DE1027649B - Process for the production of ethylene telomerizates - Google Patents

Description

GERMAN

It has been found that ethylene telomerizates can be prepared by combining ethylene with organic compounds Polyhalogen compounds or cyanogen halides, in the presence of metal halides as catalysts, under Pressure and at elevated temperature.

Particularly suitable organic polyhalogen compounds are, for. B. carbon tetrachloride, chloroform, Chloral hydrate, di- or trichloroacetic acid ester, hexachloroethane, benzotrichloride or trichloroacetonitrile. Even Mixtures of the polyhalogen compounds mentioned can be used. Metal halides prove to be particularly suitable of beryllium, calcium, magnesium, strontium, barium, aluminum, iron, zinc, tin and titanium. They can be used in amounts of 2 to 10%, preferably 4 to 5%, based on the polyhalogen compound will. Mixtures of these metal halides are also advantageous in some cases. The metal halides can either directly or on suitable supports, e.g. B. pumice stone or silica gel applied.

The reaction is carried out at an elevated temperature, for example between 80 and 220 ° C., preferably between 120 and 180 ° C. It often proves to be beneficial to initiate the reaction at a lower temperature and to increase it gradually in the course of the reaction. The same goes for the pressure, which is beneficial between should be around 50 and 300 at.

The reaction can be carried out in the presence of inert diluents, e.g. B. octane, hexadecane or dioxane, be carried out continuously or discontinuously. One leads z. B. a mixture of polyhalogen compound and ethylene through a pressure tube in which the metal halide, for example applied to a support, is is located, and collects the resulting liquid reaction product and the unreacted halogen compound in a high pressure separator. Unreacted ethylene can be recycled into the reaction vessel to be led back.

Mixtures of telomerizates containing 1 to 10 moles of ethylene are obtained, which are converted into aliphatic ω-chlorocarboxylic acids Can be converted and valuable intermediates, for example for the production of aliphatic «-Aminocarboxylic acids and other substitution products of aliphatic carboxylic acids.

Although it is known to convert olefins with the aid of catalysts which form free radicals, e.g. B. peroxides to implement in the presence of organic halogen compounds. In this case, however, the telomerization reaction proceeds in a slightly explosive manner, so that the literature warns against reacting approaches containing more than 100 g of carbon tetrachloride in the absence of water. The use of water in telomerization reactions, however, causes severe corrosion of the apparatus and, above all, has an unfavorable effect on the telomerization reaction. On the other hand, one already has a manufacturing process
of ethylene telomerizates

Applicant:

Aniline & Soda Factory in Baden
Aktiengesellschaft, Ludwigshafen / Rhein

Dr. Max Moosbrugger and Dr. Max Fischer,

Ludwigshafen / Rhine,
have been named as inventors

proposed telomerizing olefins using metal halides. In the known implementation of Olefins with alkyl monohalides in the presence of boron trifluoride are practically only addition compounds from 1 mole of olefin and 1 mole of alkyl monohalide. Also arise according to another known method from olefins and alkyl monohalides in the presence of Friedel-Crafts catalysts practically only addition compounds in a molar ratio of 1: 1 or at most such from 2 moles of olefin and 1 mole of alkyl monohalide.

The parts mentioned in the examples are parts by weight.

example 1

To a mixture of 230 parts of carbon tetrachloride and 5 parts of aluminum chloride, which are in one with In a silver-lined autoclave, ethylene is injected up to a pressure of 30 atm. Man warms up slowly to 155 ° C, increases the ethylene pressure slowly to 100 at, increases the temperature slowly 170 ° C and keeps the pressure constant at 100 at for 2 hours.

After filtering off 27 parts of insoluble residue from the filtrate and distilling off the unreacted carbon tetrachloride, 40 parts of a mixture of co-trichloromethyl-co-chloroalkanes of the general formula Cl ₃ · C - (CH ₂ - CH ₂ ) _K C1 are obtained.

