CN103664612A - Synthetic method for methyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate - Google Patents

Abstract

The invention discloses a synthetic method for methyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate, and belongs to the technical field of organic synthesis. The synthetic method comprises: taking 2,6-di-tert-butyl phenol and methyl acrylate which are most easily available as raw materials, under the catalytic effect of inorganic base sodium methanolate, performing Michael addition reaction to obtain methyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate through H-1,5 migration. The synthetic route is simple, direct and convenient.

Description

The synthetic method of 3-(3,5-di-tert-butyl-hydroxy phenyl) methyl propionate

Technical field

The invention belongs to technical field of organic synthesis, relate to the methodology of organic synthesis of a kind of 3-(3,5-di-tert-butyl-hydroxy phenyl) methyl propionate.

Background technology

Phenolic antioxidant be in all oxidation inhibitor, do not pollute, a class that nondiscoloration is best, there is good resistance of oxidation, for fields such as plastics, synthon, rubber, fuel, lubricating oil and food, especially hindered phenol antioxygen is extremely paid attention in a large number.The development research of Hinered phenols antioxidant over nearly 30 years is very active, as primary antioxidant, in field of polymer technology, is widely used.3-(3,5-di-tert-butyl-hydroxy phenyl) methyl propionate is a kind of good Hinered phenols antioxidant, be widely used at present polyolefine, polymeric amide, polyester, ABS resin, synthetic rubber, grease, coating, lubricated wet goods, be also applicable to a little packaging materials for food of dish.Have consistency good, antioxygen usefulness is high, not painted, does not pollute wash resistant.Heat-resisting, the feature such as volatility is little.With other oxidation inhibitor and with can produce synergy, in addition also can with auxiliary agent the use such as stablizer, UV light absorber, effect is relatively good.It is again the intermediate of the synthetic high-grade oxidation inhibitor of oxidation inhibitor (1010,1076,259,1098,3125 etc.) simultaneously, thereby the research of 3-(3,5-di-tert-butyl-hydroxy phenyl) methyl propionate synthesis technique just seems particularly important.

Summary of the invention

The object of the present invention is to provide a kind of 3-(3,5-di-tert-butyl-hydroxy phenyl) chemical synthesis process of methyl propionate: with the most simple and easy to get 2,6 DI-tert-butylphenol compounds and methyl acrylate are raw material, under the katalysis of mineral alkali sodium methylate, first there is Michael addition reaction, then through H-1,5 migrations obtain 3-(3,5-di-tert-butyl-hydroxy phenyl) methyl propionate.

The present invention realizes by following method:

The first step, flask after oven dry adds 2 of 1.0-2.0 part, 6 DI-tert-butylphenol compounds, use water distilling apparatus and be warming up to 80-90 ℃, under vacuum 4-6.6kpa, extract air and moisture content, after 12-20 minute, fill nitrogen to normal pressure, go vacuum, fill nitrogen for some time, be cooled to 70 ℃ of left and right, the sodium methylate that adds again 0.1-0.2 part, in the situation that stirring, still temperature is slowly warming up to 120 ℃ of left and right, methyl alcohol is steamed, now can suspend logical nitrogen, the methyl alcohol evaporation later stage, pass into nitrogen 1 hour, filling in nitrogen situation, be cooled to below 60 ℃, prepare to drip the methyl acrylate of 0.5-1.0 part, after below still temperature drop to 60 ℃, under stirring state, methyl acrylate is slowly added in still, time is 1.5 hours, dropping temperature is controlled between 60-75 ℃, at most must not be over 80 ℃, after dripping methyl acrylate, be incubated 2-3 hour, holding temperature is 80-85 ℃.After insulation for some time, temperature in the kettle is progressively warming up to 120 ℃, reaction 1-1.5 hour.

Second step, after completion of the reaction, continues to fill nitrogen, starts to be cooled to after 90 ℃, add a certain amount of 97% acetic acid, stir 30 minutes, making its pH is 5-6, after neutralizing acid, stop logical nitrogen, to the alcohol solvent that adds appropriate 85% in bottle, carry out hot melt, reflux 30 minutes, cooling 30 minutes, stop stirring, naturally after cooling below forced cooling to 0 ℃, cooling, below 0 ℃, is stirred unsuitable too fast, treat that axle limit crystal solution pastiness is that crystallization is complete, filter separation.First mother liquor is pumped, the alcohol flushing with 85%, dry.

The building-up process reaction principle of 3-(3,5-di-tert-butyl-hydroxy phenyl) methyl propionate is:

Embodiment

Embodiment 1:

Reactor after oven dry adds 206.32g2, 6 DI-tert-butylphenol compounds, use water distilling apparatus and be warming up to 80-90 ℃, under vacuum 4-6.6kpa, extract air and moisture content, after 12-20 minute, fill nitrogen to normal pressure, go vacuum, fill nitrogen for some time, be cooled to 70 ℃ of left and right, add again 5.4g sodium methylate, in the situation that stirring, still temperature is slowly warming up to 120 ℃ of left and right, methyl alcohol is steamed, now can suspend logical nitrogen, the methyl alcohol evaporation later stage, pass into nitrogen 1 hour, filling in nitrogen situation, be cooled to below 60 ℃, prepare to drip 43.05g methyl acrylate, after below still temperature drop to 60 ℃, under stirring state, methyl acrylate is slowly added in still, time is 1.5 hours, dropping temperature is controlled between 60-75 ℃, at most must not be over 80 ℃, after dripping methyl acrylate, be incubated 2-3 hour, holding temperature is 80-85 ℃.After insulation for some time, temperature in the kettle is progressively warming up to 120 ℃, reaction 1-1.5 hour.

