US3160647A - Alkylation of dialkoxy monohalo silanes - Google Patents
Alkylation of dialkoxy monohalo silanes Download PDFInfo
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- US3160647A US3160647A US111176A US11117661A US3160647A US 3160647 A US3160647 A US 3160647A US 111176 A US111176 A US 111176A US 11117661 A US11117661 A US 11117661A US 3160647 A US3160647 A US 3160647A
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- alkyl
- tert
- butyl
- silane
- tri
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- 238000005804 alkylation reaction Methods 0.000 title claims description 7
- 230000029936 alkylation Effects 0.000 title claims description 6
- 150000004756 silanes Chemical class 0.000 title description 9
- 238000000034 method Methods 0.000 claims description 30
- -1 TRI-SUBSTITUTED SILANE Chemical class 0.000 claims description 21
- 150000001350 alkyl halides Chemical class 0.000 claims description 20
- 229910052783 alkali metal Inorganic materials 0.000 claims description 15
- 150000001340 alkali metals Chemical class 0.000 claims description 15
- 239000011541 reaction mixture Substances 0.000 claims description 13
- 229910000077 silane Inorganic materials 0.000 claims description 12
- 239000000376 reactant Substances 0.000 claims description 10
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 7
- 230000000694 effects Effects 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 description 21
- 229910052708 sodium Inorganic materials 0.000 description 18
- 239000011734 sodium Substances 0.000 description 18
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 17
- 238000006243 chemical reaction Methods 0.000 description 12
- NBRKLOOSMBRFMH-UHFFFAOYSA-N tert-butyl chloride Chemical compound CC(C)(C)Cl NBRKLOOSMBRFMH-UHFFFAOYSA-N 0.000 description 10
- 239000003153 chemical reaction reagent Substances 0.000 description 9
- 150000001348 alkyl chlorides Chemical class 0.000 description 8
- 125000004432 carbon atom Chemical group C* 0.000 description 7
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 125000000753 cycloalkyl group Chemical group 0.000 description 5
- 229910052700 potassium Inorganic materials 0.000 description 5
- 239000011591 potassium Substances 0.000 description 5
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000003085 diluting agent Substances 0.000 description 4
- 150000004820 halides Chemical group 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 125000001475 halogen functional group Chemical group 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- HHOSMYBYIHNXNO-UHFFFAOYSA-N 2,2,5-trimethylhexane Chemical compound CC(C)CCC(C)(C)C HHOSMYBYIHNXNO-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical class CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 229910052792 caesium Inorganic materials 0.000 description 2
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 2
- WHYRMRWGLUKQTI-UHFFFAOYSA-N chloro(diethoxy)silane Chemical compound CCO[SiH](Cl)OCC WHYRMRWGLUKQTI-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical class CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 description 2
- YZWKKMVJZFACSU-UHFFFAOYSA-N 1-bromopentane Chemical compound CCCCCBr YZWKKMVJZFACSU-UHFFFAOYSA-N 0.000 description 1
- SKIDNYUZJPMKFC-UHFFFAOYSA-N 1-iododecane Chemical compound CCCCCCCCCCI SKIDNYUZJPMKFC-UHFFFAOYSA-N 0.000 description 1
- JQVINQQAQOYUGJ-UHFFFAOYSA-N 2,3-dimethylbutan-2-yl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C(C)(C)C(C)C JQVINQQAQOYUGJ-UHFFFAOYSA-N 0.000 description 1
- NAMYKGVDVNBCFQ-UHFFFAOYSA-N 2-bromopropane Chemical compound CC(C)Br NAMYKGVDVNBCFQ-UHFFFAOYSA-N 0.000 description 1
