimoles) was mixed with 35.4 grams (562 millimoles) of ammonium formate and then stirred at 180.degree. C. for 5 hours. Thereafter the same procedure as in preparation example 1 was performed to yield a free oil layer.
This oil layer was separated and subjected to vacuum distillation under conditions of 85.degree. C. and 0.32 millimeter mercury (mm Hg) to yield 10.2 grams (61.6 millimoles) of a benzylamine derivative, 3-methyl-4-methoxy-.alpha.-methylbenzylamine (yield, 35%).
______________________________________Elemental Analysis (%) Carbon Hydrogen Nitrogen______________________________________Found 72.2 9.3 8.7Calculated 72.7 9.2 8.5______________________________________
The structure of the derivative is as follows: ##STR14##
PREPARATION EXAMPLE 6
Preparation of Benzylamine Derivative
A mixture of 26.6 grams (210 millimoles) of ortho-chlorotoluene and 23.3 grams (252 millimoles) of propionyl chloride was dissolved in 400 milliliters of methylene chloride, and then 33.6 grams (252 millimoles) of anhydrous aluminum chloride was gradually added thereto while cooling with ice and stirring. The resulting mixture was further stirred for 3 hours while cooling with ice. The reaction mixture was allowed to stand at room temperature and stirred for 2 hours at room temperature. Then the reaction mixture was added to 1,200 milliliters of 5% hydrochloric acid, which was then allowed to separate into aqueous and organic layers. The organic layer thus obtained was washed with a 5% aqueous solution of sodium carbonate and dried over anhydrous sodium sulfate and, thereafter, the methylene chloride was distilled away under reduced pressure. Thus, as a product, 37.6 grams (206 millimoles) of 3-methyl-4-chloropropiophenone was obtained (yield, 98%).
This 3-methyl-4-chloropropiophenone in the amount of 32.2 grams (176 millimoles) was mixed with 35.4 grams (562 millimoles) of ammonium formate and then stirred at 180.degree. C. for 5 hours. Thereafter the same procedure as in preparation example 1 was performed to yield a free oil layer.
This oil layer was separated and subjected to vacuum distillation under conditions of 87.5.degree. C. and 0.52 millimeter mercury (mm Hg) to yield 22.2 grams (121 millimoles) of a benzylamine derivative, 3-methyl-4-chloro-.alpha.-ethylbenzylamine (yield, 69%).
______________________________________Elemental Analysis (%) Carbon Hydrogen Nitrogen Chlorine______________________________________Found 65.0 7.8 7.8 19.4Calculated 65.4 7.7 7.6 19.3______________________________________
The structure of the derivative is as follows: ##STR15##
PREPARATION EXAMPLE 7
Preparation of Benzylamine Derivative
A mixture of 25.7 grams (210 millimoles) of ortho-methylanisole and 23.3 grams (252 millimoles) of propionyl chloride was dissolved in 400 milliliters of methylene chloride, and then 33.6 grams (252 millimoles) of anhydrous aluminum chloride was gradually added thereto while cooling with ice and stirring. The resulting mixture was further stirred for 3 hours while cooling with ice. The reaction mixture was allowed to stand at room temperature and stirred for 2 hours at room temperaure. Then the reaction mixture was added to 1,200 milliliters of 5% hydrochloric acid, which was then allowed to separate into aqueous and organic layers. The organic layer thus obtained was washed with a 5% aqueous solution of sodium carbonate and dried over anhydrous sodium sulfate and, thereafter, the methylene chloride was distilled away under reduced pressure. Thus, as a product, 35.6 grams (200 millimoles) of 3-methyl-4-methoxypropiophenone was obtained (yield, 95%).
This 3-methyl-4-methoxypropiophenone in the amount of 31.4 grams (176 millimoles) was mixed with 35.4 grams (562 millimoles) of ammonium formate and then stirred at 180.degree. C. for 5 hours. Thereafter the same procedure as in preparation example 1 was performed to yield a free oil layer.
This oil layer was separated and subjected to vacuum distillation to yield 12.6 grams (70.4 millimoles) of a benzylamine derivative, 3-methyl-4-methoxy-.alpha.-ethylbenzylamine (yield, 40%).
______________________________________Elemental Analysis (%) Carbon Hydrogen Nitrogen______________________________________Found 73.2 9.7 7.9Calculated 73.7 9.6 7.8______________________________________
Refractive Index: n.sub.D.sup.20 =1.5278
The structure of the derivative is as follows: ##STR16##
PREPARATION EXAMPLE 8
Preparation of Benzylamine Derivative
A mixture of 25.7 grams (210 millimoles) of ortho-methylanisole and 26.8 grams (252 millimoles) of isobutyryl chloride ((CH.sub.3).sub.2 CHCOCl) was dissolved in 400 milliliters of methylene chloride, and then 33.6 grams (252 millimoles) of anhydrous aluminum chloride was gradually added thereto while cooling with ice and stirring. The resulting mixture was further stirred for 3 hours while cooling with ice. The reaction mixture was allowed to stand at room temperature and stirred for 2 hours at room temperature. Then the reaction mixture was added to 1,200 milliliters of 5% hydrochloric acid, which was then allowed to separate into aqueous and organic layers. The organic layer thus obtained was washed with a 5% aqueous solution of sodium carbonate and dried over anhydrous sodium sulfate and, thereafter, the methylene chloride was distilled away under reduced pressure. Thus, as a product, 38.8 grams (202 millimoles) of 3-methyl-4-methoxyisobutyrophenone was obtained (yield, 96%).
This 3-methyl-4-methoxyisobutyrophenone in the amount of 33.8 grams (176 millimoles) was mixed with 35.4 grams (562 millimoles) of ammonium formate and then stirred at 180.degree. C. for 5 hours. Thereafter the same procedure as in preparation example 1 was performed to yield a free oil layer.
This oil layer was separated and subjected to vacuum distillation to yield 13.6 grams (70.4 millimoles) of a benzylamine derivative, 3-methyl-4-methoxy-.alpha.-isopropylbenzylamine (yield, 40%).
______________________________________Elemental Analysis (%) Carbon Hydrogen Nitrogen______________________________________Found 74.9 10.0 7.0Calculated 74.6 9.9 7.2______________________________________
Refractive Index: n.sub.D.sup.20 =1.5236
The structure of the derivative is as follows: ##STR17##
PREPARATION EXAMPLE 9
Preparation of Benzylamine Derivative
A mixture of 31.5 grams (210 millimoles) of ortho-isopropylanisole and 19.8 grams (252 millimoles) of acetyl chloride was dissolved in 400 milliliters of methylene chloride, and then 33.6 grams (252 millimoles) of anhydrous aluminum chloride was gradually added thereto while cooling with ice and stirring. The resulting mixture was further stirred for 3 hours while cooling with ice. The reaction mixture was allowed to stand at room temperature and stirred for 2 hours at room temperature. Then the reaction mixture was added to 1,200 milliliters of 5% hydrochloric acid, which was then allowed to separate into aqueous and organic layers. The organic layer thus obtained was washed with a 5% aqueous solution of sodium carbonate and dried over anhydrous sodium sulfate and, thereafter, the methylene chloride was distilled away under reduced pressure. Thus, as a product, 39.6 grams (206 millimoles) of 3-isopropyl-4-methoxyacetophenone was obtained (yield, 98%).
This 3-isopropyl-4-methoxyacetophenone in the amount of 33.8 grams (176 millimoles) was mixed with 35.4 grams (562 millimoles) of ammonium formate and then stirred at 180.degree. C. for 5 hours. Thereafter the same procedure as in preparation example 1 was performed to yield a free oil layer.
