GB1578183A - Process for silyation - Google Patents
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- GB1578183A GB1578183A GB1142377A GB1142377A GB1578183A GB 1578183 A GB1578183 A GB 1578183A GB 1142377 A GB1142377 A GB 1142377A GB 1142377 A GB1142377 A GB 1142377A GB 1578183 A GB1578183 A GB 1578183A
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- 238000000034 method Methods 0.000 title claims description 28
- 239000003054 catalyst Substances 0.000 claims description 42
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 claims description 38
- 150000001875 compounds Chemical class 0.000 claims description 25
- 238000006243 chemical reaction Methods 0.000 claims description 23
- 239000002253 acid Substances 0.000 claims description 20
- 238000006884 silylation reaction Methods 0.000 claims description 15
- -1 trialkylsilyl ester Chemical class 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 9
- 150000007513 acids Chemical class 0.000 claims description 8
- 239000001117 sulphuric acid Substances 0.000 claims description 8
- 235000011149 sulphuric acid Nutrition 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 150000003863 ammonium salts Chemical class 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 150000003961 organosilicon compounds Chemical class 0.000 claims description 6
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 claims description 5
- 150000001449 anionic compounds Chemical class 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 150000005690 diesters Chemical class 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- DCERHCFNWRGHLK-UHFFFAOYSA-N C[Si](C)C Chemical compound C[Si](C)C DCERHCFNWRGHLK-UHFFFAOYSA-N 0.000 claims description 2
- 125000005907 alkyl ester group Chemical group 0.000 claims description 2
- 150000005840 aryl radicals Chemical group 0.000 claims description 2
- 125000004185 ester group Chemical group 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 150000003254 radicals Chemical class 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 239000011541 reaction mixture Substances 0.000 claims 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical class N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 10
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 10
- 230000035484 reaction time Effects 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 7
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 6
- 239000004202 carbamide Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 229920001296 polysiloxane Polymers 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 229910006069 SO3H Inorganic materials 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- ROHFNLRQFUQHCH-YFKPBYRVSA-N L-leucine Chemical compound CC(C)C[C@H](N)C(O)=O ROHFNLRQFUQHCH-YFKPBYRVSA-N 0.000 description 2
- 229910004727 OSO3H Inorganic materials 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- 229910007161 Si(CH3)3 Inorganic materials 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 2
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 2
- NNLPAMPVXAPWKG-UHFFFAOYSA-N trimethyl(1-methylethoxy)silane Chemical compound CC(C)O[Si](C)(C)C NNLPAMPVXAPWKG-UHFFFAOYSA-N 0.000 description 2
- MASDFXZJIDNRTR-UHFFFAOYSA-N 1,3-bis(trimethylsilyl)urea Chemical compound C[Si](C)(C)NC(=O)N[Si](C)(C)C MASDFXZJIDNRTR-UHFFFAOYSA-N 0.000 description 1
- FIADVASZMLCQIF-UHFFFAOYSA-N 2,2,4,4,6,6,8,8-octamethyl-1,3,5,7,2,4,6,8-tetrazatetrasilocane Chemical compound C[Si]1(C)N[Si](C)(C)N[Si](C)(C)N[Si](C)(C)N1 FIADVASZMLCQIF-UHFFFAOYSA-N 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- ZSCDMNARVSWRJW-UHFFFAOYSA-N CON([SiH](C)C)[Si](OC)(OC)OC Chemical compound CON([SiH](C)C)[Si](OC)(OC)OC ZSCDMNARVSWRJW-UHFFFAOYSA-N 0.000 description 1
- MMLKPGYEDAJALY-UHFFFAOYSA-N C[Si](N[Si](OC)(OC)C)(C)C Chemical compound C[Si](N[Si](OC)(OC)C)(C)C MMLKPGYEDAJALY-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004395 L-leucine Substances 0.000 description 1
- 235000019454 L-leucine Nutrition 0.000 description 1
- 229930182555 Penicillin Natural products 0.000 description 1
