GB1581731A - Process for the reaction of organosilicon compounds with anhydrides of polybasic inorganic or organic acids - Google Patents
Process for the reaction of organosilicon compounds with anhydrides of polybasic inorganic or organic acids Download PDFInfo
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- GB1581731A GB1581731A GB1141677A GB1141677A GB1581731A GB 1581731 A GB1581731 A GB 1581731A GB 1141677 A GB1141677 A GB 1141677A GB 1141677 A GB1141677 A GB 1141677A GB 1581731 A GB1581731 A GB 1581731A
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- 238000006243 chemical reaction Methods 0.000 title claims description 28
- 238000000034 method Methods 0.000 title claims description 28
- 150000003961 organosilicon compounds Chemical class 0.000 title claims description 16
- 150000008064 anhydrides Chemical class 0.000 title claims description 11
- 150000007524 organic acids Chemical class 0.000 title claims description 11
- 150000007522 mineralic acids Chemical class 0.000 title claims description 10
- 235000005985 organic acids Nutrition 0.000 title description 5
- 239000003054 catalyst Substances 0.000 claims description 37
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 claims description 20
- 239000002253 acid Substances 0.000 claims description 19
- 150000001875 compounds Chemical class 0.000 claims description 11
- -1 trialkylsilyl ester Chemical class 0.000 claims description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- 239000001117 sulphuric acid Substances 0.000 claims description 10
- 235000011149 sulphuric acid Nutrition 0.000 claims description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 9
- 150000007513 acids Chemical class 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 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
- 150000003863 ammonium salts Chemical class 0.000 claims description 5
- 150000003254 radicals Chemical class 0.000 claims description 4
- 150000001449 anionic compounds Chemical class 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 150000005690 diesters Chemical class 0.000 claims description 3
- DCERHCFNWRGHLK-UHFFFAOYSA-N C[Si](C)C Chemical class C[Si](C)C DCERHCFNWRGHLK-UHFFFAOYSA-N 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
- 238000002360 preparation method Methods 0.000 claims description 2
- 239000011541 reaction mixture Substances 0.000 claims 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 36
- 229910002092 carbon dioxide Inorganic materials 0.000 description 18
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 4
- WGGNJZRNHUJNEM-UHFFFAOYSA-N 2,2,4,4,6,6-hexamethyl-1,3,5,2,4,6-triazatrisilinane Chemical compound C[Si]1(C)N[Si](C)(C)N[Si](C)(C)N1 WGGNJZRNHUJNEM-UHFFFAOYSA-N 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- KZXOVHMEURKTMN-UHFFFAOYSA-N [diethoxy(methyl)silyl] N-diethoxysilyl-N-methylcarbamate Chemical compound C[Si](OCC)(OCC)OC(N(C)[SiH](OCC)OCC)=O KZXOVHMEURKTMN-UHFFFAOYSA-N 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000011835 investigation Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- DGIJAZGPLFOQJE-UHFFFAOYSA-N trimethylsilyl n-trimethylsilylcarbamate Chemical class C[Si](C)(C)NC(=O)O[Si](C)(C)C DGIJAZGPLFOQJE-UHFFFAOYSA-N 0.000 description 2
- JOOMLFKONHCLCJ-UHFFFAOYSA-N N-(trimethylsilyl)diethylamine Chemical compound CCN(CC)[Si](C)(C)C JOOMLFKONHCLCJ-UHFFFAOYSA-N 0.000 description 1
- 229910004727 OSO3H Inorganic materials 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-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
- 238000010521 absorption reaction Methods 0.000 description 1
- VOSJXMPCFODQAR-UHFFFAOYSA-N ac1l3fa4 Chemical compound [SiH3]N([SiH3])[SiH3] VOSJXMPCFODQAR-UHFFFAOYSA-N 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 229940088710 antibiotic agent Drugs 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 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
- 150000004657 carbamic acid derivatives Chemical class 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- HCZCGHSBNHRSLG-UHFFFAOYSA-N n,n-disilylmethanamine Chemical compound CN([SiH3])[SiH3] HCZCGHSBNHRSLG-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 125000006239 protecting group Chemical group 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 125000004665 trialkylsilyl group Chemical group 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
- C07F7/10—Compounds having one or more C—Si linkages containing nitrogen having a Si-N linkage
-
- 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
- C07F7/1896—Compounds having one or more Si-O-acyl linkages
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
Description
(54) PROCESS FOR THE REACTION OF ORANOSILICON
COMPOUNDS WITH ANHYDRIDES OF POLYBASIC
INORGANIC OR ORGANIC ACIDS
(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 reaction of organosilicon compounds having at least one silicon-nitrogen bond with anhydrides of polybasic inorganic or organic acids.
