CN101434561A

CN101434561A - Synthesis of 3-amino-4-chlorine-N-(5-chlorine-2-methyl phenyl) benzamide

Info

Publication number: CN101434561A
Application number: CNA200710158232XA
Authority: CN
Inventors: 刘起瑞
Original assignee: Individual
Current assignee: Individual
Priority date: 2007-11-13
Filing date: 2007-11-13
Publication date: 2009-05-20

Abstract

The invention relates to a synthetic method of a compound, in particular to the synthesis of 3-amino-4-chloro-N-(5-chloro-2-methylphenyl) benzamide. Pigment yellow 94 and pigment yellow 95 are applied to protoplasmic coloring of PVC and polyolefin and can also be applied to the coloration of enamel, coatings and printing ink. The 3-amino-4-chloro-N-(5-chloro-2-methylphenyl) benzamide is adopted as an important intermediate product of the organic pigments of the pigment yellow 94 and pigment yellow 95, and 3-nitryl-4-chlorobenzoic acid and 5-chloro-2-methylaniline are used as raw materials. By three steps, the 3-amino-4-chloro-N-(5-chloro-2-methylphenyl) benzamide is synthesized. The synthetic method has mild technological conditions, simple operation and applicability to industrialized production.

Description

Synthesizing of 3-amino-4-chloro-N-(5-chloro-2-aminomethyl phenyl) benzamide

Technical field

The present invention relates to a kind of synthetic method of compound, particularly 3-amino-4-chloro-N-(5-chloro-2-aminomethyl phenyl) benzamide is synthetic.

Background technology

Present external use the and domesticly not have the intermediate produced a lot, though or have production to cause production cost too high because of reasons such as industrial scale and technological line, state of the art, or poor quality.Pigment Yellow 73 94, Pigment Yellow 73 95 are used for PVC and polyolefinic dope dyeing, also can be used for the painted of enamel, coating, printing-ink.3-amino-4-chloro-N-(5-chloro-2-aminomethyl phenyl) benzamide is as the important intermediate of the pigment dyestuff of Pigment Yellow 73 94, Pigment Yellow 73 95, the domestic manufacturer production that there is no.

Summary of the invention

For overcoming the deficiencies in the prior art part, the present invention solves by following technical proposals.

Laboratory apparatus and raw material

The HITACHI-80 mass spectrograph

Elementar vario EL III elemental analyser

The micro-fusing point instrument of Yanaco MP

Tianjin, Shimidazu Lc-vp island high performance liquid chromatograph

Nicolet Magna-IR550 infrared test instrument

Agents useful for same is industrial goods, without further purification

Synthetic route

Synthesizing of 3-nitro-4-chloro-benzoyl chloride

In the 1000ml there-necked flask that has stirring and reflux, add 3-nitro-4-chloro-benzoic acid 300g, benzene 350ml and DMF5ml, temperature rising reflux, the mixed liquid of dropping 217g thionyl chloride and 50ml benzene, add half an hour, and isothermal reaction 5 hours then refluxes.Sampling analysis: 3-nitro-4-chloro-benzoic acid＜2% is reacted to terminal point, otherwise continues reaction until qualified.Reaction finishes, and static half an hour, separatory divided to fall reaction impurities, and decompression steams excessive thionyl chloride and benzene then, 3-nitro-4-chloro-benzoyl chloride (M-1), yield 96.5%, content 97%.

Synthesizing of 3-nitro-4-chloro-N-(5-chloro-2-aminomethyl phenyl) benzamide

In the 1000ml there-necked flask that has stirring and reflux, add 40g5-chloro-2-aminotoluene (M-2), 23.6g sodium bicarbonate, a spot of water and 100ml benzene, stirring is warming up to backflow, drips the mixed liquid that is dissolved with 100ml benzene and 66.6g M-1, dropwises in 30 minutes.Back flow reaction 6 hours, sampling analysis if content＜2% of M-2 is reacted to terminal point, otherwise continues reaction until qualified.Reaction finishes, and reduces to room temperature and filters, and filter cake is pulled an oar with small amount of methanol, dries, and gets 3-nitro-4-chloro-N-(5-chloro-2-aminomethyl phenyl) benzamide (M-3) 88.4g, content 98.3%, yield 92%.

Synthesizing of 3-amino-4-chloro-N-(5-chloro-2-aminomethyl phenyl) benzamide

Add 150gM-3,7.5g Ni, 600ml mixing solutions in the 1L autoclave, encloses container feeds nitrogen, divides the air of replacing for three times in the clean still; Feed hydrogen then, pressure is at 20Kg/cm ², temperature is controlled between 50～60 ℃, stirring reaction, and pressure drops to 5Kg/cm ²The time, supply pressure to 20Kg/cm ², continue reaction, when reaction no longer absorbs hydrogen (tensimeter no longer descends), continue stirring reaction half an hour again; Cool to room temperature then, slowly bleed off excessive hydrogen, and, take out reaction solution with nitrogen replacement hydrogen three times, filter, elimination insolubles, decompression steam solvent to the greatest extent, are cooled to room temperature, and adding 200ml methyl alcohol dispersed with stirring material 0.5h, filter, dry light gray solid 3-amino-4-chloro-N-(5-chloro-2-aminomethyl phenyl) benzamide 116.5g, content 98.5%, yield 85.1%.

