N-methylformamide production process

FIELD: industrial organic synthesis.

SUBSTANCE: process involves formic acid-methylamine reaction via intermediate methylammonium formate salt, which is dehydrated in presence of molybdenum trioxide catalyst dissolved in aqueous methylamine and added to formic acid in amount 2.0-4.0 wt % based on the latter. Reaction is carried out for 1-2 h in reactor filled with inert packing material having developed surface without cooling of reaction mixture, whereupon volatile products are distilled away at bottom temperature up to 190°C for 60-90 min. Bottom residue containing catalyst, after isolation of desired product, is returned to reactor.

EFFECT: reduced reaction time, reduced power consumption, improved quality of product obtained at increased yield, and diminished production waste.

5 cl, 8 ex

 

The invention relates to the field of organic chemistry, and in particular to an improved process for the preparation of N-methylformamide.

A method of obtaining N-methylformamide by heating a mixture of formamide and anhydrous polymer of formaldehyde, better paraformaldehyde, in the absence of water at a temperature of 75-105°in the presence of a catalyst (alkali metal hydroxide). The mixture was kept at the temperature for 1-2 hours, the hot mixture is filtered and receive N-methylformamide with the yield up to 98%. Without catalyst, the reaction is not [1]. In this way use formamid, the production of which is a separate process stage, making the multi-stage process and increases the cost of the finished product.

Also known is a method of obtaining N-formyl compounds by reaction of amines containing at least one H atom N with formamide in the presence of boric acid as a catalyst. Through a mixture of formamide with boric acid at a temperature of 60°To pass within 2 hours of the fast stream of the corresponding amine. Low-boiling products are removed by distillation in vacuum and get with the release of 26% of the product [2].

This method has the same disadvantages as the previous one, followed by the addition of low yield.

A method of obtaining substituted formamides formula R !N - Cho (where R is alkyl, aralkyl, cycloalkyl; R!- N or R) by the interaction of the amine of the formula RR!NH with an excess of CO2and H2at initial pressure 14-56 ATI catalyst of the formula MXn(where M is Cu, Zn, Cd; X Is F, Cl, Br, J). In the autoclave through a mixture of methylamine and catalyst at a temperature of 100-175°when the pressure for 17 hours through the mix WITH2and H2receive N-methylformamide [3]. Use in the manufacture of high pressure, explosive hydrogen leads to the complication of the equipment and organization of production.

A method of obtaining of formamide and N-substituted formamide reaction of carbon dioxide with ammonia, primary or secondary amines in the presence of oxygen at a temperature of 80-100°and pressure of 30-100 MPa in alcoholic medium (C1-C4in the presence of a catalyst (alkoxides of metals) [4]. This method has the same disadvantages as the previous one.

A method of obtaining N-substituted formamide interaction of hydrogen cyanide and an amine in the presence of water and catalyst - oxide or salt of Cu, Ag, Zn, Cd, Sn, Cr, Fe, Co, Ni, Pd or Tl [5].

This method can have only preparative value for use as raw materials of hydrocyanic acid.

A method of obtaining pure N-alkyltrimethyl reaction of olefins with hydrocyanic acid which in the presence of acid (H 2SO4, HCl). The reaction is carried out at 30-70°followed by treatment of the resulting mixture of esters of phosphoric acid for the extraction of formamide [6]. This method has the same disadvantages as the previous one.

A method of obtaining derivatives of formamide reaction of isocyanates (for example, α-naphthylisocyanate) hydrocylones (for example, SiHEt3in the presence of a catalyst (for example, PdCl2). The mixture of isocyanate with hydrocylones and the catalyst is heated in a dry nitrogen atmosphere at a temperature of 80°C for 6 hours, add methyl alcohol and get out 98% N-α-naftifine [7]. This method can have only preparative value.