- HEMQRALQJLCVBR-UHFFFAOYSA-N 2-chloro-2,3-dimethylbutane Chemical compound CC(C)C(C)(C)Cl HEMQRALQJLCVBR-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910000799 K alloy Inorganic materials 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910000573 alkali metal alloy Inorganic materials 0.000 description 1
- 150000001339 alkali metal compounds Chemical class 0.000 description 1
- 150000001347 alkyl bromides Chemical group 0.000 description 1
- 150000001349 alkyl fluorides Chemical class 0.000 description 1
- 150000001351 alkyl iodides Chemical class 0.000 description 1
- 239000002168 alkylating agent Substances 0.000 description 1
- 229940100198 alkylating agent Drugs 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- RBHJBMIOOPYDBQ-UHFFFAOYSA-N carbon dioxide;propan-2-one Chemical compound O=C=O.CC(C)=O RBHJBMIOOPYDBQ-UHFFFAOYSA-N 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- NMPRXYIATDTLDZ-UHFFFAOYSA-N chloro(diethoxy)silicon Chemical compound CCO[Si](Cl)OCC NMPRXYIATDTLDZ-UHFFFAOYSA-N 0.000 description 1
- FDFKUNYUGRRCPC-UHFFFAOYSA-N chloro(dihexoxy)silane Chemical compound Cl[SiH](OCCCCCC)OCCCCCC FDFKUNYUGRRCPC-UHFFFAOYSA-N 0.000 description 1
- 125000000113 cyclohexyl group Chemical class [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000000640 cyclooctyl group Chemical class [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- BAAAEEDPKUHLID-UHFFFAOYSA-N decyl(triethoxy)silane Chemical compound CCCCCCCCCC[Si](OCC)(OCC)OCC BAAAEEDPKUHLID-UHFFFAOYSA-N 0.000 description 1
- PKTOVQRKCNPVKY-UHFFFAOYSA-N dimethoxy(methyl)silicon Chemical compound CO[Si](C)OC PKTOVQRKCNPVKY-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical class CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000004508 fractional distillation Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 235000012054 meals Nutrition 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- HLXDKGBELJJMHR-UHFFFAOYSA-N methyl-tri(propan-2-yloxy)silane Chemical compound CC(C)O[Si](C)(OC(C)C)OC(C)C HLXDKGBELJJMHR-UHFFFAOYSA-N 0.000 description 1
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000003961 organosilicon compounds Chemical class 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- BITYAPCSNKJESK-UHFFFAOYSA-N potassiosodium Chemical compound [Na].[K] BITYAPCSNKJESK-UHFFFAOYSA-N 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 229910000058 selane Inorganic materials 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- RKSOPLXZQNSWAS-UHFFFAOYSA-N tert-butyl bromide Chemical compound CC(C)(C)Br RKSOPLXZQNSWAS-UHFFFAOYSA-N 0.000 description 1
- YTZKOQUCBOVLHL-UHFFFAOYSA-N tert-butylbenzene Chemical compound CC(C)(C)C1=CC=CC=C1 YTZKOQUCBOVLHL-UHFFFAOYSA-N 0.000 description 1
- 150000005377 tertiary alkyl halides Chemical class 0.000 description 1
- UYLCWDTWVASSCX-UHFFFAOYSA-N tridecoxysilane Chemical compound CCCCCCCCCCCCCO[SiH3] UYLCWDTWVASSCX-UHFFFAOYSA-N 0.000 description 1
- FHVAUDREWWXPRW-UHFFFAOYSA-N triethoxy(pentyl)silane Chemical compound CCCCC[Si](OCC)(OCC)OCC FHVAUDREWWXPRW-UHFFFAOYSA-N 0.000 description 1
- BJDLPDPRMYAOCM-UHFFFAOYSA-N triethoxy(propan-2-yl)silane Chemical compound CCO[Si](OCC)(OCC)C(C)C BJDLPDPRMYAOCM-UHFFFAOYSA-N 0.000 description 1
- OZWKZRFXJPGDFM-UHFFFAOYSA-N tripropoxysilane Chemical compound CCCO[SiH](OCCC)OCCC OZWKZRFXJPGDFM-UHFFFAOYSA-N 0.000 description 1
- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical class CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
- C07F7/1872—Preparation; Treatments not provided for in C07F7/20
- C07F7/1876—Preparation; Treatments not provided for in C07F7/20 by reactions involving the formation of Si-C linkages
Definitions
- alkyl trialkoxysilanes are prepared by maintaining a mixture of an alkali metahan alkyl halide and a tri-substituted silane at a temperature in the range of about 50 to about 200 C. suihcient to effect alkylation of the silane.
