DD239596A1 - METHOD FOR PRODUCING SILOXYLENE-BUTENE-2-DIOL-1,4-COMPOUNDS - Google Patents

Abstract

The invention relates to the preparation of novel siloxanyl-buten-2-diol-1,4-compounds. These are both organosiloxanyl-substituted butenediols and organosiloxanes or organopolysiloxanes having one or more butenediol substituents. The compounds according to the invention can be used as surfactants, in surfactant mixtures or as intermediates in organic synthesis chemistry or in organosilicon chemistry.

Description

Field of application of the invention

The invention relates to a process for the preparation of novel siloxanyl-butene-2-diol-1,4-compounds which are understood, on the one hand, to be organosilyl-substituted butenediols and, on the other hand, to polysiloxanes having a plurality of butenediol groups, which can be used as intermediates for organic synthetic chemistry.

Characteristic of known technical solutions

A process for the preparation of silicon-containing alkenediols has not yet been described. Only methods for the preparation of silicon-containing alkenols are discussed.

According to US Pat. No. 2,821,281, silicon-containing alkenols can be prepared by Si-H additions to acetylenic bonds, preferably in the presence of hexachloroplatinic acid, with disadvantageous high reaction temperatures and long reaction times, and the course of the reaction is very dependent on the nature of the reactants and catalyst concentration. It has also been proposed (DT-OS 2529782) to react the preparation of silicon-containing alkenols by reacting an acetylenic alcohol with a siloxane in the presence of catalytic amounts of a platinum initiator for 16 hours at 70X. However, the disadvantages of this process are a very low yield (2-20%) and the risk of spontaneous exothermic reaction.

No significant advantage brings the production in which an acetylenic alcohol and the siloxane compound as a liquid mixture in the presence of a platinum catalyst and optionally under pressure, at 100 ⁰ C continuously through a heated reactor at temperatures between 150-400 ⁰ C is passed.

Another method (DE-OS 2554001) describes the preparation by reacting an acetylenic alcohol and a H-siloxane in the vapor phase by passing the starting materials in the presence of a platinum catalyst through a heated to 210-450 ° C reaction tube. However, the disadvantages are the high working temperatures leading to signs of decomposition and the fact that this method is unsuitable for large-scale production. A method of production which is very suitable for very small amounts is the process proposed in US Pat. No. 3,971,818, according to which the reaction mixture consisting of an acetylenic alcohol and a siloxane compound in a gas-liquid chromatographic column whose separation materials are covered with a layer of platinum catalyst is very high temperatures between 300 and 400 ⁰ C and residence times of 1 to 2 seconds is implemented. The reaction product is also obtained only in yields of 30-35%.

Object of the invention

It is the object of the invention, silicon-containing alkenediols by a uniform method of butin-2-diol-1.4 or in 2-position alkyl-substituted derivatives with or without reaction of silanes and H-siloxanes or H-silanes in high yields without the use of pressure and at reaction temperatures below 150 ⁰ C.

Explanation of the essence of the invention

It has surprisingly been found that new organosilyl- or organosiloxanyl- or polyorganosiloxanyl-substituted alkenediol compounds of the general formula

where:

(Si) = organosilyl, organosiloxanyl or.

Polyorganosiloxanyl-,

R = hydrogen or lower alkyl, preferably methyl,

X = hydrogen and / or trimethylsilyl

by reacting inert, substituted or unsubstituted butyne-2- (OX) ₂ -1.4 compounds under protective gas: with SiH-group-containing organosilane, organosiloxane or polyorganosiloxane compounds in the ratio of triple bond to Si-H- Groups of 1 to 1 to 1 to 3 are catalytically reacted to the organosilyl, organosiloxanyl or polyorganosiloxanyl-substituted Buten-2- (OX) ₂ -1.4 compounds at temperatures between 20 ⁰ C and 120 ⁰ C, wherein also in excess of the Si-H group-containing compound, the alkene bond is retained. The reaction can be carried out in such a way that a mixture of butin-2-diol-1,4-compound, hexamethyldisilazane, SiH group-containing organosilane, organosiloxane or polyorganosiloxane compounds and optionally trimethylchlorosilane initially between 20 ⁰ C and 60 ⁰ C and then at 60 to 120 ⁰ C to the organosilyl, organosiloxanyl or the polyorganosiloxanyl-substituted Buten ^ the drimethylsilyO-ether-i ^ is reacted.

