DE2359298C3 - Process for the production of tetrahydrothiophene - Google Patents

Description

that corrosion of the same occurs. The advantages of the method according to the invention include

The invention relates to a method for its simple technological design.
Production of tetrahydrothiophene, which is used as an intermediate In order to increase the yield of the end product,

The reaction of tetrahydrofuran with methylene sulfoxide, sulfolane and 1,4-dihalobutane sulfur in the presence of red phosphorus is not used. The products obtained from tetrahydrothiophene in a ratio of 0.5 to 1 g atom are used as a fuel additive to carry out 1 mol of tetrahydrofuran. Extraction of aromatic hydrocarbons from the earth is recommended - it is advisable to work at a temperature between 180 and 200 ° C for the production of polysulphide elastomers.
ren, in medicine and in other branches of industry. The process for the preparation according to the invention

one. of tetrahydrothiophene is realized as follows:

A process is known for the preparation of The reaction of tetrahydrofuran with sulfur

Tetrahydrothiophene, which consists of one or phosphorus sulfides, is expediently carried out in a tetrahydrofuran with hydrogen sulfide as a sulfidie roller or stirred autoclave. The autoclave is equipped with a medium in the vapor phase with a stoichiome manometer, an electric heater and a thermal ratio of the substances mentioned between the moelement, which is connected to a temperature of-275 and 450 ° C in the presence of an aluminum regulator. The temperature controller registers the silicate catalyst and then isolates the and regulates the temperature of the process. Who implements the end product (e.g. FR-PS 20 54 144). The autoclave described in 45 is operated with stoichiometric parameters. B. P ₄ S ,, P ₂ S ₃ , P ₄ S ₇ , P ₂ S ₅ , charged to use material that increases the operating space and the Uim the yield of the end product, can pollute air and cause corrosion of steel materials. As mentioned above, sulfur is produced together with directions. The use of a sulfur 50 red phosphorus, taken in a proportion of hydrogen sulfide generator, makes the 0.5 to 1 g-atom per 1 mole of tetrahydrofuran, in the technological design of the process, complicated. Introduce the autoclave. After loading the A disadvantage of the process is that the substances are closed off the autoclave, the reaction of tetrahydrofuran with sulfur reaction mixture is heated to a given temperature and hydrogen at relatively high temperatures and keeps it at this temperature which is carried out. the duration of the procedure required. In DT-PS 12 24 749 there is also a process in which a constant pressure in the autoclave is used to produce essentially thiophene and if the completion of the reaction mixture containing tetrahydrothiophene can be recognized. It terminates the heating of the autoclave, giving, on the reaction of butanediol or 60 i ^h n cooled to room temperature and set Druckaus-tetrahydrofuran with elemental sulfur and equal forth. The autoclave is opened, the hydrogen is withdrawn, optionally in the presence of an inert reaction mixture, which is a brown viscous liquid gas, and is based under increased pressure, which represents, and the end product is isolated therefrom, for. B. Reaction at temperatures from 350 to 650 ° C in the presence of aluminum oxide, which is a metal or 65, by extraction with organic solvents or by distillation. In the latter case, the metal oxide of Vf., VII. And / or in particular which is more preferred, the end product from subgroup VIII of the periodic table contains the reaction mixture at a temperature of 116 to. 122 ⁰ C distilled off under atmospheric pressure. Around

3 4

to increase the yield of tetrahydrothiophene, 32 g (1 g atom) of ground sulfur and 15.5 g can be made from a red phosphorus after distilling off the (0.5 g atoms) and kept the final product resulting residue an additional mix with rotation of the autoclave for 36 hours Amount of the named product by extraction at 200 ° C. After the specified time had elapsed, the an organic solvent, e.g. tetrachloro 5 autoclave, cooled to room temperature and let down carbon, isolate. (Pressure equalization). For a better understanding of the present invention, the liquid reaction products formed are transferred to a distillation unit The following examples are used to make flasks and separated 19.5 g (22.2 "zo) tetrahydrothio-tetrahydrothiophene listed: phen with a boiling point of 118 to 122 ° C (760 mm