- the tri-substituted silanes which are used as one of the reactants in the present process can be represented by the formula I-iSi(0R) X wherein R is an alkyl group of up to about 12 carbon atoms, X is a halide, n is an integer from 2 to 3, inclusive, and m is an integer from 0 to 1, inclusive, n+m being equal to 3.
- the alkali metals are generally useful in conducting this process. Hence, recourse may be had to lithium, sodium, potassium, rubidium, cesium and various alkali metal alloy mixtures such as sodium-potassium alloy and the like.
- Metallic sodium is the preferred alkali metal reagent because of its low cost and availability and because of the very good results obtained by its use.
- metallic potassium is also a very effective reagent, as are mixtures of sodium and potassium.
- a temperature at which the alkali metal reagent is in the liquid state it is preferable to employ a temperature at which the alkali metal reagent is in the liquid state.
- the alkali metal can be used in the form of a dispersion or sand.
- alkyl halides can be used in the present process. Preferably these contain from 1 to about 12 carbon atoms although higher alkyl halides (e.g. compounds containing up to about 18 or more carbon atoms) can be used. The principles of this invention likewise extend to the use of cycloalkyl halides as these materials give generally equivalent results. Alkylfluorides and alkyliodides may be used but it is preferable to use alkyl halides of the middle halogensi'.e. alkyl chlorides and alkyl bromidessince these materials, especially the alkyl chlorides, provide the best results.
- tertiary alkyl halides preferably tertiary alkyl bromides and tertiary alkyl chlorides is likewise preferred because the resultant tertiary alkylated silane product is not only very useful in the chemical and allied arts but is produced in excellent yield.
- a particularly desirable embodiment of this invention is to use metallic sodium and an alkyl chloride, especially a tertiary alkyl chloride. In this way the desired alkyl trialkoxysilanes are produced in the highest yields at the lowest cost.
- tri-substituted silane has the formula HSi(OR) wherein R is an alkyl (or cycloalkyl) group, preferably containing up to about 12 carbon atoms.
- the other type of tri-substituted silane has the formula HSi(OR) X wherein R is an a kyl (or cycloalkyl) group, preferably containing up to about 12 carbon atoms and X is a halide, preferably bromide or chloride, most preferably chloride.
- reaction solvent or diluent In conducting the present process it is unnecessary to employ a reaction solvent or diluent. In other words, excellent results have been achieved simply by co-mingling the several reagents and maintaining them under the conditions described above. it is thereupon a relatively simple matter to recover the desired alkyl trialkoxysilane from the reaction mixture by standard separation techniques, as for example, fractional distillation, solvent ex traction, chromotography, or like procedures.
- inert organic solvents or diluents For this purpose hydrocarbons which are liquid under the reaction conditions are generally preferable although use can be made of inert ethers and related materials.
- hydrocarbon diluents it is desirable to use compounds which are generally inert to alkali metals under the conditions of this process, and thus effective use can be made of paraflinic hydrocarbons, cycloparaffins and inert aromatics (e.g. benzene, tert.-butyl benzene, etc). Petroleum ethers, hexanes, heptanes, octanes, nonanes, decane, undecanes, dodecanes, cyclohexanes, cycloneptanes, cyclooctanes, and the like, serve as examples of the preferred paraflins or cycloparaflins.
- paraflinic hydrocarbons e.g. benzene, tert.-butyl benzene, etc.
- the process of this invention' is conducted at a temperature in the range of about 50 to about 200 C. suflicient to effect alkylation of the trisubstituted silane reagent.
- the process tends to be somewhat exothermic and, therefore, in some instances it is unnecessary to apply heat to the reaction mixtures.
- the reaction can be readily controlled by the application of heat.
- the precise temperature for optimum results is in general a function of the nature of the several reagents employed in formulating our reaction systems. For example, when using lithium and the relatively less reactive alkyl halides it is desirable to employ temperatures approaching the upper end of the range described.