The closest way to the same destination to the claimed invention on the totality of symptoms is the method of obtaining N-methylformamide interaction equimolecular quantities of formic acid and methylamine when heated to 180-186°With simultaneous distillation of volatile substances with a gradual increase in temperature up to 190-200°so that the temperature of the vapors of volatile does not exceed 100-105°C. one of the reagents (formic acid or methylamine) with vigorous stirring and cooling slowly added second reagent with such speed that the temperature of the reaction mixture did not exceed 10-20° (the eye is about 2 hours). Then the reaction mixture is heated with a downward refrigerator to a temperature 180-186°for distillation of volatile substances, and then the temperature was raised to 190-200°so that the temperature of the vapors do not exceed 100-105°With (about 10 hours). Get N-methylformamide with the release of 79-80% and purity of 50-90 wt.%. Purification of N-methylformamide produced by distillation. [Vbesat, Wepmasterow, Redgreen, Wearabnet. Patent USSR No. 1806131, 1992].

This method of obtaining N-methylformamide on raw materials used, the chemical nature of the process and the achieved result is taken as a prototype.

The disadvantage of this process is multi-stage, duration of course of each stage, the refrigerant is used, the presence of waste (after distillation the distillation of N-methylformamide).

The present invention is an improved method of obtaining N-methylformamide of formic acid and methylamine.

The technical result - the reduction of processing time, reduction of energy consumption for the process, improving the quality and yield of the target product and reduce waste.

This technical result in the implementation of the invention is achieved in that in the known method in the interaction of formic acid with methylamine in the first stage is the formation of salts arabinogalactan (formate, methylamine), accompanied by ecoeffect, which leads to loss of part of methylamine due to its ash. Therefore, in the prototype at this stage, the heat of reaction is removed by cooling the mixture. In the second stage, carry out the decomposition of the salt at high temperature with removal of water by distillation, which requires a supply of heat to the reactor for 10 hours. After purification N-methylformamide by distillation receive CBM product, which is a waste product. The feature of the proposed method lies in the fact that the use of a catalyst based on molybdenum trioxide dissolved in aqueous methylamine, and the catalyst is introduced into formic acid number of 2.0 to 4.0 wt.%. In the presence of a catalyst for the dehydration reaction begins almost simultaneously with the reaction of salt and held for 1-2 hours. When this heat is exothermic salt formation is absorbed by the endothermic reaction of dehydration of salt. The total thermal effect of the reaction is practically close to zero and the temperature of the reaction mixture increased slightly. Heat input to the reactor is only required for distillation of volatile reaction products (water). To improve the conditions of the reaction of salt formation of liquid formic acid and gaseous methylamine and dehydration salts of the process is conducted in a reactor filled with an inert nozzle is developed surface without cooling the reaction mass within 1-2 hours, followed by distillation of the volatile products at a temperature in the cube up to 190° C for 60-90 min In the reaction, after distillation of the volatile products, get the raw N-methylformamide containing 92-94 wt.% the basic substance. After distillation of crude N-methylformamide get the target product purity of 99.3-a 99.6 wt.%. VAT residue containing the catalyst return in the process. When implementing this process wastes are not formed.

The subject invention is illustrated by the following examples of its execution.

Example 1. Obtaining a catalyst. In a round bottom flask with a capacity of 50 ml load 15 g of distilled water and 5 g of molybdenum trioxide. Through the liquid bubbled gaseous methylamine to dissolve the molybdenum trioxide. Obtain 28 g of a transparent yellowish solution. The solution is a catalyst.

Example 2. In a flask with a capacity of 0.5 liters, equipped with a thermometer, a bubbler, a downward fridge and a trap for exhaust gases, poured a glass spiral nozzle layer height of 50 mm so that the bubbler was under the packing layer. In the flask is charged with 150 g of formic acid and 1.5 g of catalyst. Through the bubbler serves gaseous methylamine at a speed of 1.0-1.2 l/min Control the temperature of the reaction mass and the value of the hydrogen ion exponent (pH). After 10 min after the start of supply of methylamine temperature of the reaction mixture rose to 60&x000B0; C. the trap was observed breakthrough of methylamine. The feed rate of methylamine was reduced to 0.3-0.4 l/min Bubbling was continued for another 4 hours before reaching the pH of the reaction mass, is equal to 7. This is sometimes observed leakage of gas in the trap. Upon reaching pH=7 raised the temperature in the bath to 190°and drove the water for 8 hours. Just had autogyros of 57.3 g of water.