This oil layer was separated and subjected to vacuum distillation to yield 17.7 grams (91.5 millimoles) of a benzylamine derivative, 3-isopropyl-4-methoxy-.alpha.-methylbenzylamine (yield, 52%).
______________________________________Elemental Analysis (%) Carbon Hydrogen Nitrogen______________________________________Found 74.3 9.8 7.4Calculated 74.6 9.9 7.2______________________________________
Refractive Index: n.sub.D.sup.20 =1.5202
The structure of the derivative is as follows: ##STR18##
PREPARATION EXAMPLE 10
Preparation of Benzylamine Derivative
A mixture of 11.9 grams (172 millimoles) of hydroxylamine hydrochloride and 8.96 grams (84.5 millimoles) of sodium carbonate was dissolved in an ethanol-water mixture. To 300 milliliters of the solution thus prepared was added dropwise 25.0 grams (130 millimoles) of 3-methyl-4-isopropoxyacetophenone while cooling with ice, and the resulting mixture was stirred at room temperature for 24 hours. The reaction mixture was poured into 300 milliliters of water and then extracted with ethyl ether. The ethyl ether was distilled away under reduced pressure to yield 24.5 grams (118 millimoles) of 3-methyl-4-isopropoxyacetophenoneoxime (yield, 91%).
A solution of 24.5 grams (118 millimoles) of 3-methylisopropoxyacetophenoneoxime in 400 milliliters of ethanol was heated. When the solution started to boil, heating was stopped, and 30.6 grams (1,330 millimoles) of metallic sodium was added while stirring and dissolved. The resulting solution was cooled and diluted with 500 milliliters of water. The reaction solution was extracted with ethyl ether. The extract was dried over anhydrous sodium sulfate and after distilling away the ethyl ether under reduced pressure, concentrated under reduced pressure to yield an oily benzylamine derivative, 3-methyl-4-isoproxy-.alpha.-methylbenzylamine:
This 3-methyl-4-isopropoxy-.alpha.-methylbenzylamine was distilled under reduced pressure to obtain 20 grams of a fraction having a boiling point of 110.degree. C./4 mmHg. The yield was 88%.
______________________________________Elemental Analysis Carbon Hydrogen Nitrogen______________________________________Found 74.9 9.8 7.1Calculated 74.6 9.9 7.2______________________________________
The structure of the derivative is as follows: ##STR19##
PREPARATION EXAMPLE 11
Preparation of Benzylamine Derivative
A mixture of 29.0 grams (120 millimoles) of ortho-methylthioanisole and 19.8 grams (252 millimoles) of acetyl chloride was dissolved in 400 milliliters of methylene chloride, and then 33.6 grams (252 millimoles) of anhydrous aluminum chloride was gradually added thereto while cooling with ice and stirring. The resulting mixture was further stirred for 3 hours while cooling with ice. The reaction mixture was allowed to stand to room temperature and stirred for 2 hours at room temperature. Then the reaction mixture was added to 1,200 milliliters of 5% hydrochloric acid, which was then allowed to separate also aqueous and organic layers. The organic layer thus obtained was washed with a 5% aqueous solution of sodium carbonate and dried over anhydrous sodium sulfate and, thereafter, the methylene chloride was distilled away under reduced pressure. Thus, as a product, 34.5 grams (191 millimoles) of 3-methyl-4-methylthioacetophenone was obtained (yield, 91%).
This 3-methyl-4-methylthioacetophenone in the amount of 31.7 grams (176 millimoles) was mixed with 35.4 grams (562 millimoles) of ammonium formate and then stirred at 180.degree. C. for 5 hours. Thereafter the same procedure as in preparation example 1 was performed to yield a free oil layer.
This oil layer was separated and subjected to vacuum distillation under conditions of 130.degree. C. and 6 millimeter mercury (mm Hg) to yield 18.2 grams (100 millimoles) of a benzylamine derivative, 3-methyl-4-methylthio-.alpha.-methylbenzylamine (yield, 57%).
______________________________________Elemental Analysis (%) Carbon Hydrogen Nitrogen Sulfur______________________________________Found 66.7 8.2 7.6 17.5Calculated 66.3 8.3 7.7 17.7______________________________________
The structure of the derivative is as follows: ##STR20##
PREPARATION EXAMPLE 12
Preparation of Benzylamine Derivative
A mixture of 25 grams (165 millimoles) of 3-chloro-4-methylcyanobenzene and 27.4 grams (165 millimoles) of CH.sub.3 MgI was heated under reflux for 8 hours in 200 milliliters of benzene.
Then, to the reaction product thus obtained, 200 milliliters of 6 Normal hydrochloric acid was added, and the resulting mixture was heated under reflux for 6 hours.
A benzene layer was separated, washed with water and then dried over anhydrous sodium sulfate. Subsequently the benzene was distilled away under reduced pressure.
Thus, as a product, 27.0 grams (160 millimoles) of 3-chloro-4-methylacetophenone was obtained (yield, 97%).
This 3-chloro-4-methylacetophenone in the amount of 29.7 grams (176 millimoles) was mixed with 35.4 grams 562 millimoles) of ammonium formate and then stirred at 180.degree. C. for 5 hours. Thereafter the same procedure as in preparation example 1 was performed to yield a free oil layer.
This oil layer was separated and subjected to vacuum distillation under conditions of 80.degree. C. and 0.25 millimeter mercury (mmHg) to yield 17.9 grams (106 millimoles) of a benzylamine derivative, 3-chloro-4-methyl-.alpha.-methylbenzylamine (yield, 60%).
______________________________________Elemental Analysis (%) Carbon Hydrogen Nitrogen Chlorine______________________________________Found 63.5 7.1 8.4 21.0Calculated 63.7 7.1 8.3 20.9______________________________________
The structure of the derivative is as follows: ##STR21##
PREPARATION EXAMPLE 13
Preparation of Benzylamine Derivative
A mixture of 49 grams (295 millimoles) of 3-methoxy-4-methylbenzoic acid, 53.9 grams (315 millimoles) of p-toluene-sulfonamide, and 129 grams (619 millimoles) of phosphorus pentachloride was prepared and then heated at 200.degree. C. while stirring. Phosphorus oxychloride was distilled at 106.degree.-112.degree. C.; and the mixture was further heated at 200.degree. C. while stirring until no distillated came out. To the reaction mixture was added while stirring and cooling with ice 120 milliliters of pyridine in small portions and further 550 milliliters of water. Crystals precipitated were separated by filtration, suspended in 200 milliliters of a 5% aqueous sodium hydroxide solution, and then stirred at room temperature for 30 minutes. These crystals were separated by filtration and the crude product thus obtained was purified by steam distillation to obtain 36.5 grams of 3-methoxy-4-methylcyano-benzene (yield, 84%).
This 3-methoxy-4-methylcyanobenzene in the amount of 35 grams (238 millimoles) was mixed with 43.5 grams (262 millimoles) of CH.sub.3 MgI and then heated under reflux for 4.5 hours in 200 milliliters of diethyl ether.
Then, to the reaction product thus obtained, 300 milliliters of 6 Normal hydrochloric acid was added, and the resulting mixture was heated under reflux for 1 hour.
A diethyl ether layer was separated, washed with water and then dried over anhydrous sodium sulfate. Subsequently the diethyl ether was distilled away under reduced pressure.
Thus, as a product, 39.0 grams (238 millimoles) of 3-methoxy-4-methylacetophenone was obtained (yield, 99%).