- JGSARLDLIJGVTE-MBNYWOFBSA-N Penicillin G Chemical compound N([C@H]1[C@H]2SC([C@@H](N2C1=O)C(O)=O)(C)C)C(=O)CC1=CC=CC=C1 JGSARLDLIJGVTE-MBNYWOFBSA-N 0.000 description 1
- NHOWCIXIMZMPAY-UHFFFAOYSA-N [[[dimethyl-(trimethylsilylamino)silyl]amino]-dimethylsilyl]methane Chemical compound C[Si](C)(C)N[Si](C)(C)N[Si](C)(C)C NHOWCIXIMZMPAY-UHFFFAOYSA-N 0.000 description 1
- QCVHOYVXCRCQDV-UHFFFAOYSA-N [dimethylsilyl(triethoxysilyl)amino]oxyethane Chemical compound C[SiH](N([Si](OCC)(OCC)OCC)OCC)C QCVHOYVXCRCQDV-UHFFFAOYSA-N 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 229930013930 alkaloid Natural products 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 239000001166 ammonium sulphate Substances 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- SMLHHBQGIJMAIM-UHFFFAOYSA-N calcium;2-dodecylbenzenesulfonic acid Chemical group [Ca].CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O SMLHHBQGIJMAIM-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229960003136 leucine Drugs 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229940049954 penicillin Drugs 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 1
- 125000004665 trialkylsilyl group Chemical group 0.000 description 1
- PGZGBYCKAOEPQZ-UHFFFAOYSA-N trimethyl-[(2-methylpropan-2-yl)oxy]silane Chemical compound CC(C)(C)O[Si](C)(C)C PGZGBYCKAOEPQZ-UHFFFAOYSA-N 0.000 description 1
- KWXCFNARSKWVBM-UHFFFAOYSA-N trimethylsilyl 2-dodecylbenzenesulfonate Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(=O)(=O)O[Si](C)(C)C KWXCFNARSKWVBM-UHFFFAOYSA-N 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 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
- C07F7/188—Preparation; Treatments not provided for in C07F7/20 by reactions involving the formation of Si-O linkages
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
(54) PROCESS FOR SILYLATION
(71) We, TH GOLDSCHMIDT AG, a German Body Corporate, of Goldschmidtstrasse 100, 4300 Essen, Germany, do hereby declare the invention for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement:
This invention relates to a process for the silylation of compounds possessing at least one active hydrogen atom, by reaction with compounds which contain the =Si-NH-Si= grouping.
The book "Neue Methoden der praparativen organischen Chemie" (New Methods of
Preparative Organic Chemistry"), volume 5, Verlag Chemie, 1967, page 208, discloses that the silylation of, for example, L-leucine can be carried out with hexamethyldisilazane in the presence of concentrated sulphuric acid at the reflux temperature (bath temperature 130 to 140"C) over a period of 30 minutes.
The journal "Journal of Organic Chemistry", 25, (1960), page 598, describes the silylation of pyrrole with hexamethyldisilazane using ammonium sulphate as the catalyst, at a temperature of 1100C and with a reaction time of 6 hours.
The same information, and yet further examples of suitable catalysts, are to be found in
German Offenlegungsschrift 2,507,882. This relates to a process for the manufacture of bis-(trimethylsilyl)-urea by reaction of urea with hexamethyldisilazane, characterised in that the reaction of urea with hexamethyldisilazane is carried out in the presence of catalytically active amounts of salts of ammonia, basic amino compounds which only contain active hydrogen in an RN-bond, whilst the nitrogen valencies not satisfied by hydrogen are satisfied by carbon, or quaternary ammonium hydroxides, with acids which in dilute aqueous solution at 25"C have an acid dissociation constant of at least 10-4.
A feature common to all processes of the prior art is that they take place at an elevated temperature and require substantial reaction times. This makes it difficult to carry out a mild silylation, especially of heat-sensitive compounds.
It can be assumed that the relatively low reactivity of hexamethyldisilazane is attributable to the steric hindrance of the SiN-bond. This accords with Noll "Chemie und Technologie der Silicone" ("Chemistry and Technology of the Silicones"), 1968, page 303, which indicates that hexamethyldisilazane only decomposes to the extent of 10% on 4 hours' exposure to boiling water.
