DD238976A1 - PROCESS FOR THE PRODUCTION OF DIORGANOSILYL (VINEGAR ACID ESTERS) - Google Patents
PROCESS FOR THE PRODUCTION OF DIORGANOSILYL (VINEGAR ACID ESTERS) Download PDFInfo
- Publication number
- DD238976A1 DD238976A1 DD27808185A DD27808185A DD238976A1 DD 238976 A1 DD238976 A1 DD 238976A1 DD 27808185 A DD27808185 A DD 27808185A DD 27808185 A DD27808185 A DD 27808185A DD 238976 A1 DD238976 A1 DD 238976A1
- Authority
- DD
- German Democratic Republic
- Prior art keywords
- acid esters
- acetic acid
- diorganosilyl
- preparation
- alkyl
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims abstract description 8
- 238000004519 manufacturing process Methods 0.000 title abstract 2
- -1 VINEGAR ACID ESTERS Chemical class 0.000 title description 2
- 229960000583 acetic acid Drugs 0.000 title 1
- 150000002168 ethanoic acid esters Chemical class 0.000 claims abstract description 12
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 5
- 238000002360 preparation method Methods 0.000 claims abstract description 5
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000012442 inert solvent Substances 0.000 claims abstract description 3
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims abstract description 3
- 150000003512 tertiary amines Chemical class 0.000 claims abstract description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims abstract 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 22
- 150000002148 esters Chemical class 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 238000003786 synthesis reaction Methods 0.000 claims description 2
- 239000000543 intermediate Substances 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- 238000005516 engineering process Methods 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- 150000003863 ammonium salts Chemical class 0.000 description 3
- JMMWKPVZQRWMSS-UHFFFAOYSA-N isopropanol acetate Natural products CC(C)OC(C)=O JMMWKPVZQRWMSS-UHFFFAOYSA-N 0.000 description 3
- 230000008707 rearrangement Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 2
- 229940011051 isopropyl acetate Drugs 0.000 description 2
- GWYFCOCPABKNJV-UHFFFAOYSA-N isovaleric acid Chemical compound CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 description 2
- 150000002560 ketene acetals Chemical class 0.000 description 2
- 239000003039 volatile agent Substances 0.000 description 2
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- YASAKCUCGLMORW-UHFFFAOYSA-N Rosiglitazone Chemical compound C=1C=CC=NC=1N(C)CCOC(C=C1)=CC=C1CC1SC(=O)NC1=O YASAKCUCGLMORW-UHFFFAOYSA-N 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 150000001243 acetic acids Chemical class 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000008648 triflates Chemical class 0.000 description 1
- GKNXALOWPZOTRL-UHFFFAOYSA-N trimethylsilyl 2-chloroacetate Chemical compound C[Si](C)(C)OC(=O)CCl GKNXALOWPZOTRL-UHFFFAOYSA-N 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
Abstract
Die Erfindung betrifft ein Verfahren zur Herstellung von Diorganosilyldi(essigsaeureestern). Ziel der Erfindung ist es, ein Verfahren zur Herstellung dieser Substanzen zu entwickeln, das keine aufwendigen Technologien und umstaendliche Reaktionsfuehrungen voraussetzt. Das Verfahren zur Herstellung der Diorganosilyldi(essigsaeureester) der allgemeinen Formelfuer R2 Me, Et, Pr R3 Alkyl, SiMe3 sowie fuer R2 H,Cl,Br R3 i-Pr, i-Bu, SiMe3 bedeutet, ist gekennzeichnet dadurch, dass Bis(trifluormethansulfonsaeure)diorganosilylester mit Essigsaeureestern unter Zusatz eines tertiaeren Amins in einem inerten Loesungsmittel umgesetzt werden.The invention relates to a process for the preparation of Diorganosilyldi (acetic acid esters). The aim of the invention is to develop a process for the preparation of these substances, which does not require complex technologies and laborious reaction procedures. The process for preparing the diorganosilyl di (acetic acid esters) of the general formula for R2 Me, Et, Pr R3 alkyl, SiMe3 and for R2 H, Cl, Br R3 i-Pr, i-Bu, SiMe3, is characterized in that bis (trifluoromethanesulfonic acid ) Diorganosilylester be reacted with acetic acid esters with the addition of a tertiary amine in an inert solvent.