According to the invention, addition of the SiH group-containing organosilane, organosiloxane or polyorganosiloxane compounds to the substituted or unsubstituted butyne-2- (OX) ₂ -1.4 compounds is carried out by UV radiation or in the presence of an organic peroxide or a transition metal compound. Preferably, hexachloroplatinic acid is used in amounts of 10 ⁴ to 10 ⁵ moles per mole of triple bond. The SiH group-containing organosilane, organosiloxane or organopolysiloxane compounds to be used are characterized in that they preferably have 1 to 8 SiH groups.

In addition, as organosilyl radicals are those having alkyl, alkoxy, aryl, aryloxy and / or chlorine atoms, as organosiloxanyl radical straight-chain, branched and / or cyclic siloxanyl radicals having 1 to 15 Si atoms and with alkyl Alkoxy, aryl, aryloxy groups and / or chlorine atoms and as polyorganosiloxanyl radicals such straight-chain or

Branched-chain polysiloxanyl radicals having from 5 to 250, preferably 3 to 120 silicon atoms and having alkyl, alkoxy, aryl, aryloxy groups and / or chlorine atoms to use.

As alkyl or alkoxy groups, methyl or methoxy and / or ethyl or ethyloxy and as aryl or aryloxy groups phenyl or phenyloxy radicals find application.

The silylation of the butene-2-dioM .4 compounds can be carried out with trimethylchlorosilane in the presence of a donor, such as e.g. B. triethylamine or pyridine or hexamethyldisilazane and trimethylchlorosilane and hexamethyldisilazane be carried out without auxiliary component.

If the mixture of reactants is heterogeneous or too viscous, it may be advantageous to carry out the operation in an inert organic solvent under working conditions. For this purpose, commonly used linear or cyclic ethers, aliphatic, aromatic and halogenated hydrocarbons are used. The novel organosilyl, organosiloxanyl or polyorganosiloxanyl-substituted butene-2-di (trimethylsilyl) ether-1,4 can be prepared with alkanols or alkanol-water mixtures to the organosilyl, organosiloxanyl or polyorganosiloxanyl-substituted butene-2-diols -1.4 be implemented.

The novel organosilyl, organosiloxanyl or polyorganosiloxanyl-substituted butene-2-diol-1,4-compounds which contain hydrolyzable atoms and / or groups, in particular chlorine atoms, bonded to silicon atoms can be cohydrolyzed with hydrolyzable siricium compounds, preferably with trimethylchlorosilane , The inventive method allows, due to the fact that all sub-processes take place without appreciable side reactions to produce siloxanyl-buten-2-diol-1,4-compounds in high purity, with a selective reaction without additional attachment of the SiH compound, even in excess thereof to which the double bond present in the end product occurs.

Another advantage of the method is the ability to carry out the synthesis as a one-pot reaction without the need for additional expensive purification operations.

embodiments

example 1

To 43 g (0.5 mol) of butyne-2-diol-1.4 and 147 g of pyridine are added with stirring and ice cooling 109.5 g (1 mol) of trimethylchlorosilane and then allowed to stir for 5 hours at room temperature. After filtration and washing the hydrochloride twice with 50 ml of diethyl ether is removed from the combined filtrate by distillation ether and pyridine. Finally, 88.5 g of 1,4-bis- (trimethylsiloxy) -butin-2 (I) remain