The reaction of hexamethyldisilazane with compounds containing active hydrogen can of course also additionally be made difficult if the particular configuration of the reactants hinders the reaction. Such is the case, for example, for tertiary butanol.
The silylation reaction which takes place with hexamethyldisilazane takes place analogously with other compounds which contain the Si-NH-Si grouping. Such silylating agents are, in addition to hexamethyldisilazane, compounds such as tetramethyldimethoxydisilazane, dimethyltetramethoxydisilazane, octamethylcyclotetrasilazane and octamethyltrisilazane.
Surprisingly, it has not been found according to this invention that certain catalysts exceptionally accelerate the silylation reaction.
Accordingly, the present invention provides a process for the silylation of a compound possessing at least one active hydrogen atom, which process comprises reaction said compound with an organosilicon compound which contains the groupSi-NH-Siin the presence of 0.01 to 5% by weight, based on the weight of the organo-silicon compound, of a catalyst which is an anionic compound which in an aqueous solution of at most 1% strength by weight lowers the surface tension of water to a value of < 50 mN m-l, or is a water-insoluble derivative of such an anionic compound, and which is:
(a) a monoester or diester of sulphuric acid,
(b) an ammonium or substituted ammonium salt of a monoester of sulphuric acid,
(c) a fluoroalkylsulphonic acid, alkylsulphonic acid, alkylarylsulphonic acid or an ammonium or substituted ammonium salt of one of these acids, or
(d) an alkyl or trialkylsilyl ester of an acid in group (c).
The catalysts used in the process of the present invention must therefore conform to both structural requirements (groups (a) to (d)) and to the specified surface tension lowering properties. Certain compounds which are usable as the catalyst are soluble in water, others are not. The surface tension lowering test is carried out using an aqueous solution containing 1% by weight of the soluble catalyst when the catalyst is soluble to the extent of 1% by weight or more in water. If the catalyst is not soluble to the extent of 1% by weight, the lowered surface tension is measured at saturation concentration. Certain derivatives usable as catalyst are insoluble, for example, the polyvalent metal salts of the acids mentioned in groups (a) to (d), such as the alkaline earth metal salts or salts of Group 3 metals of the Periodic Table. A particular example of such a derivative is calcium dodecylbenzenesulphonic acid.
By carrying out the silylation in accordance with this invention the reaction can take place at substantially lower temperatures and accordingly it becomes possible, due to the use of mild silylating conditions, also to silylate sensitive natural products, such as penicillin and alkaloids. At such lower temperatures, longer reaction times will probably be necessary.
The catalysis manifests itself particularly successfully if, by virtue of their structure, the catalysts are compatible with the system to be catalysed, inasmuch as, for example, they are soluble therein or become soluble therein during the reaction. However, this is not an essential condition.
A particularly preferred process is one in which catalysts which lower the surface tension to a value of < 38 mN m , or their water-insoluble derivatives, are used.
It is particularly surprising that the silylation reaction, which in most cases takes place in an anhydrous medium, is catalysed by compounds where a selection criterion is the extent to which the compounds lower the surface tension of water, or by derivatives which are based on these compounds and are water-insoluble. There is no obvious connection between the catalysis and the structure of the compounds.
Of the esters of sulphuric acid in groups (a) and (b), particularly active are those wherein the ester group is derived from an alkanol containing an organo-silicon radical.
A particularly preferred example of a catalyst of group (a) or (b) is an organo-silicon
compound which contains a radical of formula:
in which R is an alkyl or aryl radical, preferably methyl, R' is an alkylene radical with 3 or 4 carbon atoms and X is an ammonium or substituted ammonium radical preferably an ammonium ion, or is an alkyl or a trimethylsilyl radical.
A catalyst wherein the anion has the structure
is particularly active.
