DD289275A5 - PROCESS FOR PRODUCING NEW TITANOCENCHELATE COMPOUNDS - Google Patents

Abstract

The invention relates to a process for the preparation of novel titanocene chelate compounds of general formula I in which X is oxygen or sulfur and R is phenyl, biphenyl, naphthyl, binaphthyl, optionally mono- or polysubstituted, alkyl. The Titanocenchelatkomplexe can be important as catalysts, stabilizers and pharmaceuticals. The aim of the invention is to represent new Titanocenchelatverbindungen in a simple manner. According to the invention, titanocene chelate compounds of general formula I are obtained by reacting dicyclopentadienyltitanium dimethyl with bifunctional, organic dihydroxy compounds or their sulfur analogs. Formula I {method; manufacture; catalysts; pharmaceuticals; stabilizers; Dicyclopentadienyltitan; chelates; titanocene; complex; aprotic solvents; dihydroxybenzene; dihydroxybiphenyl; Dihydroxybinaphthyl}

Description

Λ R

Fields of application of the invention

The invention relates to a process for the preparation of Titanocenchelatverbindungen the general formula I, in which R is phenyl, biphenyl, naphthyl, binaphthyl, optionally mono- or Mehrfachsubstituiert such. B. 2-mercapto-4-methoxyphenyl, Bismethylenmalonsäurediethylester, alkyl and X is oxygen and / or sulfur. These compounds may be of importance as intermediates, catalysts, drugs or stabilizers of synthetic macromolecular substances.

Character.'stik the known prior art

Titanocene chelates are obtained by known methods by reacting dicyclopentadienyl titanium dichloride with the bifunctional ligands in the presence of sodium amide in aprotic solvents (K. ANDRÄ, Z. Chem., 7 (1967), 318; K. ANDRÄ, J. Organo-Met 11 [1968], 567; H. KÖPF, TH KLAPÖTKE, Monatsh. Chem. 117 [1986], 1003) .To-titanocene chelates with Ρ, Ρ'-donors are obtained according to known industrial processes by dissolving titanocene dichloride with the dilithium salt of Titanocene chelates with S and N donors are accessible analogously by the reaction of titanocene dichloride with the dilithium salts of o-aminothiophenol, o-phenylenediamine and 4-methyldithiocene catechol (H KÖPF, TH KLAPÖTKE Chem. Ber. 119, [1986] 1986; H. KÖPF, TH KLAPÖTKE, Z. Naturforsch. 41b [1986], 667).

Disadvantage of this method is that highly active proton acceptors or the lithium salts of the ligands - which are economically expensive to produce them - are used, the purification of the reaction products is complicated and titanocene chelates of the general formula I are therefore not yet accessible.

Object of the invention

ZJqI the invention is to develop a method that makes accessible in a simple manner, titanocene according to an economically favorable process in very good yield from technically available starting materials new Titanocenchelatverbindungen.

Presentation of the essence of the invention

The invention has for its object to produce titanocene according to a simple process in pure form and very good yields.

In accordance with the invention, titanocene chelate compounds of the general formula I

( ^c sH ₅ ) Ti /

X 2 "\

in which X is oxygen and / or sulfur, R is phenyl, biphenyl, naphthyl, binaphthyl, optionally mono- or polysubstituted, such as. B. 2-mercapto-4-methoxyphenyl, Bismethylenmalonsäurediethylester, alkyl, prepared by reacting Dicyclopentadienyltitan dimethyl in an aprotic solvent, such as. As benzene, toluene, xylene with

bifunctional organic compounds of general formula II, such as. B. 1.2-dihydroxybenzene, Ο, Ο'-Dipher.ol, α, α'-binaphthol or their sulfur analogs and in which X and R have the same meaning as in formula I, at temperatures between 290K and 415K, preferably at 360K ,

The method according to the invention is illustrated by Equation 1. By the process according to the invention, for example, the compounds described in the exemplary embodiments can be produced in finely crystalline form and in good yields.

embodiments

example 1

Dicyclopentadienyl ^ '- dlphenylendloxytltan IV. 2.0g (9.6 mmol) Dicyclopentadienyltitandimethyl be dissolved in 60ml of dry benzene and under argon with 1.78g (9.6 mmol) of 2,2'-dihydroxydiphenyl, dissolved in 40ml of dry benzene, added portionwise. In the process, methane escapes and the reaction mixture heats up. After complete addition of the ligand, stirring is continued for a further 2 hours under reflux. The solvent is then distilled off in vacuo and the residue is mixed with 50 ml of η-hexane. After filtration, the reaction product is washed with a mixture of 20 ml of η-hexane and 10 ml of ether and dried in vacuo.

Mp .: 197-203 ° C Yield 98%

Mol-weight: 362.28

Analysis for (C ₆ H ₆ I ₂ Ti (O ₂ C ₁₂ He)

Calculated: C 72.94% H 5.00% Ti 13.22%

Found: C 73.28% H 5.34% Ti 13.37%

Example 2

DlcyclopentadlenylMDlthloethylenetentane IV. 3.0 g (14.4 mmol) of dicyclohexadienyltitandi-butyl are dissolved in 50 ml of dry benzene and added dropwise under argon with a mixture of 1.36 g (14.4 mmol) of 1,2-dithioglycol (1, 2-ethanedithiol) in 30 ml of dry benzene. Initially, slow gas evolution is accelerated by heating to about 50 ° C during dropping. After one hour, the methane evolution is completed.

Refluxing for two hours completes the reaction. Thereafter, the solvent is distilled off in vacuo and the residue with η-hexane added urfd filtered. The finely crystalline product is washed with η-hexane and dried in vacuo.

Mp. Yield 98%

Mol weight: 270.27

Analysis for (C ₆ H ₆ I ₂ Ti (S ₂ C ₂ H ₄ )

calc .: C 53.33% H 5.22% S 23.73% Ti 17.72%

Found: C 53.84% H 5.76% S 23.25% Ti 17.96%

Equation 1:

2932? *

R + 2CH

Claims (1)

A process for the preparation of titanocene chelate compounds of general formula I ₁ in which X is oxygen or sulfur and R is phenyl, diphenyl, naphthyl, binaphthyl, optionally mono- or polysubstituted, such as. B. 2-mercapto-4-methoxyphenyl, Bismethylenmalonsäurediethylester, alkyl, characterized in that dicyclopentadienyltitanium dimethyl in an aprotic solvent such. B. benzene, toluene or xylene with bifunctional organic compounds of the general formula II in which X and R have the same meaning as in formula I, such as. B. 1.2-dihydroxybenzene, Ο, Ο'-diphenol, α, α'-binaphthol or their sulfur analogues, at temperatures between 290K and 415 K, preferably at 360K, be implemented. For this a page formulas