This 3-methoxy-4-methylacetophenone in the amount of 38 grams (231 millimoles) was mixed with 46.7 grams (741 millimoles) of ammonium formate and then stirred at 180.degree. C. for 6 hours. Thereafter the same procedure as in preparation example 1 was performed to yield a free oil layer. This oil layer was separated and subjected to vacuum distillation under conditions of 80.degree.-83.degree. C. and 1 millimeter mercury (mm Hg) to yield 19.3 grams (117 millimoles) of a benzylamine derivative, 3-methoxy-4-methy-.alpha.-methylbenzylamine (yield, 60%).
______________________________________Elemental Analysis (%) Carbon Hydrogen Nitrogen______________________________________Found 72.4 9.3 8.6Calculated 72.7 9.2 8.5______________________________________
The structure of the derivative is as follows: ##STR22##
PREPARATION EXAMPLE 14
Preparation of Benzylamine Derivative
A mixture of 55.5 grams (408 millimoles) of ortho-ethoxytoluene and 38.4 grams (489 millimoles) of acetyl chloride was dissolved in 250 milliliters of methylene chloride, and then 65.2 grams (489 millimoles) of anhydrous aluminum chloride was gradually added thereto while cooling with ice and stirring. The resulting mixture was further stirred for 0.5 hour while cooling with ice. Then the reaction mixture was added to 500 milliliters of 5% hydrochloric acid, which was then allowed to separate into aqueous and organic layers. The organic layer thus obtained was washed with a 5% aqueous solution of sodium carbonate and dried over anhydrous sodium sulfate and, thereafter, the methylene chloride was distilled away under reduced pressure. Thus, as a product, 68.3 grams (384 millimoles) of 3-methyl-4-ethoxyacetophenone was obtained (yield, 94%).
This 3-methyl-4-ethoxyacetophenone in the amount of 20.0 grams (112 millimoles) was mixed with 22.6 grams (358 millimoles) of ammonium formate and then stirred at 180.degree. C. for 5 hours. The reaction mixture was dissolved in 200 milliliters of benzene, washed with water and dried over anhydrous sodium sulfate, and thereafter the benzene was distilled away under reduced pressure. To the product as obtained after distillation of the benzene was added 172 milliliters of a 5% aqueous solution of sodium hydroxide, and the resulting mixture was stirred at 70.degree. C. for 26 hours. The mixture was cooled, and then 200 milliliters of ethyl ether was added thereto and the resulting organic layer was separated.
This organic layer was subjected to vacuum distillation under conditions of 95.degree.-96.8.degree. C. and 2 millimeter mercury (mm Hg) to yield 9.0 grams (50.0 millimoles) of a benzylamine derivative, 3-methyl-4-ethoxy-.alpha.-methylbenzylamine (yield, 45%).
______________________________________Elemental Analysis (%) Carbon Hydrogen Nitrogen______________________________________Found 73.9 9.5 7.9Calculated 73.7 9.6 7.8______________________________________
The structure of the derivative is as follows: ##STR23##
PREPARATION EXAMPLE 15
Preparation of Benzylamine Derivative
A mixture of 50.0 grams (367 millimoles) of ortho-ethylanisole and 34.6 grams (441 millimoles) of acetyl chloride was dissolved in 200 milliliters of methylene chloride, and then 58.8 grams (441 millimoles) of anhydrous aluminum chloride was gradually added thereto while cooling with ice and stirring. The resulting mixture was further stirred for 0.5 hour while cooling with ice. Then the reaction mixture was added to 500 milliliters of 5% hydrochloric acid, which was then allowed to separate into aqueous and organic layer. The organic layer thus obtained was washed with a 5% aqueous solution of sodium carbonate and dried over anhydrous sodium sulfate and, thereafter, the methylene chloride was distilled away under reduced pressure. Thus, as a product, 62.3 grams (349 millimoles) of 3-ethyl-4-methoxyacetophenone was obtained (yield, 95%).
This 3-ethyl-4-methoxyacetophenone in the amount of 29.4 grams (165 millimoles) was mixed with 31.2 grams (495 millimoles) of ammonium formate and then stirred at 180.degree. C. for 5 hours. Thereafter the same procedure as in preparation example 14 was performed to yield a free oil layer. This oil layer was separated and subjected to vacuum distillation under conditions of 94.degree.-95.degree. C. and 1.8 millimeter mercury (mm Hg) to yield 17.0 grams (95.0 millimoles) of a benzylamine derivative, 3-ethyl-4-methoxy-.alpha.-methylbenzylamine (yield, 58%).
______________________________________Elemental Analysis (%) Carbon Hydrogen Nitrogen______________________________________Found 73.6 9.5 7.9Calculated 73.7 9.6 7.8______________________________________
The structure of the derivative is as follows: ##STR24##
PREPARATION EXAMPLE 16
Preparation of Benzylamine Derivative
A mixture of 32 grams (165 millimoles) of 3-methyl-4-bromocyanobenzene and 27.4 grams (165 millimoles) of CH.sub.3 MgI was heated under reflux for 8 hours in 200 milliliters of diethyl ether.
Then, to the reaction product thus obtained, 200 milliliters of 6 Normal hydrochloric acid was added, and the resulting mixture was heated wnder reflux for 6 hours.
A diethyl ether layer was separated, washed with water and then dried over anhydrous sodium sulfate. Subsequently the diethyl ether was distilled away under reduced pressure.
Thus, as a product, 34.1 grams (160 millimoles) of 3-methyl-4-bromoacetophenone was obtained (yield, 97%).
This 3-methyl-4-bromoacetophenone in the amount of 37.5 grams (176 millimoles) was mixed with 35.4 grams (562 millimoles) of ammonium formate and then stirred at 180.degree. C. for 5 hours. Thereafter the same procedure as in preparation example 1 was performed to yield a free oil layer.
This oil layer was separated and subjected to vacuum distillation to yield 5.7 grams (26 millimoles) of a benzylamine derivative, 3-methyl-4-bromo-.alpha.-methylbenzylamine (yield, 15%).
______________________________________Elemental Analysis (%) Carbon Hydrogen Nitrogen Bromine______________________________________Found 50.7 5.6 6.6 37.1Calculated 50.5 5.7 6.5 37.3______________________________________
The structure of the derivative is as follows: ##STR25##
PREPARATION EXAMPLE 17
Preparation of Benzylamine Derivative
A mixture of 25 grams (158 millimoles) of ortho-chlorothioanisole and 14.8 grams (189 millimoles) of acetyl chloride was dissolved in 250 milliliters of methylene chloride, and then 25.2 grams (189 millimoles) of anhydrous aluminum chloride was gradually added thereto while cooling with ice and stirring. The resulting mixture was further stirred for 20 minutes while cooling with ice. The reaction mixture was added to 1,200 milliliters of 5% hydrochloric acid, which was then allowed to separate into aqueous and organic layers. The organic layer thus obtained was washed with a 5% aqueous solution of sodium carbonate and dried over anhydrous sodium sulfate and, thereafter, the methylene chloride was distilled away under reduced pressure. Thus, as a product, 29.6 grams (147 millimoles) of 3-chloro-4-methylthioacetophenone was obtained (yield, 93%).
This 3-chloro-4-methylthioacetophenone in the amount of 29.6 grams (147 millimoles) was mixed with 37.0 grams (588 millimoles) of ammonium formate and then stirred at 180.degree. C. for 5 hours. Thereafter the same procedure as in preparation example 1 was performed to yield a free oil layer.
This oil layer was separated and subjected to vacuum distillation under conditions of 132.0.degree.-132.5.degree. C. and 1.8 millimeter mercury (mm Hg) to yield 21.4 grams (106 millimoles) of a benzylamine derivative, 3-chloro-4-methylthio-.alpha.-methyl-benzylamide (yield, 72%).
