DE2711092C2 - Use of a nitrogen-containing organosilicon compound as a silylating agent - Google Patents
Use of a nitrogen-containing organosilicon compound as a silylating agentInfo
- Publication number
- DE2711092C2 DE2711092C2 DE19772711092 DE2711092A DE2711092C2 DE 2711092 C2 DE2711092 C2 DE 2711092C2 DE 19772711092 DE19772711092 DE 19772711092 DE 2711092 A DE2711092 A DE 2711092A DE 2711092 C2 DE2711092 C2 DE 2711092C2
- Authority
- DE
- Germany
- Prior art keywords
- silylation
- compounds
- sulfamate
- group
- agent
- 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.)
- Expired
Links
- 239000003795 chemical substances by application Substances 0.000 title claims description 13
- -1 nitrogen-containing organosilicon compound Chemical class 0.000 title claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 238000006884 silylation reaction Methods 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 7
- 150000002894 organic compounds Chemical class 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 150000003961 organosilicon compounds Chemical class 0.000 claims description 5
- IIACRCGMVDHOTQ-UHFFFAOYSA-M sulfamate Chemical compound NS([O-])(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-M 0.000 claims description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 4
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid Chemical class NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 230000001133 acceleration Effects 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 229910052710 silicon Chemical group 0.000 claims description 2
- 239000010703 silicon Chemical group 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims 4
- 239000001257 hydrogen Substances 0.000 claims 4
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 4
- 125000000217 alkyl group Chemical group 0.000 claims 3
- YGZSVWMBUCGDCV-UHFFFAOYSA-N chloro(methyl)silane Chemical compound C[SiH2]Cl YGZSVWMBUCGDCV-UHFFFAOYSA-N 0.000 claims 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims 2
- NNWLMTLHOGRONX-UHFFFAOYSA-N 1-trimethylsilylpropan-2-one Chemical compound CC(=O)C[Si](C)(C)C NNWLMTLHOGRONX-UHFFFAOYSA-N 0.000 claims 1
- 239000005046 Chlorosilane Substances 0.000 claims 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims 1
- CIUQDSCDWFSTQR-UHFFFAOYSA-N [C]1=CC=CC=C1 Chemical compound [C]1=CC=CC=C1 CIUQDSCDWFSTQR-UHFFFAOYSA-N 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 1
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 claims 1
- 239000003814 drug Substances 0.000 claims 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims 1
- 239000002184 metal Substances 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- 229920001296 polysiloxane Polymers 0.000 claims 1
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 claims 1
- 229910052717 sulfur Chemical group 0.000 claims 1
- 239000011593 sulfur Chemical group 0.000 claims 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 10
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 10
- 239000002253 acid Substances 0.000 description 8
- 238000001030 gas--liquid chromatography Methods 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 5
- 150000007513 acids Chemical class 0.000 description 4
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-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
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- 238000003786 synthesis reaction Methods 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
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- 239000005711 Benzoic acid Substances 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 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 2