After completion of the reaction, continue to fill nitrogen, start to be cooled to after 90 ℃, add a certain amount of 97% acetic acid, stir 30 minutes, making its pH is 5-6, after neutralizing acid, stop logical nitrogen, to the alcohol solvent that adds appropriate 85% in bottle, carry out hot melt, reflux 30 minutes, cooling 30 minutes, stop stirring, naturally after cooling below forced cooling to 0 ℃, cooling, below 0 ℃, is stirred unsuitable too fast, treat that axle limit crystal solution pastiness is that crystallization is complete, filter separation.First mother liquor is pumped, the alcohol flushing with 85%, dry.Obtain 3-(3,5-di-tert-butyl-hydroxy phenyl) methyl propionate 23.5g(mp62-64 ℃, content 98.55%, yield 79.9%).Embodiment 2:

Reactor after oven dry adds 185.69g2, 6 DI-tert-butylphenol compounds, use water distilling apparatus and be warming up to 80-90 ℃, under vacuum 4-6.6kpa, extract air and moisture content, after 12-20 minute, fill nitrogen to normal pressure, go vacuum, fill nitrogen for some time, be cooled to 70 ℃ of left and right, add again 4.86g sodium methylate, in the situation that stirring, still temperature is slowly warming up to 120 ℃ of left and right, methyl alcohol is steamed, now can suspend logical nitrogen, the methyl alcohol evaporation later stage, pass into nitrogen 1 hour, filling in nitrogen situation, be cooled to below 60 ℃, prepare to drip 38.75g methyl acrylate, after below still temperature drop to 60 ℃, under stirring state, methyl acrylate is slowly added in still, time is 1.5 hours, dropping temperature is controlled between 60-75 ℃, at most must not be over 80 ℃, after dripping methyl acrylate, be incubated 2-3 hour, holding temperature is 80-85 ℃.After insulation for some time, temperature in the kettle is progressively warming up to 120 ℃, reaction 1-1.5 hour.

After completion of the reaction, continue to fill nitrogen, start to be cooled to after 90 ℃, add a certain amount of 97% acetic acid, stir 30 minutes, making its pH is 5-6, after neutralizing acid, stop logical nitrogen, to the alcohol solvent that adds appropriate 85% in bottle, carry out hot melt, reflux 30 minutes, cooling 30 minutes, stop stirring, naturally after cooling below forced cooling to 0 ℃, cooling, below 0 ℃, is stirred unsuitable too fast, treat that axle limit crystal solution pastiness is that crystallization is complete, filter separation.First mother liquor is pumped, the alcohol flushing with 85%, dry.Obtain 3-(3,5-di-tert-butyl-hydroxy phenyl) methyl propionate 21.4g(mp62-64 ℃, content 98.60%, yield 81.1%).

Claims (4)

1. a 3-(3,5-di-tert-butyl-hydroxy phenyl) synthetic method of methyl propionate, it is characterized in that with the most simple and easy to get 2,6 DI-tert-butylphenol compounds and methyl acrylate are raw material, under the katalysis of mineral alkali sodium methylate, first there is Michael addition reaction, then through H-1,5 migrations obtain 3-(3,5-di-tert-butyl-hydroxy phenyl) methyl propionate.

2. the synthetic method of 3-according to claim 1 (3,5-di-tert-butyl-hydroxy phenyl) methyl propionate, is characterized in that occurring Michael addition reaction under the katalysis of mineral alkali sodium methylate.

3. the synthetic method of 3-according to claim 1 (3,5-di-tert-butyl-hydroxy phenyl) methyl propionate, is characterized in that through H-1, and 5 migrations obtain 3-(3,5-di-tert-butyl-hydroxy phenyl) methyl propionate.

4. the synthetic method of 3-according to claim 1 (3,5-di-tert-butyl-hydroxy phenyl) methyl propionate, is characterized in that concrete operation step:

The first step, flask after oven dry adds 2 of 1.0-2.0 part, 6 DI-tert-butylphenol compounds, use water distilling apparatus and be warming up to 80-90 ℃, under vacuum 4-6.6kpa, extract air and moisture content, after 12-20 minute, fill nitrogen to normal pressure, go vacuum, fill nitrogen for some time, be cooled to 70 ℃ of left and right, the sodium methylate that adds again 0.1-0.2 part, in the situation that stirring, still temperature is slowly warming up to 120 ℃ of left and right, methyl alcohol is steamed, now can suspend logical nitrogen, the methyl alcohol evaporation later stage, pass into nitrogen 1 hour, filling in nitrogen situation, be cooled to below 60 ℃, prepare to drip the methyl acrylate of 0.5-1.0 part, after below still temperature drop to 60 ℃, under stirring state, methyl acrylate is slowly added in still, time is 1.5 hours, dropping temperature is controlled between 60-75 ℃, at most must not be over 80 ℃, after dripping methyl acrylate, be incubated 2-3 hour, holding temperature is 80-85 ℃.After insulation for some time, temperature in the kettle is progressively warming up to 120 ℃, reaction 1-1.5 hour;

Second step, after completion of the reaction, continues to fill nitrogen, starts to be cooled to after 90 ℃, add a certain amount of 97% acetic acid, stir 30 minutes, making its pH is 5-6, after neutralizing acid, stop logical nitrogen, to the alcohol solvent that adds appropriate 85% in bottle, carry out hot melt, reflux 30 minutes, cooling 30 minutes, stop stirring, naturally after cooling below forced cooling to 0 ℃, cooling, below 0 ℃, is stirred unsuitable too fast, treat that axle limit crystal solution pastiness is that crystallization is complete, filter separation.First mother liquor is pumped, the alcohol flushing with 85%, dry.