Examples of suitable monoesters or diesters of sulphuric acid (group (a)) are CH3-(CH2)7-OSQH CH3-(CH2)11-OSO3H CH3-(CH2)17-OSO3H
Suitable salts of the monoesters of sulphuric acid group (b)) are ammonium and substituted ammonium salts for example,
CH3-(CH2)13-OSO3 . NH4
The two latter compounds can be prepared in accordance with German Patent
Specification 1,157,789 and German Patent Specification 1,179,937.
Particularly suitable catalysts of group (c) are dodecylbenzenesulphonic acid, alkylsulphonic acids with 8 to 20 carbon atoms in the alkyl radical, fluoroalkylsulphonic acids with 4 to 16 carbon atoms and sulphonic acids modified by an organo-silicon structure, as well as the ammonium and substituted ammonium salts of these compounds.
Examples of such compounds are: C8Hl,SO3H
C14H29S 3H
Cl8H37S 3H
where X has the meaning already indicated.
Compounds of this type can be prepared in accordance with French Patent Specification 1,198,096.
The alkyl esters and trialkylsilyl esters, especially the trimethylsilyl esters, of the acids mentioned in (c), have also proved particularly useful (group (d)). Examples of such compounds are:
C14H29SO3-Si(CH3)3
C8Hl7SO3-Si(CH3)3 The high activity of the catalysts employed according to the invention manifest itself in the fact that, for example, hexamethyldisilazane in the presence of the catalysts reacts spontaneously with water even at room temperature. This must be regarded as surprising if it is borne in mind that according to the passage, cited above, in the book "Chemie und
Technologie der Silicone" ("Chemistry and Technology of the Silicones" reaction only takes place to the extent of 10% even after 4 hours' treatment of hexamethyldisilazane with boiling water, in the absence of a catalyst. The catalysts known from the prior art are also incapable of allowing a spontaneous reaction to take place.
The technical advance achieved by the process according to the invention is documented in more detail, and explained, in the Examples which follow, by comparing the activity of catalysts of the prior art with the catalysts to be employed in the process according to the invention.
Example 1
1.61 g of dodecylbenzenesulphonic acid are added to 148.0 g of t-bùtanol (2.0 mols) and 161.0 g of hexamethyldisilazane (1.0 mol) in a 500 ml round-bottomed flask equipped with a reflux condenser, drying tube and paddle stirrer. At a reaction temperature of 20"C, 81.7% of the t-butanol had been converted to trimethyl-t-butoxysilane after a reaction time of 4.5 hours. The conversion was determined by gas chromatography (boiling point 103.5"C/760 mm Hg).
Comparative ' Example 2
By carrying out Example 1 without a catalyst, only 1% conversion was achieved fter the same reaction time of 4.5 hours at 200C.
Example 3
120.2 g of isopropanol (2.0 mols) are reacted, in an apparatus as described in Example 1, with 161 g of hexamethyldisilazane (1.0 mol) at 20"C in the presence of 1;61 g of dodecylbenzenesulphonic acid trimethylsilyl ester. After a reaction time of 105 minutes, 75% of the isopropanol had been converted to trimethylisopropoxysilane.
Comparative Example 4
In a comparative experiment without catalyst, 2.6% of trimethylisopropoxysilane were found after carrying out the reaction in the same way as in Example 3.
Examples 1 and 5 to 11 are shown in tabular form. The silylation of t-butanol by hexamethyldisilazane at 200C, with a reaction time of 4.5 hours and a catalyst concentration of, in each case, 1.0% by weight (= 0.74 g, based on t-butanol) was used as an example, 74
g of t-butanol (1 mol) being reacted with 80.5 g of hexamethyldisilazane. The catalyst
activity follows from the yield achieved.
The surface tensions were determined by the Lecomte du Noisy ring pull-off method.
(The method is described, for example, in: Goldschmidt informiert, 2/74, No. 29, pages 10
and 12 (1974)).
