DE1194415B - Process for the preparation of beta-organosilyl-alpha-cyanopropionic acid esters - Google Patents
Process for the preparation of beta-organosilyl-alpha-cyanopropionic acid estersInfo
- Publication number
- DE1194415B DE1194415B DEF41853A DEF0041853A DE1194415B DE 1194415 B DE1194415 B DE 1194415B DE F41853 A DEF41853 A DE F41853A DE F0041853 A DEF0041853 A DE F0041853A DE 1194415 B DE1194415 B DE 1194415B
- Authority
- DE
- Germany
- Prior art keywords
- preparation
- acid esters
- organosilyl
- beta
- alpha
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000000034 method Methods 0.000 title claims description 8
- 238000002360 preparation method Methods 0.000 title claims description 4
- -1 alkyl cyanoacetate Chemical compound 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 150000003512 tertiary amines Chemical class 0.000 claims description 3
- 239000012442 inert solvent Substances 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical class [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- CNTRZROSTQPQPP-UHFFFAOYSA-N bromomethyl-ethoxy-dimethylsilane Chemical compound CCO[Si](C)(C)CBr CNTRZROSTQPQPP-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- 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 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000005840 aryl radicals Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- AOIHZRBXZRWRBG-UHFFFAOYSA-N bromomethyl-diethoxy-methylsilane Chemical compound CCO[Si](C)(CBr)OCC AOIHZRBXZRWRBG-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- WBLIXGSTEMXDSM-UHFFFAOYSA-N chloromethane Chemical compound Cl[CH2] WBLIXGSTEMXDSM-UHFFFAOYSA-N 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- ZIUSEGSNTOUIPT-UHFFFAOYSA-N ethyl 2-cyanoacetate Chemical compound CCOC(=O)CC#N ZIUSEGSNTOUIPT-UHFFFAOYSA-N 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000004508 fractional distillation Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 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
- 229920001296 polysiloxane Polymers 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
- C08G77/26—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen nitrogen-containing groups
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
Description
Verfahren zur Herstellung von B-Organosilyla-cyanpropionsäureestem Die Erfindung betrifft die Herstellung von Verbindungen der allgemeinen Formel worin n gleich 1 oder 2, jeder Substituent R ein Alkyl-oder Arylrest, vorzugsweise Methyl oder Phenyl, und jeder der Substituenten R' und R" ein Alkylrest, vorzugsweise mit weniger als 5 C-Atomen, ist.Process for the preparation of B-organosilyla-cyanpropionic acid esters The invention relates to the preparation of compounds of the general formula where n is 1 or 2, each substituent R is an alkyl or aryl radical, preferably methyl or phenyl, and each of the substituents R 'and R "is an alkyl radical, preferably having fewer than 5 carbon atoms.
Erfindungsgemäß erhält man diese S-Organosilyla-cyanpropionsäureester, indem man einen Cyanessigsäurealkylester der allgemeinen Formel mit einem Organobrommethylsilan der allgemeinen Formel RnSi(OR')3-n - CH2Br in Gegenwart eines tertiären Amins bei Temperaturen zwischen 80 und 200°C umsetzt. Das Reaktionsgemisch kann mit einem inerten Lösungsmittel, wie Toluol, Xylol, Petroleum oder Di-n-butyläther. verdünnt sein. Als tertiäres Amin ist beispielsweise Triäthylamin zu verwenden. Als Beispiele der Organobrommethylsilane seien Dimethyl (äthoxy) - brommethylsilan und Methyl-diäthoxy-brommethylsilan genannt.According to the invention, these S-organosilyla-cyanopropionic acid esters are obtained by adding an alkyl cyanoacetate of the general formula with an organobromomethylsilane of the general formula RnSi (OR ') 3-n - CH2Br in the presence of a tertiary amine at temperatures between 80 and 200 ° C. The reaction mixture can be mixed with an inert solvent such as toluene, xylene, petroleum or di-n-butyl ether. be diluted. Triethylamine, for example, can be used as the tertiary amine. Examples of the organobromomethylsilanes are dimethyl (ethoxy) bromomethylsilane and methyl diethoxybromomethylsilane.