- the more reactive alkali metal species notably sodium or potassium
- the more reactive alkyl halides e.g. the chlorides
- Example II The general procedure of Example 1 was repeated using 0.15 mole of triethoxysilane, 0.15 mole of tert.-butyl chloride and 0.40 mole of sodium as the reactants. In this instance 2,2,5-trimethylhexane was used as reaction diluent. The reaction was conducted primarily at a temperature of 110 C. Tert.-buty1 triethoxysilane was produced in 22 percent yield.
- COMPARATIVE EXAMPLE B The same general procedure of Comparative Example A was repeated several times except that an approximately equivalent quantity of methyl trimethoxysilane, methyl trie'thoxysilane, or methyl triisopropoxysilane was used instead of the phenyl trimethoxysilane.
- the respective products of these runs were found to be tert.-'outyl methyl dimethoxysilane, tert.-butyl methyl diethoxysilane and tert.-butyl methyl diisopropoxysilane.
- Example III The general procedure of Example I was repeated using 9.2 g. (0.4 mole) of sodium, 23.2 g. (0.15 mole) of chlorodiethoxysilane, and 13.9 g. (0.15 mole) of tert.- butyl chloride. Tert.-butyl triethoxysilane, 26.5 percent yield, was obtained as determined by gas chromatography analysis.
- a feature of the above embodiment of this invention in which a halo tri-substituted silane (HSi(OR) X) is used as the silane reactant is that a rearrangement occurs in such a way as to produce a significant yield of the desired alkyl trialkoxysilane product.
- Another feature of this embodiment is the fact that when a halo tetrasubstituted silaneRSi(OR) X-is used in place of the halo tri-substituted' silaneHSi(OR) X-no reaction occurs. This is borne out by the Work summarized in the following table.
- tert.-butyl chloride and metallic sodium use can be made of tert.-butyl sodium for reaction with the various tri-substituted silanes in order to produce the corresponding tert.-butyl trialkoxy silanes.
- silanes produced by our process have, inter alia, the various utilities described in US. Patent 2,985,678, the entire disclosure of which is incorporated herein by the foregoing reference.
- the alkyl trialkoxysilanes can be used in the production of siloxanes and other valuable silicon-containing compounds and/ or polymers. Consequently, the products formed by the present process are useful in the manufacture of engine and industrial lubricants and hydraulic fluids, heat exchange media and the like.
- a process of preparing alkyl trialkoxysilanes which comprises maintaining a mixture of an alkali metal, an alkyl halide and a tri-substituted silane at a temperature in the range of about 50 to about 200 C. sutficient to effect alkylation of said silane and recovering said alkyl trialkoxysilane from the reaction mixture; said silane reactant being characterized by having the formula HSi(OR) X wherein R is an alkyl group of up to about 12 carbon atoms and X is a halide, said process being further characterized in that at least about one mole of said alkyl halide is used per mole of said silane.
- a process according to claim 1 wherein said alkyl halide is an alkyl chloride.
- alkyl halide is a tert.-alkyl halide.
- a process of preparing tert.-butyl triethoxysilane which comprises reacting sodium, tert.-butyl chloride and diethoxychlorosilane at a temperature in the range of about to about C., and recovering said tort.- butyl triethoxysilane from the reaction system, said process being further characterized in that about one mole of tert.-butyl chloride is used per mole of diethoxychlorosilane.
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Description
United States Patent Ofl ice 3,166,647 Patented Dec. 8, 1964 3,16%,647 ALKYLATIGN F DIALKGXY MGNGHALG SELANES This invention relates to, and has as its chief objective, the provision of a novel alkylation process which is especially adapted for the preparation of alkyl trialkoxysilanes.
According to this invention alkyl trialkoxysilanes are prepared by maintaining a mixture of an alkali metahan alkyl halide and a tri-substituted silane at a temperature in the range of about 50 to about 200 C. suihcient to effect alkylation of the silane. The tri-substituted silanes which are used as one of the reactants in the present process can be represented by the formula I-iSi(0R) X wherein R is an alkyl group of up to about 12 carbon atoms, X is a halide, n is an integer from 2 to 3, inclusive, and m is an integer from 0 to 1, inclusive, n+m being equal to 3.
