The method of obtaining n,n-diethylmetatoluamide


(57) Abstract:

The inventive product is N, N-diethylmetatoluamide. Reagent 1: m-tolarova acid. Reagent 2: diethylamin. Reaction conditions: diethylamin served in a mixture with a solvent (benzene, toluene, m-xylene) in the ratio 1:1 under the layer of the reaction mixture with vigorous stirring at 200 - 220oWith continuous and direct the azeotropic distillation of the mixture of solvent, water and unreacted diethylamine in the presence of a catalyst-complexing compounds P(3), or B.

The invention relates to methods of obtaining N,N-diethyl-meta-toluamide (DETA), which is one of the best repellents, and can be used in the chemical and pharmaceutical industries.

A method of obtaining DEATH metal, which consists in the interaction m-Truelove acid (MTC) with thionyl chloride or other gloriously agents (l3, COCl2c the formation of the acid chloride m-Truelove acid, separation, distillation and further processing the last diethylamino with subsequent vacuum distillation of the obtained raw DEATH metal [1]

The disadvantage of this method is the use of a large number gloriously agents, strong corrosion of the rim, solid waste, including vacuum-evaporating device of the acid chloride m-Truelove acid, and gaseous emissions containing Hcl and SO2.

Also known more promising method of obtaining DATA from m-Truelove acid without intermediate formation of the acid chloride in the presence of titanium compounds (of 0.0001-0.1 g per 1 g MTC). Use TiCl4, Ti(OAlk)4where Alk C3-C18, complex compounds of titanates with triethanolamine, tetraethyleneglycol; titanium acetylacetonate. The process is conducted in an organic solvent azeotropic distillation of water and solvent recovery. Output DETA 68-74% [2]

The advantage of this method is the exception to the stage of obtaining the acid chloride, which leads to the reduction of aggressive waste.

The disadvantage of this method is the use as catalysts of toxic titanium compounds that can get into the final product, as well as the duration of the process at a fairly high temperature (220-235aboutWith over 40 hours). Technological design method using a nozzle Dean-stark to return the solvent to the reaction mass does not allow sufficiently removed from the reaction mass water due to the formation of ternary mixture of the reaction (conversion of 93% yield 68-74%).

The invention allows to reduce the duration of the process, to reduce the temperature of the process, to use more available and cheaper catalysts, as well as to increase the output of diethyltoluamide.

The essence of the proposed method lies in the fact that N,N-diethyl-meta-toluamide produced by the interaction meta-Truelove acid with diethylamine when heated (200-220about(C) in the presence of a catalyst (compounds 3-valent phosphorus and boron) and a solvent, forming an azeotrope with eye-catching during the reaction with water, when the continuous supply of diethylamine in a mixture solvent (1: 1) under a layer of reaction mass at a temperature of 200-230aboutWith and in continuous distillation of a mixture solvent of water and unreacted diethylamine through direct refrigerator with a reflux condenser, which contributes to more complete removal of water from the reaction mass and a shift in the equilibrium towards formation of diethyltoluamide.

The condensate can then be regenerated.

P R I m e R 1. 50 g (0.36 m) m-Truelove acid, 1 ml of diethylamine and 1 ml of xylene, 1,25 g H3RHO3(0,015 m) are loaded into a flask of 250 ml, equipped with a stirrer, thermometer, addition funnel for reagent supply under layer Rea is Argonaut azeotrope with xylene excess moisture from m-Truelove and of phosphorous acid and at a temperature of 200aboutFrom start to apply under the layer of the reaction mixture, a mixture of diethylamine with xylene (1:1). Formed during the reaction water azeotrope is distilled off with xylene and unreacted by diethylamino. The condensate is collected in a receiver and then subjected to regeneration. Duration of response of 9 o'clock

After the reaction mass is then cooled to a temperature of 60aboutC and washed with 50 ml of 25% aqueous sodium chloride solution containing 1 l 1.1 g sodium hydroxide. Stirred at 60about1 h, transferred into a separating funnel and separate the lower aqueous layer, which then goes on acidification and isolation of unreacted m-Truelove acid. The upper layer containing diethyltoluamide, washed again with 40 ml of 25% aqueous solution of sodium chloride at 60aboutC, divided by a separating funnel. The organic layer containing DETA, is subjected to vacuum rectification. Basic fraction Argonauts at a residual pressure: 5 mm at 133aboutC, 10 mm at 146-148aboutC.