Description
Diorganosilyldi(essigsäuren) und ihre Derivate sind bisher nicht beschrieben. Bekannt sind lediglich Triorganosilylessigsäureester, die durch Umsetzung von metallierten Essigsäureestern mitTriorganohalogensilanen (R. J. Fessenden und J. S. Fessenden, J. Org. Chem. 32,3535 (1967); J. R. Gold, L. H. Sommer und F. C. Whitemore, J. Amer. Chem. Soc. 70,2874 (1948)) beziehungsweise durch Umsetzung von Essigsäureestern mitTriflaten (H. Emde und G. Simchen, Synthesis 1977,867) entstehen.Diorganosilyldi (acetic acids) and their derivatives have not previously been described. Known are only triorganosilylacetic acid esters prepared by reacting metallated acetic acid esters with triorganohalosilanes (RJ Fessenden and JS Fessenden, J. Org. Chem. 32, 3535 (1967); JR Gold, LH Sommer and Whitemore, J. Amer. Chem , 2874 (1948)) or by reaction of acetic acid esters with triflates (H. Emde and G. Simchen, Synthesis 1977,867).
Ziel der Erfindung ist es, ein Verfahren zur Herstellung von Diorganosilyli(essigsäureestern) zu entwickeln, das keine aufwendigen Technologien und umständliche Reaktionsführungen voraussetzt.The aim of the invention is to develop a process for the preparation of Diorganosilyli (acetic acid esters), which does not require complex technologies and cumbersome reactions.
Die technische Aufgabe der Erfindung ist es, ein Verfahren zu entwickeln, das es erlaubt, ausgehend von einfach zugänglichen Verbindungen die Diorganosilyldi(essigsäureester) in glatter Reaktion zu gewinnen.The technical object of the invention is to develop a process which makes it possible, starting from readily available compounds, to obtain the diorganosilyldi (acetic acid esters) in a smooth reaction.
Es wurde gefunden, daß Bis(trifluormethansulfonsäure)diorganosilylester mit Essigsäureestern unter Zusatz eines tertiären Amins gemäß Gl. (1) zu Ketenacetalen reagieren. Die Reaktion wird bei 0°C in einem inerten Lösungsmittel, vorzugsweise Ether, durchgeführt.It has been found that bis (trifluoromethanesulfonic acid) diorganosilyl ester with acetic acid esters with the addition of a tertiary amine according to Eq. (1) react to ketene acetals. The reaction is carried out at 0 ° C in an inert solvent, preferably ether.
1 2 3 °°C RjSiCOSO2CF3)2 + 2 R-CH2-COOR-5 + 2 NEt3 ►1 2 3 °° C RjSiCOSO 2 CF 3 ) 2 + 2 R-CH 2 -COOR- 5 + 2 NEt 3 ►
R2Si(O-C=CHR2J2 + 2 (Et3NH)+(OSO2CF3)" OR3 R 2 Si (OC = CHR 2 J 2 + 2 (Et 3 NH) + (OSO 2 CF 3 ) "OR 3
In Abhängigkeit von den Substituenten R2 und R3 lagern sich die Ketenacetale gemäß Gl. (2) in die Diorganosilyldi(essigsäureester) um.Depending on the substituents R 2 and R 3 , the ketene acetals store according to Eq. (2) into the diorganosilyl di (acetic acid esters).
