JPS595151A - Preparation of n-substituted carbamoylbenzene and its nucleus-substituted derivative - Google Patents

Abstract

PURPOSE:To obtain the titled compound in high yield and purity, by adding a halogenated benzoyl slowly and dropwise to N-(higher alkyl or alkenyl)amine in a specific solvent in the presence of a base, and dissolving and removing the neutralized salt with water. CONSTITUTION:In the dehydrohalogenative condensation of an N-(higher alkyl or alkenyl)amine of formula R<1>-NH2 (R<1> is higher alkyl or alkenyl) with a halogenated benzoyl of formula I (X is halogen; R<2> is lower alkyl, etc.; n is 0-5) or its nucleus-substituted derivative, said N-(higher alkyl or alkenyl)amine is dissolved in a chlorine compound solvent (e.g. chloroform), said halogenated benzoyl is added slowly and dropwise in the form of liquid or solid to the solution in the presence of a basic substance (e.g. NaOH), and the produced neutralized salt is dissolved and removed with water or hot water to obtain the objective compound of formula II.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention is based on the general formula (wherein Bl is a higher alkyl or alkenyl group,
几2 is a lower alkyl group, a lower alkoxy group, a lower alkoxycarbonyl group, a halogen atom, or an aryl group optionally substituted with the above-described substituent, and n is 0 to
The present invention relates to a method for producing N-higher alkyl or alkenylcarbamoylbenzene represented by the formula (an integer of 5) and a nuclear substituted product thereof.

Conventionally, in order to produce N-higher alkyl or alkenylcarbamoylbenzene having the above structure and its nuclear substituted product, N-higher alkyl or alkenylamine is dissolved in an organic solvent such as toluene, and a benzoyl halide or its nucleus is dissolved. This has been carried out by dropping a substituent and heating to cause a dehydrohalogenation condensation reaction. However, this method has the problem that the condensation product is colored and is difficult to decolor even after repeated recrystallization, and the condensation product is strongly acidic, so a neutralization step is required. Furthermore, since hydrogen halide is released during the reaction, a treatment device for the hydrogen halide is also required. On the other hand, a method is also known in which a basic substance for neutralizing hydrogen halide is present in this reaction system. Washing the condensation product with water is not practical because it causes gelation of the condensation product and reduces the yield. For example, when an aromatic hydrocarbon is used as a reaction solvent, gelation occurs in the condensation product upon washing with water, making separation and recovery of the target product extremely difficult.

The present inventor has completed the present invention as a result of extensive research in order to overcome the above-mentioned drawbacks of conventional methods.

That is, according to the present invention, an N-higher alkyl or alkenylamine represented by the general formula % (wherein Bl is a higher alkyl or alkenyl group) and a general formula (wherein, X is a halogen atom, 2 is a lower alkyl group, a lower alkoxy group, a lower alkoxyl group, an I?nyl group, a halogen atom, or an aryl group which may be substituted with a substituent as mentioned above, and n is an integer of θ to 5. ) In the method of dehydrohalogenation condensation of benzoyl halide or its nuclear substituted product represented by Below, the halogenated benzoyl or its nuclear substituted product is gradually added in liquid or solid form to perform a condensation reaction, and after the reaction is completed,
An N-higher alkyl or alkenyl carbohydrate represented by the general formula (wherein Bl, rL2 and n have the same meanings as above), characterized by dissolving and removing the neutralized salt produced by adding water or hot water. - A method for producing moylbenzene and its nuclear substituted product is provided.

The N-higher alkyl or alkenylamine used in the present invention is represented by the following general formula.

R' -Nl2(n) In the formula, l is a higher alkyl or alkenyl group, and the number of carbon atoms thereof is generally 10 to 30, preferably 8 to 22.

The halogenated benzoyl or its nuclear substituted product used in the present invention is represented by the following general formula.

In the formula, X is a halogen atom such as chlorine or bromine, and
is a lower alkyl group, for example, an alkyl group having 1 to 6 carbon atoms such as methyl, ethyl, propyl, hexyl, a lower alkoxy group, an alkoxy group having 1 to 6 carbon atoms such as methoxy, ethoxy, zoropoxy, hekynroxy, lower alkoxy carbonyl group, e.g. methoxycarbonyl,
Even if it is substituted with an alkoxycarbonyl group having an alkoxy group having 1 to 6 carbon atoms such as etquincardanyl, proboxycardinyl, hexyloxycarzenyl, a halogen atom such as chlorine or bromine, or the above-mentioned substituent. Good idea.
represents a group such as phenyl, tolyl, etc. n is O~
is an integer of 5, and when n is 2 to 5, 2 to 5 substituents It2 can be the same or different.

In the present invention, a chlorine compound-based solvent is used as the solvent. Such solvents include, for example, tetrachloroethylene, chloroform, l,2-dichloroethane,
Calcium such as trichlorethylene.

The amount of this solvent to be used is preferably determined in relation to the solubility of the desired product, and is generally at least the theoretical amount that completely dissolves the desired product at the reaction temperature, and usually 1 % of the theoretical amount.
~2 times the amount is used. The proportion of be/diyl chloride used is 1 to 1.5 mol, preferably 1 to 1.1 mol, per 1 mol of N-higher alkyl or alkenylamine. In addition, the dropping ratio of benozoyl halide is N
- 0.00001 to 0.003 mol per second, preferably o, o, per mol of higher alkyl or alkenylamine
The ratio is from oos to 0.0004 mole. Furthermore, the reaction of the present invention is carried out in the presence of a basic substance, and the amount of the basic substance is such as to maintain the reaction system at pH 7 to 101, preferably pH 7.5 to 9. is added dropwise in the form of an aqueous solution. Specific examples of the basic substance include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide.