- 235000011054 acetic acid Nutrition 0.000 description 2
- 235000010233 benzoic acid Nutrition 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 2
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-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
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- HSHGZXNAXBPPDL-HZGVNTEJSA-N 7beta-aminocephalosporanic acid Chemical compound S1CC(COC(=O)C)=C(C([O-])=O)N2C(=O)[C@@H]([NH3+])[C@@H]12 HSHGZXNAXBPPDL-HZGVNTEJSA-N 0.000 description 1
- GEHMBYLTCISYNY-UHFFFAOYSA-N Ammonium sulfamate Chemical compound [NH4+].NS([O-])(=O)=O GEHMBYLTCISYNY-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-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
- CZBUSWDBGOLOCH-UHFFFAOYSA-N N1C(CC1)S(=O)O Chemical class N1C(CC1)S(=O)O CZBUSWDBGOLOCH-UHFFFAOYSA-N 0.000 description 1
- 229910003849 O-Si Inorganic materials 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229910003872 O—Si Inorganic materials 0.000 description 1
- 229930182555 Penicillin Natural products 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001412 amines Chemical class 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
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- HYDKNNPDQVDKMG-UHFFFAOYSA-N bis(trimethylsilyl)sulfamic acid Chemical compound C[Si](C)(C)N([Si](C)(C)C)S(O)(=O)=O HYDKNNPDQVDKMG-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical class [H]OC(*)=O 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- DQEFDZIXXACIOR-UHFFFAOYSA-N methylsilyl benzoate Chemical compound C[SiH2]OC(=O)C1=CC=CC=C1 DQEFDZIXXACIOR-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 229940056360 penicillin g Drugs 0.000 description 1
- 150000002960 penicillins Chemical class 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
- 238000002360 preparation method Methods 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 229940079877 pyrogallol Drugs 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000004819 silanols Chemical class 0.000 description 1
- 150000003431 steroids Chemical class 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- UABFFWVEXACZGD-UHFFFAOYSA-N trimethyl(pentoxy)silane Chemical compound CCCCCO[Si](C)(C)C UABFFWVEXACZGD-UHFFFAOYSA-N 0.000 description 1
- 239000005051 trimethylchlorosilane Substances 0.000 description 1
- SIOVKLKJSOKLIF-HJWRWDBZSA-N trimethylsilyl (1z)-n-trimethylsilylethanimidate Chemical compound C[Si](C)(C)OC(/C)=N\[Si](C)(C)C SIOVKLKJSOKLIF-HJWRWDBZSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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)
Description
[RTl2SI]2NH[RTl 2 SI] 2 NH
mit Ammonlumsulfamat. Diese Umsetzung geht im einzelnen aus DE-OS 27 11 091 hervor.
Jede organische oder Organoslliclumverbindung mit wenigstens einer an Kohlenstoff oder an Silicium
gebundenen OH und/oder NH-Gruppe im Molekül kann nach dem erfindungsgemäß zu verwendenden
Mittel sllyllert werden. Beispiele für solche organische und Organosiliclumverblndungen sind Alkohole, wie
Isopropanol, n-Hexanol, Octadecanol und Benzylalkohol,
Glycole und Polyglycole, wie Äthylenglycol und Hydroxyendgruppen enthaltende Poly(alkylenoxlde),
Phenole wie Phenol selbst, m-KresoI, p-Xylenol, Pyrogallol
und 2,6-Dl-sek.-butylphenol, Mono- und Polycarbonsäuren, wie Essigsäure, Propionsäure, Benzoesäure,
Oxalsäure, Malonsäure und Maleinsäure, Amine wie Äth)Iendlamln, Dläthylentrlamln und Anilin und Silanole
und Siloxanole, wie Dlphenylsllandlol und 1,3-Dlmethyl-l,3-dlphenyl-dislloxandiol-l,3.
Erflndungsge-with ammonium sulfamate. This implementation can be seen in detail from DE-OS 27 11 091.
