DD238614A1 - PROCESS FOR PREPARING POLY-ORGANIA-SLENO POLYACETYLENE - Google Patents

Abstract

The invention relates to a process for the preparation of poly-organylseleno-polyacetylenes. Such compounds have significance as polymer materials, as intermediates for the synthesis of organic electron conductors and selenhaltiger polymers. The preparation is effected according to the invention by polymerizing organylselenoacetylenes in the presence of a nickel salt-phosphine complex.

Description

wherein R ¹ and R ² are as defined above and η may be from 3 to 10 and higher.

Field of application of the invention

The invention relates to a process for the preparation of poly-organylseleno-polyacetylenes. Such compounds are important as polymeric materials, as intermediates for the synthesis of polymeric organic electron conductors and selenium-containing polymers.

Characteristic of the known technical solutions

Poly-organylseleno-polyacetylenes are a previously not described type of compound.

Object of the invention

The aim of the invention is to develop a process for the preparation of poly-org nylseleno polyacetylenes under mild reaction conditions.

Explanation of the essence of the invention

The invention has for its object to synthesize poly-organylseleno-polyacetylene under mild reaction conditions. According to the invention, this object is achieved in that organylseleno-acetylenes of the formula I.

IR ¹ -Se C = CR ²

wherein R ¹ and R ^{2 are} alkyl, such as. Methyl, ethyl, propyl, i -propyl, t-butyl; Cycloalkyl, such as. Cyclopentyl, cyclohexyl; Aralkyl, such as benzyl, phenyl-ethyl; Aryl, wiez. As phenyl, naphthyl or heterocyclyl, such as ζ. Β. Thienyl or furyl; R ^{2 may} also be hydrogen or a group such as Se-R ³ ; wherein R ^{3 has} the meaning given above for R ¹ ; wherein R ¹ and R ² or R ¹ and R ³ may be identical; wherein R ¹ and / or R ² or R ³ may be substituted by groups such as alkoxy, alkylthio, vinyl, allyl, cyano or halogen, in the presence of a catalyst of formula II

Il Ni (PR ⁴ R ⁵ R ⁶ J ₂ X ¹ X ²

wherein R ⁴ , R ⁵ and R ^{6 have} the meaning given above for R ¹ and may be identical or different groups; where both the radicals R ⁴ "" ^{6 of} a phosphine ligand and the two phosphine ligands can be connected to one another via at least one of their radicals; where z. B. the following phosphine ligands can be realized: trimethylphosphine, triethylphosphine, tris / 3-cyanoethylphosphine, tri-cyclohexylphosphine, Tribenzylphosphin, triphenylphosphine, dibutylphenylphosphine, cyclohexyl-benzylphenylphosphine, P-butyl-phospholane, 1,2-bis-diphenylphosphino-ethane; X ¹ and X ² ligands such as. For example, chloride, bromide, iodide, cyanide, rhodanide, where X ¹ and X ² may be identical; wherein the catalyst of formula II can be used both as a finished complex and in the form of its components, in an organic solvent such as. As tetrahydrofuran, acetonitrile, butanol or methylene chloride in the temperature range between -30 ° C to + 100 ° C, preferably at 15 ° C to 3O ⁰ C to poly-organylseleno-polyacetylenes of the formula III

R ¹ -Se

Λ *

R ²

wherein R and R ² are as defined above and η may be from 3 to 10 and higher.

embodiments

The polyorganylseleno-polyacetylenes of the formula IM prepared according to the different variants are listed in Table 1. All reactions are carried out in the absence of oxygen.

version 1

To a solution or suspension of the catalyst of formula II in THF (2OmMoI · Γ ¹ ) is added an acetylene of the formula I (molar ratio catalyst / monomer of V2 to ^ / 500, preferably V20 to V100) and stirred until acetylene is no longer reacted becomes.

(Control by thin layer chromatography). Solid precipitated products are filtered off with suction, otherwise the product is initially precipitated by addition of a suitable solvent (for example methanol or acetone). Purification can be accomplished by dissolution (e.g., in methylene chloride) and re-precipitation.

Variant 2

The procedure is as described in [Variant 1 using acetonitrile as solvent.

Variant 3

Dissolve or suspend in butanol necessary for the formation of a complex of formula II amounts of nickel salt NiX ¹ X ² (possibly

as a hydrate, such as. B. NiBr ₂ · 3 H ₂ O) and phosphine, adds after completion of the complex formation of an acetylene of formula I (molar ratio as indicated in variant 1) and works after completion of the reaction as described in variant 1.

Table 1 Poly-organylseleno-polyacetylenes of the Formula III Catalyst of the Formula II (R ⁴ = R ⁵ = R ⁶ = Ph; X ¹ = X ² )

yield Version 1) 2) 77 2 2) 60 1 2) 33 1 3) 24 2 4) 38 2 3) 51 2 2) 13 1

Me-Se

Me-Se

Et-Se

n-prop-Se

Bz-Se

Ph

1) polymerization at 25 ⁰ C performed

2) molar ratio of catalyst / acetylene = Vso

3) Catalyst / acetylene molar ratio = V100

4) Catalyst / acetylene molar ratio = V25

a me b me C et d n-Prop e Bz f et G me

9 ± 1

6 + 1

6 ± 1

5 + 1

6 ± 1

5 ± 1

Claims (1)

Invention claim: Process for the preparation of poly-organylseleno-polyacetylenes, characterized in that organylselenoacetylenes of the formula I IR ¹ -Se C = CR ^z wherein R ¹ and R ^{2 are} alkyl, such as. Methyl, ethyl, propyl, i -propyl, t-butyl; Cycloalkyl, such as. Cyclopentyl, cyclohexyl; Aralkyl such as benzyl, phenyl-ethyl; Aryl, wiez. Phenyl, naphthyl or heterocyclyl such as thienyl or furyl; R ^{2 may} also be hydrogen or a group such as Se-R ³ ; wherein R ^{3 has} the meaning given above for R ¹ ; wherein R ¹ and / or R ^: or R ³ may be substituted by groups such as alkoxy, alkylthio, vinyl, allyl, cyano or halogen, in the presence of a catalyst of formula II II Ni (PR ⁴ R ⁵ R ⁶ J ₂ X ¹ X ² wherein R ⁴ , R ⁵ and R ^{6 have} the meaning given above for R ¹ and may be identical or different groups; where both the radicals R ⁴ " ^{6 of} a phosphine ligand and the two phosphine ligands can be connected to one another via at least one of their radicals, where the following phosphine ligands can be realized, for example: trimethylphosphine, triethylphosphine, tris-β-cyanoethylphosphine, tricyclohexylphosphine, tribenzylphosphine, Triphenylphosphine, dibutylphenylphosphine, cyclohexylbenzylphenylphosphine, p-butylphospholane, 1,2-bis-diphenyl-phosphino-ethane; X ¹ and X ^{2 may be} ligands such as chloride, bromide, iodide, cyanide, rhodanide, where X ¹ and X ² , wherein the catalyst of formula II can be used both as a finished complex and in the form of its components, in an organic solvent such as tetrahydrofuran, acetonitrile, butanol or methylene chloride in the temperature range between -30 ⁰ C to +100 ⁰ C, preferably at 15 ° C to 30 ⁰ C to poly-organylseleno-polyacetylenes of the formula III