GB2108139A - Silylation process - Google Patents
Silylation process Download PDFInfo
- Publication number
- GB2108139A GB2108139A GB08229035A GB8229035A GB2108139A GB 2108139 A GB2108139 A GB 2108139A GB 08229035 A GB08229035 A GB 08229035A GB 8229035 A GB8229035 A GB 8229035A GB 2108139 A GB2108139 A GB 2108139A
- Authority
- GB
- United Kingdom
- Prior art keywords
- organic
- bis
- silylation
- silylating
- compound
- 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.)
- Granted
Links
- 238000000034 method Methods 0.000 title claims abstract description 17
- 238000006884 silylation reaction Methods 0.000 title abstract description 10
- 150000003961 organosilicon compounds Chemical class 0.000 claims abstract description 11
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 9
- 150000002894 organic compounds Chemical class 0.000 claims abstract description 7
- 230000001476 alcoholic effect Effects 0.000 claims abstract description 4
- 150000001875 compounds Chemical class 0.000 claims abstract description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 2
- 239000013543 active substance Substances 0.000 abstract description 2
- 125000005263 alkylenediamine group Chemical group 0.000 abstract description 2
- 230000001681 protective effect Effects 0.000 abstract description 2
- 229910052710 silicon Chemical group 0.000 abstract description 2
- 239000010703 silicon Chemical group 0.000 abstract 1
- 239000003795 chemical substances by application Substances 0.000 description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 6
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 4
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- AOZQTURTLIEFNQ-UHFFFAOYSA-N n,n'-bis(trimethylsilyl)ethane-1,2-diamine Chemical compound C[Si](C)(C)NCCN[Si](C)(C)C AOZQTURTLIEFNQ-UHFFFAOYSA-N 0.000 description 4
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- GVFVNBDEGKVHNR-UHFFFAOYSA-N n,n'-bis(trimethylsilyl)hexane-1,6-diamine Chemical compound C[Si](C)(C)NCCCCCCN[Si](C)(C)C GVFVNBDEGKVHNR-UHFFFAOYSA-N 0.000 description 3
- NKTOLZVEWDHZMU-UHFFFAOYSA-N 2,5-xylenol Chemical compound CC1=CC=C(C)C(O)=C1 NKTOLZVEWDHZMU-UHFFFAOYSA-N 0.000 description 2
- FHTGJZOULSYEOB-UHFFFAOYSA-N 2,6-di(butan-2-yl)phenol Chemical compound CCC(C)C1=CC=CC(C(C)CC)=C1O FHTGJZOULSYEOB-UHFFFAOYSA-N 0.000 description 2
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- UQEAIHBTYFGYIE-UHFFFAOYSA-N hexamethyldisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 description 2
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 2
- -1 nitrogen-containing organosilicon compounds Chemical class 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- 239000000825 pharmaceutical preparation Substances 0.000 description 2
- 229940127557 pharmaceutical product Drugs 0.000 description 2
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 2
- 239000005051 trimethylchlorosilane Substances 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
- BZKFMUIJRXWWQK-UHFFFAOYSA-N Cyclopentenone Chemical compound O=C1CCC=C1 BZKFMUIJRXWWQK-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- JOOMLFKONHCLCJ-UHFFFAOYSA-N N-(trimethylsilyl)diethylamine Chemical compound CCN(CC)[Si](C)(C)C JOOMLFKONHCLCJ-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- NYPUZXXENROZDZ-UHFFFAOYSA-N [2,6-di(butan-2-yl)phenoxy]-trimethylsilane Chemical compound CCC(C)C1=CC=CC(C(C)CC)=C1O[Si](C)(C)C NYPUZXXENROZDZ-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- KXDAEFPNCMNJSK-UHFFFAOYSA-N benzene carboxamide Natural products NC(=O)C1=CC=CC=C1 KXDAEFPNCMNJSK-UHFFFAOYSA-N 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- OLLFKUHHDPMQFR-UHFFFAOYSA-N dihydroxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](O)(O)C1=CC=CC=C1 OLLFKUHHDPMQFR-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000004508 fractional distillation Methods 0.000 description 1
- 229940051250 hexylene glycol Drugs 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- KGQCHUUKOBTAQP-UHFFFAOYSA-N n,n'-bis[butyl(dimethyl)silyl]pentane-1,5-diamine Chemical compound CCCC[Si](C)(C)NCCCCCN[Si](C)(C)CCCC KGQCHUUKOBTAQP-UHFFFAOYSA-N 0.000 description 1
- IHLYKMGMGZRASN-UHFFFAOYSA-N n,n'-bis[dimethyl(phenyl)silyl]butane-1,4-diamine Chemical compound C=1C=CC=CC=1[Si](C)(C)NCCCCN[Si](C)(C)C1=CC=CC=C1 IHLYKMGMGZRASN-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229920000233 poly(alkylene oxides) Polymers 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229940127293 prostanoid Drugs 0.000 description 1
- 150000003814 prostanoids Chemical class 0.000 description 1
- 229940079877 pyrogallol Drugs 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 150000004819 silanols Chemical class 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000008096 xylene Substances 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)
Abstract
A process for silylating an organic or organosilicon compound having alcoholic hydroxyl groups or silicon bonded hydroxyl groups comprises contacting the compound with an N,N'-bis(triorganosilyl)alkylene- diamine. Useful in the protective silylation of hydroxyl groups during the synthesis of certain biologically active substances.