Any organic or organosilicon compound with at least one OH and / or NH group bonded to carbon or silicon in the molecule can be silylated according to the agent to be used according to the invention. Examples of such organic and organosilicon compounds are alcohols such as isopropanol, n-hexanol, octadecanol and benzyl alcohol, glycols and polyglycols such as ethylene glycol and poly (alkylene oxides) containing hydroxyl end groups, phenols such as phenol itself, m-cresol, p-xylenol, and pyrogallol , 6-Dl-sec.-butylphenol, mono- and polycarboxylic acids, such as acetic acid, propionic acid, benzoic acid, oxalic acid, malonic acid and maleic acid, amines such as eth) iendlamine, diethylenetrlamine and aniline, and silanols and siloxanols such as diphenylsilandlol and 1,3-dimethylol -l, 3-dlphenyl-dislloxanediol-l, 3. Invention
ss maß lassen sich vor allem biologisch aktive Substanzen oder Ihre Vorläufer sllylleren, wie Penicilline und Steroide. Hierbei Ist die zu silyHerende Gruppe gewöhnlich eine OH-Gruppe In Form einer Carboxylgruppe (-CO.OH) oder einer -C.OH-Gruppe. Von der Erflndung kann daher beispielsweise mit Vorteil Gebrauch gemacht werden zur schützenden Sllyllerung von Penicillin G während seiner Überführung In 6-Amlnopeniclllansäure, zur schützenden Sllyllerung von 6-Amlnopenlclllansäure während ihrer Überführung In 6-Acylamldopenlclllansäuren und zur schützenden Sllyllerung von 7-Aminocephalosporansäure und 7-Amldodesacetoxycephalosporansäure während Ihrer Überführung In 7-AcylamldocephalosporansSuren und 7-Acylamldodes-Above all, biologically active substances can be used or their precursors such as penicillins and steroids. Here the group to be established is common an OH group in the form of a carboxyl group (-CO.OH) or a -C.OH group. From the invention can therefore be used to advantage, for example, for the protective synthesis of penicillin G during its conversion into 6-aminopenicllanic acid, for the protective silylation of 6-aminopenic acid during its conversion into 6-acylamdopenic acid and for the protective synthesis of 7-aminocephalosporanic acid and 7-amldodeacetoxycephalosporanic acid during your transfer to 7-acylamldocephalosporan acids and 7-acylamldodes-
acetoxycephalosporansäuren. Weiter kann die Erfindung beispielsweise auch Anwendung finden bei der Überführung von ö-Acylamidopenlclllansäuresulfoxiden in 7-Acylamldodesacetoxycephalosporansäuren und der Herstellung der Silylester von Azetidin-2-sulfinaten. ■acetoxycephalosporanic acids. The invention can also for example also find application in the conversion of δ-acylamidopenlclllansäuresulfoxiden in 7-acylamldodesacetoxycephalosporanic acids and the Preparation of the silyl esters of azetidine-2-sulfinates. ■
Zur Durchführung der Silyierung können die erfindungsgemäß als Sicherungsmittel dienenden Sulfamatverbindungen und die zu silylierenden Verbindungen in den verschiedensten Verhältnissen eingesetzt wenden. Die im Einzelfall angewandten Verhältnisse hängen in einem gewissen Maß von dem gewünschten Silylierungsgrad ab. Wenn man alle vorhandenen OH und/oder NH Gruppen silylieren möchte, dann wird das Sulfamat vorzugsweise in einem stöchiometrischen Überschuß angewandt. iäThe sulfamate compounds which serve as securing agents according to the invention can be used to carry out the silyation and the compounds to be silylated are used in a wide variety of ratios. The ratios used in the individual case depend to a certain extent on the desired degree of silylation away. If you want to silylate all existing OH and / or NH groups, then the sulfamate is preferably used in a stoichiometric excess. iä
Die erfindungsgemäße Silylierungsreaktion kann in Gegenwart oder Abwesenheit eines Verdünnungsmittels durchgeführt werden. Verdünnungsmittel, die falls erwünscht, verwendet werden können, sind inerte organische Lösungsmittel, wie Toluol, Xylol, Benzol, Hexan, Dichlorreeuian und Dimethylformamid. Ein Nebenprodukt der Silylierungreaktion Ist Sulfaminsäure. Diese Verbindung ist in den meisten organischen Lösungsmitteln unlöslich und kann deshalb bei Verwendung eines geeigneten organischen Lösungsmittels leicht durch Abgießen oder Filtrieren entfernt werden.The silylation reaction according to the invention can be carried out in the presence or absence of a diluent be performed. Diluents which can be used if desired are inert organic Solvents such as toluene, xylene, benzene, hexane, dichloroethane and dimethylformamide. A By-product of the silylation reaction is sulfamic acid. This compound is insoluble in most organic solvents and can therefore be used in Use of a suitable organic solvent easily removed by pouring or filtering.
