KR970006245B1 - N-benzoyl-c-(1-methyltetrazol-5-thio)-imidoyl chloride derivatives and method for the production thereof - Google Patents

Abstract

N-benzoyl-C-(1-methyltetrazol-5-thio)imidoyl chloride of general formula(I) and its derivative are prepared by reacting benzotriazol with benzoylimidoyl dichloride of general formula(III) made from benzoylisothiocyanate of general formula(II) in an organic solvent. The produced compound is useful as an intermediate of medicines or agricultural medicines. In the above formula, X means one of hydrogen, methyl, chloride and nitro group.

Description

N-benzoyl-C (l-methyltetrazol-5-thio) imidoyl chloride derivative and preparation method

The present invention relates to a N-benzoyl-C- (l-methylterazole-5-thio) amidoyl chloride derivative which is a novel compound of the formula (1) and a preparation method thereof.

Wherein X represents a hydrogen halogen, an alkyl group or a nitiro group.

The compounds of formula 1 described above are usefully used as pharmaceuticals and pesticide intermediates as novel compounds.

Compounds similar to the compounds of the present invention are known from Journal of Chemical Society, Perkin 2, 1046-51, 1975 and Korean Patent Application No. 91-4337 to Kim Chun-Seok, but the compounds are completely different from those of Formula 1 .

In the general formula (1), the alkyl group represented by X includes C _{1 to} C ₄ lower alkyl groups such as methyl, ethyl, propyl, and butyl groups. Among them, methyl group is preferred, and halogen is chlorine and cancellation, but chlorine is preferable. .

The above substituents are preferably substituted at the 4-position of the benzene ring.

Compounds of the present invention are prepared by reacting 1 equivalent of benzoylimidoyl dichloride of Formula 3 prepared from benzoylisothiocyanate of Formula 2 with 1 equivalent of 5-mercapto-1-5-methylthiadiazole.

The above-described method of formula (1) is carried out in an organic solvent, in which case dioxane, diethyl ether, tetrahydrofuran and the like are used as the organic solvent.

X has the meaning mentioned above.

Compounds other than the compound of Formula 2 and the compound of Formula 3, wherein X = Cl in the compound of Formula 1, are also novel compounds.

The benzoyl isothiocyanate of formula (2) dissolves benzoyl chloride or substituted benzoyl clonide and anhydrous potassium isocyanocyanate in an organic solvent such as dioxane, diethyl ether or tetrahydrofuran and is blocked with oxygen inflow. It is prepared by heating to reflux for a time. The potassium isothiocyanate used in this method is dried in a hot air circulation oven at 110 ° C. for 10 hours to completely remove moisture.

In order to prevent the reaction system from coming into contact with oxygen, the reactor is sealed and a condenser with a moisture inflow prevention device is attached or nitrogen is introduced into the reactor so that the reaction proceeds under nitrogen pressure. Organic solvents that do not affect the reaction may be used as the organic solvent, but benzene is preferable.

The benzoylimidoyl dichloride of formula (3) is prepared by dissolving the benzoylisothiocyanate or substituted benzoyl isocyanate of formula (3) prepared above in an organic solvent, in particular carbon tetrachloride, and reacting with dry chlorine gas for about 6 hours to 3 days. Manufacture. In this method, dry chlorine gas is injected into a carbon tetrachloride solution in which benzoylisothiocyanate is dissolved for about 6 hours, and the reaction solution is saturated with chlorine gas, and left for about 3 days to complete the reaction. do. Dry chlorine gas uses chlorine gas obtained by passing chlorine gas into sulfuric acid to remove moisture and passing glass wool and then removing sulfuric acid with chlorine gas.

The compound of Formula 1 is prepared by dissolving the compound of Formula 3 in an organic solvent and reacting dropwise with benzotriazole dissolved in the same solvent. Dioxane, diethyl ether or tetrahydrofuran is used as a solvent to be used. If necessary, triethylamine, a reaction accelerator, is dissolved in the same solvent and added in small portions.

Hereinafter, the present invention will be described in detail by way of examples.

Example 1

Synthesis of 4-nitrobenzoylisothiocyanate

27.8 g of 4-nitrobenzoyl chloride and 17.5 g of anhydrous potassium isothiocyanate (molecular weight = 185.5) were refluxed for 6 hours in a 250 ml round flask equipped with a condenser with a water inflow prevention device containing 100 ml of benzene solution. After confirming that there was no residual benzotrochloride, the reaction was terminated, potassium chloride was filtered off, benzene was removed, and distilled under high fitting to give 29.7 g of 4-nitrobenzoylisothiocyanate (molecular weight = 208.1).

MP: 131 ° C. yield: 95%

NMR: d: 8-8.5 (4H)

Example 2

Synthesis of 4-nitrobenzoylimidoyl dichloride

20 g (0.096 mol) of 4-nitrobenzoyl isothiocyanate prepared in Example 1 was sufficiently dissolved in 150 ml of anhydrous carbon tetrachloride, the dehydrated and dried chlorine gas was saturated for 6 hours, left for 3 days, and the precipitate was filtered, followed by carbon tetrachloride. Was distilled off under high vacuum to synthesize 20 g of 4-ritrobenzoylimidoyl dichloride (molecular weight = 247).