______________________________________Elemental Analysis (%)Carbon Hydrogen Nitrogen Chlorine Sulfur______________________________________Found 53.5 6.1 6.7 17.7 16.0Calculated 53.6 6.0 6.9 17.6 15.9______________________________________
The structure of the derivative is as follows: ##STR26##
PREPARATION EXAMPLE 18
Preparation of Benzylamine Derivative
A mixture of 50 grams (454 millimoles) of ortho-fluorotoluene and 42.8 grams (545 millimoles) of acetyl chloride was dissolved in 250 milliliters of methylene chloride, and then 72.7 grams (545 millimoles) of anhydrous aluminum chloride was gradually added thereto while cooling with ice and stirring. The resulting mixture was further stirred for 2 hours while cooling with ice. Then the reaction mixture was added to 1,200 milliliters of 5% hydrochloric acid, which was then allowed to separate into aqueous and organic layers. The organic layer thus obtained was washed with a 5% aqueous solution of sodium carbonate and dried over anhydrous sodium sulfate and, thereafter, the methylene chloride was distilled away under reduced pressure. Thus, as a product, 67.9 grams (446 millimoles) of 3-methyl-4-fluoroacetophenone was obtained (yield, 98%).
This 3-methyl-4-fluoroacetophenone in the amount of 29.6 grams (195 millimoles) was mixed with 49.1 grams (779 millimoles) of ammonium formate and then stirred at 180.degree. C. for 5 hours. Thereafter the same procedure as in preparation example 1 was performed to yield a free oil layer.
This oil layer was separated and subjected to vacuum distillation under conditions of 48.degree. C. and 0.2 millimeter mercury (mm Hg) to yield 23.5 grams (153 millimoles) of a benzylamine derivative, 3-methyl-4-fluoro-.alpha.-methylbenzylamine (yield, 78%).
______________________________________Elemental Analysis (%) Carbon Hydrogen Nitrogen______________________________________Found 70.8 7.8 9.0Calculated 70.6 7.9 9.1______________________________________
The structure of the derivative is as follows: ##STR27##
PREPARATION EXAMPLE 19
Preparation of Benzlamine Derivative
A mixture of 26 grams (206 millimoles) of ortho-fluoroanisole and 19.4 grams (247 millimoles) of acetyl chloride was dissolved in 200 milliliters of methylene chloride, and then 33.0 grams (247 millimoles) of anhydrous aluminum chloride was gradually added thereto while cooling with ice and stirring. The resulting mixture was further stirred for 1.5 hours while cooling with ice. The reaction mixture was added to 1,200 milliliters of 5% hydrochloric acid, which was then allowed to separate into aqueous and organic layers. The organic layer thus obtained was washed with a 5% aqueous solution of sodium carbonate and dried over anhydrous sodium sulfate and, thereafter, the methylene chloride was distilled away under reduced pressure, and the residue was recrystallized from ethanol. Thus, as a product, 30.4 grams (181 millimoles) of 3-fluoro-4-methoxyacetophenone was obtained (yield, 88%).
This 3-fluoro-4-methoxyacetophenone in the amount of 29 grams (172 millimoles) was mixed with 34.8 grams (552 millimoles) of ammonium formate and then stirred at 180.degree. C. for 5 hours. Thereafter the same procedure as in preparation example 1 was performed to yield a free oil layer.
This oil layer was separated and subjected to vacuum distillation under conditions of 89.degree.-91.degree. C. and 1 millimeter mercury (mm Hg) to yield 19.9 grams (118 millimoles) of a benzylamine derivative, 3-fluoro-4-methoxy-.alpha.-methylbenzylamine (yield, 69%).
______________________________________Elemental Analysis (%) Carbon Hydrogen Nitrogen______________________________________Found 64.0 7.2 8.4Calculated 63.9 7.1 8.3______________________________________
The structure of the derivative is as follows: ##STR28##
PREPARATION EXAMPLE 20
Preparation of Benzylamine Derivative
A mixture 34.9 grams (210 millimoles) of ortho-diethoxybenzene and 19.8 grams (252 millimoles) of acetyl chloride was dissolved in 400 millimeters of methylene chloride, and then 33.6 grams (252 millimoles) of anhydrous aluminum chloride was gradually added thereto while cooling with ice and stirring. The resulting mixture was further stirred for 3 hours while cooling with ice. The reaction mixture added to 1,200 milliliters of 5% hydrochloric acid, which was then allowed to separate into aqueous and organic layers. The organic layer thus obtained was washed with a 5% aqueous solution of sodium carbonate and dried over anhydrous sodium sulfate and, thereafter, the methylene chloride was distilled away under reduced pressure. Thus, as a product, 35.0 grams (168 millimoles) of 3,4-diethoxyacetophenone was obtained (yield, 80%).
And then a mixture of 11.9 grams (172 millimoles) of hydroxylamine hydrochloride and 8.96 grams (84.5 millimoles) of sodium carbonate was dissolved in an ethanol-water mixture. To 300 milliliters of the solution thus prepared was added dropwise 27.1 grams (130 millimoles) of 3,4-diethoxyacetophenone while cooling with ice, and the resulting mixture was stirred at room temperature for 24 hours. The reaction mixture was poured into 300 milliliters of water and then extracted with ethyl ether. The extract was dried over anhydrous sodium sulfate and, thereafter, the ethyl ether was distilled away under reduced pressure to yield 28.7 grams (129 millimoles) of 3,4-diethoxyacetopheneoxime (yield, 99%).
A solution of 28.7 grams (129 millimoles) of 3,4-diethoxyacetophenoneoxime in 400 milliliters of ethanol was heated. When the solution started to boil, heating was stopped, and 30.6 grams (1,330 millimoles) of metallic sodium was added while stirring and dissolved. The resulting solution was cooled and diluted with 500 milliliters of water. The reaction solution was extracted with ethyl ether. The extract was dried over anhydrous sodium sulfate and after distilling away the ethyl ether under reduced pressure, concentrated under reduced pressure to yield a solid product.
This product was purified by recrystallization from ethanol to obtain 19.7 grams of a benzylamine dervative, 3,4-diethoxy-.alpha.-methylbenzylamine. The yield was 73%.
______________________________________Elemental Analysis (%) Carbon Hydrogen Nitrogen______________________________________Found 68.7 9.2 6.6Calculated 68.9 9.1 6.7______________________________________
Melting point: 100.3.degree.-101.8.degree. C.
The structure of the derivative is as follows: ##STR29##
PREPARATION EXAMPLE 21
Preparation of Benzylamine Derivative
A mixture of 40.8 grams (210 millimoles) of ortho-dinormalpropoxybenzene and 19.8 grams (252 millimoles) of acetyl chloride was dissolved in 400 milliliters of methylene chloride, and then 33.6 grams (252 millimoles) of anhydrous aluminum chloride was gradually added thereto while cooling with ice and stirring. The resulting mixture was further stirred for 3 hours while cooling with ice. The reaction mixture was added to 1,200 milliliters of 5% hydrochloric acid, which was then allowed to separate into aqueous and organic layers. The organic layer thus obtained was washed with a 5% aqueous solution of sodium carbonate and dried over anhydrous sodium sulfate and, thereafter, the methylene chloride was distilled away under reduced pressure. Thus, as a product, 41.6 grams (176 millimoles) of 3,4-dinormalpropoxyacetophenone was obtained (yield, 84%).