In vielen Fällen setzt die Reaktion nach dem Vermischen des Suifamats und der zu silylierenden organischen und/oder Organoslliclumverbindung spontan ein. Wenn erwünscht können jedoch auch zur Beschleunigung der Reaktion und/oder zur Erleichterung der Gewinnung des Reaktionsprodukte e'"/öhte Temperaturen, zum Beispiel von 30 bis 140° C angewandt werden.In many cases the reaction continues after the suifamate and the organic to be silylated have been mixed and / or organosilicate compound spontaneously. If desired, however, it can also be used for acceleration the reaction and / or to facilitate the recovery of the reaction products e '"/ ohte temperatures, for example from 30 to 140 ° C can be used.
Silyllerungsreaktionen werden häufig ;am Schutz von OH- und/oder NH-Gruppen während organischer Synthesen angewandt. Hierbei ist es üblich, die SiIyI-gruppe durch Umsetzung mit Wasser von der organischen Verbindung zu entfernen. In dieser Stufe als Nebenprodukt etwa vorhandene Sulfaminsäure kann von dem Reaktionsgemisch in wäßriger Lösung entfernt und danach, falls erwünscht durch Erwärmen dieser Lösung oder durch Stehenlassen derselben, In Ammonlumblsulfat Obergeführt werden.Silylation reactions are frequent; at the protection of OH and / or NH groups applied during organic syntheses. Here it is common to use the SiIyI group to be removed from the organic compound by reaction with water. At this stage as Any sulfamic acid present by-product can be removed from the reaction mixture in aqueous solution and thereafter, if desired, by heating this solution or by allowing it to stand, in ammonium sulfate Be carried over.
Durch die folgenden Beispiele wird die Erfindung welter erläutert.The invention is illustrated by the following examples Welter explains.
2,22 g (0,03 Mol) n-Butanol werden zu einer Lösung von 7,20 g (0,03 MoI) Trlmethylsilyltrlmethylsllylsulfamat 2.22 g (0.03 mol) of n-butanol are added to a solution of 7.20 g (0.03 mol) of methylsilyltrimethylsllyl sulfamate
(CHjLSlNHSOjSKCH,),(CHjLSlNHSOjSKCH,),
5555
In 25 cmJ trockenem Dlchlonnethan von 30 ° C gegeben. Nach dem Vermischen erfolgt sofort eine exotherme Reaktion, und Sulfaminsäure fällt aus. Nach 30 Minuten bei 3O0C wird die Mischung filtriert und das Flltrat destilliert, wodurch 4,06 g (92,7«) n-Butoxytrlmethylsllan vom Kp 123e C erhalten werden. Die Analyse durch Gasflüssigkeitschromatographie ergibt eine Reinheit von über 98%.Put in 25 cm J dry chlorine film at 30 ° C. After mixing, an exothermic reaction occurs immediately and sulfamic acid precipitates. After 30 minutes at 3O 0 C, the mixture is filtered and the Flltrat distilled to give 4.06 g (92.7 ") n-Butoxytrlmethylsllan, bp 123 e C are obtained. Analysis by gas-liquid chromatography shows a purity of over 98%.
Nach der in Beispiel 1 beschriebenen Arbeitsweise werden untar Verwendung von 2,64 g (0,03 Mol) n-Pentano! anstelle von n-Butanol 4,42 g (92*) n-Pentoxytrimethylsilan erhalten. Kp 149° C, Reinheit 98% (Gasflüssigkeitschromatographie).Following the procedure described in Example 1, using 2.64 g (0.03 mol) n-Pentano! instead of n-butanol, 4.42 g (92 *) n-pentoxytrimethylsilane were obtained. Bp 149 ° C, purity 98% (gas-liquid chromatography).
Analyse, SiC8H20O:
berechnet: Si 17,52;
gefunden: Si 17,63.Analysis, SiC 8 H 20 O:
calculated: Si 17.52;
found: Si 17.63.
Die in Beispiel 1 beschriebene Arbeltswelse wird unter Verwendung von 3,66 g (0,03 Mol) Benzoesäure anstelle von n-Butanol wiederholt. Es werden 5,51 g (94,7%) Trlmethylsilylbenzoat vom Kp 67 bis 68° C bei 1,0 mm Hg erhalten. Die Reinheit Hegt über 98% (Gasflüssigkeitschromatographie).The work described in Example 1 is made using 3.66 g (0.03 mol) of benzoic acid repeated instead of n-butanol. 5.51 g (94.7%) of methylsilyl benzoate with a boiling point of 67 ° to 68 ° C. are obtained 1.0 mm Hg was obtained. The purity is over 98% (gas-liquid chromatography).
