DD152547A1 - METHOD FOR THE CATALYTIC SYNTHESIS OF SULFUR DIIMIDES - Google Patents

Abstract

The invention relates to a process for the catalytic synthesis of sulfur diimides with the aid of metal complexes and sigma organometallic compounds of the transition group metals. According to the invention, all complex compounds and sigma organo compounds of the subgroups are suitable which have a high electron density at the central atom sufficient to cleave off sulfur dioxide and which can react with N-sulfinylamines either by addition or substitution of labile ligands. Examples of catalytically active compounds include the 2,2'-dipyridyl-cyclooctadiene (1.5) nickel (0) and the 2,2'-dipyridyl-diethyl-nickel (II), which convert N-sulfinylamines into sulfur diimides when heated to 110 ° C ,

Description

Title of the invention

Process for the catalytic synthesis of sulfur diimides

Field of application of the invention

The invention relates to a process for the synthesis of sulfur diimides from H-sulfinyl compounds,

Characteristic of the known technical solutions

The stoichiometric synthesis of sulfur diimides from N-sulfinyl compounds is known. The methods known for this purpose each require stoichiometric amounts of special auxiliary bases which are expensive, must be prepared in part by complex processes and, after the reaction, are obtained as waste products of complicated composition which can no longer be used.

As bases, e.g. used: sodium hydride, potassium t-butylate, sodium, lithium alcoholate, lithium phenyl and other similar bases to be prepared in accordance with

2 E-NSO + Base: * E-NSN-E + Base (SO ₂ )

derivatives

in polar or nonpolar solvents at temperatures up to 100 ⁰ C Schwefeldiimide of N-sulfinyl compounds (HH Hörhold, KD Elossmann supply & J. BeckmtfJP 64-705.

H. H. Hörhold u. Chem., 211 »621 (1969), G. Leandri u. P. Rebora Gazz. chim. Italian £ 8, 50 (1957).

It is further known that sulfur diimides can be obtained by a stoichiometric method from sulfur tetrafluoride and arylamines or aryl amino sulfide difluoride and aryl amines, "(R. Cramer J. Org. Chem., 26, 3476 (1961) the transamidation of Disulfonylschwefeldiimiden in the course of a stoichiometric reaction with N-SuIfinylaminen (USSR Patent 154264), In both cases, the reactions are not catalytic, while the production of sulfur tetrafluoride requires a considerable preparative effort, which must be assumed by aggressive elemental fluorine v / earth "

Object of the invention-object of the present invention is to develop a relatively inexpensive, generally applicable synthesis of sulfur diimides.

Explanation of the essence of the invention

The object of the invention is to develop a catalytic process for the synthesis of sulfur diimides, in which the elimination of sulfur dioxide from N-sulfinylamines takes place with the aid of metal complexes or G " organoazo compounds of the transition metal metals."

It has been found that this goal is met when metal complex compounds or '6'-organo compounds of the transition group metals are used as catalysts, which have a high effective electron density at the central

atom, and containing either labile ligands that can be exchanged for N-sulfinylamines, whereby the high electron density is retained at the central atom, or can add the ϊΤ-sulfinylamines.

Catalysts effective according to the invention are: Metal complexes of the ITebengruppen of the periodic table with formal oxidation states -3 to +2 of the general composition:

[ML _a I _b L 'cL' ^^ m ^ o ^ a ^ c ^ d ¹ Ί [

Organometallic compounds of the lifting group metals of the general composition:

where M, M *, M * * can be adrenal metals of the formal oxidation states -3 to +2, and are preferably metals of the eighth group,

A is an alkali metal of the formal oxidation state + 1, which is optionally still solvated, L, L ¹ , L ¹ ', L ^{111 are} one or mehrzählige ligands that set necessary for the elimination of sulfur dioxide high electron density at the central atom, and in part can be exchanged for N-sulfinylamines, wherein the high electron density at the central atom, which is necessary for the elimination of sulfur dioxide, is maintained.