And then a mixture of 11.9 grams (172 millimoles) of hydroxylamine hydrochloride and 8.96 grams (84.5 millimoles) of sodium carbonate was dissolved in an ethanol-water mixture. To 300 milliliters of the solution thus prepared was added dropwise 30.5 grams (130 millimoles) of 3,4-dinormalpropoxyacetophenone while cooling with ice, and the resulting mixture was stirred at room temperature for 24 hours. The reaction mixture was poured into 300 milliliters of water and then extracted with ethyl ether. The extract was dried over anhydrous sodium sulfate and, thereafter, the ethyl ether was distilled away under reduced pressure to yield 32.0 grams (127 millimoles) of 3,4-dinormalpropoxyacetophenoneoxime (yield, 98%).
A solution of 32.0 grams (127 millimoles) of 3,4-dinormalpropoxyacetophenoneoxime in 400 milliliters of ethanol was heated. When the solution started to boil, heating was stopped, and 30.6 grams (1,330 millimoles) of metallic sodium was added while stirring and dissolved. The resulting solution was cooled and diluted with 500 milliliters of water. The reaction solution was extracted with ethyl ether. The extract was dried over anhydrous sodium sulfate and after distilling away the ethyl ether under reduced pressure, concentrated under reduced pressure to yield asolid product.
This product was purified by recrystallization from ethanol to obtain 20.6 grams of a benzylamine derivative, 3,4-dinormalpropoxy-.alpha.-methylbenzylamine. The yield was 68%.
______________________________________Elemental Analysis (%) Carbon Hydrogen Nitrogen______________________________________Found 70.6 9.7 6.0Calculated 70.8 9.8 5.9______________________________________
The structure of the derivative is as follows: ##STR30##
PREPARATION EXAMPLE 22
Preparation of Benzylamine Derivative
A mixture of 32.0 grams (210 millimoles) of ortho-ethylthiotoluene and 19.8 grams (252 millimoles) of acetyl chloride was dissolved in 400 milliliters of methylene chloride, and then 33.6 grams (252 millimoles) of anhydrous aluminum chloride was gradually added thereto while cooling with ice and stirring. The resulting mixture was further stirred for 3 hours while cooling with ice. Then the reaction mixture was added to 1,200 milliliters of 5% hydrochloric acid, which was then allowed to separate into aqueous and organic layers. The organic layer thus obtained was washed with a 5% aqueous solution of sodium carbonate and dried over anhydrous sodium sulfate and, thereafter, the methylene chloride was distilled away under reduced pressure. Thus, as a product, 30.1 grams (155 millimoles) of 3-methyl-4-ethylthioacetophenone was obtained (yield, 74%).
This 3-methyl-4-ethylthioacetophenone in the amount of 29.1 grams (150 millimoles) was mixed with 37.1 grams (590 millimoles) of ammonium formate and then stirred at 180.degree. C. for 5 hours. Thereafter the same procedure as in preparation example 14 was performed to yield a free oil layer.
This oil layer was separated and subjected to vacuum distillation under conditions of 128.degree. C. and 10 millimeter mercury (mm Hg) to yield 11.7 grams (60.0 millimoles) of a benzylamine derivative, 3-methyl-4-ethylthio-.alpha.-methylbenzylamine (yield, 40%).
______________________________________Elemental Analysis (%) Carbon Hydrogen Nitrogen Sulfur______________________________________Found 67.5 8.8 7.1 16.6Calculated 67.7 8.7 7.2 16.4______________________________________
The structure of the derivative is as follows: ##STR31##
PRODUCTION EXAMPLES 1-6, 8-16, and 18-25
Preparation of Triazine Derivative
2,6-Dichloro-4-amino-s-triazine (16.4 grams (0.1 mole)) was dissolved in 55 grams of acetone, and then 0.1 mole of Benzylamine Derivative as prepared in the foregoing Preparation Examples was added thereto. Subsequently 8.4 grams (0.1 mole) of sodium hydrogencarbonate dissolved in 60 grams of water was added at 0.degree.-5.degree. C. while stirring. Then the mixture was gradually heated to 50.degree. C. over 1 hour.
Then the mixture was cooled, and the product obtained was isolated, washed with water and then dried to obtain a Benzylaminotriazine Derivative shown in Table 1-A.
To a mixture of 90 grams of isopropyl alcohol and 60 grams of 15% sodium methylmercaptide which had been heated to 50.degree.-60.degree. C. was added a prescribed amount of the above Benzylaminotriazine Derivative while stirring. The resulting reaction mixture was heated under reflux for 3 hours while stirring, and then cooled to 10.degree. C. and poured into ice water.
The product thus obtained was isolated, washed with water and then dried to yield a Triazine Derivative shown in Table 1-B.
Analytical results are shown in Table 1-B and Table 1-C.
TABLE 1-A__________________________________________________________________________ Benzylaminotriazine DerivativeProduction YieldExample No. Benzylamine Derivative Name (%) Amount__________________________________________________________________________ **(g) 1 Preparation Example 1 2-chloro-4-amino-6-(3'-chloro-4'-methoxy-.alpha.-methy lbenzylamino 95 28.8 s-triazine 2 Preparation Example 2 2-chloro-4-amino-6-(3',4'-dimethoxy-.alpha.-methylbenz ylamino)- 94 29.1 s-triazine 3 Preparation Example 3 2-chloro-4-amino-6-(3',4'-dimethyl-.alpha.-methylbenzy lamino)- 97 26.9 s-triazine 4 Preparation Example 4 2-chloro-4-amino-6-(3',4'-dichloro-.alpha.-methylbenzy lamino)- 96 30.6 s-triazine 5 Preparation Example 5 2-chloro-4-amino-6-(3'-methyl-4'-methoxy-.alpha.-methy lbenzylamino)- 95 27.9 s-triazine 6 Preparation Example 6 2-chloro-4-amino-6-(3'-methyl-4'-chloro-.alpha.-ethylb enzylamino)- 95 29.7 s-triazine 8 Preparation Example 7 2-chloro-4-amino-6-(3'-methyl-4'-methoxy-.alpha.-ethyl benzylamino)- 96 29.5 s-triazine 9 Preparation Example 8 2-chloro-4-amino-6-(3'-methyl-4'-methoxy-.alpha.-isopr opylbenzylamino)- 95 30.6 s-triazine10 Preparation Example 9 2-chloro-4-amino-6-(3'-isopropyl-4'-methoxy-.alpha.