CS229088B1 - 1-0-/3-triethoxysilylpropyl/-a 1-0-/3-diethoxymethylsilylpropyl/substituted 2,3 to 4,5-di-o-isopropylidene-d-arabitol and method of preparing same - Google Patents

Description

The invention relates to 1-O- (3-triethoxysilylpropyl) - and 1-O- (3-diethoxymethylsilylpropyl) substituted 2,3: 4,5-di-O-isopropylidene-D-arabitol and a process for its preparation.

In chromatography and many other fields, such as the immobilization of biologicals, transition metal complexes, etc., there is a need to functionalize inorganic carriers with groups containing chiral centers.

The compounds of the invention allow for such functionalization and additionally provide a carrier with a high number of organically bound hydroxyl groups.

The present invention provides 1-O- (3-triethoxysilylpropyl) - and 1-O- (3-diethoxymethylsilylpropyl) -substituted 2,3: 4,5-di-O-isopropylidene-D-arabitol of formula I

Zo (C ₂ H ₅ O) ₂ R 5 (CH ₂ ) ₃ OCH ₂ -C 1-4 -CH-CH-CH ₂ O (I) wherein R is methyl or ethoxy.

These novel compounds can be prepared, for example, by addition of triethoxysilane or diethoxymethylsilane to 1-O-alkyl-2,3: 4,5-di-O-isopropylidene-D-arabitol of formula II ch ₂ = ch-ch ₂ -o-ch ₂ -c

2 (II)

The reaction may be carried out without solvent or in an aprotic solvent, preferably at elevated temperature and in the presence of commonly known hydrosilylation catalysts. The reactant ratio is governed by the stoichiometry of the reaction, but an excess of one of the reactants may also be utilized.

The starting material of formula (II) is readily accessible by reacting an allyl halide with 2,3: 4,5-di-O-isopropylidene-D-arabitol, which can be prepared from D-arabitol and acetone in the presence of a water scavenger. The reaction can be carried out equally well with the enantiomeric derivative of L-arabitol, whereby the L-enantiomer of the compound of formula (I) is obtained. Similarly, the reaction isomeric with meso-ribitol and xylitol.

The following examples characterize the compounds of the invention without limiting or restricting it. The weights are in parts by weight.

Example 1

The reaction vessel is charged with 3,100 parts of 1-O-allyl-2,3: 4,5-di-O-isopropylidenarabitol, 490 parts of a 0.01 M solution of chloroplatinic acid in tetrahydrofuran, and then 3.250 parts of trietoxysilane and the mixture are added dropwise. The mixture was heated at 120 ° C for 24 h. Distillation gave 1-O- (3-triethoxysilylpropyl) -2,3,4,5-di-O-isopropylidenarabitol in 45% yield.

For C ₂ q ^ ₀ OqSí (mol. Weight 436.61) + calculated: 55.02% C 9.23% H Found: 55.2% C, 9.31% H.

Boiling point: 140 to 150 ° C / 13 Pa

Weight Mass Spec .: M ⁺ = 436, 421 (-CH ₃ ), 205 [- (CH 2 Si (OCH ₂ CH ₃ ) ₃ ], 1663 [-SHOCH ₈ CH ₃ ],]

Example 2

Example 1 was repeated except that diethoxymethylsilane was used instead of trietoxysilane. There was obtained 1-O- (3-diethoxymethylsilylpropyl) -2,3: 4,5-di-O-isopropylidenarabitol in a yield of 4.1%.

For C ₁₉ H ₃ gO _? Si (mol. 406.59) calculated: C 56.12, H 9.41, found C 56.31, H 9.27.

Boiling point: 135-145 ° C / 10 Pa.

Claims (2)

OBJECT OF THE INVENTION 1. 1-O- (3-triethoxysilylpropyl) - and 1-O- (3-diethoxymethylsilylpropyl) substituted 2,3: 4,5-di-O-isopropylidene-D-arabitol of formula I, > (C ₂ H ₅ O) ₂ RS (CH ₂ ) ₃ O-CH ₂ c / i-CH-CH-CH ₂ (I) wherein R is methyl or ethoxy. 2. A process according to claim 1, wherein triethoxysilane or diethoxymethylsilane is reacted with 1-O-allyl-2,3: 4,5-di-O-isopropylidenarabitol.