The alkali metals are generally useful in conducting this process. Hence, recourse may be had to lithium, sodium, potassium, rubidium, cesium and various alkali metal alloy mixtures such as sodium-potassium alloy and the like. Metallic sodium is the preferred alkali metal reagent because of its low cost and availability and because of the very good results obtained by its use. However, metallic potassium is also a very effective reagent, as are mixtures of sodium and potassium. When using lithium, sodium, potassium or various alloys thereof it is preferable to employ a temperature at which the alkali metal reagent is in the liquid state. However, if desired the alkali metal can be used in the form of a dispersion or sand.
A wide variety of alkyl halides can be used in the present process. Preferably these contain from 1 to about 12 carbon atoms although higher alkyl halides (e.g. compounds containing up to about 18 or more carbon atoms) can be used. The principles of this invention likewise extend to the use of cycloalkyl halides as these materials give generally equivalent results. Alkylfluorides and alkyliodides may be used but it is preferable to use alkyl halides of the middle halogensi'.e. alkyl chlorides and alkyl bromidessince these materials, especially the alkyl chlorides, provide the best results. The use of tertiary alkyl halides, preferably tertiary alkyl bromides and tertiary alkyl chlorides is likewise preferred because the resultant tertiary alkylated silane product is not only very useful in the chemical and allied arts but is produced in excellent yield.
A particularly desirable embodiment of this invention is to use metallic sodium and an alkyl chloride, especially a tertiary alkyl chloride. In this way the desired alkyl trialkoxysilanes are produced in the highest yields at the lowest cost.
Reference to the above general formula relative to the tri-substituted silane will show that there are two specific types thereof which are used pursuant to this invention. One type of tri-substituted silane has the formula HSi(OR) wherein R is an alkyl (or cycloalkyl) group, preferably containing up to about 12 carbon atoms.
The other type of tri-substituted silane has the formula HSi(OR) X wherein R is an a kyl (or cycloalkyl) group, preferably containing up to about 12 carbon atoms and X is a halide, preferably bromide or chloride, most preferably chloride.
From our experimental work it appears that the proportions of the several ingredients of our reaction mixture are not critical. However, when using the unhalogenated tri-substituted silane reagents the best yields of desired alkyl trialkoxysilanes are favored by using from about 2 to about 5 moles of such tri-substituted silanes per mole of the alkyl halide. When using the halogenated tri-substituted silane reagents the best yields of desired product occur when there is used at least about 1 mole (e.g. from about 1 to about 5 moles) of alkyl halide per mole of such halogenated tri-substituted silane. When using either type of tri-substituted silane reagent it is generally helpful to use an excess of alkali metal relative to the amount of alkyl halide employed. It will be understood, however, that departures from the foregoing ranges consistent with the principles of this invention may be made without departing from the spirit and scope thereof. Such permissive deviations will now be apparent to those skilled in the art.
In conducting the present process it is unnecessary to employ a reaction solvent or diluent. In other words, excellent results have been achieved simply by co-mingling the several reagents and maintaining them under the conditions described above. it is thereupon a relatively simple matter to recover the desired alkyl trialkoxysilane from the reaction mixture by standard separation techniques, as for example, fractional distillation, solvent ex traction, chromotography, or like procedures. However, Where greater control of temperature is desired recourse may be had to inert organic solvents or diluents. For this purpose hydrocarbons which are liquid under the reaction conditions are generally preferable although use can be made of inert ethers and related materials. Of the preferred hydrocarbon diluents it is desirable to use compounds which are generally inert to alkali metals under the conditions of this process, and thus effective use can be made of paraflinic hydrocarbons, cycloparaffins and inert aromatics (e.g. benzene, tert.-butyl benzene, etc). Petroleum ethers, hexanes, heptanes, octanes, nonanes, decane, undecanes, dodecanes, cyclohexanes, cycloneptanes, cyclooctanes, and the like, serve as examples of the preferred paraflins or cycloparaflins.