Description
SPECIFICATION
Silylation process
This invention relates to a process for the silylation of organic and organosilicon compounds.
It is known that silyl groups may be transferred from certain organo silicon compounds to other organosilicon compounds or to organic compounds having one or more reactive hydrogen atoms in the molecule. This so-called silylation process has been employed for a number of years on a commercial scale, especially in the synthesis of pharmaceutical products. Organosilicon compounds which have been employed as silylating agents in such a process include the trialkylchorosilanes, for example trimethylchlorosilane, and certain nitrogen-containing organosilicon compounds, hexamethyldisilazane being one of those most commonly used. However, although the presently used silylating agents perform satisfactorily there has been a continuing search for silylating agents having the advantage of improved efficiency.
According to this invention there is provided a process for silylating an organic or organosilicon compound which comprises contacting an organic or an organosilicon compound having in the molecule one or more carbon-bonded alcoholic OH groups or silicon-bondedOH groups with a silylating agent which is a compound having the general formula
(R3Si) NH (CH2)xNH (SiR3) wherein each R represents an alkyl group having from 1 to 4 carbon atoms, a vinyl group or a phenyl group and x is an integer of from 2 to 6 inclusive.
In the general formula of the silylating agents employed according to the process of this invention R may be methyl, ethyl, propyl, butyl, vinyl or phenyl and x may be an integer from 2 to 6 inclusive. Generally, in the practice of the invention the R groups are preferably methyl.
Examples of the operative silylating agents are therefore, N,N'-bis(trimethylsilyl)ethylenediamine, N,N'-bis(dimethylphenylsilyl) tetramethylenediamine, N,N'-bis(butyldimethylsilyl)pentamethylenediamine and N,N'-bis (trimethylsilyl)hexamethylenediamine.
The silylating agents employed in the process of this invention may be prepared by the reaction of a triorganochlorosilane R3SiCI and an alkylene diamine.
Any organic or organosilicon compound having at least one alcoholic -OH bonded directly to a carbon atom or a hydroxyl group bonded to a silicon atom may be silylated according to the process of this invention. Examples of such organic and organosilicon compounds are alcohols e.g. isopropanol, n-hexanol, octadecanol and benzyl alcohol, glycols and polyglycols e.g.
ethylene glycol, hexylene glycol and hydroxyterminated poly(alkylene oxides), phenols e.g.
phenol, m-cresol, p-xylenol, pyrogallol and 2,6-disecbutylphenol and silanols and siloxanols e.g.
diphenylsilanediol and 1 ,3-dimethyl-1, 3 diphenyldisiloxanediol-1 ,3. The process of this invention finds particular application in the silylation of certain biologically active substances or the precursors thereof, a procedure which is carried out on the commercial scale in connection with the synthesis and modification of pharmaceutical products. For example, the process of this invention may be employed to effect the protective silylation of hydroxyl groups during the synthesis of prostanoids wherein the Ci 1-OH group of cyclopentenone system may be silylated and coupled with an organometallic hydroxyl group-containing side chain in which the hydroxyl group is also silylated.
In the performance of the process of this invention the silylating agent and the compound to be silylated may be employed in widely varying proportions, depending on the degree of silylation required. When the maximum degree of silylation is sought it is preferred to employ the silylating agent in a stoichiometric excess of silyl groups to -OH groups.
The silylation reaction may be carried out in the presence or absence of a diluent. Diluents which may be employed include inert organic solvents, for example toluene, xylene, benzene and dimethyl formamide. Some reaction will in many cases take place spontaneously on mixing the reactants at normal temperatures, e.g. 40 to 1 500C may be employed to expedite the reaction and/or facilitate recovery of the reaction product.