MP: 55 ℃ Decomposition yield: 85%

NMR: d: 8-8.5 (4H)

Example 3

Synthesis of p-nitrobenzoyl-C- (1-methylterazole-5-thio) imidoylchloride

2.5 g of 4-ritrobenzoylimidoyl dichloride and 1.16 g of 5-mercapto-1-methyltetrazole (molecular weight: 116.06) prepared in Example 2 were dissolved in tetrahydrofuran and 1.01 g of triethylamine in the same solvent. Slowly drop and stir vigorously. The salt was removed by filtration and purified by recrystallization, distillation and chromatography to give 2.7 g of p-nitrobenzoyl-C- (1-methyltetrazol-5-thio) imidoylchloride.

Yield: 81%, MP: 143 ° C

NMR: d: 7-8.2 multi (4H), 2.8d s. (3H)

Example 4

Synthesis of 4-nitrobenzoylisothiocyanate

15.5 g (0.1 mol) of 4-nitrobenzoyl chloride (molecular weight: 155.45) and 27.9 g of anhydrous potassium isothiocyanate (0.15 mol) were refluxed in a benzene solution for 6 hours to confirm that no acid chloride remained and the reaction was terminated. After filtering potassium chloride, benzene was removed and distilled under high pressure to synthesize 15.23 g of 4-nitrobenzoylisothiocyanate.

Molecular Weight: 177.06

Oil condition at room temperature, yield: 86%

NMR: d: 7-8 (4H), 2.3 (3H)

Example 5

Synthesis of 4-Litrobenzoylimidoyl Dicloid

18 g (0.1 mol) of 4-nitrobenzoylisothiocyanate was sufficiently dissolved in 150 ml of anhydrous carbon tetrachloride, the dried chlorine gas was saturated for about 3-6 hours, left for 3 days, the precipitate was filtered, and carbon tetrachloride was distilled. Distillation under electric distillation to synthesize 23 g of 4-ritrobenzoylimidoyl dichloride (molecular weight = 215.9).

MP: 55 ° C., yield: 85%

NMR: d: 7-8 (4H), 2.3 (3H)

Example 6

Synthesis of p-nitrobenzoyl-C- (1-methyltetrazol-5-thio) imidoyl chloride

Dissolve 16 g of 5-mercapto-1-methyltetrazole in dioxane and 1.01 g of triethylamine in the same solvent and stir vigorously while slowly adding dropwise. Filtration was carried out to remove salts and purified by recrystallization distillation and chromatography to synthesize 2.7 g of p-methyl-benzoyl-C- (1-methyltetrazol-5-thio) imidoyl chloride.

NMR: d: 7-8.2 multi (4H), 2.8d s. (3H), 2.5d s. (3H)

MP: 127 ° C .; Yield: 90%

Example 7

Synthesis of N-benzoyl-C- (1-methyltetrazol-5-thio) imidoyl chloride

2.36 g (0.01 mol) of N-benzoylimidoyl chloride and 1.16 g of 5-mercapto-1-methyltetrazole (molecular weight: 116.06) are dissolved in dioxane and 1.01 g of triethylamine is slowly added dropwise to the same solvent. Stir. The salt was removed by filtration and purified by recrystallization, distillation and chromatography to synthesize 2.4 g of N-benzoyl-C- (1-methyl tetrazol-5-thio) imidoyl chloride.

Yield: 68%; MP: 157 ℃

NMR: d: 7-8.2 multi (4H), 2.8d s. (3H)

Example 8

Synthesis of p-chlorobenzoyl-C- (1-methyltetrazol-5-thio) imidoyl chloride

2.4 g of 4-chlorobenzoylimidoyl dichloride (molecular weight = 236.4) and 1.16 g of 5-mercapto-1-methylterazole (molecular weight 116.06) were dissolved in diethyl ether, and 1.01 g of triethylamine was slowly added dropwise to the same solvent. Stir strongly while The salt was removed by filtration and purified by recrystallization, distillation and chromatography to synthesize 2.69 g of p-chlorobenzoyl-C- (1-methyltetrazol-5-thio) imidoyl chloride.

Yield: 85%; MP: 136 ℃

NMR: d: 7-8.2 multi (4H), 2.8d s. (3H)

Claims (2)

N-benzoyl-C- (1-methyltetrazol-5-thio) imidoyl chloride represented by Formula 1 and its derivatives [Formula 1] Wherein X represents one of hydrogen, methyl, chlorine and nitro group. A process for preparing N-benzoyl-C- (1-methyltetrazol-5-thio) imidoyl chloride of Chemical Formula 1 described above by reacting benzoylimidoyl dichloride of Chemical Formula 3 with benzotriazole in an organic solvent. [Formula 1] [Formula 2]