As described above, the process of this invention'is conducted at a temperature in the range of about 50 to about 200 C. suflicient to effect alkylation of the trisubstituted silane reagent. In general, the process tends to be somewhat exothermic and, therefore, in some instances it is unnecessary to apply heat to the reaction mixtures. However, when somewhat higher temperatures are desired the reaction can be readily controlled by the application of heat. The precise temperature for optimum results is in general a function of the nature of the several reagents employed in formulating our reaction systems. For example, when using lithium and the relatively less reactive alkyl halides it is desirable to employ temperatures approaching the upper end of the range described. Conversely, when using the more reactive alkali metal species, notably sodium or potassium, and the more reactive alkyl halides, e.g. the chlorides,
lower temperatures can be. used to good advantage. Those skilled in the art will now understand the principles to be followed relative .to the. temperature conditions for use in achieving the maximum benefits of this invention. As a rule of thumb, however, very excellent resultshave been achieved at temperatures of about to about C. especially when using sodium and tertiary alkyl chlorides. For this reason these particular temperatures are preferred.
Our work has shown that benefits are achieved by agitating the reaction mixture so as to provide good mixing of and contact among the reactants. For example we have found it desirable to equip the reaction vessel with stirring means operated at speeds of as high as 5,000 r.p.m. Nevertheless this agitation procedure is unnecessary as the reaction will proceed even when the reactants are maintained in a relatively quiescent state.
This invention will be still further understood by reference to the following specific examples in which all percentages are by weight.
EXAMPLE I To 19.5 g. (0.85 mole) of molten sodium in 172.2 g. (1.05 moles) of triethoxysilane was added 32.3 g. (0.35 mole) of tert.-butyl chloride. Rapid stirring (5,000 r.p.m.) was employed, and the temperature of the reaction mixture was maintained at 110 C. by the rate of addition. After the addition was complete, the reaction mixture was heated at 110 C. for one-half hour and filtered. There was no condensate in the Dry Ice-acetone trap. Distillation gave no distillate boiling in the triethoxysilane range, Bl. 134 C. The boiling point of the material collected was 160-169 C. Gas chromatography revealed that 41.0 g. (53.3 percent yield) of tert.-butyl triethoxysilane had been produced, the identity of this product having been established by comparison with an authentic sample of tert.-butyl triethoxysilane prepared in an independent synthesis. A lesser quantity of tetraethoxysilane was also detected in the product.
Repetition of the above general procedure using in one instance tert.-butyl bromide and potassium metal and in another instance tert.-butyl iodide and cesium metal in place of the tert.-butyl chloride and sodium metal results in the formation of the same principal productviz. tert.- butyl triethoxysilane. Similarly, substitution of the equivalent amounts of 2-chloro-2,3-dimethylbutane, n-amyl bromide, n-decyl iodide and isopropyl bromide for the tert.-butyl chloride in the above procedure results in the formation respectively of 1,1,2-trimethylpropyl triethoxysilane, amyl triethoxysilane, decyl triethoxysilane and isopropyl triethoxysilane.
EXAMPLE II The general procedure of Example 1 was repeated using 0.15 mole of triethoxysilane, 0.15 mole of tert.-butyl chloride and 0.40 mole of sodium as the reactants. In this instance 2,2,5-trimethylhexane was used as reaction diluent. The reaction was conducted primarily at a temperature of 110 C. Tert.-buty1 triethoxysilane was produced in 22 percent yield.
Repetition of the procedure of Example 11 using in one instance tripropoxysilane and in another instance tridecoxysilane instead of the triethoxysilane results in the formation respectively of tert.-butyl tripropoxysilane and tert.-butyl tridecoxysilane.
A feature of the above embodiment in which a trialkoxysilane (HSi(OR) isused as a reactant is our finding that the product is of an entirely diiferent type as compared with the product produced when conducting the analogous reaction employing a tetra-substituted silane of the formula R'Si(OR) (R being an alkyl and R an alkyl or aryl group). In the latter instance an alkoxy group of the tetra-substituted silane is replaced by the alkyl group of the alkyl halide. This is demonstrated by the following comparative examples.
