CS212937B1 - Cyclohexyldiphenylchlorsilan and method of preparation of the same - Google Patents

Description

The present invention relates to a non-described chemical compound of cyclohexyldiphenylchlorosilane of the general formula (C8H4XCgH3) ₂ SiCl and a process for its preparation.

Compounds of the formula R ^ SiX ^ rgr wherein R p ^R g ^R 3 ^ou 3® ^or 4 substituents g ^anicka aliphatic and aromatic, and X is an activated inorganic easily exchangeable substituent such as halogen, hydroxy or hydrogen, more recently gained considerable importance as intermediate the synthesis of organosilicon chromic esters, which serve as extremely active catalyst components in the low pressure polymerization of .alpha.-olefins, particularly ethylene.

In addition to perfenylated chromic acid silyl esters, alkyl diphenylsilyl esters have recently become preferred. One of these is chromium acid 1 bia (cyclohexyldiphenylailyl) ester, the synthesis of which requires a suitable cyclohexyldiphenylellyl-containing compound as a starting material. One of the most desirable compounds has been the hitherto unwritten compound cyclohexyldiphenylohlorellan.

The object of the present invention is an unwritten compound of cyclohexyldiphenylchlorosllan {CgH-QHCgHgJgSiCl of structural formula

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The invention furthermore relates to the synthesis of cyclohexyldiphenylchlorosilane by the conversion of diphenyldichlorosilane with cyclohexyllithium in an organic solvent medium, preferably a hydrocarbon, according to the equation (C ₆ H ₅ ) ₂ SiCl ₂ + C ₆ H ₁ = (C ₆ H ₅ ) ₂ .

The reaction can be advantageously carried out in an environment of C8-C8 aliphatic saturated hydrocarbons, in particular n-pentane, where cyclohexyllithium can be prepared in a yield of about 60% of the theory of lithium sand and cyclohexyl chloride. Since cyclohexyllithium is poorly soluble in the cited solvents, it is converted into solution by the addition of diethyl ether for the purpose of this conversion. However, against increased decomposition by diethyl ether, the active agent must be protected by cooling to -20 ° C and maintained at low temperatures by external cooling during addition to the (C ₈ H ₂ ) ₂ SiCl ₂ solution. The conversion takes place under an inert gas at atmospheric pressure at temperatures of 35 to 50 ° C, preferably at the boiling point of the solvent used. The product is isolated after filtration of the lithium chloride by distilling off the solvent and vacuum fractional distillation and rectifying the residue. The yield of cyclohexaldiphenylchlorosil was 75% of theory.

The synthesis of the preparation is demonstrated by the following example.

Example

A solution of 118 g (1 mol) of cyclohexyl chloride in 200 ml of n-pentane is added in small portions under inert gas to a suspension of 17.5 g (2.5 mol) of lithium sand in 500 ml of dry n-pentane over 2 hours. During the dosing period, the mixture is kept at a gentle boiling point by the reaction heat. After mixing the two components, the reaction mixture is stirred for a further 1 hour and heated to gentle reflux, then cooled to -20 ° C and the resulting cyclohexyllithium is dissolved by adding 200 ml of dry diethyl ether. A solution of cyclohexyllithium containing 0.58 moles of the active ingredient was filtered from the solids into a cooled separator and added to a solution of 111 ml of diphenyldichlorosilane (0.52 mol) in 300 ml of n-pentane over 1 hour. The reaction was kept at a gentle boiling point by the heat of reaction and was warmed slightly for an additional hour after the addition. After cooling, the reaction mixture was filtered and the precipitated lithium chloride was washed with n-pentane. The combined n-pentane solutions were freed from solvent and oily by distillation. The residue is fractionally distilled under vacuum. The bulk passes at a pressure of 1.1 kPa at a temperature.

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Mp 200-203 ° C. Yield: 121 g of a colorless oil

76.5% of theory.

The same preparation was obtained in 63% yield by reaction under otherwise identical conditions in n-hexane at 45 ° C.

Product features and identification:

The product is a colorless, oily liquid that is absolutely stable in the dry. In the humid air, it smells of hydrogen chloride released by hydrolysis.