ίο Torr), df 1,000, η? 1.5010 from.
example 1

In a steel, 1 liter roller autoclave, which is equipped with a manometer and a system In a steel, 0.51 capacity autoclave, which is equipped for controllable heating (electrical preheater, 15 with a mechanical stirrer, a mano-thermocouple, potentiometer), meter and a system for controllable heating, one brought 72 g (1 mol) of tetrahydrofuran and (electrical preheater, thermocouple, potentio-32 g (1 g atom) of ground sulfur and held meter), one brought 72 g (1 mol) TEDA reaction mixture while rotating the autoclave trahydrofuran and 46 g (about 0.2 mol) of PhoE-18 hours at 200 ⁰ C. at the end of said 20 phorsulfid P ₂ S ₅ and stopped, the reaction mixture time, the autoclave was boiled down to room temperature with stirring for 6 hours at 195 ° C. After this cools; it was released (pressure equalization) and the time mentioned, the autoclave on space formed brown liquid product *; cooled to a distile temperature; it was let down (pressurized flask transferred. Distillation became the same). The dark brown liquid pro-17.1g (23.2%) unreacted tetrahydrofuran 25 products were transferred to a still flask to a boiling point of 64 ⁰ C (760 mm Torr) and from there by distillation 44.5 g (50.3% ) Tetra-10.5 g (11.9%) tetrahydrothiophene of a boiling thiophene with a boiling point of 118 to 122 ⁰ C point of 118 to 122 ° C (760 mm Torr), df 1,000, (760 mm Torr), df 0 , 9998, n | ° 1.5020 isolated.
n ^! o 1.5010 isolated, which agrees with the literature (boiling point 116 to 122 ³ C at 760 mm 30 Example 6
Torr, df 1,000, n> ₀ ° 1.5010; EE Reid, “Organic

Chemistry of Bivalent Sulfur «, v. III, New York, In the steel autoclave described in Example 5

1960, p. 90). 72 g (1 mol) of tetrahydrofuran, 45 g, were brought

(a little over 0.2 mol) phosphorus sulfide P ₂ S ₅ a and

At 1 2 35, the mixture was kept for 6 hours with stirring

175 ° C. The discharge of the reaction mixture from

72 g (1 mol) of tetrahydrofuran were placed in the steel rolling autoclave described in Example 1 and the isolation of the end product was carried out in an autoclave; 32 g (1 g atom) of ground sulfur and 31 g were carried out from the reaction mixture as in Example 5 . 40 g was obtained (45.2%) Tetrahvdro- (1 g atom) of red phosphorus and kept the overall 40 thiophen a boiling point of 118-122 ⁰ C mixed with rotating the autoclave for 6 hours at (760 mm Torr), df 1,000, n ^! g 1.5015.
18O ⁰ C. After the specified time, the

Autoclave cooled to room temperature; Example 7

tenses (pressure equalization) and the brown ones formed

liquid products are transferred to a distillation flask. 45 In the steel autoclave described in Example 5 to (a little over 0.2 mole) phosphorus sulfide P ₂ S ₅ and 122 ° C (760 mm Torr), ^ ⁰ 1,000, «^ 1,000, n ^s _D ^o 1.5010, the mixture kept stirring for 6 hours at isolated . 215 ° C. The discharge of the reaction mixture from

Example 3 ⁵ ° ^ ^em autoclave and the isolation of the end product

from the reaction mixture were as in Example 5

In the steel roll described in Example 1 carried out. This gave 36 g (40.4%) Tetrahydroautoklav were brought 144 g (2MoI) tetrahydro- thiophen a boiling point of 118 to 122 ⁰ C furan, 64 g (2 g-atoms) ground sulfur, and (760 mm Torr), df 1.000 , / i | ° 1.5015.
62 g (2 g-atoms) of red phosphorus and kept the 55

Mixture with rotation of the autoclave for 2 hours Example 8

at 200 ° C. After the specified time has elapsed

the autoclave is cooled to room temperature and placed in the steel, 1 liter roller autoclave,