The concentration of the basic substance in the aqueous solution when added dropwise to the reaction system is:
It is usually 5 to 60% by weight, preferably 10 to 40% by weight. The reaction temperature is generally 30 to 90°C, preferably 4°C.
The temperature is 0 to 70°C.

In the present invention, after the reaction is substantially completed, the temperature of the reaction system is adjusted to 3 to 20°C, preferably 5 to 10°C, higher than the reaction temperature.
C. and maintained at this temperature for 5 to 40 minutes, preferably 10 to 30 minutes, to complete the reaction. Thereafter, water or hot water was added to the reaction product for 1 hour.
About 0 to 50% (volume), preferably about 10 to 30%, is added and mixed, and the neutralized salt of the basic substance and hydrogen halogenide is eluted into water. By performing this operation 1 to 3 times, a highly pure product can be obtained. In this case, the operating temperature is 40-7
Maintain temperature in the range of 0°C. The reaction product is then heated to a temperature of 25
Stir and cool to about ~15°C to crystallize the target product. In this way, a slurry-like mixture of crystals of the target product (lO~451% by weight), solvent (35~85% by weight), and water (10~55% by weight) is obtained, and this mixture contains water. The crystals are less likely to adhere to the walls of the reaction tank and can be smoothly removed from the reaction tank. This slurry-like mixture is subjected to solid-liquid separation using a solid-liquid separation means such as filtration or centrifugation, and the obtained solid is dried to form a product.

According to the method of the present invention, since a chlorine compound is used as a solvent in the coexistence of a basic substance, there are no problems such as coloring of the product, which were seen in conventional methods. When washing with water, the desired product can be easily obtained in high yield without causing gelation.

Next, the present invention will be explained in more detail with reference to Examples.

Example N - 134.75 i of octadecylamine was placed in a container equipped with a thermometer, a stirring device, a benzoyl chloride dropping device, a 25% caustic soda aqueous solution dropping device and a release valve, together with 375 cc of tetrachlorethylene, and the mixture was heated to 55 ml with a water bath.
The mixture was heated and dissolved at ℃. After completely dissolving, set the water temperature to 53°C, then start stirring, and at the same time
5. Start dripping 901 of caustic soda aqueous solution. After 5 to 6 drops of a 25% aqueous sodium hydroxide solution are added dropwise, the addition of Pe/Silua 2,677 chloride is started. The dropping rate is approximately 0.5 r/min for 25% caustic soda aqueous solution and 0.5 r/min for benzoyl chloride.
Drop at a speed of about 41. Hydrochloric acid gas can be seen in the reaction tank immediately after dropping, but it is only to the extent that it stays inside the reaction tank. The dropwise addition was completed in about 3 hours, and the reaction temperature was 54-62°C. After the reaction was completed, the mixture was heated at 60 to 65°C for 15 minutes to complete the reaction, and then 150 cc of 50°C warm water was added to dissolve the sodium chloride. After dissolution, cooling and crystallization were performed while stirring in a room. Cool to 17°C with tap water, pass through a suction port, and dry at room temperature to obtain white flaky crystals with a melting point of 87-88°C.
1.247 was obtained.

The yield was 97%.

Furthermore, by conducting a similar experiment using N-laurylamine instead of the N-octadecylamine, it was found that the melting point was 6.
N as white flaky crystals at 8-69°C with a yield of 93cm.
-A nuclear substituted product of laurylcarnoζmoylbenze/ was obtained.

Similarly, by using 4-methoxybenzoyl-benzoyl chloride in place of the benzoyl chloride, melting point 1
17-118℃ as white 7-piece crystals, yield 96%
It was possible to obtain a nuclear substituted product of N-octadecylcal/nomoylbenzene corresponding to the benz/diyl chloride nuclear substituted product. Similarly, by conducting a similar experiment using 4-methyl-benzoyl chloride, 4-methoxybenzoyl chloride, 4-chlorobenzoyl chloride, and 4-phenyl-benzoyl chloride in place of the benzoyl chloride,
Nuclear substitution products of N-octadecylcal/ζmoylbenzene corresponding to these nuclear substitution products of benzoyl chloride could be obtained.

For comparison, instead of the chlorine compound solvent,
An experiment was conducted in the same manner except that toluene and ethanol were used. When toluene was used, gelation occurred when hot water for dissolving neutralized salts was added. However, when ethanol was used, the condensation product was colored, and although recrystallization was repeated twice, the color could not be removed. Furthermore, the yield was 5 to 10% lower than when a chlorine compound solvent was used.

Patent applicant: Ricoh Co., Ltd. Agent Patent Attorney Toshiaki Ikeura

Claims (1)

[Claims] (1) N-higher alkyl or alkenylamine represented by the general formula % formula % (wherein, l is a higher alkyl or alkenyl group) and the general formula (wherein, X is a halogen atom, R2 is a lower alkyl group) group, a lower alkoxy group, a lower alkosecicalzenyl group, a halogen atom, or an aryl group which may be substituted on the nucleus with a substituent such as the above, and n is an integer of 0 to 5. In the method of dehydrohalogenation condensation of halogenated benzoyl or its nuclear substituted product, the N-
A condensation reaction is carried out by gradually adding the halogenated be/diyl or its nuclear substituted product in liquid or solid form to a solution in which higher alkyl or alkenylamine is previously dissolved in a chlorinated compound solvent in the presence of a basic substance. General formula (wherein 几1.B2 and 口 have the same meanings as above)
A method for producing an N-higher alkyl or alkenyl carmoylbenzene represented by the following formula and a nuclear substituted product thereof.