KR970006241B1 - N-alroyl-c-(benzotriazol)imidoyl chloride derivatives and method for the production thereof - Google Patents

Abstract

N-benzoyl-C-(benzotriasol) imidoyl chloride and its derivative indicated by a general formula(I) is prepared by reacting a benzoyl imidoyl dichloride of a general formula(III) with benzotriasol in a organic solvent. The prepared imidoyl chloride derivative is used as an intermediate for medicines and agricultural medicines. In the above formula, X means hydrogen, halogen atom, low-level alkyl, low-level alkoxy and nitro group.

Description

N-benzoyl-C- (benzotriazole) imidoyl chloride derivative and preparation method

The present invention relates to a N-benzoyl-C- (benzotriazole) imidoyl chloride derivative, which is a novel compound of general formula (I), and a preparation method thereof.

In the formula, X represents hydrogen, halogen, alkyl group, alkoxy group or nitiro group.

The compounds of the general formula (I) 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 Korean Patent Application No. 91-4337, such as Journal of Chemical Society, Perkin2 1046-51, 1975, and Kim Chun-Seok, but these compounds are completely different from the compounds of Formula (I). Compound.

In general formula (I), as the alkyl group represented by X, there are C ₁ -C ₄ lower alkyl groups such as methyl, ethyl, propyl, and butyl groups, among which methyl group is preferable. The alkoxy group includes C ₁ -C ₄ lower alkyl groups such as methoxy, ethoxy, propoxy and butoxy groups, but methoxy is preferable. Halogens include chlorine and cancellation, of which chlorine is preferred.

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

The compound of general formula (I) according to the present invention is prepared by reacting benzoylimidoyl dichloride of general formula (III) prepared from benzoylisothiocyanate of general formula (II) in benzotriazole and an organic solvent.

X has the meaning mentioned above.

The above-described method of formula (I) is carried out in an organic solvent. In this case, dioxane, diethyl ether, tetrahydrofuran or the like is used as the organic solvent.

Compounds except for the compound of formula (II) and the compound of formula (III) used for the preparation of general formula (I) described above except for the compound wherein X = Cl are novel compounds.

The benzoyl isothiocyanate of formula (II) is a state in which benzoyl chloride or substituted benzoyl chloride and anhydrous potassium isothiocyanate are dissolved in an organic solvent such as dioxane, diethyl ether or tetrahydrofuran and the oxygen inflow is blocked. Prepared by heating under reflux for about 8 hours. Anhydrous potassium isothiocyanate used in this method is used to remove moisture by drying at 110 ° C. for 10 hours in a hot air circulation oven.

To ensure that the reaction system does not come into contact with oxygen, either seal the reactor and attach a condenser with a water inlet protector, or introduce nitrogen 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.

Benzoylimidoyl dichloride of formula (III) is prepared by dissolving benzoyl isothiocyanate or substituted benzoyl isothiocyanate of formula (II) prepared above in an organic solvent, in particular carbon tetrachloride, It is prepared by reacting for about 3 days. In this method, dry chlorine gas is introduced into a carbon tetrachloride solution in which benzoyl isocyanocyanate is dissolved over 6 hours, and the reaction solution is saturated with chlorine gas, and left for about 3 days to complete the reaction. . 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 the general formula (I) is prepared by dissolving the compound of the general formula (III) in an organic solvent and reacting by dropwise addition of 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

4-nitro benzoylisochiocyanate synthesis

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 no nitrobenzoyl chloride remained, the reaction was terminated, potassium chloride was filtered off, benzene was removed, and distilled under high fit to obtain 29.7 g of 4-nitro benzoyl isothiocyanate (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-nitrobenzoylisothiocyanate prepared in Example 1 was sufficiently dissolved in 150 ml of anhydrous carbon tetrachloride, and the hydrated chlorine gas was saturated for 6 hours, left for 3 days, and the precipitate was filtered, followed by carbon tetrachloride. Distillation and distillation under high vacuum synthesized 20 g of 4-nitrobenzoylimidoyl dichloride (molecular weight = 247).

MP: 55 ° C. (decomposition) yield: 85%

NMR: d, 8-8.5 (4H)

Example 3

Synthesis of 4-nitrobenzoylisothiocyanate

15.5 g (0.1 mol) of 4-methylbenzoyl 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, and after confirming that no acid chloride remained, the reaction was terminated. After filtering potassium chloride, benzene was removed and distilled under high pressure to obtain 15.23 g of 4-methylbenzoylisothiocyanate.

Molecular Weight: 177.06

Oil condition at room temperature

Yield: 86%

NMR: d, 708 (4H), 2.3 (3H)

Example 4

Synthesis of P-methylbenzoylimidoyl Dichloride

18 g (0.1 mol) of 4-methylbenzoylisothiocyanate 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 off under high vacuum. Distillation synthesized 23 g of 4-methylbenzoylimidoyl dichloride (molecular weight = 215.9).

MP: 55 ° C. yield: 85%

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

Example 5

Synthesis of P-methyl-benzoyl-C-benzotriazolimidoyl chloride

2.15 g (0.01 mol) of 4-methylbenzoylimidoyl dichloride (molecular weight 214) is dissolved in tatrahydrofuran, and 2.32 g (0.02 mol) of benzotriazole is dissolved in the same solvent and slowly stirred dropwise. Filtration was carried out to remove salts and purified by recrystallization, distillation and chromatography to synthesize 2.66 g of P-methyl-benzoyl-C-benzotriazolimidoyl chloride (molecular weight 298 g).

MP: 56 ° C. (decomposition) yield: 89%

NMR: d, 7-8.2multi (8H), 2.3 (3H)

Example 6

Synthesis of Benzoyl-C- (benzotriazole) imidoyl chloride

2.02 g of benzoylimidoyl dichloride (molecular weight 201.9) is dissolved in benzene, and 23.8 g of benzotriazole is dissolved in the same solvent and slowly stirred by dropwise addition. Filtration removed the salt, and the residue was purified by recrystallization distillation and chromatography to obtain 2.4 g of benzoyl-C- (benzotriazole) imidoyl chloride.

MP: 155 ° C (decomposition) yield: 86%

NMR: d, 7-8 (9H)

Example 7

Synthesis of p-chlorobenzoyl-C-benzotriazole imidoyl chloride

2.36 g (0.01 mol) of 4-chlorobenzoylimidoyl dichloride (molecular weight 236.4) is dissolved in dioxane, and 23.8 g (0.02 mol) of benzotriazole (molecular weight 119.13) is dissolved in the same solvent and slowly stirred dropwise. The salt was removed by filtration and purified by recrystallization distillation and chromatography to synthesize 2.85 g of p-chlorobenzoyl-C-benzotriazolimidoyl chloride (molecular weight 317).

MP: 135 ° C. (decomposition) yield: 90%

NMR: d, 7-8.2multi (8H)

Claims (2)

N-benzoyl-C (benzotriazole) imidoyl chloride represented by general formula (I) and its derivatives. Wherein X represents a group selected from methyl, chloro and nitro groups. A process for preparing N-benzoyl-C- (benzotriazole) imidoyl chloride of general formula (I) by reacting benzoylimidoyl dichloride of general formula (III) with benzotriazole in organic solvent.