DD211118A1 - PROCESS FOR THE PREPARATION OF PER-ORGANYL THIOPOLYACETYLENE - Google Patents

Abstract

The invention relates to a process for the preparation of per-organylthio-polyacetylenes. Such compounds are important as polymeric materials and as intermediates for the synthesis of polymeric organic electron conductors and sulfur-containing polymers. The preparation is effected according to the invention in that bis-organylthio-acetylenes are polymerized in the presence of a nickel salt-phosphine complex.

Description

243503

Process for the preparation of per-organylthio-polyacetylenes Field of application of the invention

The invention relates to a method for Herateilung of per-organylthio-polyacetylenes. Such compounds are important as polymer materials, as intermediates for the synthesis of polymeric organic electron conductors and sulfur-containing polymers.

Characteristic of the known technical solutions

Per-organylthio-polyacetylenes are a previously unknown type of polymer.

Object of the invention

Zi-Pl of the invention is to develop a process for the preparation of per-organylthio-polyacetylenes from readily available external products.

-г. 2D3503 Б

Explanation of the essence of the invention

The invention has for its object to synthesize per-organylthiopolyacetylene from readily available Auagangsprodukten. According to the invention, this object is achieved by the fact that bis-organylthio-acetylenes of the formula I.

R ¹ Ρ *

j ft ² -y ¹ -S-Csc-SX ² -R ⁵ R ^{3 й}

where χ, χ is a saturated carbon and / or a tetravalent silicon atom, RR is hydrogen (only when χ or X and 7Γ carbon); Alkyl, cycloalkyl, alkenyl, cycloalkenyl · aryl, such as ζ. As phenyl or naphthyl, optionally substituted, ζ. Β. by alkyl, halogen, dialkylamino, vinyl · alkoxy, alkylthio, in the presence of a catalyst of formula II

Wherein R is alkyl, such as. B · methyl, ethyl, butyl, β-cyanoethyl, cyclohexyl · aryl, such as ζ. Phenyl, tolyl; Aralkyl, such as. в. Benzyl, p-alkylbenzyl; Heterocyclyl, such as ζ. Furyl, thienyl; A is an anion such as As chloride, bromide or rhodanide may be, wherein the catalyst can be used both as a finished complex and optionally in the form of its components, in an organic solvent such. B. tetrahydrofuran, acetonitrile or butanol in the temperature range between -30 ° C to +100 ⁰ C, preferably at 15 ⁰ C to 30 ⁰ C to per-

24,3503 5

organylthio-polyacetylenes of the formula III

R "R ² R ⁵ X ^ S

1 9 1 (^

where X, Χ, R-R have the abovementioned meaning and η can be from 3 to 30 higher.

embodiments

The perorganylthio-polyacetylenes of the formula III prepared according to the various variants are listed in Table 1. All reactions are carried out in the absence of oxygen.

Embodiment 1

To a solution or suspension of the catalyst of formula II in THF (25m mol · 1) is added an acetylene of the formula I (molar ratio catalyst / monomer of 1/5 to 1/500, preferably 1/20 to 1/80) and Stir until no more acetylene is detectable (control by Tinnschichtchromatographie). The work-up is carried out either by suction of precipitated products or by precipitation with a suitable solvent (eg., Methanol or acetone) and optionally redissolving and precipitation.

Embodiment 2

The procedure described in Example 1 using acetonitrile as solvent.

243503 5

Excursion ticket 3

The amount of chelating salt and phoaphin ligand necessary for the formation of a complex of formula II is dissolved or euapped in butanol. After completion of the complex formation, acetylene of the formula I is added (molar ratio as indicated in Reaction Example 1) and, after completion of the reaction, the same as in the precipitation 1 indicated on.

Table 1 per-organylthio-polyacetylenes of the formula III

III X R ¹ R ² R ³ R ⁴ R ⁵ R ⁶ yield variant a) σ H H H H H H % 92 1 b) σ H H H H H H 40 2 c) σ CH ^ H H сн ₃ H H 23 1 d) с CH ^ H H сн ₃ H H 75 2 e) σ Ph H H Ph H H 32 1 f) с Ph H H Ph H H 60 2 G) с H H H H H H 50 3

Catalyzer: NiBr ₂ · (Ph ₃ P) ₂ molar ratio catalyst / monomer: 1/70

η j 30

26. Ш 198Ί * Ο »ϋ У; о

Claims (2)

243503 5 Invention8ana pruch Process for the preparation of per-organylthio-polyacetylenes characterized in that bis-organylthio-acetylenes of the formula I where χ, JT is a saturated carbon and / or a four-membered silicon atom, RR is hydrogen (only if X or X ¹ and X ^{2 is} carbon). Alkyl, cycloalkyl, alkenyl, cycloalkenyl; Aryl, like ζ. As phenyl or naphthyl, optionally substituted, ζ. в. by alkyl, halogen, dialkylamino, vinyl; Alkoxy, alkylthio may be in the presence of a catalyst of formula II 7
where R is alkyl, such as. Methyl, ethyl, butyl, β-cyanoethyl, cyclohexyl; Aryl, like ζ. в. phenyl, tolyl; Aralkyl, such as ζ. в. Benzyl, p-alkylbenzyl; Heterocyclyl, such as ζ. в. Furyl, thionyl; A an .Anion like ζ. As chloride, bromide or rhodanide may be, wherein the catalyst can be used both as a finished complex and optionally in the form of its components, in an organic solvent such. B tetrahydrofuran, acetonitrile or butanol in the temperature range between -30 ⁰ C to + 100 ⁰ C, preferably at 15 ⁰ C to 30 ⁰ C to per- 26. HQY. - «243503 5 organylthio-polyacetylenes of the formula Ш 1 ? 1 6
where X, λ, R-R have the abovementioned meaning and η can be from 3 to 30 and higher. 26. HQV. 1982 * 050 506