 Yield: 70% of theory

Sdp-0.1 = 55 ^° C

ng "= 1.4338 ^

¹ H-NMR: = OSiCH ₃ = 0.35 ppm

70 g (0.3 mol) of this optionally distilled compound I are heated to 95 ° C and after reaching this temperature with 80 g (0.36 mol) of heptamethyltrisiloxane containing 0.1 ml of 0.1 M hexachloroplatinic acid in isopropanol, added. The temperature rises to 120 ° C. The mixture is allowed to stir for 5 hours at this temperature and optionally after removal of any remaining starting compounds by distillation 133g of 1,4-bis (trimethylsiloxy) -2-heptamethyltrisiloxanyl-butene-2 (II). Yield: 97% of theory

Sdp-0.05 = 96-C

ng ⁰ = 1.4281

¹ H-NMR: ö _S iCH ₃ (ether) = 0.33; ösiCH ₃ (Siioxane) = 0.37 ppm

It is desilylated 100g (0.22 mol) of compound II with 40g of water by reacting the mixture at 90 to 100 ⁰ C under reflux and stirring for 6 hours. The aqueous phase is separated off, extracted with diethyl ether and the organic phase is dried together with the ether extracts. After removal of the volatiles, 57 g of 2-heptamethyltrisiloxanylbutene-2-diol-1,4 (III) are obtained.

Yield: 84% of theory Sdp-0.1 = 120-122X ng ⁰ = 1.4429

¹ H-NMR: 5siCH ₃ = o, 43 ppm

Example 2>

86 g (1 mol) of butyn-2-diol-1.4 and 108.6 g (0.67 mol) of hexamethyldisilazane are added to a flask which has been purged with inert gas, and 85 g (0.78 mol) of trimethylchlorosilane are slowly added dropwise to this mixture with stirring and ice-cooling , Stirring is then continued for 2 hours at room temperature, the ammonium chloride formed is filtered off and the precipitate is washed 2-3 times with diethyl ether. After distillative removal of the volatile constituents from the filtrate, 221 g of compound I are obtained with the physical properties given in Example 1. Yield: 95% of theory.

To 150 g (0.65 mol) of the compound I and 0.3 ml of the catalyst mentioned in Example 1 are added dropwise at a temperature of 30-40 ⁰ C with stirring and gradual heating to 12O ⁰ C 155g (0.7 mol) Heptamethyltrisiioxan. The mixture is allowed to stir at this temperature until the reaction is complete, giving 265 g of the compound II which has the properties given in Example 1

 Yield: 90% of theory.

For desilylation of this compound, the procedure is as in Example 1.

Example 3

To a mixture consisting of 85 g (1 mol) of butyne-2-dioM.4,108,6g (0.67 mol) of hexamethyldisilazane and 150 ml of η-hexane is added by slow dropwise addition with stirring and ice cooling 76g (0.7 mol) of trimethylchlorosilane. The mixture is stirred for 2 hours at room temperature, filtered from the ammonium chloride and removed by distillation excess starting materials and the solvent. There remain 190.5 g of the compound I with the properties given in Example 1. Yield: 83% of theory.

This compound is hydrosilylated according to Example 1.200 g (0.44 mol) of the addition product II are dissolved in 140 g of methanol and the solution heated to boiling under reflux. Already during the alcoholysis, the resulting trimethylmethoxysilane distilled off and removed after the reaction, the excess methanol. This leaves 119 g of 2-Heptamethyltrisiloxanyl-buten-2-diol-1.4, which is characterized according to Example 1. Yield: 88% of theory.

Example 4

10 g (116 mmol) of butyne-2-dioM .4 are reacted with 19.7 g (122 mmol) of hexamethyldisilazane with stirring at room temperature, the ammonia formed in the reaction being driven off by bubbling inert gas through the reaction mixture. A temperature increase to 36-38 ⁰ C indicates the beginning of the reaction, which is completed after 60 minutes. If appropriate, the mixture is stirred while stirring until 4O ⁰ C until the product is NH ₃ -free.

In this way, 25.7 g of the compound I with the properties given in Example 1 are obtained.

Yield: 96% of theory.