Sc ! o o CH3 C)i3 (cH3) 3 85 4 F o rl (V O c\ d I Ha n N . > | Y m 4} M tn Qmcn cdr(O 6 C12N25-S03-S(CH3)3 3 33.4 U] 04 . ~ . . ~ LC cn \O In -SO3H y, 70.5 t > H o O n o u O H r10 rl m O In In O rl 9 H2S04 5.5 10 (N114)2eo4 0.6 11 1.7 U ^ | n X B @ | ~ a 0n X 8 0e =n =e I 0n 0e | O N 8 = ~ U mw U U U U > O m vS 0 > o H u Examples 12 and 13 and Comparative Examples 14 to 16
These Examples show the catalyst activity for the silylation of urea. Here catalysts to be used according to the invention are compared with catalysts named in German
Offenlegungsschrift 2,507,882 for the silylation of urea by means of hexamethyldisilazane.
In each case, 500 ml (2.4 mols) of hexamethyldisilazane, 60 g (1 mol) of urea and 0.33 g of catalyst (= 0.55% by weight catalyst content, relative to urea) are reacted in a round flask, provided with a stirrer and reflux condenser, at 800C. In order to compare the catalyst activity, the reaction time tR needed, in each case, in order to detect half the amountof NH3 liberated during the silylation is determined; alternatively, in the case of the less active catalysts of the prior art, the amount of NH3 formed during the reaction time tR is determined.
Example Catalyst (1% by weit) Reaction Reaction time tR (mN/rn) product (,') cli 12 (cH3)3-si-o-si-si-(CH3)3 50 2 hra. 15.' 20.0 (Cli2) 0-SO3 . i-c3H7NH2+ t C12H25-SO3H o e m | | u (V P Exarnf4le C)i -SO3N 10.8 2 hrs. 15' 70.5 3 15 (NH4)2s04 m 2 m o 6 r( In rl 0 d NH4Cl ; fi hrs. 30' ~ N N H ot o o o n o o H U n i d @ xn O xe r UN H > o S 71 n E 9 H , E Example 17
16.1 g (0.1 mol) of hexamethyldisilazane, 0.18 g of the catalyst of Example 5 and 1.8 g (0.2 inol) of water are successively introduced, at 20"C, into a 100 ml reaction flask. The reaction takes place simultaneously and exothermically, the ammonia formed being determined in order to measure the rate of reaction. The conversion is 50% after 4 minutes and 93% after 6 minutes.
Comparative Example 18
A comparative experiment carried out in accordance with Example 17, without the use of a catalyst, proved negative. No conversion was detectable.
Example 19
43.2 g (0.154 mol) of dimethyltetraethoxydisilazane, 14.15 g (0.308 mol) of ethanol and 1.5 g of dodecylbenzenesulphonic acid are heated in a 100 ml flask for 1 hour to 1000C, whilst stirring. The conversion to methyltriethoxysilane, determined by gas chromatography, is 92.6%.
Comparative Example 20
Using the same conditions as in Example 19, but without addition of the dodecylbenzenesulphonic acid catalyst, 8.3% conversion to :methyltriethoxysilane is achieved.
Claims (12)
1. A process for the silylation of a compound possessing at least one active hydrogen atom, which process comprises reacting said compound with an organo-silicon compound which contains the group Si-NH-Si-- in the presence of 0.01 to 5% by weight, based on the weight of the organo-silicon compound, of a catalyst which is an anionic compound which in an aqueous solution of at most 1% strength by weight lowers the surface tension of water to a value of < 50 mN m-, or is a water-insoluble derivative of such an anionic compound, and which is:
(a) a monoester or diester of sulphuric acid,
(b) an ammonium or substituted ammonium of a monoester of sulphuric acid,
(c) a fluoroalkylsulphonic acid, alkylsulphonic acid, alkylarylsulphonic acid or an ammonium or substituted ammonium salt of one of these acids, or
(d) an alkyl or trialkylsilyl ester of an acid in group (c).
2. A process according to claim 1 in which the catalyst is a compound which lowers the surface tension of water to a value of < 38 mN . m-1, or a water-insoluble derivative thereof.
3. A process according to claim 1 or 2 wherein the catalyst is soluble in the reaction mixture or becomes soluble therein during the reaction.
4. A process according to claim 1, 2 or 3 in which the ester of sulphuric acid in the catalyst of group (a) or (b) is one wherein the ester group is derived from an alkanol containing an organo-silicon radical.