V COMPARATIVE EXAMPLE A To 19.5 g. (0.85 mole) of molten sodium and 207.9 g. (1.05 moles) of phenyltrirnethoxysilane in 200 ml. of 2,2,5-trimethylhexane was added slowly 32.3 g. (0.35 mole) of tert.-butyl chloride. The reaction mixture was was added at a rate that wouldmaintain a temperature of stirred rapidly (5,000 r.p.m.), and the tert.-butyl chloride 4 C. in the reaction mixture. After the addition was complete, the reaction mixture was maintained at C. for one-half hour. Filtration of the reaction mixture followed by distillation gave 162 g. of material distilling between 110124 C. at mm. Redistillation of this fraction gave a product boiling in the range of 220224 C. and containing 0.6 percent chlorine. Analysis of this distillate by gas chromatography gave 20 mole percent of starting material-ire. phenyl trimethoxysilane (identified by an authentic sample)-1and 80 mole percent of phenyl tert.- butyl dimethoxysilane (identified by its infrared spectrum). I
COMPARATIVE EXAMPLE B The same general procedure of Comparative Example A was repeated several times except that an approximately equivalent quantity of methyl trimethoxysilane, methyl trie'thoxysilane, or methyl triisopropoxysilane was used instead of the phenyl trimethoxysilane. The respective products of these runs were found to be tert.-'outyl methyl dimethoxysilane, tert.-butyl methyl diethoxysilane and tert.-butyl methyl diisopropoxysilane.
As seen from Comparative Examples A and B the use of tetra-substituted silane resulted in the replacement of an alkoxy group by an alkyl group from the alkyl halide alkylating agent; In contrast, the process of this invention results in the replacement of the hydrogen of the trisubstituted silane by the alkyl group, thereby producing an entirely different class of product.
EXAMPLE III The general procedure of Example I was repeated using 9.2 g. (0.4 mole) of sodium, 23.2 g. (0.15 mole) of chlorodiethoxysilane, and 13.9 g. (0.15 mole) of tert.- butyl chloride. Tert.-butyl triethoxysilane, 26.5 percent yield, was obtained as determined by gas chromatography analysis.
Repetition of the procedure described in Example III using in one instance bromodibutoxysilane and in another instance chlorodihexoxysilane instead of the chlo-' rodiethoxysilane produces tert.-butyl tributoxysilane and tert.-butyl trihexoxysilane respectively.
A feature of the above embodiment of this invention in which a halo tri-substituted silane (HSi(OR) X) is used as the silane reactant is that a rearrangement occurs in such a way as to produce a significant yield of the desired alkyl trialkoxysilane product. Another feature of this embodiment is the fact that when a halo tetrasubstituted silaneRSi(OR) X-is used in place of the halo tri-substituted' silaneHSi(OR) X-no reaction occurs. This is borne out by the Work summarized in the following table.
Tabie.Attempted Alkylation of Methyl Dialkoxy Halo 1 Sodium was employed as a dispersion. No tert.-butyl silicon product was detected in the reaction mixtures of Runs 1-3, inclusive. We conclude, there fore, that in the embodiment of this invention in which a halo tri-substituted silane is used (i.e. I-ISi(OR) X) the presence of the silicon-hydrogen bond is essential in order to effect the desired monoalkylation.
A wide variety of tri-substituted silanes and alkyl (or cycloalkyl) halides of the type described above are available for use in practicing the process of this invention.
Inasmuch as the nature of these materials is well known to those skilled in the art it would serve no useful purpose to set forth additional exemplifications thereof. Suffice it to say that when the various reactants of the type defined herein are combined and subjected to the reaction conditions noted above, the results characterizing this invention are accomplished.
While this invention has been discussed in relation to the use of an alkyl halide, and alkali metal and a trisubstituted silane as reactants, it will be understood that a preformed alkyl (or cycloalkyl) alkali metal compound (RM, R being an alkyl or cycloalkyl group of up to about 12 carbon atoms and M being an alkali metal) can be used along with the tri-substituted silane. In short, instead of using the combination of an alkali metal and an alkyl halide one can use an equivalent amount of the corresponding organo alkali metal compound. Thus in place of tert.-butyl chloride and metallic sodium use can be made of tert.-butyl sodium for reaction with the various tri-substituted silanes in order to produce the corresponding tert.-butyl trialkoxy silanes.