-me thylbenzylamino)- 96 30.9 s-triazine11 Preparation Example 10 2-chloro-4-amino-6-(3'-methyl-4'-isopropoxy-.alpha.-me thylbenzylamino)- 95 30.6 s-triazine12 Preparation Example 11 2-chloro-4-amino-6-(3'-methyl-4'-methylthio-.alpha.-me thylbenzylamino)- 96 29.7 s-triazine13 Preparation Example 12 2-chloro-4-amino-6-(3'-chloro-4'-methyl-.alpha.-methyl benzylamino)- 96 28.6 s-triazine14 Preparation Example 13 2-chloro-4-amino-6-(3' -methoxy-4'-methyl-.alpha.-meth ylbenzylamino)- 95 27.9 s-triazine15 Preparation Example 14 2-chloro-4-amino-6-(3'-methyl-4'-ethoxy-.alpha.-methyl benzylamino)- 96 29.5 s-triazine16 Preparation Example 15 2-chloro-4-amino-6-(3'-ethyl-4'-methoxy-.alpha.-methyl benzylamino)- 96 29.5 s-triazine18 3-methyl-4-chloro-.alpha.- 2-chloro-4-amino-6-(3'-methyl-4'-chloro-.alpha.-methyl benzylamino)- 95 28.2 methylbenzylamine s-triazine19 3-methyl-4-bromo-.alpha.- 2-chloro-4-amino-6-(3'-methyl-4'-bromo-.alpha.-methylb enzylamino)- 95 32.5 methylbenzylamine s-triazine20 Preparation Example 17 2-chloro-4-amino-6-(3'-chloro-4'-methylthio-.alpha.-me thylbenzylamino)- 94 31.0 s-triazine21 Preparation Example 18 2-chloro-4-amino-6-(3'-methyl-4'-fluoro-.alpha.-methyl benzylamino)- 93 26.1 s-triazine22 Preparation Example 19 2-chloro-4-amino-6-(3'-fluoro-4'-methoxy-.alpha.-methy lbenzylamino)- 96 29.5 s-triazine23 Preparation Example 20 2-chloro-4-amino-6-(3',4'-diethoxy-.alpha.-methylbenzy lamino)- 94 31.7 s-triazine24 Preparation Example 21 2-chloro-4-amino-6-(3',4'-dinormalpropoxy-.alpha.-meth ylbenzylamino)- 93 34.0 s-triazine25 Preparation Example 22 2-chloro-4-amino-6-(3'methyl-4'-ethylthio-.alpha.-meth ylbenzylamino)- 94 30.4 s-triazine__________________________________________________________________________ *shown by the number of Prepartion Example where Benzylamine Derivative used had been prepared, except for Production Example Nos. 18, 19 **the amount added to a mixture of isopropyl alcohol and sodium methylmercaptide
TABLE 1-B Triazine Derivative Analytical result Production Elemental analysis (%)*.sup.1 Example No. Name Yield (%) Melting point (.degree.C.) C H N S Cl Structure 1 2-methylthio-4-amino-6-(3'-chloro-4'-methoxy-.alpha.-methyl-benzylamin o)-s-triazine 95 66.1-67.2 48.3(47.9) 4.9(5.0) 21.4(21.5) 9.7(9.8) 10.8(10.9) ##STR32## 2 2-methylthio-4-amino-6-(3',4'-dimethoxy-.alpha.-methylbenzylamino)-s-t riazine 96 65.9-67.0 52.5(52.2) 5.9(6.0) 21.6(21.8) 9.9 (10.0) -- ##STR33## 3 2-methylthio-4-amino-6-(3',4'-dimethyl-.alpha.-methylbenzylamino)-s-tr iazine 94 161.0-161.9 58.4(58.1) 6.7(6.6) 24.3(24.2) 10.6(11.1) -- ##STR34## 4 2-methylthio-4-amino-6-(3',4'-dichloro-.alpha.-methylbenzylamino)-s-tr iazine 96 157.8-158.7 44.0(43.6) 4.0(4.0) 21.4(21.2) 9.5(9.7) 21.1 (21.5) ##STR35## 5 2-methylthio-4-amino-6-(3'-methyl-4'-methoxy-.alpha.-methyl-benzylamin o)-s-triazine 94 113.5-114.2 55.1(55.1) 6.3(6.3) 23.2(22.9) 10.3(10.5) -- ##STR36## 6 2-methylthio-4-amino-6-(3'-methyl-4'-chloro-.alpha.-ethyl-benzylamino) -s-triazine 95 56.7-57.8 51.5(51.9) 5.7(5.6) 21.8(21.6) 10.0(9.9) 11.0(11.0) ##STR37## 8 2-methylthio-4-amino-6-(3'-methyl-4'-methoxy-.alpha.-ethyl-benzylamino )-s-triazine 96 136.6-137.3 56.3(56.4) 6.5(6.6) 21.9(22.0) 10.2(10.0) -- ##STR38## 9 2-methylthio-4-amino-6-(3'-methyl-4'-methoxy-.alpha.-isopropyl-benzyla mino)-s-triazine 94 63.0-64.2 57.7(57.6) 6.9(7.2) 21.2(21.0) 9.5(9.6) -- ##STR39## 10 2-methylthio-4-amino-6-(3'-isopropyl-4'-methoxy-.alpha.-methyl-benzyl amino)-s-triazine 94 80.5-81.8 57.3(57.6) 7.1(7.0) 21.2(21.0) 9.5(9.6) -- ##STR40## 11 2-methylthio-4-amino-6-(3'-methyl-4'-isopropoxy-.alpha.-methyl-benzyl amino)-s-triazine 94 103.2-104.1 57.3(57.6) 7.0(7.0) 21.0(21.0) 9.8(9.6) -- ##STR41## 12 2-methylthio-4-amino-6-(3'-methyl-4'-methylthio-.alpha.-methyl-benzyl amino)-s-triazine 95 118.8-119.7 52.3(52.3) 5.9(6.0) 21.6(21.8) 20.2(19.9 ) -- ##STR42## 13 2-methylthio-4-amino-6-(3'-chloro-4'-methyl-.alpha.-methyl-benzylamin o)-s-triazine 96 155.3-156.3 50.3(50.4) 5.3(5.2) 22.8(22.6) 10.3(10.4) 11.3(11.4) ##STR43## 14 2-methylthio-4-amino-6-(3'-methoxy-4'-methyl-.alpha.-methyl-benzylami no)-s-triazine 94 110.6-111.2 55.0(55.1) 6.4(6.3) 22.8(22.9) 10.6(10.5) -- ##STR44## 15 2-methylthio-4-amino-6-(3'-methyl-4'-ethoxy-.alpha.-methyl-benzylamin o)-s-triazine 96 108.7-109.6 56.5(56.4) 6.7(6.6) 22.0(22.0) 10.1(10.0) -- ##STR45## 16 2-methylthio-4-amino-6-(3'-ethyl-4'-methoxy-.alpha.-methyl-benzylamin o)-s-triazine 96 110.5-111.4 56.5(56.4) 6.7(6.6) 21.9(22.0) 10.1(10.0) -- ##STR46## 18 2-methylthio-4-amino-6-(3'-methyl-4'-chloro-.alpha.-methyl-benzylamin o)-s-triazine 91 163.4-164.3 50.9(50.4) 5.2(5.2) 22.8(22.6) 10.1(10.4) 11.0(11.4) ##STR47## 19 2-methylthio-4-amino-6-(3'-methyl-4'-bromo-.alpha.-methyl-benzylamino )-s-triazine 91 167.1-168.2 43.9(44.1) 4.6(4.5) 19.6(19.8) 9.2(9.1) 22.0*.sup.2(22.5) ##STR48## 20 2-methylthio-4-amino-6-(3'-chloro-4'-methylthio-.alpha.-methyl-benzyl amino)-s-triazine 92 118.1-119.8 45.9(45.7) 4.8(4.7) 20.5(20.5) 18.6(18.7 ) 10.2(10.4) ##STR49## 21 2-methylthio-4-amino-6-(3'-methyl-4'-fluoro-.alpha.-methyl-benzylamin o)-s-triazine 93 110.5-112.5 53.2(53.2) 5.5(5.5) 24.2(23.9) 11.0(10.9) -- ##STR50## 22 2-methylthio-4-amino-6-(3'-fluoro-4'-methoxy-.alpha.-methyl-benzylami no)-s-triazine 94 94.4-96.0 50.6(50.5) 5.3(5.2) 22.4(22.6) 10.5(10.4) -- ##STR51## 23 2-methylthio-4-amino-6-(3',4'-diethoxy-.alpha.-methylbenzylamino)-s-t riazine 93 150.6-151.2 55.1(55.0) 6.7(6.6) 19.8(20.0) 9.0(9.2) -- ##STR52## 24 2-methylthio-4-amino-6-(3',4'-dinormalpropoxy-.alpha.-methyl-benzylam ino)-s-triazine 92 -- 57.5(57.3) 7.1(7.2) 18.4(18.6) 8.4(8.5) -- ##STR53## 25 2-methylthio-4-amino-6-(3'-methyl-4'-ethylthio-.alpha.-methyl-benzyla mino)-s-triazine 93 102.9-104.2 53.5(53.7) 6.4(6.3) 20.7(20.9) 19.2(19.1) -- ##STR54## *.sup.1 A numeral in the brackets means the calculated value of the Elemental analysis. *.sup.2 The ratio of bromine atom (Br) is shown in place of that of chlorine atom (Cl).