R* Si(O-C=CHR2)- > RoSi(CH-COOR3 )o (2)R * Si (OC = CHR 2 ) - > RoSi (CH-COOR 3 ) o (2)
OR"5 ROR " 5 R
R1= Alkyl, ArylR 1 = alkyl, aryl
R2= Me, Et, Pr R3= Alkyl, SiMe3 R2= H, Cl, Br R3= ±-Pr, i-Bu, SiMe3 R 2 = Me, Et, Pr R 3 = alkyl, SiMe 3 R 2 = H, Cl, Br R 3 = ± -Pr, i-Bu, SiMe 3
Ist R2 ein Substituent mit +I-Effekt, so kann R3 ein beliebiger Alkylrest sein. Besitzt R2 hingegen einen -I-Effekt, so wird ein vollständiger Verlauf der Umlagerung nur erreicht, wenn R3 ein sterisch anspruchsvoller Substituent ist. Sind R2 oder R3 aromatische Reste, so wird keine Umlagerung beobachtet. Die Substituenten R1 besitzen keinen Einfluß auf die Umlagerung. Die gemäß Gl. (2) erhaltenen Ester sind hellgelbe Flüssigkeiten, die sich mit Ausnahme des Dimethylsilyldi(essigsäureisopropylesters) bei der Vakuumdestillation zersetzen. Aus NMR-Untersuchungen wurde eine Reinheit der Verbindungen von über 90% ermittelt.If R 2 is a substituent with + I effect, then R 3 may be any alkyl radical. On the other hand, if R 2 possesses an -I effect, a complete course of the rearrangement is achieved only if R 3 is a sterically demanding substituent. If R 2 or R 3 are aromatic radicals, no rearrangement is observed. The substituents R 1 have no influence on the rearrangement. The according to Eq. (2) esters obtained are pale yellow liquids which decompose with the exception of Dimethylsilyldi (isopropyl acetate) in the vacuum distillation. From NMR investigations, a purity of the compounds of more than 90% was determined.
Imfolgenden soll die Erfindung anhand von Beispielen näher erläutert werden:In the following the invention will be explained in more detail by means of examples:
Dimethylsilyldi(essigsäure-isopropylester):Dimethylsilyldi (acetic acid isopropyl ester):
In einem Dreihalskolben mit Tropftrichter, Rührer und Rückflußkühler legt man unter Stickstoffatmosphäre 4,1 g (0,04 mol) Essigsäure-isopropylesterin 50 ml absolutem Ether vor. Bei 00C tropft man eine Mischung aus 7,8 g (0,022 mol) Me2Si(OSO2CF3)2, 4,4g (0,044 mol) NEt3 und 100 ml absolutem Ether zu. Anschließend wird auf Raumtemperatur erwärmt und vier Stunden gerührt. Das Ammoniumsalz der Trifluormethansulfonsäure setzt sich als rotbraunes Öl ab und wird abgetrennt. Man destilliert den Ether ab und fraktioniert im Vakuum.4.1 g (0.04 mol) of isopropyl acetate in 50 ml of absolute ether are placed in a three-necked flask with dropping funnel, stirrer and reflux condenser under a nitrogen atmosphere. At 0 ° C., a mixture of 7.8 g (0.022 mol) of Me 2 Si (OSO 2 CF 3 ) 2 , 4.4 g (0.044 mol) of NEt 3 and 100 ml of absolute ether is added dropwise. It is then warmed to room temperature and stirred for four hours. The ammonium salt of trifluoromethanesulfonic acid precipitates as a red-brown oil and is separated off. The ether is distilled off and fractionated in vacuo.