Table 1 Parts Boiling point at 0.02 mm 17th 36 to 60 ° C 16 60 to 80 ° C 6.6 80 to 85 ° C 13.2 Residue 70S 959/413

Table 3

at Telogen
Parts approach solvent Reaction conditions hours ⁰ C Acid number from the Pressure * at Parts Reaction product Molar ratio relationship
TslosfGii too O game CCl ₄ catalyst
Dear n-heptane 27 150 30 to 100 30th Kp. Telogen to C ₂ H ₄ C ₂ H ₄ ** to 2 230 AlCl ₃ 70 100 to 200 6.5 Bp 30 = 60 to 160 ° C 1: 8.18 CCl ₄ 5 - 14th 150 30 to 100 18th (Residue) 1: 4.23 CTJ 3 300 BeCl ₂ 100 to 200 6.7 _{B.p. 30} = 80 to 90 ° C 1: 3.10 CCl ₄ 10 - 8th 150 30 to 100 50 (Residue) 1: 2.57 CD 4th 300 SnCl ₄ 100 to 200 3 _{B.p. 30} = 70 to 175 ° C 1: 2.65 to 4.9 CCl ₄ 10 - 25th 150 20 to 80 81 (Residue) 1: 2.45 5 250 ZnCl ₂ -170 80 to 200 6.2 Bp ₁₁₀ = 80 to 155 ° C 1: 2.8 to 4.5 CCl ₄ 30th n-pentane 21 100 20 to 150 48 (Residue) 1: 2.76 6th 500 FeCl ₃ 200 -146 150 to 200 5 Bp _lo = 70 to 120 ° C 1: 2.4 to 2.8 CCl ₄ 40 - 21 150 20 to 80 87 (Residue) 1: 2.71 7th 300 TiCl ₄ -190 80 to 200 9 Bp ₁₁₀ = 80 to 145 ° C 1: 2.6 to 3.2 CCl ₄ 10 - 19th 130 20 to 80 212 (Residue) 1: 1.84 8th 800 ZnCl ₂ -160 80 to 200 Bp ₁₁₈ = 60 to 95 ° C 1: 2.9 (about 20%) 1: 2.64 CCl ₄ Silica gel 80 - 23 131 30 to 80 50 9 900 ZnCl ₂ (20%) -164 80 to 200 Bp _w = 56 to 99 ° C 1: 2.98 1: 3.59 CCl ₄ on pumice stone 90 17th 133 30 to 80 275 10 500 CaCl ₂ -168 80 to 200 Bp ₁₉ = 80 to 100 ° C 1: 2.7 1: 3 CCl ₄ 20th 18th 146 30 to 70 727 11 2200 CaCl ₂ -150 70 to 300 CCl ₄ 110 - 17th 158 30 to 150 508 saponified directly 12th 1200 ZnCL, (20%) 150 to 300 CCl ₄ pumice 29 140 30 to 50 331 saponified directly 13th 1200 OU
ZnCl ₂ (20%) 50 to 300 CCl ₄ 60 21 146 30 to 80 454 saponified directly 14th 1200 CaCl ₂ -149 80 to 300 CCl ₄ 60 15th 125 30 to 80 188 saponified directly 15th 1000 FeCl ₃ -130 80 to 300 CCl ₄ 50 - 34 158 30 to 100 697 saponified directly 16 1000 SrCl ₂ 100 to 300 CCl ₄ 50 - 40 146 30 to HO 626 saponified directly 17th 1000 BaCl ₂ -149 CCl ₄ 50 20th 140 30 to 90 622 saponified directly 18th 2200 MgCl ₂ 90 to 300 110 * The pressure was brought to the first mentioned value in all cases and is in progress saponified directly ** Calculated from the
is the response to the latter value increases. O-halocarboxylic acids obtained from telomerizates.

Continuation of table 3 Telogen catalyst Other telogens ⁰ C Pressure * at Parts Reaction product Molar ratio density at Parts Dear Reaction conditions *** 105 20 to 85 45 Telogen to C ₂ H ₁ Telomerizate game 13th Kp. COCl ₂ AlCl ₃ hours -148 85 to 200 20th 19th 13th 12th Bp ₇ = 70 to 120 ° C 1.398 140 10 150 20 to 80 35 _Bp . 0r05 = 74 to 170 ° C (n-heptane)
10S 24 (Residue) CCl ₃ -COOCH ₃ JL \ J * j
AlCl ₃ -156 80 to 200 11 20th 23 154 30 to 100 537 ^κ Ρ ο, ο2 = 70 to 100 ° C 1: 1.4 to 2.3 1.364 250 5 287 (Residue) CCl ₃ -COOCH ₃ CaCl ₂ -168 100 to 200 180 21 18th 70 Bp. _{0> 2} = 62 to 141 ° C 1: 3.42 1.176 500 20th 150 30 to 80 350 Bp _{> 8} = 190 to 240 ° C 1: 2.78 254 (Residue) 1: 3.45 to 4.63 CCl ₃ CN CaCl ₂ -170 80 to 200 96 22nd 13th 183 30 to 110 18th _{B.p. 3O} = 150 to 200 ° C 1: 3.1 to 3.0 500 20th 16 (Residue) ClCN 56 AlCl ₃ -184 110 to 150 2 23 5 11 150 to 200 Bp _u = 70 to 92 ° C C ₂ H ₄ : Cl: CN 1.403 (n-pentane) (Residue) 2.14: 3: 0.9 (Nitromethane) 165 30 to 100 65 20th 46 CHCl ₂ COOCH ₃ CaCl ₂ -168 100 to 200 19th 24 27 150 30 to 80 44 Bp _u = 86 to 136 ° C 1: 1.96 1.336 670 30th -170 80 to 200 (Residue) CCl ₃ CHO CaCl ₂ 154 30 to 80 36 1: 2.02 1,439 25th 695 30th 14th -167 80 to 200 CHCl ₃ CaCl ₂ 153 30 to 90 404 1.473 26th 800 40 14th 189 C ₂ Cl ₆ CaCl ₂ -181 90 to 150 185 27 36 150 to 200 30th _{B.p. 8O} = 46 to 80 ° C 1.245 400 40 156 30 to 80 331 Bp ₁₁₆ = 100 to 190 ° C CH ₂ Cl ₂
400 -180 80 to 135 235 (Residue) C ₆ H ₆ CCl ₃ CaCl ₂ 135 to 200 96 1.197 28 300 30th 36 Kp.i2-i5 = 103 to 180 ° C (Residue)