Hydrosilylated 20 g (86.8 mmol) of undistilled compound I as described in Example I with 19.3 g (86.8 mmol) of heptamethyltrisiloxane in the presence of 0.05 ml of the described catalyst. This gives 32.5 g of compound II, which is further processed without prior distillation.

Yield: 83% of theory.

To carry out the desilylation, the procedure according to Example 3, by treating 30 g (66.2 mmol) of the compound Il for 9 hours at 65-70 ⁰ C with 16 ml of methanol.

After working up by distillation remain 14.5 g of 2-heptamethylbutene-2-diol-1.4 III.

Yield: 71% of theory.

The physical properties of the compounds I, II and III are identical to those given in Example I.

Example 5

10 g (116 mmol) of butyne-2-diol-1.4 are reacted with 19.7 g (122 mmol) of hexamethyldisilazane with stirring and room temperature, the ammonia formed in the reaction being driven off by bubbling inert gas through the reaction mixture. A temperature increase to 36-38 ⁰ C indicates the beginning of the reaction, which is already completed after 60 minutes. If appropriate, the mixture is stirred while stirring until 4O ⁰ C until the product is NH ₃ -free. There remain 25 g (108.5 mmol) of 1,4-bis (trimethylsiloxy) butyn-2.

Subsequently, hydrosilylation according to Example 1 with 24.1 g (108.5 mmol) heptamethyltrisiloxane in the presence of 0.05 ml of the described catalyst.

This gives 43 g (95 mmol) of 1-bis-trimethylsiloxyl-heptamethyltrisiloxanyl-butene, which is subsequently subjected to desilylation according to Example 3 with 30.4 g (0.95 mol) of methanol. After removal of the readily volatile fractions finally remain 28g 2-Heptamethyltrisiloxanyl-buten-2-diol-1 A ₁ corresponding to an overall yield of 78%.

Examples

A mixture consisting of 10 g (43.4 mmol) of 1,4-bis (trimethylsiloxy) -butyne-21.6.5 g (43.9 mmol) of pentamethyldisiloxane and 0.05 ml of the described catalyst is heated at 115 ° C. for 60 minutes and left under further stirring Stir for 60 minutes at this temperature. There are thus obtained 14.5 g of 1,4-bis (trimethylsiloxy) -2-pentamethyldisiloxanyl-buten-2 (IV) having the following physical constants:

Yield: 88% of theory.

Sdp-1,1 = 102 ° C

ng ⁰ = 1.4310

¹ H-NMR: δ SiCH ₃ = 0.34; 0.55 ppm

7.5 g (19.8 mmol) of this compound are reacted with 6.5 g (198 mmol) of methanol over the course of 2 hours at the boiling point and simultaneous removal of the trimethylmethoxysilane formed. Subsequently, the excess methanol is distilled off and finally recovered 4.3 g of 2-Pentamenthyldisiloxanyl-buten-2-diol-1.4 (V).

Yield: 93% of theory.

Sdp-0.5 = 120 ^° C

ng ⁰ = 1.4542

¹ H NMR: δ SiCH ₃ = 0.39; 0.54 ppm

Example 7

A mixture consisting of 115 g (0.5 mol) of 1,4-bis (trimethylsiloxy) -butin-2.49 g (0.52 mol) of dimethylchlorosilane and 0.3 ml of the described catalyst is heated at 120 ° C. for 60 minutes and allowed to stand for a further 30 minutes at this temperature. If necessary, after removal of excess starting materials by distillation, 145 g of 1,4-bis (trimethylsiloxy) -2-dimethylchlorosilyl-butene-2 (VI) are obtained.

Subsequently, 100 g (0.26 mol) of this compound, mixed with 100 g (0.92 mol) of trimethylchlorosilane and 200 ml of diethyl ether, are introduced into a mixture of 300 g of ice and 200 ml of ether. The temperature should not exceed 2O ⁰ C. The mixture is then stirred for 3 more hours at room temperature, the ether layer is separated, washed with water until neutral and dried over Na ₂ SO ₄ . After working up by distillation, 2-pentamethyldisiloxanyl-buten-2-diol-1.4 (V), which has the physical properties given in Example 5, is obtained. Yield: 62% of theory.

