DE1468136A1 - Process for the preparation of benzene and toluenesulphonic acid chlorides - Google Patents

Description

g) Int. Cl .:

FEDERAL REPUBLIC OF GERMANY C07c

GERMAN

PATENT OFFICE German class: 12 o, 23/03

Offenlegungsschrift 1468136

File number: P 14 68 136.8 (K 48998) Filing date: February 19, 1963

Disclosure date: March 19, 1970

Exhibition priority: -

Union priority Date: Country:
File number:

19th February 1962

Netherlands

274975

Name: Process for the production of benzene and toluenesulphonic acid chlorides

€>

Addition to: Eliminated from: Applicant: Koninklijke Zwavelzuurfabrieken v / h Ketjen N.V., Amsterdam

Representative: Berg, Dipl.-Chem. Dr. rer. nat. W. J .; Stapf, Dipl.-Ing. O. F .; Patent Attorneys, 8000 Munich

Named inventor: de Jong, Jan Ide, Blaricum (Netherlands)

Notification according to Art. 7, Paragraph 1, Paragraph 2, No. 1 d. Ges. V. September 4, 1967 (Federal Law Gazette IS. 960): December 10, 1968

© 3.70 009812/1826 6 120

U68136

V / eh 11 298 Ν). JUNE 1969

P Ik 68 136.8
New documents

Attorney file 11 298

KOUIHKLIJKfc 2WAV ££ .ZÜUnr / iDRIEXES v / h KETJEIT U.V., liieuwendoinnorkada 1 -3, Amsterdam.

"Method for Horstollunc of Benzene * and Toluo1-sulfο cüurochlo ride. "

The present invention relates to an ancestor eur Horetallucg from Ii on zol- and To luo loulfo ohlo riden der general iorncl

-SO ₂ Cl, R '

in which R is hydrogen or a methyl group,

-

009812/1826 Neuy document? ¹ "! ( ^Art; ί

BATHROOM OWGINAL.

U68136

by reacting the corresponding sulfonic acids with Chlorosulfonic acid In the presence of an inert organic Solvent, whereby sv.ei layers form.

It is known to produce organic sulfochlorides by converting an organic sulfonic acid with chlorosulfonic acid according to the general equation

Ar S Ο, Η * Cl SO, H -— * Ar SO ₀ Cl 4 H ₀ SO. (in which Ar means an aromatic best).

With this method, there is generally an excess of Chlorosulfonic acid used to give a satisfactory yield to achieve organic sulfochloride.

The separation of the organic sulfochloride from the. Henktionogeiaisch causes difficulties. It is true that k? Mn ιπαη Distill the sulphurous chloride but pass through the Increase in temperature and the concentration of sulfuric acid resinification and charring appear during the distillation. That is why the organic one has been suggested Sulphochloride in the form of such a solution in one with the sulfuric acid (chlorosulphonic acid) arylsulphonic acid layer immiscible solvent from the reaction 3 mixture to separate and this suIfoChloridlösung in usual Way to work up.

009812/1826
BAD ORiQINAL

H68136

For example, in Journal American Chemical Society 22 (1948), Page 375, right column, last paragraph to page 376, left column first paragraph, anisole dissolved in chloroform, this solution is mixed with chlorosulfonic acid, the reaction is mixed After the reaction has ended, poured onto ice, put the bag in a cabinet and another one rortion of fresh chloroform added «The Chlorol'ormextrakt is gev / asohon three times with water, then drunk knot and the chloroform is distilled off

In Ho over on V.oyl, Lcthodcn derorganischen Chemie, Volume ZX , - (1955) »page 5691 third paragraph from the bottom, it is recommended to stir the resulting Culfoohlorld mixture into a solvent-ice mixture, or to add a solvent to the chlorosulfonic acid, whereby the saponification is occasionally prevented by the strong Siiurolöoung

Xn Organio Synthesis, Coll. Vol. I, Second Edition, Since · 86, lines 2 to 4 it is stated that in the production of Senzolsulfochlorld the aas sulfuric acid, Bonzoleulfonic acid, chlorosulfonic acid and uenzola sulfochloride existing Roaktiongeoisch on egg, with tetra-chlorocarbon mixes, separates the excess oil as quickly as possible and the water layer with a new one Portion of carbon tetrachloride sole. The combined Extracts are processed in the usual journey

; ■>

009812/1826
BATH ORIGINAL

U68136

In all of these cases there will be an excess of chlorosulfonic acid applied and the reaction mixture poured onto ice

The inventive method of heratelluncs by Üenzol- and toluenesulfonyl chloride of the general lormol

in which R is hydrogen or the methyl group, duroh Reaction of the corresponding sulfonic acids with chlorosulfonic acid in the presence of an inert, organic solvent, at low temperatures, robei itself swel Forming layers now consists in separating the organic layer from the acidic layer with water washes and worked up in the usual »ice duroh distillation.