* The pressure was in all cases
*** Trials 19 to 28 were

brought to the first-mentioned value and increased in the course of the reaction to the last-mentioned value,
carried out in autoclaves made of chromium-nickel steel.

Table 2

Boiling points of the compounds Cl (CH ₂ - CH ₂ ) _n C Cl ₃

η == 1 Kp. ₂₄
η = 2 Κρ. ₂₄
η = 3 Κρ. ₂₄
η = 4 Κρ. _2Ο

159 ° CD ₂₀ 1.4463

59 ° CD ₂₀ 1.4463

112 ° CD ₂₀ 1.3416

143 ° CD ₂₀ 1.2535

168 ° CD ₂₀ 1.1943

Further examples using other metal chlorides and telogens are shown in Table 3.

The molar ratio of telogen to C ₂ A ₄ can also be calculated from the acid number or the molecular weight of the co-halocarboxylic acids formed during the saponification of the process products. In Examples 10 to 18, the molar ratio of telogen to C ₂ A ₄ obtained in this way is given. The saponification of the telomerizates to give the corresponding («-halocarboxylic acids is carried out as follows: In each case 100 parts of the reaction product [Cl ₃ C (CH ₂ CH ₂ ) _n Cl] freed from the catalyst and excess carbon tetrachloride are added to 150 parts at 90 ° / ₀ sulfuric acid heated under .Rückfluß on the steam bath for 16 hours, then mixed with 15 parts of water and the residual hydrogen chloride filtered off with suction under vacuum. the mixture is diluted with 200 parts of ice water, treated with diatomaceous earth and nitrided. the filter residue is in the Soxhlet apparatus, the filtrate in a Liquid extraction apparatus is extracted exhaustively with ether. The ether solutions are combined, washed with water until the filtrate is free of mineral acid, and the ether is distilled off. Finally, it is dissolved in 10 η sodium hydroxide solution and the alkaline solution is extracted with ether, in which the

dissolve unsaponifiable parts. The alkaline aqueous solution is acidified with hydrochloric acid and again with Ether extracted. After distilling off the ether, a mixture of pure ω-chlorocarboxylic acids is obtained, their average ratio of telogen to ethylene is derived from the acid number or their molecular weight results. In Examples 19 to 28, the crude telomerizate was distilled and the fractions, depending on the type of the applied telogen identified by determination of C, H, N, O or halogen. From the composition, The ratio of telogen to ethylene was determined from the density and the boiling point.

Claims (1)

PATENT CLAIM: Process for the production of ethylene telomerizates, characterized in that ethylene is pressurized at elevated temperature with organic polyhalogen compounds or cyanogen halides, in the presence of Metal halides as catalysts, is implemented. Considered publications: Excerpts from German patent applications, Vol. 6 (November 10, 1948) J73596IVb / 12o; Swiss Patent No. 271 369; French Patent No. 943 239; U.S. Patent Nos. 2,533,052, 2,533,053; Swedish patent specification No. 129 090 (as a report in Chemisches Centralblatt 1951, II, 1358); Canadian Patent No. 465 843 (as a report in Chemisches Centralblatt 1951, I, 927); J. Amer. Chem. Soc, 72, pp. 2213-2216 (1950). © 709 95Ϊ / 413 ¹ 4.5S