German Patent Specification 1,157,226 describes a process for the manufacture of organosilicon compounds in which organosilicon compounds which contain at least one silicon-nitrogen bond are reacted with anhydrides of polybasic inorganic or organic acids. Examples of suitable acid anhydrides for the reaction are CO2, P2S2 and phthalic anhydride, and it describes the reaction of an acid anhydride with, inter alia, N-(trimethylsilyl) -diethylamine.
However, further investigations have shown that the reaction is especially inhibited if more than one silicon atom is bonded to the same nitrogen atom (see "Journal of
Chemical Society", A 1967, page 362). These investigations show that CO2, CS2 and
COS, under reaction conditions up to 30 atmospheres and 1000C do not react with trisilylamine nor with N-methyldisilylamine.
In "Journal of Organo Metallic Chemistry", 1972, C 16, it is stated that the introduction of CO2 into hexamethyldisilazane is possible only with low yields, and even this has been unreproducible.
The present invention provides a process for the preparation of an adduct of an organosilicon compound having at least one silicon-nitrogen bond and an anhydride of a polybasic inorganic or organic acid, which process comprises reacting the organosilicon compound with the anhydride of a polybasic inorganic or organic acid in the presence of 0.1 to 5% by weight based on the weight of the organosilicon 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 a water-insoluble derivative of such a 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 the carrying out of the process in the presence of the specific catalysts defined for this invention, it is possible to introduce anhydrides also into those organosilicon compounds for which the reaction is partially or completely inhibited and thus to initiate or accelerate the reaction or to be able to carry it out under milder reaction conditions.
The reaction is preferably carried out in the presence of 0.1 to 2% by weight of the catalyst, and the catalyst is preferably an anionic compound which lowers the surface tension of water, in an aqueous solution of at most 1% strength by weight, to a value 38 mN/m or a water-insoluble derivative thereof.
The surface tension of the aqueous solutions can be determined, for example, by means of the ring pull-off method according to Lecomte du Noiiy.
Catalysis takes place particularly successfully if the catalysts, on the basis of their structure, are compatible with the system to be catalysed, for example in that they are soluble or become soluble during the reaction. However, this is not a compulsory condition.
Of the esters of sulphuric acid in groups a) and b), particularly effective are those in which the ester group is derived from an alkanol containing an organosilicon radical.
A particularly preferred example of a catalyst of group a) or b) is an organosilicon 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 a monovalent ammonium or substituted ammonium radical, preferably ammonium. or an alkyl or a trimethylsilyl radical.
A catalyst, the anion of which has the structure
is particularly effective.
Examples of suitable monoesters or diesters of sulphuric acid (group a)) are CH,-(CH2)7-OSO,H CH2( CH2) 11-OSO,H CH,-(CW) 17-OSO3H
Suitable salts of monoesters of sulphuric acid (group b)) are ammonium or substituted ammonium salts, for example,
The two latter compounds can be manufactured according to German Patent
Specification 1,157,789 and German Patent Specification 1,179,937.
Suitable catalysts of the group c) are, in particular, dodecylbenzenesulphonic acid, alkylsulphonic acids with 8 to 20 carbon atoms in the alkyl radical, fluoroalkylsulphonic acids with 4 to 16 carbon atoms and organosilicon-modified sulphonic acids as well as the salts of these compounds.
