SU1342409A3 - Method of producing lower aliphatic allyl-amines - Google Patents

Abstract

The invention relates to aliphatic lower alkylamines — intermediate products for the manufacture of rubber products, pesticides, pharmaceuticals. To simplify the process, when reacting the corresponding amine or ammonia with olefin, another catalyst is used - acetone, methyl ethyl ketone, mercury, MOgCl, or iron pentacarbonyl in combination with triethyl phosphite, Other conditions - irradiation with light with a wavelength of 1900-4000 A. As the latter, mercury, mercury-argon, xenon lamps are used. When keeping the reagents for 4 hours, the conversion is It exhibits a 6,9-15,1% and yield - up to 79.1%. This method eliminates the need for high heat and pressure, which greatly simplifies the process. 1 hp f-ly, 2 tab. CO 1 hE 4: About CO

Description

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This invention relates to a perfect method for the preparation of aliphatic lower alkylamines, which are widely used in the national household of intermediate products in the manufacture of rubber products, pharmaceutical products, insecticides, etc.

The purpose of the invention is to simplify the process.

Example 1, 18.2 mol of ammonia is charged to a reaction system consisting of a 1 liter tank of a stainless steel quartz reactor to illuminate the solution with actinic light, and a circulation pump. UV source placed outside

quartz reactor. Both the reactor and the 20 used mercury lamp lamps receive and the light source is enclosed in small outlets, as the mercury cylinder is made of stainless steel. Then ethylene is loaded into the system to a pressure of 2 bO psi. (about 1.8 kg / cm and dissolve 2.3 mol of ethylene in ammonia. Before switching on the lamp, the solution circulates for about 0.5 h to achieve complete mixing of the reactants and to cool the reaction mixture to 7-8 C, B This reaction time is not observed. A liquid reaction mixture circulating under high pressure (autogenous) is irradiated with various ultraviolet lamps for the periods indicated in Table 1. The results of chromatographic analysis of the final mixture of gases are also given in Table 1. Power conversion is given over ethylene, and the output value refers to a mixture of MONO-, di-, and triethylamines. A high-energy xenon pulsed lamp gives energy of 25 joules at a distance of 10 cm with a hole of 1 mm; the maximum energy in the emission spectrum of this is 3000 A, moreover, most of the radiation corresponds to wavelengths in the interval 1800 - 2200 A.

Table 1

Continuation of table 1

Deuterium 4.0 6.9 68.5

Xenon high energy pulse 0,5 8,1 79,1

c Impul low energy 4.0

From the data table. 1 shows that when

The lamp does not emit below 2200 A. The same is observed when using xenon pulsed

25 lamps of low energy, which gives an energy of 25 J at a distance of 10 cm with an aperture of 13 mm and the maximum emission in the spectrum of which falls on 4000 A.

30 Example 2, A mixture of 18.2 mol of ammonia and 0.9 mol of acetone is loaded into the reaction system described in Example 1, then ethylene is admitted to this system, 2.3 mol of which

35 is dissolved in said ammonia and acetone solution. After circulating the solution for 0.5 h, turn on a deuterium lamp with a wavelength of 1850-4000 A and maintain

40 solution under irradiation for 4 h, Analysis of the final mixture by gas chromatography gives a degree of conversion of ethylene equal to 27.9%, and the yield of MONO-, di- and triethylamine equal to

45 72.1%.

Example 3, A mixture of 18.2 mol of ammonia, 1.82 mol of 1-butene and 0.9 mol of acetone is loaded into the reaction system described in example 1

gQ and repeat this experiment, except that a 550 W mercury lamp is used as the light source, with a wavelength within 2200-13700 A with the main part

gg emissions below 4000 A; Liquid mixture under high pressure circulated for 4 hours at 8 ° C; Gas chromatography results and their mass spectrometry results

indicate the degree of conversion in N ethyl-n-butylamine, equal to 7.0%. When acetone is not used, product formation is not observed.

Example 4. A mixture of 17.0 mol of ammonia, 1.72 mol of 1-octene and 0.88 mol of acetone is loaded into the reaction system described in Example 1 and the mixture is circulated for 5 hours at 8 C. As a source of UV radiation, This experiment uses a mercury lamp with a power of 550 W, with a wavelength ranging from 2200-13700 A with the main part of the emission below 4000 A. The product (oktylamine, 2.2 g) is collected by distillation at 180 Cu identified by NMR. Additional identification is performed by titration. In the case where acetone is not used, no product is formed.