The following examples illustrate the invention.
Example 1
N,N'-bis(trimethylsilyl)ethylenediamine (1.02g; 0.005 mole), 2,6-di-secbutylphenol (2.06g; 0.01 mole) and dry dichloromethane (5 ml) were mixed together and maintained at 300C for 30 minutes.
Examination of the mixture by gas-liquid chromotography after this time had elapsed showed that 66.4% by weight of the phenol reactant had been converted to the silylated derivative 2,6-di-secbutylphenoxytrimethylsilane.
The experiment was repeated employing the same reaction time and conditions except that the
N,N'-bis(trimethylsilyl)ethylenediamine was replaced in turn by known silylating agents. The percentage conversions obtained were as follows:
Hexamethyldisilazane 4.2
Hexamethyldisilazane/trimethyl
chlorosilane (equimolar
mixture) 7.2
Trimethylsilyldiethylamine 20.9
N,N'-bis(trimethylsilyl)hexa
methylenediamine 20.0
N,N'-bis(trimethylsilyl)urea 9.0
Example 2
Benzyl alcohol (5.4g; 0.05 mol), N,N'-bis (trimethylsilyl)ethylenediamine (6.129; 0.03 mol) and dry dichloromethane (50 ml) were refluxed together for 30 minutes. The mixture was cooled and subjected to fractional distiilation under vacuum to yield 7.8 g (86%) of the trimethylsilyl- ether of benzyle alcohol.
Example 3
Hexan-1-ol (5.19; 0.05 mol), N,N'-bis (trimethylsilyl) hexamethylenediamine (7.8g; 0.03 mol) and dry dichloromethane (5Oml) were refluxed together for 30 minutes. The mixture was cooled and fractional distillation under vacuum yielded 3.99 (45%) of the trimethylsilylether of hexan-1 -ol.
Claims (3)
1. A process for silylating an organic or organosilicon compound which comprises contacting an organic or an organosilicon compound having in the molecule one or more carbon-bonded alcoholic OH groups or silicon-bonded QH groups with a silylating agent which is a compound having the general formula
(R3Si) NH (CH2)xNH (SiR3) wherein each R represents an alkyl group having from 1 to 4 carbon atoms, a vinyl group or a phenyl group and x is an integer of from 2 to 6 inclusive.
2. A process as claimed in Claim 1 wherein each R is methyl.
3. A process as claimed in Claim 1 or Claim 2 substantially as described with reference to the
Examples herein.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB08229035A GB2108139B (en) | 1981-10-13 | 1982-10-12 | Silylation process |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB8130924 | 1981-10-13 | ||
| GB08229035A GB2108139B (en) | 1981-10-13 | 1982-10-12 | Silylation process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| GB2108139A true GB2108139A (en) | 1983-05-11 |
| GB2108139B GB2108139B (en) | 1985-01-23 |
Family
ID=26280961
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB08229035A Expired GB2108139B (en) | 1981-10-13 | 1982-10-12 | Silylation process |
Country Status (1)
| Country | Link |
|---|---|
| GB (1) | GB2108139B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5885924A (en) * | 1995-06-07 | 1999-03-23 | W. R. Grace & Co.-Conn. | Halogenated supports and supported activators |
| WO2011031943A1 (en) * | 2009-09-10 | 2011-03-17 | Bridgestone Corporation | Compositions and methods for producing poly-aminofunctionalized polymerization initiators and corresponding polymers |
-
1982
- 1982-10-12 GB GB08229035A patent/GB2108139B/en not_active Expired
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5885924A (en) * | 1995-06-07 | 1999-03-23 | W. R. Grace & Co.-Conn. | Halogenated supports and supported activators |
| US6403518B2 (en) | 1995-06-07 | 2002-06-11 | W. R. Grace & Co.-Conn. | Supported catalyst composition derived from halogenated supports and support activators |
| US6432863B2 (en) | 1995-06-07 | 2002-08-13 | W. R. Grace & Co.-Conn. | Halogenated supports and supported activators |
| WO2011031943A1 (en) * | 2009-09-10 | 2011-03-17 | Bridgestone Corporation | Compositions and methods for producing poly-aminofunctionalized polymerization initiators and corresponding polymers |
| US8729204B2 (en) | 2009-09-10 | 2014-05-20 | Bridgestone Corporation | Compositions and method for producing poly-aminofunctionalized polymerization initiators and corresponding polymers |
Also Published As
| Publication number | Publication date |
|---|---|
| GB2108139B (en) | 1985-01-23 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PCNP | Patent ceased through non-payment of renewal fee |