By using the manufacturing process according to the invention high yields, based on the chlorosulfonic acid used, can be achieved, such as from the Boigons can be seen. In the examples v. There was no or almost No chlorculfonic acid applied over ChusD.

Reection v.-ird at low temperatures, preferably

■ like 20 and 40 ⁰ C carried out. It collects

t - 5 -

0 09812/1826

BAD ORIGINAi.

the resulting iSulfochlorld In the solvent phase. When the reaction is complete, the organic phase is separated from the sulfuric acid phase. Preferably, the sulfuric acid phase is extracted with a fresh solvent and the extract is added to the organic phase. Organic substances, which in addition to sulfones also contain unreacted chlorosulfonic acid, are vasified acid-free. The solvent is then distilled off, the water still present in the azeotropic mixture being removed at the same time. If necessary, further solvent is added or the solvent which has been distilled off is passed back in until all of the water is removed. The temperature is then increased in order to separate off the remaining solvent from the sulfo chloride by distillation. On this basis, if one starts from approximately equivalent amounts of chlorosulfonic acid and sulfonic acid, yields of £ 80 of theory can be achieved. or above »in relation to the corresponding suIfonotture.

The sulfo chloride obtained in this way is practically pure and contains only small amounts of copper from which it can be separated off by rapid distillation. After that _; the Jjulfoohlorid can be exposed to temperatures of 195 to 2UO ⁰ C without gumming or decomposition occurs.

To carry out the process according to the invention can

009812/1826
BATH ORIGINAL

U68136

a gros89 number of Löoungaiaittcln have been used. Dlece must, however, meet the following requirements: You Düsoon against all Iieaktionsverbindungen, so Sulfuric acid, chlorosulphonic acid, sulphonic acid and sulphochloride be inert and cute solvent for the emerging Be sulfoch] orid.

Suitable solvents are generally cycloparaffins like cyolohexone, also halogenated aliphatic hydrocarbons such as chloroform, carbon tetrachloride, 1,2-dichloroethane, iCetraohlorethane, rentachlorofluoroethane.

When toluene is sulfonated with sulfuric acid, a mixture of predominantly o- and p-toluenesulfonic acid and et * ao m-toluenesulfonic acid is obtained. By fractional crystallization can be separated and the Iucmoren danaoh in the corresponding iJulfochloride be converted · Va *, however, the mixture can ioomorcn toluenesulfonic erfindungognmässen the process be converted directly into a mixture of the isomeric Toluoloulfochloride also NaOH. These oils can be separated from the sulfons by distillation and then separated by fractional distillation. This last-mentioned method is preferred by KU because the isomeric toluenesulfochlorides can be separated more easily by fractional distillation than the isomeric toluenesulfonyl acids by fractional crystallization.

009812/1826 - 7 -

BATH ORIGINAL

U68136

For a further explanation, <K »s reasoning 3geaüeeen procedure Now some games follow, which take advantage of the Invention to bring printing.

o-Toluenesulfonyl chloride from o-ioluenesulfonic acid t

172 g o-Toluolaulfoneäure "1UOO g of carbon tetrachloride and mixed 13Ue Chloraulfoneüurt · i) a3 mixture is stirred for one hour at 40 ⁰ C. The carbon tetrachloride layer is separated from the sulfuric acid layer , after which this layer is stirred with 40 g of fresh carbon tetrachloride for 15 minutes at 40 ° C. The combined Totrachlorkohlenetoffsohiohten were washed drelnal Bit 2½ cnr Tassor and the carbon tetrachloride is distilled off under reduced pressure · Yield of o-ttilfochlorld ι 170 g. Yield 89 * of theory absorbed on toluenesulphonic acid and 81 pounds of th, absorbed on chlorosulphonic acid.