Examples

According to Example 4 is obtained by reacting 10g of 1,4-bis (trimethylsiloxy) -butin-2 (43,4mmol) with 22.6g (43.4mmol) Pentadecamethylheptasiloxan in the presence of 0.05, ml of the catalyst described 32g 1.4-bis (trimethylsiloxy ) -2-pentadecamethylheptasiloxanyl-buten-2 (VII) having the following physical constants:

Yield: 98.5% of theory.

Sdp-5x10 ~ ³ = 152 ⁰ C

ng ⁰ = 1.4220 '

¹ H NMR: δ SiCH ₃ = 0.38; 0.44; 0.60 ppm. 20 g (26.7 mmol) of this compound according to Example 4 are subjected to methanolysis, giving 16 g of pentadecamethylheptasiloxanyl-buten-2-diol-1,4 (VIII).

Yield: 97.5% of theory.

ng ⁰ = 1.4172

¹ H NMR: δ SiCH ₃ = 0.38; 0.42; 0.56 ppm

Example 9

While stirring, 10 g (43.4 mmol) of 1,4-bis (trimethylsiloxy) -butin-2 7.8 g (49.7 mmol) of phenylmethylchlorosilane and 0.05 ml of the described catalyst are added. The temperature rises rapidly to 12O ⁰ C, if necessary to reach the reaction temperature by heating. After a few hours of reaction time, 14.2 g of 1,4-bis (trimethylsiloxy) -2-phenylmethyl-chlorosilyl-buten-2 (XI) are obtained. Yield: 81% of theory.

10 g (25.8 mmol) of this compound are cohydrolyzed with 10.5 g (96.7 mmol) of trimethylchlorosilane, by adding 50 ml of ether to this mixture and the resulting solution is added with stirring to 50 g of ice-water. The procedure according to Example 6 and removed by distillation under reduced pressure volatile products. This leaves 5 g of tetramethylphenyl-disiloxanylbutene-2-diol-1,4 (XII). Yield: 78% of theory. ¹ H-NMR: 6SiCH ₃ = 0.33 6SiC ₆ H ₅ = 7.25

Example 10

According to Example 1, 23 g (0.1 mol) of 1,4-bis (trimethylsiloxy) -butin-2 are hydrosilated with 50.5 g (0.1 mol) of an Si-H group-containing methylpolysiloxane having an Si-H content of 0 , 2%, in the presence of 0.1 ml of the described catalyst solution. This gives 73 g of the corresponding 1,4-bis (trimethylsiloxy) -2-polysiloxanyl-butene-2 (XIII).

20 g of this compound are treated according to Example 4 with 22 g of methanol. Finally, 14.5 g of the relevant 2-polyorgano (methyl) siloxanyl-buten-2-diol-1.4 (XIV) are obtained.

Yield: 90.5% of theory.

¹ H NMR: SiCH ₃ = 0.30-0.38 Hydrolylation of butyn-2-diol-1.4

Example 11

116 g (1.35 mol) of butyn-2-diol-1.4 are added under stirring and N ₂ atmosphere with 300 g (1.35 mol) heptamethyltrisiloxane and 0.7 ml of the described catalyst solution and this mixture is at a temperature between 120 and 13O ⁰ C 4 hours tang around. After working up by distillation, 255 g of 2-Heptamethyltrisi! Oxanyl-buten-2-diol-1.4 with a GC purity of 40-65%. Yield: 62% Sdp-0.4: 135-138 ° C ¹ H-NMR: δ SiCH ₃ = 0.40 ppm ng ⁰ : 1.4372

Claims (12)