PRODUCTION EXAMPLE 7
Preparation of Triazine Derivative
Sodium hydroxide (5.0 grams (0.125 mole)) was dissolved in a mixed solvent of 15 milliliters of water and 25 milliliters of isopropyl alcohol, and then 7.8 grams (0.125 mole) of ethylmercaptan was added thereto. The mixture was heated to 50.degree.-60.degree. C., and then 27.9 grams (0.095 mole) of 2-chloro-4-amino-6-(3'-methyl-4'-methoxy-.alpha.-methylbenzylamino)-s-triazine as obtained in Production Example 5 was added thereto while stirring. The reaction mixture was heated under reflux for 3 hours while stirring, and then cooled to 10.degree. C. and poured into ice water.
The product thus obtained was isolated, washed with water and then dried to yield a triazine derivative, 30.0 grams of 2-ethylthio-4-amino-6-(3'-methyl-4'-methoxy-.alpha.-methylbenzylamino)-s-triazine in the yield of 94%. Analytical results of the triazine derivative are shown as follows and are shown in Table 1-C.
Melting point: 96.5.degree.-97.4.degree. C.
______________________________________Elemental analysis (%)Carbon Hydrogen Nitrogen Sulfur Chlorine______________________________________Found 56.4 6.6 21.7 10.1 5.1Calculated 56.4 6.6 22.0 10.0 5.0______________________________________
The structure is as follows: ##STR55##
PRODUCTION EXAMPLE 17
Preparation of Triazine Derivative
2,6-Dichloro-4-amino-s-triazine (16.4 grams (0.1 mole)) was dissolved in 55 grams of acetone, and then 21.4 grams (0.1 mole) of 3-methyl-4-bromo-.alpha.-methylbenzylamine as prepared in Preparation Example 16 was added thereto.
Subsequently 8.4 grams (0.1 mole) of sodium hydrogen-carbonate dissolved in 60 grams of water was added at 0.degree.-5.degree. C. while stirring. Then the mixture was gradually heated to 50.degree. C. over 1 hour. Then the mixture was cooled, and the product obtained was isolated, washed with water and then dried to obtain 2-chloro-4-amino-6-(3-methyl-4'-bromo-.alpha.-methylbenzylamino)-s-triazine in the yield of 95%.
Sodium hydroxide (5.0 grams (0.125 mole)) was dissolved in a mixed solvent of 15 milliliters of water and 25 milliliters of isopropyl alcohol, and then 7.8 grams (0.125 mole) of ethylmercaptan was added thereto. The mixture was heated to 50.degree.-60.degree. C., and then 34.0 grams (0.095 mole) of 2-chloro-4-amino-6-(3'-methyl-4'-bromo-.alpha.-methylbenzylamino)-s-triazine was added thereto while stirring. The reaction mixture was heated under reflux for 3 hours while stirring, and then cooled to 10.degree. C. and poured into ice water.
The product thus obtained was isolated, washed with water and then dried to yield a triazine derivative, 32.9 grams of 2-ethylthio-4-amino-6-(3'-methyl-4'-bromo-.alpha.-methylbenzylamino)-s-triazine in the yield of 94%. Analytical results of the triazine derivative are shown as follows and are shown in Table-C.
Melting point: 163.4.degree.-164.6.degree. C.
______________________________________Elemental analysis (%)Carbon Hydrogen Nitrogen Sulfur Bromine______________________________________Found 45.7 5.0 18.8 8.5 22.0Calculated 45.7 4.9 19.0 8.7 21.7______________________________________
The structure is as follows: ##STR56##
TABLE 1-C Production IR*.sup.1 (KBr) (cm.sup.-1) proton-NMR*.sup.2 (ppm) solvent: CDCl.sub.3, Example No. Triazine Derivative NH.sub.2 NH s-triazine internal standard: tetramethylsilane (TMS) 1 2-methylthio-4-amino-6-(3'-chloro-4'-methoxy-.alpha.-methylbenzylamino )-s-triazine 3460, 3330 3290 1540 2 2-methylthio-4-amino-6-(3',4'-dimethoxy-.alpha.-methyl-benzylamino)-s- triazine -- -- -- 1540 ##STR57## 3 2-methylthio-4-amino-6-(3',4'-dimethyl-.alpha.-methyl-benzylamino)-s-t riazine 3460, 3340 3280 1540 ##STR58## 4 2-methylthio-4-amino-6-(3',4'-dichloro-.alpha.-methyl-benzylamino)-s-t riazine 3470, 3340 3290 1550 ##STR59## 5 2-methylthio-4-amino-6-(3'-methyl-4'-methoxy-.alpha.-methylbenzylamino )-s-triazine 3470, 3340 3300 1550 ##STR60## 6 2-methylthio-4-amino-6-(3'-methyl-4'-chloro-.alpha.-ethyl-benzylamino) -s-triazine 3510, 3430 3300 1540 ##STR61## 7 2-ethylthio-4-amino-6-(3'-methyl-4'-methoxy-.alpha.-methylbenzylamino) -s-triazine 3480, 3340 3300 1550 ##STR62## 8 2-methylthio-4-amino-6-(3'-methyl-4'-methoxy-.alpha.-ethylbenzylamino) -s-triazine 3470, 3340 3260 1550 ##STR63## 9 2-methylthio-4-amino-6-(3'-methyl-4'-methoxy-.alpha.-isopropylbenzylam ino)-s-triazine -- -- -- 1550 ##STR64## 10 2-methylthio-4-amino-6-(3'-isopropyl-4'-methoxy-.alpha.-methylbenzyla mino)-s-triazine -- -- -- 1550 ##STR65## 11 2-methylthio-4-amino-6-(3'-methyl-4'-isopropoxy-.alpha.-methylbenzyla mino)-s-triazine 3480, 3330 3290 1550 ##STR66## 12 2-methylthio-4-amino-6-(3'-methyl-4'-methylthio-.alpha.-methylbenzyla mino)-s-triazine 3470, 3340 3300 1540 ##STR67## 13 2-methylthio-4-amino-6-(3'-chloro-4'-methyl-.alpha.-methylbenzylamino )-s-triazine 3460, 3340 3290 1550 ##STR68## 14 2-methylthio-4-amino-6-(3'-methoxy-4'-methyl-.alpha.-methylbenzylamin o)-s-triazine 3470, 3330 3290 1540 ##STR69## 15 2-methylthio-4-amino-6-(3'-methyl-4'-ethoxy-.alpha.-methylbenzylamino )-s-triazine 3480, 3340 3300 1550 ##STR70## 16 2-methylthio-4-amino-6-(3'-ethyl-4'-methoxy-.alpha.-methylbenzylamino )-s-triazine 3490, 3330 3290 1540 ##STR71## 17 2-ethylthio-4-amino-6-(3'-methyl-4'-bromo-.alpha.-methyl-benzylamino) -s-triazine 3490, 3340 3290 1550 ##STR72## 18 2-methylthio-4-amino-6-(3'-methyl-4'-chloro-.alpha.-methylbenzylamino )-s-triazine 3460, 3340 3280 1550 ##STR73## 19 2-methylthio-4-amino-6-(3'-methyl-4'-bromo-.alpha.-methylbenzylamino) -s-triazine 3470, 3330 3290 1540 ##STR74## 20 2-methylthio-4-amino-6-(3'-chloro-4'-methylthio-.alpha.-methylbenzyla mino)-s-triazine 3460, 3340 3290 1540 ##STR75## 21 2-methylthio-4-amino-6-(3'-methyl-4'-fluoro-.alpha.-methyl-benzylamin o)-s-triazine 3470, 3340 3290 1540 ##STR76## 22 2-methylthio-4-amino-6-(3'-fluoro-4'-methoxy-.alpha.-methylbenzylamin o)-s-triazine 3470, 3340 3270 1540 ##STR77## 23 2-methylthio-4-amino-6-(3',4'-diethoxy-.alpha.-methyl-benzylamino)-s- triazine 3500, 3400 3360 1530 ##STR78## 24 2-methylthio-4-amino-6-(3',4'-dinormalpropoxy-.alpha.-methylbenzylami no)-s-triazine -- -- -- 1540 ##STR79## 25 2-methylthio-4-amino-6-(3'-methyl-4'-ethylthio-.alpha.-methylbenzylam ino)-s-triazine 3460, 3340 3290 1540 ##STR80## *.sup.1 Infrared Absorption Spectrum *.sup.2 Proton Nuclear Magnetic Resonance
Examples 1-25
(1) Preparation of herbicide
97 parts by weight of talc as carrier, 1.5 parts by weight of alkylarylsulfonate as surfactant (trade name: Neo pelex, manufactured by Kao-Atlas KK) and 1.5 parts by weight of a mixture of nonionic type and anionic type surfactant (trade name: Sorpol 800A, manufactured by Toho Kagaku Kogyo KK) were homogeneously ground and mixed to obtain a carrier for a wettable powder.