Got 193,6 g of crude N-methylformamide content: N-methylformamide - 92 wt.%; salt - 4.2 wt.%; acid - 1.9 wt.%.

After rectification on glass laboratory column received 163,5 g of N-methylformamide content: the main substance of 99.3 wt.%; salt - 0.1 wt.%; acid - 0.2 wt.%.

The output product of formic acid of 85%.

Example 3. In the conditions of example 2 in the reactor was loaded with 2.5 g of catalyst. Through the bubbler serves gaseous methylamine at a speed of 1.0-1.2 l/min Control the temperature of the reaction mass and the value of the hydrogen ion exponent (pH). After 10 min after the start of supply of methylamine temperature of the reaction mass rose to 55-60°C. In the trap breakthrough of methylamine was not observed. The feed rate of methylamine was reduced to 0.3-0.4 l/min Bubbling was continued for further 3 hours until reaching the pH of the reaction mass, is equal to 7. Upon reaching pH=7 raised the temperature in the bath to 190°and drove the water for 5 hours. Just had autogyros of 57.8 g of water.

Got 193,8 g of crude N-IU Informatica with the contents:

N-methylformamide - 92,3%by weight; salt - 3.2 wt.%; acid and 1.8 wt.%.

After rectification on glass laboratory column received 168,4 g of N-methylformamide content: the basic substance was 99.4 wt.%; salt - 0.1 wt.%; acid to 0.18 wt.%.

The output product of formic acid was 87.5%.

Example 4. In the conditions of example 2 to a reactor loaded 3.0 g of catalyst. Through the bubbler serves gaseous methylamine at a speed of 1.0-1.2 l/min Control the temperature of the reaction mass and the value of the hydrogen ion exponent (pH). After 30 min after the start of supply of methylamine temperature of the reaction mass rose to 40-50°C. In the trap breakthrough of methylamine was not observed. The feed rate of methylamine reduced to 0.8-1.0 l/min Bubbling was continued for another 1.5 hours until reaching the pH of the reaction mass, is equal to 7. Upon reaching pH=7 raised the temperature in the bath to 190°and drove the water for 1.5 hours. Just had autogyros to 58.2 g of water.

Got 195,6 g of crude N-methylformamide with the contents:

N-methylformamide - of 92.5 wt.%, salt - 2.6 wt.%; acid - 1.6 wt.%.

After rectification on glass laboratory column received 178,5 g of N-methylformamide content: the basic substance was 99.4 wt.%; salt - 0.1 wt.%; acid to 0.18 wt.%.

The yield of the product in formic acid of 92.7%.

Example 5. In the conditions of example 2 in the reactor was loaded with 4.5 g of catalyst. Through the bubbler on the with gaseous methylamine at a speed of 1.0-1.2 l/min Control the temperature of the reaction mass and the value of the hydrogen ion exponent (pH). After 30 min after the start of supply of methylamine temperature of the reaction mass rose to 40-50°C. In the trap breakthrough of methylamine was not observed. The bubbling was continued for another hour before reaching the pH of the reaction mass, is equal to 7. Upon reaching pH=7 raised the temperature in the bath to 190°and drove the water for 80 minutes. Just had autogyros of 58.3 g of water.

Received of 193.5 g of crude N-methylformamide with the contents:

N-methylformamide ratio was 94.3 wt.%; salt to 0.92 wt.%; acid and 0.8 wt.%.

After rectification on glass laboratory column received 177 g of N-methylformamide content: basic substance - 99,46 wt.%; salt to 0.08 wt.%; acid - 0.06 wt.%.

The output product of formic acid is 92%.

Example 6. In the conditions of example 2 to a reactor loaded 6.0 g of catalyst. Through the bubbler serves gaseous methylamine at a speed of 1.0-1.2 l/min Control the temperature of the reaction mass and the value of the hydrogen ion exponent (pH). After 30 min after the start of supply of methylamine temperature of the reaction mass rose to 40-50°C. In the trap breakthrough of methylamine was not observed. The bubbling was continued for another 30 minutes until reaching the pH of the reaction mass, is equal to 7. Upon reaching pH=7 raised the temperature in the bath to 190°and drove water over 60 minutes. Only the pursued 58,4 g of water.