Invention claim: 1. A process for the preparation of novel organosilyl- or organosiloxanyl-substituted or polyorganosiloxanyl-substituted alkenediol compounds of the general formula (Si) -C -OB ₂ -OJC
HC-CR ₂ -OX where: (Si) = organosilyl, organosiloxanyl or. Polyorganosiloxanyl-,
R = hydrogen or lower alkyl, preferably Methyl-, X = hydrogen and / or trimethylsilyl characterized in that substituted or unsubstituted butyne-2- (OX) ₂ -1.4 compounds under protective gas with SiH group-containing organosilane, organosiloxane or polyorganosiloxane compounds in the ratio 3-fold bond to SiH groups of 1 to 1 to 1 to 3 catalytically to the organosilyl, organosiloxanyl or polyorganosiloxanyl-substituted butene-2- (0X) _r 1 4 compounds at temperatures between 20 ⁰ C and 120 ⁰ C are reacted. 2. The method according to item 1, characterized in that a mixture of butin-2-diol-1,4-compound, hexamethyldisilazane, SiH-containing organosilane, organosiloxane or polyorganosiloxane compounds and optionally trimethylchlorosilane initially 20 ° C and 60 ⁰ C and then at 6O ⁰ C to 120 ⁰ C to the organolyl, organosiloxanyl or the polyorganosiloxanyl-substituted butene-2-di (trimethylsilyl) ethers-1.4 are reacted. 3. The method according to items 1 and 2, characterized in that the addition of SiH-containing organosilane, organosiloxane or polyorganosiloxane compounds to the substituted or unsubstituted butyne-2- (OX) ₂ -1.4 compounds by UV Radiation or in the presence of an organic peroxide or a transition metal compound takes place. 4. The method according to item 1 to 3, characterized in that the addition is carried out in the presence of hexachloroplatinic acid in amounts of 10 ~ ⁴ to 10 ~ ⁵ moles per mole triple bond. 5. Process according to items 1 to 3, characterized in that the SiH group-containing organosilane, organosiloxane or organopolysiloxane compounds to be used preferably have 1 to 8 SiH groups. 6. The method according to items 1 and 2, characterized in that the organosilyl radicals are those having alkyl, alkoxy, aryl, aryloxy groups and / or chlorine atoms, as organosiloxanyl radicals straight-chain, branched-chain and / or cyclic siloxanyl Radicals having 2 to 15 Si atoms and having alkyl, alkoxy, aryl, aryloxy groups and / or chlorine atoms and as polyorganosiloxanyl radicals such straight-chain or branched-chain polysiloxanyl radicals having 5 to 250, preferably 3 to 120 Silicon atoms and with alkyl, alkoxy, aryl, aryloxy groups and / or chlorine atoms, can be used. 7. The method according to item 6, characterized in that the alkyl or alkoxy groups methyl or methoxy and / or ethyl or ethyloxy and the aryl or aryloxy groups phenyl or phenoxy radicals are. 8. Process according to items 1 and 2, characterized in that the silylation of the butyne-2-diol-i.4-compounds is carried out with trimethylchlorosilane and / or hexamethyldisilazane. 9. The method according to the items 1,2,3 and 8, characterized in that the reaction takes place in organic solvents. 10. The method according to item 9, characterized in that are used as the organic solvent inert linear or cyclic ethers, aliphatic, aromatic or halogenated hydrocarbons. 11. The method according to item 1 and 2, characterized in that the new organosilyl, organosiloxanyl or. Polyorganosiloxanyl-substituted Buten-2-di (trimethylsilyl) ether-1.4 are reacted with alkanols or alkanol-water mixtures to the organosilyl, organosiloxanyl or polyorganosiloxanyl-substituted butene-2-diols-1.4. 12. The method according to item 1 and 2, characterized in that the new organosilyl, organosiloxanyl or polyorganosiloxanyl-substituted butene-2-diol-i.4 compounds, the silicon-bonded hydrolyzable atoms and / or groups, in particular chlorine atoms , are hydrolysed with hydrolyzable silicon compounds, preferably with trimethylchlorosilane.