Examples of compounds of this type are:
in which X has the meaning already indicated.
Compounds of this type can be manufactured according to French Patent Specification 1,198,096.
The alkyl esters and the trialkylsilyl esters, especially the trimethylsilyl esters, of the acids mentioned in c) have also proved to be particularly useful (group d)).
Examples of these compounds are:
C14H2SO3-Si(CH,)3 and C8H1,SO,-Si(CH3), The process according to the invention is particularly suitable for introducing anhydrides of polybasic inorganic or organic acids into hexamethyldisilazane or dialkoxytetramethyldisilazane. Using the example of hexamethyldisilazane, the reaction with carbon dioxide can be represented by the following reaction equation:
Catalyst (CH3)2SiNHSi (CH,) + CO2 - (CH2) ,Si-NHO-Si(CH3), 'II 0 The Table which follows gives surface tension values of catalysts, which are effective according to the invention, in a 1% strength by weight aqueous solution. As a catalyst which is not according to the invention p-toluene-sulphonic acid is not sufficiently effective as the surface tension value is too high.
Catalyst Surface tension y of the
catalyst in a 1% strength
aqueous solution (mN/m)
(CH3)3SiO-S1iO-Si(cH3)3 20.0 20.0 (cH12)? OSO3 i-C3H7NH2 3 C3H7NH2 C12H25 t S03 32.8 C6 13S 3 22.7 S03H 70 .5 pCE1 S03H 70.5 Depending on the effectiveness of the catalyst, in some cases the reaction proceeds at room temperature, and in other cases at moderately elevated temperature. Depending on the effectiveness of the catalyst, the reaction can also in some cases be carried out under normal pressure. When the process is carried out without increasing the pressure, the reaction temperature is generally appropriately increased; the level of the temperature being limited by the boiling point of the silazane chosen and the decomposition temperature of the carbamic acid derivative formed.
The compounds which can be manufactured according to the invention are exceptionally reactive silylating agents which can be used, for example, as protective group transfer agents in the synthesis of antibiotics.
The process according to the invention is illustrated in still further detail with the aid of the folfowing Examples:
EXAMPLE 1.
161 g (1 mol) of hexamethyldisilazane and 1.61 g of an organosilicon compound of the formula
are initially introduced into a 500 ml reaction flask which is fitted with a stirrer, reflux condenser, thermometer and gas inlet tube. Carbon dioxide is passed into the hexamethyldisilazane against an excess pressure of 5 mm Hg until the mixture is completely saturated, whilst simultaneously heating to 800 C.
After a reaction time of 2 hours, the reaction product is allowed to cool, the
N-trimethylsilylcarbamic acid trimethylsilyl esters crystallising out. The reaction product is obtained in a yield of 94%. The product, crystallised out from hexane, has a melting point of 80"C.
Comparative EXAMPLE 2.
The reaction of CO2 with hexamethyldisilazane is attempted according to Example 1, but without a catalyst. No reaction can be detected.
EXAMPLE 3.
161 g (1 mol) of hexamethyldisilazane is reacted with CO2 in the presence of 1.61 g of trimethylsilyl dodecylbenzenesulphonate at 550C under a CO2 gas pressure of 15 kp/cm2 in a pressure reactor. The reaction to give N-trimethylsilylcarbamic acid trimethylsilyl ester is effected to an extent of 97% after 3 hours. The melting point of the crude product is 790C.
Comparative EXAMPLE 4.
No reaction could be detected in a camparison experiment carried out according to Example 3 but without a catalyst EXAMPLE 5.
74.06 g (0.5 mol) of o-phthalic anhydride, 250 ml of anhydrous benzene and 0.8 g of dodecylbenzenesulphonic acid are introduced into a 500 ml reaction flask fitted with a stirring device and dropping funnel. 80.5 g of hexamethyldisilazane are introduced via the dropping funnel at room temperature. The o-phthalic anhydride which is initially dispersed in the benzene dissolves quantitatively in the course of 2.5 hours with the formation of trimethylsiloxy/trimethylsilylamino derivative of ophthalic acid.
