CS212938B1 - Cyclohexyldiphenylsilanol and method of making the same - Google Patents

Description

Compounds of formula R 1 -R 8 R 8 R 8 SiX, where R 8, R 8 and R 8 are aromatic, aliphatic or alicyclic organic substituents and X is an easily interchangeable inorganic substituent such as halogen atom, hydroxyl group and the like have recently gained considerable importance as chromic acids, which are used as essential constituents of highly active systems to catalyze low-pressure polymerization of o-olefins, especially ethylene. In addition to the perfenylated chromium esters (R 1 -figs and R 3 -cgH 2), analogous esters with a single phenyl substituent replaced by an alkyl group have recently started to be used. One of these is the chromic acid bis (cyclohexyldiphenylsilyl) ester, the synthesis of which requires a suitable cyclohexyldiphenylsilyl-containing compound as a starting component. The hitherto unwritten compound cyclohexyldiphenylsilanol appears to be the most preferred.

The present invention provides a compound of cyclohexyldiphenylsilanol (C 8 H 9 X C 9 H 4) g SiOH Structural Formula

212 S38

The invention furthermore relates to the synthesis of cyclohexyldiphenylsilanol by the hydrolysis of cyclohexyldlphenyl halosilane of the structural formula

O

wherein X is chlorine, bromine or iodine by the action of aqueous sodium or potassium bicarbonate solutions in a heterogeneous solvent system consisting of an organic solvent and water. As organic solvents can be used ethers, aromatic hydrocarbons or halogenderivétů hydrocarbons, preferably diethyl ether, benzene or carbon tetrachloride, reaction proceeds according to the formula ^(C 6 H ₁₎ (C ₆ ^H 5) ₂ + HCO Six "-> ₍₆ c h _{i, l} ) (c ₆ h ₅ ) ₂ sulfur + X + co ₂

The hydrolysis is carried out at room temperature with a slight excess of the alkaline reactant and is completed by heating to the boiling point of the more volatile solvent system for one hour. The isolation is carried out by separating the solvent layers, drying the organic layer and crystallizing from a concentrated solution by adding a saturated aliphatic hydrocarbon to C8, preferably hexane. The yield exceeds 85% of theory.

The synthesis of the preparation is demonstrated by the following examples:

Example 1

To a mixture of 100 ml of diethyl ether and a solution of potassium bicarbonate (24 g, 0.24 mol) in water (200 ml) was added, with stirring, a solution of cyclohexyldiophenylohloraline (52.4 g, 0.174 mol) in diethyl ether (150 ml) over 1 hour. The mixture is then heated to the boiling point of the organic solvent with stirring for an additional hour. After cooling, the layers were separated, the ether was washed four times with 50 ml of water each time and dried over anhydrous sodium sulfate. The filtered solution is concentrated by distillation until the solid phase begins to precipitate. 50 ml of hexane are added and heated to boiling. The solution was cooled to give a coarse crystalline product which was filtered off with suction, capped with pentane and dried in vacuo. It yields 42 g of a white crystalline product, which represents 85.6% of theory.

212 938

Example 2

A solution of 41.7 g (0.139 mol) of cyclohexyldiphenylchlorosan in 100 ml of benzene was added over 1 hour to a mixture of 50 ml of benzene and a solution of 16.8 g ((0.2 b)) of sodium bicarbonate in 200 ml of water. After cooling, separation of the layers and drying of the benzene layer, two-thirds of the benzene were carefully distilled off by the addition of 100 ml of hexane, and upon cooling a crystalline product precipitated which was filtered off with suction, pentane covered and dried under vacuum.

34 g of white crystalline product are obtained (87.2% of theory).

In the yields of 85-92%, the same product was obtained by hydrolyzing the cyclobhexyldiphenylbromailane and cyclohexyldiphenyl iodosilane according to Example 1.

In 87-90% yields, the same preparation was obtained by hydrolysis in the presence of potassium or sodium bicarbonate according to Example 1 in environments where the organic component of the system was toluene, dichloromethane, chloroform and carbon tetrachloride. The prepared preparations were preferably recrystallized from chloroform-hexane or benzene-hexane (1: 1 v / v).