Got 194,8 g of crude N-methylformamide with the contents:

N-methylformamide - 94,4%by weight; salt to 0.14 wt.%; acid and 0.8 wt.%.

After rectification on glass laboratory column received 179 g

N-methylformamide content: the basic substance is a 99.6 wt.%; salt - 0.07 wt.%; acid - 0.09 wt.%.

The yield of the product in formic acid - 93%.

Example 7. In the conditions of example 2 to a reactor loaded 9 g of catalyst. Through the bubbler serves gaseous methylamine at a speed of 1.0-1.2 l/min Control the temperature of the reaction mass and the value of the hydrogen ion exponent (pH). After 30 min after the start of supply of methylamine temperature of the reaction mass rose to 40-50°C. In the trap breakthrough of methylamine was not observed. The bubbling was continued for another 30 minutes until reaching the pH of the reaction mass, is equal to 7. Upon reaching pH=7 raised the temperature in the bath to 190°and drove water over 60 minutes. Just had autogyros 58.5 g of water.

Got to 194.6 g of crude N-methylformamide with the contents:

N-methylformamide ratio was 94.3 wt.%; salt and 0.12 wt.%; acid and 0.8 wt.%.

After rectification on glass laboratory column received 178 g of N-methylformamide content: the basic substance was 99.4 wt.%; salt to 0.08 wt.%; acid and 0.08 wt.%.

The yield of the product in formic acid - 92,5%.

Example 8. In the conditions of example 2 to a reactor loaded VAT residue after rivers is eficacia raw N-methylformamide. Through the bubbler serves gaseous methylamine at a speed of 1.0-1.2 l/min Control the temperature of the reaction mass and the value of the hydrogen ion exponent (pH). After 30 min after the start of supply of methylamine temperature of the reaction mass rose to 40-50°C. In the trap breakthrough of methylamine was not observed. The bubbling was continued for another 30 minutes until reaching the pH of the reaction mass, is equal to 7. Upon reaching pH=7 raised the temperature in the bath to 190°and drove water over 60 minutes. Just had autogyros 58.5 g of water.

Got 193,8 g of crude N-methylformamide with the contents:

N-methylformamide - to 93.3 wt.%, salt and 0.12 wt.%; acid - 0.6 wt.%.

After rectification on glass laboratory column received 179 g of N-methylformamide content: the main substance of 99.3 wt.%; salt - 0.06 wt.%; acid and 0.08 wt.%.

The yield of the product in formic acid - 93%.

Sources of information

1. Gredy Dennis, Stott Reginald Richard. Eng. Pat. No. 1092632, 1967.

2. Huber Ludwig Konrad. Pat. USA. No. 3347916, 1967.

3. Haynes Peter, Kohnie Josef P., Staudh Lynn H. Pat. USA. No. 3530182, 1970.

4. Hawthorne, John O., Schlosberg Samuel C. U.S. Pat. USA. No. 3781352, 1973.

5. Takahashi Of Josey, Fukuoka Yohai. Jap. Pat. No. 35526, 1970.

6. Hensel Jorg, Schaeter Hans, Schreyer Gerd. Pat. The Federal Republic of Germany. No. 2144230, 1976.

7. Nagai, Yoichiro, Oshima, Iwao, Inaba, Nobuichi. Jap. Pat. No. 56-21030, 1973; No. 48-121633, 1981.

8. Vbesat, Wepmasterow, Redgreen, Wearabnet. Patent USSR No. 1806131, 1992.

1. The way p is the receipt of an N-methylformamide of formic acid and methylamine through the formation of an intermediate salt of formate, methylamine with subsequent dehydration of the salt using a catalyst of molybdenum trioxide, characterized in that the use of catalyst based on molybdenum trioxide dissolved in aqueous methylamine, which is injected in formic acid number of 2.0 to 4.0 wt.% from the last.

2. The method according to claim 1, wherein the process is conducted in a reactor filled with an inert nozzle with a developed surface, without cooling the reaction mass within 1-2 h followed by distillation of the volatile products at a temperature in the cube up to 190°C for 60-90 minutes

3. The method according to claim 1, characterized in that the VAT residue containing the catalyst, after separation of the target product are returned to the reactor.



 

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