Pressure equalization made. The formed brewers with a manometer and a system for the NEN liquid reaction products were equipped in a 60 controllable heating, one brought a distillation flask and transferred 96 g (50.2%) of tetra, 72 g (1 mol) of tetrahydrofuran and 72.6 g (almost hydrothiophene with a boiling point of 116 to 122 ° C 0.33 mol) phosphorus sulfide P ₄ S ₃ and kept the Re- (760 mm Torr), df 1.000, n'g 1.5010 separated. action mixture with rotation of the autoclave 6 hours

at 200 ^° C. After the specified time has elapsed

B is ρ ie 1 4 ⁶ 5, the autoclave was cooled to room temperature,

and it was relaxed (pressure equalization). One over-

The dark brown liquid reacautoclave formed was carried in the tall roller described in Example 1 72 g (1 mol) of tetrahydrofuran, tion products were brought into a still and separated

10 g (13.5 ° / ») tetrahydrothiophene with a boiling point of 118 to 122 ° C (760 mm Torr), d? 1,000, nf 1.5010 from.

Example 9

72 g (1 mol) of tetrahydrofuran and 52.2 g (about €, 33 mol) of phosphorus sulfide P ₂ S _{3 were placed in the steel, 1 liter roller autoclave, which is equipped with a manometer and a system for controllable heating} the reaction mixture while rotating the autoclave for 6 hours at 195 ° C. After the stated time had elapsed, the autoclave was cooled to room temperature and the pressure was released (pressure equalization). The formed dark brown liquid products were transferred into a distillation flask and isolated 40 g (45.5 ° / o) tetrahydrothiophene having a boiling point 118-122 ⁰ C (760 mm Torr), d '° 1.000 / ^s i ₀ ° 1, 5010.

Example IGi

_{72 g (1 mol) of tetrahydrofuran and 49.8 g (about 0.143 mol) of phosphorus sulfide P 4} S _{7 were placed} in the steel, 1 liter roller autoclave, which is equipped with a manometer and a system for controllable heating Reaction

mixed with rotation of the autoclave for 6 hours at 200 ° C. After the stated time had elapsed, the autoclave was cooled to room temperature and the pressure was released (pressure equalization). The yellow-brownish liquid reaction products formed were transferred to a distillation flask and 17 g (19.3%) of tetrahydrothiophene having a boiling point of 118 to 122 ° C (760 mm Torr), d? 1.000, n% ° 1.5010 from.

Claims (3)

The invention is based on the object, sin claims: Process for the preparation of tetrahydrothiophene by reacting tetrahydrofuran with a 1. A process for the production of tetrahydrofuran in the stoichiometric ratio of thiophene by reacting tetrahydrofuran 5 with heating followed by isolation of the stoichiometric end product with a sulphidating agent while avoiding the loss of ratio of the substances mentioned so that it makes it possible To choose em nontoxic heating with subsequent isolation of the end product and explosion-proof sulphidation agent, characterized in that the temperature at which the starting materials react with one another to react with sulfur or phosphorus io others, and the technological sulphides as sulphidation agents at one temperature - see design of the procedure to be simplified,
temperature from 175 to 215 ° C. This object is achieved in that one as 2. The method according to claim 1, characterized in sulphidation agent sulfur or phosphorus sulphide indicates that the reaction with sulfur is used and the reaction with tetrahydrofuran fei as a sulfiding agent in the presence of 15 with the sulfiding agent at a temperature red phosphorus, taken in a ratio of 175 to 215 ° C. from 0.5 to 1 g atom per 1 mole of tetrahydrofuran, The use of these sulfidating agents in the performs. method according to the invention, namely by Schwe- 3. The method according to claim 2, characterized in that fei and phosphorus sulfides, makes it possible to characterize the work that the reaction with sulfuric conditions can be significantly improved (the said fei as sulfidating agents in the presence of reagents are non-toxic and explosion-proof) and red phosphorus between 180 and 200 ⁰ C by carrying out the reaction under milder conditions (between 175 and 215 ⁰ C). When using the sulphidating agents mentioned, one can 25 carry out the process in steel devices without