Uelsplel 2

p-Toluoleulfoohlorld from p-t Toluolsulfonsttur · 172 g F-toluenesulfonic acid, 1C00 g carbon tetrachloride and ■■ · 130 g of chlorosulfonic acid are vermisoht and wild thereafter stirred ileaktionseeialsch a utunde at 40 C. You Tetrmchlorkohlcnuto ff layer is then voa the

009812/1876

BATH ORIGINAL

" ⁸ "'H68136

Sulfuric acid is separated off, which is extracted for 15 minutes at 5 ° C. with a further 400 g of carbon tetrachloride. Finally, the combined carbon tetrachloride layers are washed three times with 200 cm * of water and the carbon tetrachloride is distilled off under reduced pressure. Yield of p-toluenesulfoohlorldi 174 g. Yield t S2f d.Th. based on toluene ■ ulfonic acid. *

Example "3

Geiaiβch of o-, m- and p-Töluoloulfochlorid from the enttpreohenden mixture dor sulfonic acids ι 172 g of a mixture of o-, m- and p-Toluolsulfonsüurea, 1000 g carbon tetrachloride and 130 g chlorosulfonic acid are mixed and the Renktlonsverbindungen is then one «hour · stirred at 4O ⁰ C for the Tetraohlorkohlenstoff- • ohicht is then separated from dor üchwefclsüureschicht which 15 minutes, stirred at ⁰ C 4U again with 1000 g of carbon tetrachloride. Finally, the combined carbon tetrachloride layers are washed three times with 200 cm of water and the carbon tetrachloride is distilled under reduced pressure. IUs are obtained 166 j of Gotaisohee from o-, m- and ρ -To luolsulf0 chlorides cn ι extensions G79 & d.Th. based on toluenesulphonic acid ittiA 79 / i d.Th

009812/1826 "■: ·, _

BAD ORfGtNAL

U68136

Belaplel 4

ToluoleulfoChlorid from toluenesulfonic ι To a mixture of 172 'g Toluolsulfonaäur "and 600 g DichlorUthan 120 are added 97 £ β strength of chlorosulfonic acid and the whole is stirred for one hour at 40 ⁰ C. The dichloroethane layer is separated off and washed with water until it is free from acid, after which the dichloroethane is distilled off under reduced pressure. Yield of toluenesulfonyl chloride t 154 .g. Aueboute Θ1ί * d.Th. say on xoluenesulfonic acid.

Example 5

Toluene sulfonic chloride aua Toluoloulfone & ure t An Oemleoh of 172 g of toluene sulfonic acid and 1000 g of tetraulfonic acid is mixed with 130 g of chlororeulfonic acid and then stirred ^{at 40 0 C for one hour.} The Tetrachloräthansohloht is dnnach separated from the sulfuric acid layer "rich old 1000 g Tetraohloräthan again 15 Uinuton long at 4O ⁰ C is stirred. Finally, the combined tetrachloride extracts are acid-freezed with water and then the xetrachloroethane is distilled off under reduced pressure. Yield of toluenesulfoohlorLd 162 g. Yield t 85 α d.Th. based on Toluoleulfonsüur · and 77 / i d.Th. bozogon on chlorosulfonic acid.

- 10 -

BATH ORIGINAL

H68136

Example 6

Denzoleulfochlorid or BenzolbuIfonsäure ι 79 g benzenesulfonic acid, 40% carbon tetrachloride and 70 g chlorosulfonic acid are mixed and ^{cerified for one hour at 40 0} C, the carbon tetrachloride layer is separated and the carbon tetrachloride is stirred again with 200 g carbon tetrachloride. The combined Totrachlorkohlenstoffsohichten be washed free of acid with FasDor, after which the abdestillicrt carbon tetrachloride, UNJ ZVAR initially at atinosfhäriochem pressure, the last parts whereas at 100 ⁰ C and 5 mm pressure are distilled off. Yield of benzenesulfo-chloride 67 g. Yield 75 ^ of theory based on benzenesulfonic acid and &J> fi d.Th. based on chlorosulfonic acid.

Toluene sulfochloride from toluenesulfonic acid t

172 g ToluolsulfoneUure been stirred for one hour at 4O ⁰ C and 117 B of chlorosulfonic acid and 800 g Cyolohoxan. The Cyclohexansohicht _y is then separated again after which the mixture is stirred Sohwefelsäureschicht 15 minutes with 200 g of cyclohexane. The combined cyclohexane are washed free of acid with water, and then the cyolohexane is distilled off under reduced pressure. / usbnutc of toluene sulfochloride ι 157 g. Yields 82.5% of that based on toluene sulfonic acid and B2.5% of that based on chloro sulfonoic acid.

009812/1826

- 11 BAD ORIGINAL

Claims (1)

-n- U68136 Claim: Process for the production of benzene and toluenesulphonic acid chlorides of the general formula In which R denotes hydrogen or the methyl group, m is obtained from reaction mixtures obtained by reacting the corresponding sulfonic acids with chlorosulfonic acid at low temperatures in the presence of diluents, whereby two layers are formed, characterized in that an inert solvent is present from the start or added in the course of the reaction, after the reaction has ended, the solvent phase is separated off from the acidic layer, washed acid-free with water and worked up in the usual way by distillation. f 009812/1826 l ~. .m MMarltnon l »rt 7IUtWjNrI