Comparative EXAMPLE 6.
No reaction could be detected in a comparison experiment carried out according to Example 5 but without a catalyst
EXAMPLES 7 to 14.
Examples 7 to 14 were carried out as in Examples 3 and 4 in a pressure reactor.
In these Examples, hexamethyldisilazane was reacted with CO2 at 550C under a CO2. gas pressure of 15 kp/cm2 during a reaction time of 3 hours in the presence of catalysts, which are effective according to the invention, at a catalyst concentration of 2% by weight.
Examples 7 to 14 are listed below in tabular form.
9 C6F13S03NH4 90.5 aa rl u 11 a\ o vo 3 as o 94 o r( wo 4 u o C12H25-SO3-CH3 92 aiid R H u . . .
H H e t e > s X ^en 4 o 6 Q > a e O O O t s4 t o I I I ~ H rn n N N N 4 r D H H 4 H Q U U U U Q U U ≈ b o o d H H ~ H H X EXAMPLE 15.
0.2 g of the catalyst of Example 1 are added to 20 g of hexamethylcyclotrisilazane and the mixture is reacted with CO2 at 20 C under a CO2 pressure of 25 atmospheres.
3.23 g of CO2 react with hexamethylcyclotrisilazane. The absorption of CO2 corresponds to a CO2 incorporation of 0.8 mol of CO2 in 1 mol of hexamethylcyclotrisilazane.
Comparative EXAMPLE 16.
No reaction could be detected in a comparison experiment carried out according to Example 15 but without a catalyst.
EXAMPLE 17.
29.7 g (106 mols) of dimethyltetraethoxydisilazane and 0.3 g of dodecylbenzenesulphonic acid are stirred at 70"C under a CO pressure of 40 kp/cm2 in a pressure reactor for 24 hours. 34.7 g of a liquid product are obtained.
In order to measure the CO2 content of this substance, 2N sulphuric acid is added to 2.725 g thereof, whilst stirring, until no further gas is formed. The gas formed is collected in an inverted 250 ml measuring cylinder filled with sulphuric acid. 183 ml of COO are measured.
The conversion to N-methyldiethoxysilylcarbamic acid methyldiethoxysilyl ester is accordingly 97%.
Comparative EXAMPLE 18.
Under the same conditions as in Example 17, but without the catalyst dodecylbenzenesulphonic acid, no conversion to N-methyldiethoxysilylcarbamic acid methyldiethoxysilyl ester takes place.
Claims (14)
1. A process for the preparation of an adduct of an organosilicon compound having at least one silicon nitrogen bond and an anhydride of a polybasic inorganic or organic acid, which process comprises reacting the organosilicon compound with the anhydride of a polybasic inorganic or organic acid in the presence of 0.1 to 5% by weight based on the weight of the organosilicon 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 a water insoluble derivative of such a 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).
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 or a water-insoluble derivative thereof.
3. A process according to claim 1 or 2 carried out in the presence of 0.1 to 2% by weight of the catalyst based on the weight of the organosilicon compound.
4. A process according to claim 1, 2 or 3 in which the catalyst is soluble in the reaction mixture or becomes soluble therein during the reaction.
5. A process according to any one of the preceding claims in which the ester of sulphuric acid in the catalyst of group a) or b) is one in which the ester group is derived from an alkanol containing an organosilicon radical.
6. A process according to claim 5 in which the catalyst of group a) or b) is an organosilicon compound which contains a radical
in which R is an alkyl or aryl radical, R' is an alkylene radical with 3 or 4 carbon atoms and X is a monovalent ammonium or substituted ammonium radical, or an alkyl or trimethylsilyl radical.