A herbicidal wettable powder was prepared by grinding and mixing homogeneously 90 parts by weight of the above obtained carrier for the wettable powder with 10 parts by weight of one of the triazine derivatives prepared as reported in the Table I-B of the Production Examples 1-25.
(2) Results of biological tests
Treatment under submerged condition
A 1/15500-are porcelain pot was filled with the soil of a paddy field and seeds of Echinochloa crus-galli L., Cyperus difformis L., Rotala indica (Willd.) Koehne var. uligirosa (Miq.) Koehne., Scirpus juncoides Roxb. var. Hotarui Ohwi and Monochoria vaginalis Presl var. plantaginea (Roxb.) Solms-Laub. were sown uniformly in the upper layer of the soil. And then the tubers of Cyperus serotinus Rottb. and Sagittaria pygmaea Miq. were planted in the soil, thereafter young rice plants of the second-leaf stage were transplanted.
When the weeds were germinated, a predetermined amount of a diluted solution of a herbicide prepared as reported in paragraph (1) hereinbefore was uniformly applied dropwise to the surface of the water and then the pot was kept in a green-house and sprinkled with water at appropriate time intervals.
Table 2 reports the evaluation of the herbicidal effect and the phytotoxicity to the paddy rice plants at 20 days after application of the herbicide. In Table 2, the amount of the herbicide means the amount of the active component, 100 grams/10 ares. The phytotoxicity and herbicidal effect were evaluated respectively according to the following scale by determining the dry weight.
Phytotoxicity to the paddy rice plants:
______________________________________0 ratio to an untreated pot 100%1 " 95-99%2 " 90-94%3 " 80-89%4 " 60-79%5 " 50-69%______________________________________
Herbicidal effect:
______________________________________0 ratio to the untreated pot 100%1 " 61-99%2 " 21-60%3 " 11-20%4 " 1-10%5 " 0%______________________________________
Comparative Example 1
The same procedure as in Example 1 was carried out except that 2-methylthio-4,6-bis(ethylamino)-s-triazine (trade name: Gybon) shown in the following formula (A) was used in place of the triazine derivative prepared as reported in the Production Example 1. The results are shown in Table 2.
Comparative Example 2
The same procedure as in Example I was carried out except that 2-methylthio-4-methylamino-6-(.alpha.,.alpha.-dimethylbenzylamino)-s-triazine (Japanese Patent Publication No. 8261/1974) shown in the following formula (B) was used in place of the triazine derivative prepared as reported in the Preparation Example 1. The results are shown in Table 2.
Comparative Example 3
The same procedure as in Example 1 was carried out except that 2-chloro-4-isopropylamino-6-(.alpha.,.alpha.-dimethylbenzylamino)-s-triazine (Japanese Patent Publication No. 8262/1974) shown in the following formula (C) was used in place of the triazine derivative prepared as reported in the Production Example 1. The results shown in Table 2. ##STR81##
TABLE 2__________________________________________________________________________ Herbicidal effect Amount of Cyperus Scirpus juncoides Cyperus Annual Sagitaria Phytotoxicity Triazine herbicide Echinochloa serotinus Roxb. var. difformis broadleaf pygmaea to the paddyNo. derivative (gram/10 ares) crus-galli L. Rottb. Hotarui Ohwi L. weeds Mig. rice__________________________________________________________________________ plantsExample 1 Production 100 5 5 5 5 5 5 0 Example 1Example 2 Production 100 5 3 5 5 5 5 0 Example 2Example 3 Production 100 5 5 5 5 5 5 0 Example 3Example 4 Production 100 5 5 5 5 5 5 0 Example 4Example 5 Production 100 5 5 5 5 5 5 0 Example 5Example 6 Production 100 5 5 5 5 5 5 0 Example 6Example 7 Production 100 5 5 5 5 5 5 0 Example 7Example 8 Production 100 5 5 5 5 5 5 0 Example 8Example 9 Production 100 4 2 3 5 5 2 0 Example 9Example 10 Production 100 4 3 5 5 5 3 0 Example 10Example 11 Production 100 5 5 5 5 5 5 0 Example 11Example 12 Production 100 5 5 5 5 5 5 0 Example 12Example 13 Production 100 5 5 5 5 5 5 0 Example 13Example 14 Production 100 5 5 5 5 5 5 0 Example 14Example 15 Production 100 5 5 5 5 5 5 0 Example 15Example 16 Production 100 5 5 5 5 5 5 0 Example 16Example 17 Production 100 4 2 2 5 5 2 0 Example 17Example 18 Production 100 5 5 5 5 5 5 0 Example 18Example 19 Production 100 5 5 5 5 5 3 0 Example 19Example 20 Production 100 5 5 5 5 5 5 0 Example 20Example 21 Production 100 5 5 5 5 5 3 0 Example 21Example 22 Production 100 5 5 5 5 5 5 0 Example 22Example 23 Production 100 5 5 3 5 5 4 0 Example 23Example 24 Production 100 5 5 3 5 5 3 0 Example 24Example 25 Production 100 5 5 4 5 5 3 0 Example 25Comparative formula [A] 100 5 2 3 5 5 3 2Example 1Comparative formula [B] 100 4 0 1 5 5 0 0Example 2Comparative formula [C] 100 5 0 0 1 1 0 0Example 3__________________________________________________________________________ *shown by the number of Production Example in which the triazine derivative used had been prepared, except for Comparative Examples 1.about.3

Number	Name	Date
2335045	D'Alelio et al.	Nov 1943
3156690	Dexter et al.	Nov 1964
3746710	Kuhne et al.	Jul 1973
4544402	Schnurbusch et al.	Oct 1985
4562251	Fulton et al.	Dec 1985

Triazine derivatives, a process for preparing the derivatives, and herbicides containing the derivatives as the effective component

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