Get a 58.3 g of DETA with the content of the main product 98%

Conversion ITC 96%

Output DETA 83% loaded acid, 86.5% of the new reaction.

P R I m m e R 2. 50 g m-Truelove acid, 1 ml of diethylamine, 1 ml of benzene and 1.25 g of phosphorus is with benzene (1:1). The reaction takes place analogously to example 1. Duration of 8 hours Output DETA 81% loaded on acid.

P R I m e R 3. In the examples 1 and 2 begin to apply the mixture of diethylamine with toluene at 200aboutC. the Reaction proceeds analogously to examples 1 and 2. The results of the process similar to example 1.

P R I m e R 4. 30 g (0,217 m) m-Truelove acid, 2 ml of benzene, 2.35 g (0,017 g-m) trichloride phosphorus load into a flask of 100 ml, equipped as described in examples 1 and 2, and at 200aboutServed with a mixture of m-xylene/diethylamine under the layer of the reaction mass. After 7 h, the conversion of m-Truelove acid is 97.5%

P R I m e R 5. The 4-necked flask with a capacity of 250 ml, equipped as described in example 1, a reflux condenser, a load of 50 g m-Truelove acid, 1.5 g of boric acid and 1 ml of diethylamine and m-xylene. The reaction mass is heated until complete melting MTC when stopped the mixer, then the mixer and continue heating. At a temperature of 220aboutFrom start to dispense a mixture of diethylamine with m-xylene in the amount of 150 ml and a 1:1 ratio. Loading the mixture is held for 7 hours at a temperature of 220aboutC. during the reaction is carried out continuous removal of unreacted diethylamine, m-xylene and reacts is 15 minutes, then poured into a separating funnel, separate the organic layer from the water containing Na-salt of unreacted m-Truelove acid and conduct vacuum distillation, selecting the main fraction at a temperature of 151aboutC and a vacuum of 10 mm RT.article Get to 46.8 g trademark DEATH metal containing 95,25% m-DETA, representing 80.6% of the downloaded MTC.

P R I m e R 6 (comparative). In conditions of experiments 1 and 2 the mixture flow diethylamine with the solvent is carried out at 180aboutC. After 20 h the reaction mixture was detected 12% DETA.

P R I m e R 7 (comparative prototype). 50 g (0.36 m) m-Truelove acid, 6.5 g of diethylamine (0,09 m) and 0.36 g of phosphorous acid are loaded into a flask of 250 ml with a nozzle Dean-stark, filled with benzene and a reflux condenser. The reaction mixture is heated to melting m-Truelove acid and stirred for 22 hours at a temperature of 220-235aboutC. In the first 3-4 h observed the separation of water from the reaction mass and defending her in the nozzle Dean-stark, then a couple of benzene, water and diethylamine form nonshared mixture.

Diethylamine (25 g, 0,37 m) served under a layer of the reaction mixture for 18 hours After exposure of the reaction mass is treated as described in example 1. Get 11,98 ocrotiti the duration of the process from 35-40 to 7-10 hours at the temperature decrease with 220-235 to 200-220aboutTo use available and cheap catalysts (compounds 3-valent phosphorus and boron H3PO3, PCl3, POCl3H3BO3. In addition, the technological design of the method, it is permanently removed from the reaction mass of water with the solvent and excess diethylamine allows you to increase the conversion-Truelove acid up to 96-99% and, accordingly, to increase the output of diethyltoluamide.

The METHOD of OBTAINING N,N-DIETHYLMETATOLUAMIDE the interaction of metatoluidine acid with diethylamine at 200 - 220oIn the presence of a catalyst and solvent - aromatic hydrocarbon azeotropic distillation of the water formed, characterized in that diethylamin served in the mixture with the solvent in a ratio of 1 : 1 under the layer of the reaction mixture with vigorous stirring and continuous direct the azeotropic distillation of the mixture of solvent, water and unreacted diethylamine, at the same time as the catalyst is used complexing compound of trivalent phosphorus or boron, and as the aromatic solvent is benzene or toluene, or betaxolol.


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