7. A process according to claim 6 in which R is methyl.
8. A process according to claim 6 or 7 in which X is an ammonium ion.
9. A process according to any one of claims 1 to 4 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.
10. A process according to any one of claims 1 to 4 and 9, in which the catalyst of group d) is an alkyl or trimethylsilyl ester of an acid in group c).
11. A process according to any one of the preceding claims in which the organosilicon compound is hexamethyldisilazane or a dialkoxytetramethyldisilazane.
12. A process according to any one of the preceding claims in which the anhydride of a polybasic inorganic or organic acid is CO2 or phthalic anhvdride.
13. A process according to claim 1 substantially as described in any one of
Examples 1, 3, 5, 7 to 15, and 17.
14. A silylating agent whenever prepared by a process as claimed in any one of the preceding claims.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB1141677A GB1581731A (en) | 1977-03-17 | 1977-03-17 | Process for the reaction of organosilicon compounds with anhydrides of polybasic inorganic or organic acids |
| DE19772758884 DE2758884C3 (en) | 1977-03-17 | 1977-12-30 | Process for the reaction of organosilicon compounds with anhydrides of polybasic inorganic or organic acids |
| IT4805978A IT1102381B (en) | 1977-03-17 | 1978-02-15 | Organic silicon cpd. reaction with polybasic acid anhydride - is catalysed by anion-active cpds. which lower surface tension of water |
| ES467617A ES467617A1 (en) | 1977-03-17 | 1978-03-07 | Process for the reaction of organosilicon compounds with anhydrides of polybasic inorganic or organic acids |
| JP3050278A JPS53116326A (en) | 1977-03-17 | 1978-03-16 | Method of reacting organo siliceous compound having at least one siliconnnitrogen linkage with poly basic inorganic or organic acid unhydride |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB1141677A GB1581731A (en) | 1977-03-17 | 1977-03-17 | Process for the reaction of organosilicon compounds with anhydrides of polybasic inorganic or organic acids |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| GB1581731A true GB1581731A (en) | 1980-12-17 |
Family
ID=9985814
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB1141677A Expired GB1581731A (en) | 1977-03-17 | 1977-03-17 | Process for the reaction of organosilicon compounds with anhydrides of polybasic inorganic or organic acids |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JPS53116326A (en) |
| DE (1) | DE2758884C3 (en) |
| ES (1) | ES467617A1 (en) |
| GB (1) | GB1581731A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2167754A (en) * | 1984-12-01 | 1986-06-04 | Dynamit Nobel Ag | Process for the simultaneous production of carboxylic acid trimethylsilyl esters and silylated carboxylated amides |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4803371B2 (en) * | 2006-06-16 | 2011-10-26 | 信越化学工業株式会社 | (Poly) amido acid triorganosilyl ester and method for producing (poly) imide |
-
1977
- 1977-03-17 GB GB1141677A patent/GB1581731A/en not_active Expired
- 1977-12-30 DE DE19772758884 patent/DE2758884C3/en not_active Expired
-
1978
- 1978-03-07 ES ES467617A patent/ES467617A1/en not_active Expired
- 1978-03-16 JP JP3050278A patent/JPS53116326A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2167754A (en) * | 1984-12-01 | 1986-06-04 | Dynamit Nobel Ag | Process for the simultaneous production of carboxylic acid trimethylsilyl esters and silylated carboxylated amides |
Also Published As
| Publication number | Publication date |
|---|---|
| DE2758884C3 (en) | 1979-11-22 |
| DE2758884B2 (en) | 1979-04-05 |
| DE2758884A1 (en) | 1978-09-21 |
| JPS53116326A (en) | 1978-10-11 |
| JPS5616157B2 (en) | 1981-04-14 |
| ES467617A1 (en) | 1978-10-16 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PS | Patent sealed | ||
| PCNP | Patent ceased through non-payment of renewal fee | ||
| PCNP | Patent ceased through non-payment of renewal fee |
Free format text: IN PAT.BUL.4970,PAGE 1808, FOR 1581731 READ 1481731 |
|
| PCNP | Patent ceased through non-payment of renewal fee |