Product features and identification:

The product is air-stable, colorless, needle-like crystals, well soluble in benzene, diethyl ether, chloroform, dichloromethane, alcohol, acetone, practically insoluble in hydrocarbons such as pentane, hexane.

Melting point: 146-148 ° C.

Table I

Elemental analyzes for C ₂₂ gH Slo

Content% 0 H Si active H calculated 76.54 7.85 9.94 0.357 found 76.28 7.91 9.71 0.356

Infrared spectrum.

The wave numbers and assignment of absorption bands are shown in Table II. The infrared spectrum was acquired cyklohexyldifenylchlorsilsnu Fna Specord IR instrument 75j in a range from 400 to 4000 in EMT-KBr 0.26 mm cuvette (solution in CCl ^, E _2). Interpretation of the strips was performed based on vibration analysis and comparison with spectra.

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Table II

Infrared spectrum of cyclohexyldiphenylailanol

aba. vapor (cm ¹ ) assignment aba. vapor (cm ^-1 ) assignment 420 w - (C-C) Fh 1760 • vw comb. 495 va X-sanz.Ph 1810 vw and 523 harm. V8 X — sens.rti 1870 vw (C-H) Hx 612 vw <% (CCC) Ph 1952 vw 695 va ring breathing Ph 2845 va 706 sh X-senz.Ph 2895 sh P (C-H) Cy 722 ve Γ (Si-C) Cy 2920 ve, 735 ve - (C-H) Ph 2997 m 815 vs-b V (Si-0) 3009 m 841 8 3022 m y (C-H) R 1 883 m In (C-C) Cy 3048 8 903 in (C-H) Ph 3068 WITH 991 m (C-H) Ph 3085 ah and 1026 w ZS (C-H) Ph 3425 m-b (OH) asoc. : 1033 w (C-H) Ri 3682 and V (OH) 1068 w h 1115 ve X-senz.Ph Ph - phenyl 1166 w A (C-H) Ph Cy - cyclohexyl i: 1183 m S (C-H) Ph X-aenz. - sensitive on aububitution 1255 w (S (C-H)) Ph 1295 vw (C-H) Ph Strip intensities 1317 vw Mp (C-H) Ph va - very strong 1368 vw 1 (CH ₂ ) Cy s - strong 1418 ve V (C-C) Fh b - wide 1438 with ^ (CH 3 JCy m - medium 1475 w V (C-C) Ih w - weak 1581 w V (C-C) Ph vw - very Weak ah - fold

analogous compounds, especially triphenylsilanol, cyclohexane and cyclohexanol. The spectrum 'can be unambiguously Identified by the presence of groups of phenyl, cyclohexyl and Si-O-H' ·

212 938 ¹³ C (1 ') and ²⁹ Si 1 H NMR spectra.

^{The 13} C (¼) NMR spectrum was measured at 25.00 MHz, the ²⁹ Si @ 1 H NMR spectrum at 19.74 MHz, using a 25% solution of the substance in deuteriochloroform with tetramethylsilane as the internal standard. ¹³ Οι ^^ «= O; Λ ^ .Ο /

The measurements were performed at 25 ° C. Chemical shift values are expressed in ppm.

¹³ C PhJ NMR Spectrum:

£ (0 ^ 8 135.2 <i (c ₅ ) = 25.4 <T (C ₂ ) = 134.5 ^ (Cg) or (C ^) = 27.8 Γ (0 ₃ ) «127.6 ťf (C ^) or (Cg) = 26.7 ? f (C ₄ ) = 129.5 í (c ₈ ) = 26.7

^{The 13} C and ²⁹ Si NMR spectra unequivocally demonstrate the identity and predicted structure of the compound as well as the high degree of purity of the preparation.

Claims (3)

Object of the invention 2. A process for the preparation of cyclohexyldiphenylsilanol according to claim 1, wherein the cyclohexyldiphenylsilane is of the structural formula: O wherein X is chlorine, bromine or iodine, hydrolyzes with an aqueous solution of sodium or potassium bicarbonate in a heterogeneous solvent system consisting of an organic solvent and water. 3. Process according to claim 2, characterized in that ethers, aromatic hydrocarbons or halogenated derivatives of aliphatic hydrocarbons, preferably diethyl ether, benzene or carbon tetrachloride, are used as organic solvents.