The silanes produced by our process have, inter alia, the various utilities described in US. Patent 2,985,678, the entire disclosure of which is incorporated herein by the foregoing reference. For example, the alkyl trialkoxysilanes can be used in the production of siloxanes and other valuable silicon-containing compounds and/ or polymers. Consequently, the products formed by the present process are useful in the manufacture of engine and industrial lubricants and hydraulic fluids, heat exchange media and the like.
We claim:
1. A process of preparing alkyl trialkoxysilanes which comprises maintaining a mixture of an alkali metal, an alkyl halide and a tri-substituted silane at a temperature in the range of about 50 to about 200 C. sutficient to effect alkylation of said silane and recovering said alkyl trialkoxysilane from the reaction mixture; said silane reactant being characterized by having the formula HSi(OR) X wherein R is an alkyl group of up to about 12 carbon atoms and X is a halide, said process being further characterized in that at least about one mole of said alkyl halide is used per mole of said silane.
2. A process according to claim 1 wherein said alkali metal is sodium.
3. A process according to claim 1 wherein said alkyl halide is an alkyl chloride.
4. A process according to claim 1 wherein said alkali metal is sodium and said alkyl halide is an alkyl chloride.
5. A process according to claim 1 wherein said alkyl halide is a tert.-alkyl halide.
6. A process according to claim 1 wherein said alkali metal is sodium and said alkyl halide is a tort-alkyl chloride.
7. A process of preparing tert.-butyl triethoxysilane which comprises reacting sodium, tert.-butyl chloride and diethoxychlorosilane at a temperature in the range of about to about C., and recovering said tort.- butyl triethoxysilane from the reaction system, said process being further characterized in that about one mole of tert.-butyl chloride is used per mole of diethoxychlorosilane.
References Cited in the file of this patent UNITED STATES PATENTS 2,444,784 Meals July 6, 1948 2,521,267 Tiganik Sept. 5, 1950 FOREIGN PATENTS 573,906 Great Britain Dec. 12, 1945 OTHER REFERENCES Friedel et al.: Annalen der Chemie, vol. 143, 1867, pages 124-7.
Chappelow et a1: Jour. of Organic Chem, vol. 27, April 1962, pages 1409-14.
Eaborn: Organosilicon Compounds, Academic Press Inc., New York, publ., 1960, pages 19-31.
Peake et a1.: Jour. Am. Chem. 800., vol. 74 (1952), pp. 1526-8.
Claims (1)
1. A PROCESS OF PREPARING ALKYL TRIALKOXYSILANES WHICH COMPRISES MAINTAINING A MIXTURE OF AN ALKALI METAL, AN ALKYL HALIDE AND A TRI-SUBSTITUTED SILANE AT A TEMPERATURE IN THE RANGE OF ABOUT 50 TO ABOUT 200*C. SUFFICIENT TO EFFECT ALKYLATION OF SAID SILANE AND RECOVERING SAID ALKYL TRIALKOXYSILANE FROM THE REACTION MIXTURE; SAID SILANE REACTANT BEING CHARACTERIZED BY HAVING THE FORMULA
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Cited By (1)
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US3334123A (en) * | 1963-10-09 | 1967-08-01 | Dow Corning | Haloethersilanes |
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GB573906A (en) * | 1943-04-22 | 1945-12-12 | Revertex Ltd | Process for the production of organo substituted silicon compounds |
US2444784A (en) * | 1946-03-01 | 1948-07-06 | Gen Electric | Method of preparation of alkylated silanes |
US2521267A (en) * | 1947-09-08 | 1950-09-05 | Uddeholms Ab | Method of alkylating alkoxy silanes |
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GB573906A (en) * | 1943-04-22 | 1945-12-12 | Revertex Ltd | Process for the production of organo substituted silicon compounds |
US2444784A (en) * | 1946-03-01 | 1948-07-06 | Gen Electric | Method of preparation of alkylated silanes |
US2521267A (en) * | 1947-09-08 | 1950-09-05 | Uddeholms Ab | Method of alkylating alkoxy silanes |
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US3334123A (en) * | 1963-10-09 | 1967-08-01 | Dow Corning | Haloethersilanes |
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