Example 5 A mixture consisting of 8.68 mol of ethylamine, 1.4 mol of 1-butene and 0.7 mol of methyl ethyl ketone is loaded into the reaction system described in example 1, by circulating said reaction mixture for 4 hours at 8 with the use of a 550 V mercury lamp with a wavelength within 2200 - 13700 A with the main part of the emission below 4000 A, a 1-butene conversion rate of 5.0% is achieved and the N-ethyl-n-butylamine yield is 100%,

Example 6, A mixture of 5.0 mol of n-butylamine, 0.5 mol of acetone and 0.84 mol of ethylene is loaded into the reaction system described in Example 1, by circulating said reaction mixture for 4 hours, at B C using a mercury lamp with a power of 550 W, with a wavelength ranging from 2200-13700 A to the main part of the emission below 4000 A, an ethylene conversion degree of 12.0% is achieved and the yield of N-ethyl-n-butylamine is 100%

Example 7. A mixture of 7.60 moles of dimethylamine, 1.15 moles of ethylene and 0.0023 moles of Mo1,2 is loaded into the reaction system described in example 1, by circulating said reaction mixture over an ionic mixture

ABOUT

4 hours at 8 ° C, ethylene conversion is 10%, and the total consumption of dimethylethylamine, diethylmethyl-amine, and triethylamine is about

Lo 100% (when using a 550 W mercury lamp)

Example 8. A mixture of 4.04 mol

i-butylamine, 0.221 mol of iron pentacarbonyl and 0.221 mol of triethylphosphite are loaded under a pressure of 250 psi, inch (about 1.75 kg / cm) of ethylene at 35 ° C in the reaction system described in example 1, A high pressure mercury UV lamp of 550 watts is used in the light source. The reaction mixture is circulated for 4 h.

under constant radiation. The results of the analysis of the products indicate the presence of a degree of conversion on n-butyl-amine, equal to 15.5%, with the production of M ethyl-n-butylamine,

Example 9, 18.2 mol of ammonia and 0.18 mol of ammonium chloride () are loaded into a 1 liter cycling system equipped with a circulation pump, a cooling coil and a glass cylindrical reactor i. An ultraviolet lamp is placed next to the reactor, and the lamp is transferred, together with the reactor, into a reflecting cylindrical casing made of stainless steel. Ethylene is then loaded into the system at a pressure of about 250 psig. inch (about 1.75 kg / cm). Received by

the solution is circulated for about 0.5 hours (or until the temperature of the reaction mixture reaches 7–8 s). Then turn on the lamp and irradiate the solution for 4 hours,

In order to illustrate the effect of glass and amorphous silica as a material for the reactor and an irradiation lamp, Table 2 shows. Figure 2 shows the results of eight experiments using the procedure described above. Four out of eight experiments on the reactor wall are made of ordinary quartz glass, while the remaining four experiments use a reactor with

glass walls made of amorphous silica (Suprasil ®). In both series of 4 experiments in two of them were used to irradiate the lamp, the windows of which were made of ordinary quartz, and in the other two. The experiments of each series are: py, windows of which are made of glass from amorphous silicon dioxide.

(Suprasil ®). The degree of conversion (in%) is given in table. 2, based on the amount of chlorine quartz available

Less than .1

Amorphous silica

ten

High pressure mercury lamp, power 550 W,

Xenon Pulsed High Intensity Lamp

with a wavelength within 1800-11000 A and mostly 1800-2200 A,

Example 10 Gaseous ammonia ethylene, helium and mercury vapors are simultaneously subjected to ultraviolet radiation in a single-pass reaction system consisting of flow controllers, a stainless steel vaporizer and a quartz reaction chamber. The stream of gels is first passed through elemental mercury heated to about 200 ° C, after which ammonia with olefin in the presence of

catalyst,

about the fact that, in order to simplify the process, the latter is carried out in

Helium and mercury vapors are immediately mixed with a mixture of ethylene and (1: 1 by volume) after which the resulting mixture is introduced into the reaction chamber. The reaction chamber is irradiated with a mercury wave of 1900-4000 Au photocatalyst, a low-pressure lamp, which uses acetone, methyl ethyl ketone, mercury, or iron pentacarbonyl in combination.

the presence of a light source with

Noah outside the reactor and from a long wave almost completely 2537 A, Gas at the outlet

from the reactor is collected and analyzed; the reaction product is identified as ethylamine, having a purity of 85-98%,

Thus, the proposed method is simpler in comparison with Compiler C, Polkova Editor N, Kishtulinets Tehred I.Popovich Proofreader M, Pozho

4447/58

Circulation 371 Subscription

VNIIPI USSR State Committee

for inventions and discoveries 113035, Moscow. Zh-35, Raushsk nab., D, 4/5

Production and printing company, Uzhgorod, st. Project, 4

ammonium, because in each case, the product yield is almost quantitative.

Table 2

40

thirty

40

100

100

100

known, since it eliminates the need for a process at high temperature and pressure,

Claims (1)

Invention Formula 1, A method of producing aliphatic lower alkylamines by reacting a primary or secondary amine or catalyst, 1900-4000 Au of photocatalyst, known as acetone, methyl ethyl ketone, mercury, or iron pentacarbonyl in combination so that, in order to simplify the process, the latter is carried out 1900-4000 Au waves of photocatalyst used as acetone, methyl ethyl ketone, mercury, or iron pentacarbonyl in combination the presence of a light source with with triethylphosphine. 2, Method non.i, characterized in that the process is carried out in a reactor with walls of amorphous silica glass.