Dieses Verfahren vermeidet die Nachteile des bekannten Herstellungsweges über die Organochlormethylsilane, bei dem das schwierig und gefährlich zu handhabende Natrium verwendet wird und der als Lösungsmittel absoluten Alkohol erfordert, dessen aufwendige Gewinnung hier unumgänglich ist, weil ein auch nur geringer Wassergehalt zur Bildung von NaOH und dieses im Reaktionsgemisch zur hydrolytischen Abspaltung des Chlormethylrestes vom Silicium führt. Ein weiterer Vorteil ist, daß die Reaktion in dem erfindulngsgemäßen Verfahren schneller abläuft. This method avoids the disadvantages of the known manufacturing route about the organochloromethylsilanes, which are difficult and dangerous to handle Sodium is used and the solvent requires absolute alcohol, its expensive extraction is unavoidable here because there is only a low water content for the formation of NaOH and this in the reaction mixture for hydrolytic cleavage of the chloromethyl radical from silicon. Another benefit is that the response runs faster in the process according to the invention.
Die nach dem erfindungsgemäßen Verfahren erhaltenen Ester sind wertvolle Zwischenprodukte, aus denen man nach bekannten Methoden cyan- und carboxyfunktionelle Die und höhere Polysiloxane herstellen kann. The esters obtained by the process according to the invention are valuable Intermediate products from which cyano- and carboxy-functional ones can be obtained by known methods Can produce and higher polysiloxanes.
Beispiel Ein Gemisch von 985 g (5 Mol) Dimethyläthoxybrommethylsilan, 622 g (5,5 Mol) Cyanessigsäureäthylester, 607 g (6 Mol) Triäthylamin und 11 Toluol erhitzt man 8 Stunden unter Rückfluß. Das dabei ausgeschiedege Bromsalz trennt man durch Filtrieren ab. Es enthält, durch'Titration nach Auflösen in Wasser bestimmt, 840/0 des eingesetzten Broms. Example A mixture of 985 g (5 mol) of dimethylethoxybromomethylsilane, 622 g (5.5 mol) of ethyl cyanoacetate, 607 g (6 mol) of triethylamine and 11 toluene the mixture is refluxed for 8 hours. The bromine salt precipitated in the process is separated by filtration. It contains, determined by titration after dissolving in water, 840/0 of the bromine used.
Aus dem Filtrat isoliert man durch fraktionierte Destillation den B-Dimethyläthoxysilyl-a-cyanpropionsäureäthylester; Kp.1,5 = 100C; nD20 = 1,4334. The filtrate is isolated by fractional distillation B-dimethylethoxysilyl-a-cyanopropionic acid ethyl ester; B.p. 1.5 = 100C; nD20 = 1.4334.
Die Analyse ergibt: 52,380/0 C, 6,00/0 N, Molgewicht 216. The analysis gives: 52.380 / 0 C, 6.00 / 0 N, molecular weight 216.
Für C10H19N03Si berechnet: 52, 37°/o C, 6,1% N, Molgewicht 229. Calculated for C10H19N03Si: 52.37 ° / o C, 6.1% N, molecular weight 229.
Claims (1)
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEF41853A DE1194415B (en) | 1964-01-29 | 1964-01-29 | Process for the preparation of beta-organosilyl-alpha-cyanopropionic acid esters |
| FR2547A FR1421134A (en) | 1964-01-29 | 1965-01-20 | Process for preparing esters of beta-organosilyl-alpha-cyanopropionic acids |
| BE658620D BE658620A (en) | 1964-01-29 | 1965-01-21 | |
| GB3579/65A GB1035283A (en) | 1964-01-29 | 1965-01-27 | Production of ª‰-organosilyl-ª‡-cyanopropionic acid esters |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEF41853A DE1194415B (en) | 1964-01-29 | 1964-01-29 | Process for the preparation of beta-organosilyl-alpha-cyanopropionic acid esters |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE1194415B true DE1194415B (en) | 1965-06-10 |
Family
ID=7098842
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DEF41853A Pending DE1194415B (en) | 1964-01-29 | 1964-01-29 | Process for the preparation of beta-organosilyl-alpha-cyanopropionic acid esters |
Country Status (4)
| Country | Link |
|---|---|
| BE (1) | BE658620A (en) |
| DE (1) | DE1194415B (en) |
| FR (1) | FR1421134A (en) |
| GB (1) | GB1035283A (en) |
-
1964
- 1964-01-29 DE DEF41853A patent/DE1194415B/en active Pending
-
1965
- 1965-01-20 FR FR2547A patent/FR1421134A/en not_active Expired
- 1965-01-21 BE BE658620D patent/BE658620A/xx unknown
- 1965-01-27 GB GB3579/65A patent/GB1035283A/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| BE658620A (en) | 1965-05-17 |
| GB1035283A (en) | 1966-07-06 |
| FR1421134A (en) | 1965-12-10 |
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