Embodiment

Synthesizing of 3-nitro-4-chloro-benzoyl chloride

Synthesizing of 3-nitro-4-chloro-N-(5-chloro-2-aminomethyl phenyl) benzamide

Synthesizing of 3-amino-4-chloro-N-(5-chloro-2-aminomethyl phenyl) benzamide

Add 150g M-3,7.5g Ni, 600ml mixing solutions in the 1L autoclave, encloses container feeds nitrogen, divides the air of replacing for three times in the clean still; Feed hydrogen then, pressure is at 20Kg/cm ², temperature is controlled between 50～60 ℃, stirring reaction, and pressure drops to 5Kg/cm ²The time, supply pressure to 20Kg/cm ², continue reaction, when reaction no longer absorbs hydrogen (tensimeter no longer descends), continue stirring reaction half an hour again; Cool to room temperature then, slowly bleed off excessive hydrogen, and, take out reaction solution with nitrogen replacement hydrogen three times, filter, elimination insolubles, decompression steam solvent to the greatest extent, are cooled to room temperature, and adding 200ml methyl alcohol dispersed with stirring material 0.5h, filter, dry light gray solid 3-amino-4-chloro-N-(5-chloro-2-aminomethyl phenyl) benzamide 116.5g, content 98.5%, yield 85.1%.

Chloro-benzoyl chloride is fixed as 0.1mol, has designed an orthogonal test, and the factor, level and test-results are as follows:

The table 3.1 M-3 orthogonal test factor and level

Table 3.2 M-3 Orthogonal experiment results

Orthogonal experiment results is discussed

(1) as can be seen, along with the increase (being mol ratio from 0.95 to 1.05) that adds the M-2 amount, the yield of DT increases afterwards earlier and reduces, and a maximum value is arranged by table 3.1.From the cost of material and the difficulty or ease of aftertreatment, we think that option A 2 is more satisfactory.

(2) as can be seen, in three kinds of different catalyzer, triethylamine and pyridine effect are more or less the same by table 3.2, but significantly better than sodium bicarbonate.This is that it is obvious to tie up sour effect because triethylamine and pyridine are soluble in the reaction solution (benzene) as organic bases, makes to react carry out thorough; And sodium bicarbonate is insoluble in the benzene, ties up sour DeGrain, and the reaction times is longer.At present 9.5 yuan/Kg of triethylamine, 34.5 yuan/Kg of pyridine, and sodium bicarbonate only has 1.2 yuan/Kg, earlier sodium bicarbonate is dissolved as add less water in reaction help the carrying out that react, and yield obviously improves.We think that still option b 3 is better from the cost consideration of product, promptly make catalyzer with sodium bicarbonate.

Claims

1, the synthetic method of 3-amino-4-chloro-N-(5-chloro-2-aminomethyl phenyl) benzamide is characterized in that

Synthetic route

2, the synthetic method of 3-amino as claimed in claim 1-4-chloro-N-(5-chloro-2-aminomethyl phenyl) benzamide is characterized in that

Synthesizing of 3-nitro-4-chloro-benzoyl chloride

In the 1000ml there-necked flask that has stirring and reflux, add 3-nitro-4-chloro-benzoic acid 300g, benzene 350ml and DMF5ml, temperature rising reflux, the mixed liquid of dropping 217g thionyl chloride and 50ml benzene, add half an hour, and isothermal reaction 5 hours then refluxes.Sampling analysis: 3-nitro-4-chloro-benzoic acid＜2% is reacted to terminal point, otherwise continues reaction until qualified.

Synthesizing of 3-nitro-4-chloro-N-(5-chloro-2-aminomethyl phenyl) benzamide

In the 1000ml there-necked flask that has stirring and reflux, add 40g5-chloro-2-aminotoluene (M-2), 23.6g sodium bicarbonate, a spot of water and 100ml benzene, stirring is warming up to backflow, drips the mixed liquid that is dissolved with 100ml benzene and 66.6g M-1, dropwises in 30 minutes.Back flow reaction 6 hours, sampling analysis if content＜2% of M-2 is reacted to terminal point, otherwise continues reaction until qualified.

Synthesizing of 3-amino-4-chloro-N-(5-chloro-2-aminomethyl phenyl) benzamide

Add 150g M-3,7.5gNi, 600ml mixing solutions in the 1L autoclave, encloses container feeds nitrogen, divides the air of replacing for three times in the clean still; Feed hydrogen then, pressure is at 20Kg/cm2, and temperature is controlled between 50～60 ℃, stirring reaction, and pressure drops to 5Kg/cm ²The time, supply pressure to 20Kg/cm ², continue reaction, when reaction no longer absorbs hydrogen (tensimeter no longer descends), continue stirring reaction half an hour again; Cool to room temperature then, slowly bleed off excessive hydrogen, and, take out reaction solution with nitrogen replacement hydrogen three times, filter, elimination insolubles, decompression steam solvent to the greatest extent, are cooled to room temperature, and adding 200ml methyl alcohol dispersed with stirring material 0.5h, filter, dry light gray solid 3-amino-4-chloro-N-(5-chloro-2-aminomethyl phenyl) benzamide 116.5g, content 98.5%, yield 85.1%.