5. A process according to claim 4 in which the catalyst of group (a) or (b) is an organo-silicon compound which contains a radical of formula
in which R is an alkyl or aryl radical, R' is an alkylene radical with 3 or 4 carbon atoms and
X an ammonium or substituted ammonium radical, or is an alkyl or trimethylsilyl radical.
6. A process according to claim 5 wherein R is methyl.
7. A process according to claim 1, 2 or 3 in which the catalyst of group (c) is dodecylbenzenesulphonic acid, an alkylsulphonic acid with 8 to 20 carbon atoms in the alkyl radical or a fluoroalkylsulphonic acid with 4 to 16 carbon atoms.
8. A process according to claim 1, 2, 3 or 7 in which the catalyst of group (d) is an alkyl ester or trimethylsilyl ester of an acid in group (c).
9. A process according to any one of the preceding claims wherein the compound containing the group Si-NH-Si is hexamethyldisilazane.
10. A process according to any one of the preceding claims wherein the compound possession at least one active hydrogen atom is a said compound specifically identified herein.
11. A process according to claim 1 substantially as described in any one of Examples 1, 3, 5 to 7, 12, 13, 17 and 19.
12. A silylated compound whenever produced by a process as claimed in any one of the preceding claims.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB1142377A GB1578183A (en) | 1977-03-17 | 1977-03-17 | Process for silyation |
| DE19772757936 DE2757936C3 (en) | 1977-03-17 | 1977-12-24 | Process for silylation |
| ES466836A ES466836A1 (en) | 1977-03-17 | 1978-02-09 | Process for silyation |
| IT4810778A IT1105284B (en) | 1977-03-17 | 1978-02-17 | Silylating cpds. contg. active hydrogen - using anion-active catalysts which lower surface-tension, e.g. sulphate ester(s), sulphonic acids and their ester(s) |
| JP3050178A JPS53116325A (en) | 1977-03-17 | 1978-03-16 | Method of silylizing compound having at least one active hydrocen atoms |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB1142377A GB1578183A (en) | 1977-03-17 | 1977-03-17 | Process for silyation |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| GB1578183A true GB1578183A (en) | 1980-11-05 |
Family
ID=9985961
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB1142377A Expired GB1578183A (en) | 1977-03-17 | 1977-03-17 | Process for silyation |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JPS53116325A (en) |
| DE (1) | DE2757936C3 (en) |
| ES (1) | ES466836A1 (en) |
| GB (1) | GB1578183A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6218498B1 (en) | 1996-12-27 | 2001-04-17 | Wacker-Chemie Gmbh | Organosilicon compounds having urea groups, method for producing same and their utilization |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IL63100A0 (en) * | 1980-07-04 | 1981-09-13 | Gist Brocades Nv | Trimethylsilylation of organic compounds and certain trimethylsilylated thiols obtained thereby |
| US5233882A (en) * | 1990-07-12 | 1993-08-10 | General Motors Corporation | Remote control lever module |
-
1977
- 1977-03-17 GB GB1142377A patent/GB1578183A/en not_active Expired
- 1977-12-24 DE DE19772757936 patent/DE2757936C3/en not_active Expired
-
1978
- 1978-02-09 ES ES466836A patent/ES466836A1/en not_active Expired
- 1978-03-16 JP JP3050178A patent/JPS53116325A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6218498B1 (en) | 1996-12-27 | 2001-04-17 | Wacker-Chemie Gmbh | Organosilicon compounds having urea groups, method for producing same and their utilization |
Also Published As
| Publication number | Publication date |
|---|---|
| DE2757936A1 (en) | 1978-09-21 |
| DE2757936B2 (en) | 1979-03-08 |
| DE2757936C3 (en) | 1979-10-31 |
| JPS5616156B2 (en) | 1981-04-14 |
| JPS53116325A (en) | 1978-10-11 |
| ES466836A1 (en) | 1978-10-01 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PS | Patent sealed | ||
| PCNP | Patent ceased through non-payment of renewal fee |