Kp: 76-78°C/10-2 Torr Ausbeute: 61 %Bp: 76-78 ° C / 10- 2 Torr Yield: 61%
Phenylmethylsilyldi(propionsäuremethylester):Phenylmethylsilyldi (propionate):
In einer wie unter 1. beschriebenen Apparatur werden 3,5 g (0,04 mol) Propionsäuremethylester in 50 ml Ether vorgelegt. Bei 00C tropft man ein Gemisch aus 9,2g (0,022 mol) PhMeSi(OSO2CF3I2,4,5g (0,044 mol) NEt3 und 100 ml Ether zu. Anschließend wird 2 Stunden bei Raumtemperatur gerührt. Nach Abtrennung des Ammoniumsalzes wird der Ether abdestilliert, die flüchtigen Bestandteile werden im Vakuum entfernt. Der Ester wird als hellgelbes Öl erhalten.In an apparatus as described under 1. 3.5 g (0.04 mol) of propionic acid methyl ester in 50 ml of ether. At 0 0 C is added dropwise to a mixture of 9.2 g (0.022 mol) PhMeSi (OSO 2 CF 3 I 2, 4.5 g (0.044 mol) NEt 3 and 100 ml of ether. The mixture is then stirred for 2 hours at room temperature. After separation of the ammonium salt, the ether is distilled off, the volatiles are removed in vacuo and the ester is obtained as a light yellow oil.
Ausbeute: 84%Yield: 84%
DimethylsilyldKchloressigsäuretrimethylsilylester):DimethylsilyldKchloressigsäuretrimethylsilylester):
6,7g (0,04 mol) Chloressigsäuretrimethylsilylester werden in 50ml Ether vorgelegt. Bei 0°C wird ein Gemisch aus 7,8g (0,022 mol) Me2Si(OSO2CF3I2,4,5g (0,044 mol) NEt3 und 100 ml Ether zugetropft. Anschließend wird 24 Stunden bei Raumtemperatur gerührt. Das Ammoniumsalz wird abgetrennt, der Ether abdestilliert. Die flüchtigen Bestandteile werden im Vakuum entfernt. Der Silylester wird als hellgelbes Öl erhalten.6.7 g (0.04 mol) of trimethylsilyl chloroacetate are placed in 50 ml of ether. At 0 ° C., a mixture of 7.8 g (0.022 mol) of Me 2 Si (OSO 2 CF 3 I 2 , 4.5 g (0.044 mol) of NEt 3 and 100 ml of ether is added dropwise, followed by stirring at room temperature for 24 hours Ammonium salt is separated, the ether is distilled off, the volatiles are removed in vacuo, and the silyl ester is obtained as a light yellow oil.
Ausbeute: 83%Yield: 83%
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DD27808185A DD238976A1 (en) | 1985-07-01 | 1985-07-01 | PROCESS FOR THE PRODUCTION OF DIORGANOSILYL (VINEGAR ACID ESTERS) |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DD27808185A DD238976A1 (en) | 1985-07-01 | 1985-07-01 | PROCESS FOR THE PRODUCTION OF DIORGANOSILYL (VINEGAR ACID ESTERS) |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DD238976A1 true DD238976A1 (en) | 1986-09-10 |
Family
ID=5569204
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DD27808185A DD238976A1 (en) | 1985-07-01 | 1985-07-01 | PROCESS FOR THE PRODUCTION OF DIORGANOSILYL (VINEGAR ACID ESTERS) |
Country Status (1)
| Country | Link |
|---|---|
| DD (1) | DD238976A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0395434A3 (en) * | 1989-04-28 | 1991-08-07 | Shin-Etsu Chemical Co., Ltd. | Organosilicon compound |
| WO2010120973A1 (en) * | 2009-04-17 | 2010-10-21 | Dow Global Technologies Inc. | Procatalyst composition with silyl glutarate and method |
-
1985
- 1985-07-01 DD DD27808185A patent/DD238976A1/en not_active IP Right Cessation
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0395434A3 (en) * | 1989-04-28 | 1991-08-07 | Shin-Etsu Chemical Co., Ltd. | Organosilicon compound |
| WO2010120973A1 (en) * | 2009-04-17 | 2010-10-21 | Dow Global Technologies Inc. | Procatalyst composition with silyl glutarate and method |
| US8247341B2 (en) | 2009-04-17 | 2012-08-21 | Dow Global Technologies Llc | Procatalyst composition with silyl glutarate and method |
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