Suitable ligands are, preferably: 2.2 ^f dipyridyl, substituted bipyridyl, 1,10-phenanthroline, 1,4-diazabutadienes, tetraalkylethylenediamines, substituted amines and chelating monodentate amines, mono- or polydentate ligand, derivatives of pyridine, or a multidentate olefins and alkynes "

& ί

E may be alkyl or aryl radicals, as well as cyclopentadienyl radicals, it being possible for identical or different radicals R to be bonded in the complex.

a, b, c, d, r, x, y, ζ can take serte between 0 and 6, with the proviso that a + b. + c + d at most corresponds to the maximum coordination number of the given central metal * The reaction can be either without solvent or in conventional inert organic solvents, such as benzene, ioluen, 2ylen, dioxane γ / ground. The temperatures are adjustable between 20 ⁰ C and 180 ⁰ C, the pressure can be up to 40 atm, but it can also be operated at atmospheric pressure or in a vacuum. The metal complexes can be used either alone or in combination with excess ligands. It is possible to generate the catalysts in situ and to use them without prior isolation. The reaction can proceed in a homogeneous phase or as a heterogeneous reaction.

Preferred catalytically active metal complex compounds are, for example:

(dipy: 2.2'-dipyridyl, Ri alkyl, aryl)

-CpCo (COD) '(Cp: cyclopentadienyl- ¹ ) dipylii (COD) (COD: cyclooctadiene-1 ^)

These compounds have a sufficiently high electron density at the central atom and react sufficiently fast with N-sulfinylamines.

embodiments

Example 1 ,

0.7 g of 2.2 ^l -dipyridylcyclooctadiene (i.5) nickel (0) are heated to boiling with 30 g of H-sulfinylaniline under argon. The solution turns red and a brown-red median falls.

The mixture is heated for 1 hour at 11O ⁰ O and fractionally distilled. Initially, unreacted IT-sulfinyl aniline passes over, then in vacuo at 1 torr of diphenyl-sulfur-1-diimide ·

Yield: 12 g.

Example 2:

0.7 g ^. ^ '- Dipyridyl-diethyl-nickeKlI) are heated to II5 ⁰ C with ^ O g N-sulfinylaniline in 25 ml of toluene. The work-up is carried out as described above,

Yield: 1 g of diphenyl sulfur dioxide.

Example J> i

0.7 g of 2.4-dimethyl-2.2-cyclooctadiene ¹ dipyridyl (i.5) nickel (O) are heated with 15 g of H-SuIfinyl-p-toluidine under argon at ⁰ C II5. The work-up is carried out as described in Example 1.

Yield: 6 g of sulfur diimide.

Claims (5)

- D - Srfindungsanspruch 1. A process for the catalytic synthesis of sulfur diimides from N-sulfinylamines characterized in that are used as catalysts metal complexes or 6 "organometallic the Febengruppen, which have a sufficient for the catalytic sulfur dioxide cleavage electron density at the central atom and with N-sulfinylamines either under addition or by exchanging labile bound ligands. 2. The method according to item 1, characterized in that as metal complexes or € T-organo compounds compounds · of the type [MLaLJLJ-LJ-] ₍ [M ^ ₀ '«L ₃ LJLJ« LJ ··] \ [^ L ₃ LJLJ can be used, ¥ ^ obei M, M ¹ , M ¹¹ subgroup metals of the formal oxidation states can be -J to +2, A is an alkali metal of the foroial oxidation stage + 1, L, L ¹ , L ¹¹ , L ¹ '* on or are multivalent ligands, which set a sufficiently high titanium ion density at the central atom for the catalytic sulfur dioxide cleavage, a, b, c, d, q, x, y, z, m, η, o assume values between 0 and 6, E alkyl, aryl or cyclopentadienyl radicals. 3. The method according to item 1 and 2, characterized in that the catalysts used either alone or in combination with • excess ligand L v / earth » 4. The method according to item 1, characterized in that the metal complexes or S- organo compounds either generated in situ and used without prior isolation or after previous isolation. 5. The method according to item 1 and 4, characterized in that it is carried out without solvent or in conventional inert organic solu tion In at! Temperatures between 20 ⁰ C and 180 ⁰ C and pressures between 0.1 and 40 atm are used »