Boiling point: 200 to 203 ° C at 1.1 kPa

158-160 ° C at 0.45 kPa.

Refractive index: nt = 1.5780.

Specific gravity: 1099.3 kgm ³ (at 20.5 ° C>.

Table I

Elemental analysis results for C 18 H 18 SiCl 2

Content element (%) C H Si Cl calculated . 71.86 7.03 9.33 11.78 found 72.01 7.42 9.28 11.30 -

Infrared spectrum

The wave numbers and assignment of absorption bands are shown in Table II. The infrared spectrum of cyclohexyldiphenylchlorosilane was obtained on a Specord IR-75 in the range of 400-4000 cm @ -1 in a KBr cuvette of 0.02 mm. Interpretation of the bands was performed on the basis of vibration analysis and by comparison and spectra of similar compounds, in particular triphenylchlororeilane, triphenylsllanol, cyclohexane and cyclohexanol. In the spectrum, the presence of phenyl groups, cyclohexyl groups and vibrations of Si-C, respectively, can be clearly identified. Si-Cl.

AND

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Table II

Infrared spectrum of cyclohexyldiphenylchlorosilane

abs. band (cnT ^) assignment abs. Fri (cm ^- · * ·) assignment 422 m (C-C) Ph 1476 m Ό (G-C) Ph 492 vs X-senz.Ph · 1582 m in> (C-C) Ph 520 ve X-senz.Ph 1762 vw 546 vs >> (Si-Cl) 1811 w comb. 616 w (CCC) Ph 1877 w Q harm. 695 vs ring breathing Ph 1950 w N - (C-H) - 707 vs X-senz.Ph 2844 vs 721 with (Sl-C) Cy 2829 - V (C-H) Cy 736 vs J - (C-H) Fh 2920 ve. 744 w (G-H) Ph 2998 * m 811 m In (C-C) Cy 3010 m 840 m (C-H) Ph 3022 m (C-H) Ph 884 m p (C-C) Cy 3048 with 905 m (C-H) H 1 3068 8 992 with ^ (C-H3Eb 3085 ^W. 1022 m Mp (C-H) Ph 1031 m (C-H) Ph Hi - phenyl 1068 m (1 (C-H)) Ph Cy - cyclohexyl 1113 vs X-senz.Ph X-sens. - Substance-sensitive steam. tuci 1165 m (C-H) Hi 1180 m A > (C-H) Ih Strip intensities 1257 m (C-H) Ph VB - very strong 1296 w Ph (C-H) Ph s - strong 1319 w A (C-H) lh m - medium 1369 w 1 (CH ₂ ) Cy w - weak 1421 vs -iKC-C) Ph vw - very weak 1440 vs 1 (CH ₂ ) Cy sh - fold

and ²⁹ Si (¼} NMR spectrum of pli} NMR spectra were measured at 25.00 MHz, ²⁹ Si (¼} NMR spectrum at 19.74 MHz, using a 25% solution of the substance in deuteriochloroform.

212,937 tetramate with thyleilane as the internal standard (»0.0, < ²⁹ sí > tms &gt; 0). The measurements were performed at 25 ° C.

Chemical shift values are expressed in ppm.

(¼} NMR spectrum:

Acp - ^ 132.7 _(C5) «26.5 i _(C2) = 134.6 <f (C) or _(C?)« 27.6 <I (c ₃₎ β 127.9 <T ( _C?) or (C) = 26.6 <f (C ₄₎ = 130.2 <f (C ₈₎ = 26.5

² _and 9 g £ NMR spectra unambiguously confirm the identity and the structure of the compound as well as a high degree of purity of the preparation.

Claims (3)

First Cyklohexyldifenylchlorsilan (CGH ^) (CGH _{5) 2} SiCl structural formula 2. A process for the preparation of cyclohexyldiphenylchlorosilane according to claim 1, characterized in that the diphenyldichlorosilane is reacted with [beta] -cyclohexyl lithium in an environment of organic solvents, preferably saturated hydrocarbons. 3. Process according to claim 2, characterized in that aliphatic saturated hydrocarbons or C8, preferably n-pentane, are used as solvents.