Die in Beispiel ! beschriebene Arbeitsweise wird unter Verwendung von 6,18 g (0,03 Mol) 2,6-Dl-(sek.-butyDphenoI, einem sterisch gehinderten Phenol, anstelle von n-Butanol wiederholt. Es werden 7,92 g (95%) 2,6-Di(sek.-butyl)phenoxytrimethyls!lan vom Kp 77° C bei 0,6 mm Hg erhalten. Die Reinheit liegt über 98% (Gasflüssigkeitschromatographie).The one in example! described procedure is using 6.18 g (0.03 mol) of 2,6-Dl- (sec-butyDphenoI, a sterically hindered phenol, instead of n-butanol. There are 7.92 g (95%) 2,6-di (sec-butyl) phenoxytrimethylsilane with a boiling point of 77 ° C. at 0.6 mm Hg. The purity lies over 98% (gas-liquid chromatography).
Analyse, SiC17H30O:
berechnet: Si 10,08;
gefunden: Si 10,63.Analysis, SiC 17 H 30 O:
calculated: Si 10.08;
found: Si 10.63.
Die In Beispiel 1 beschriebene A'V-Uswelse wird unter Verwendung von 1,80 g (0,03 MoI) Essigsäure anstelle von n-Butanol wiederholt. Es werden 3,68 g (93%) Acetoxytrlmethylsllan vom Kp 102 bis 103° C erhalten. Die durch Gasflüssigkeitschromatographie bestimmte Reinheit liegt über 98%.The A'V-Uswelse described in Example 1 is using 1.80 g (0.03 mol) acetic acid instead of n-butanol. It will be 3.68 g (93%) Acetoxytrlmethylsllane with a boiling point of 102 to 103 ° C obtain. The purity determined by gas-liquid chromatography is over 98%.
Analyse, SlC5H12O:
berechnet: Sl 21,24;
gefunden: Si 20,79.Analysis, SlC 5 H 12 O:
calculated: Sl 21.24;
found: Si 20.79.
Analyse SlC7H11O:
berechnet: Sl 19,20;
gefunden: Sl 18,40.Analysis SlC 7 H 11 O:
calculated: Sl 19.20;
found: Sl 18.40.
6565
Verschiedene Anteile von 2,06 g (0,010 MoI) 2,6-Dl-(sek.-butyl)-phenol In 5 ml trockenem Dlchlormethan werden mit verschiedenen Sllyllerungsmltteln behande't und zwar entweder mit 0,010 Mol eines monofunktlonellen oder mit 0,005 Mol eines dlfunktlonellen. Nach 30 Minuten bei 30° C wird die Umwandlung des Phenols in 2,6-Dl-(sek.-butyl)-phenoxytrlmethylsllan In Gew.-% durch Gasflüssigkeitschromatographie ermittelt. Es werden folgende Ergebnisse erhalten:Various proportions of 2.06 g (0.010 mol) of 2,6-Dl- (sec-butyl) -phenol 5 ml of dry chloromethane are treated with various detergents either with 0.010 mol of a monofunctional or with 0.005 mol of a dlfunctional. To 30 minutes at 30 ° C, the conversion of the Phenol in 2,6-Dl- (sec-butyl) -phenoxytrlmethylsllane in% by weight determined by gas-liquid chromatography. The following results are obtained:
Umwandlung in %Conversion in%
Trimethylsilyltrimethylsilylsulfamat 100,0Trimethylsilyltrimethylsilylsulfamate 100.0
N,O-bis(Trimethylsilyl)-acetamid 75N, O-bis (trimethylsilyl) acetamide 75
Trimethylsilyldiäthylamin 51Trimethylsilyl diethylamine 51
Fortsetzungcontinuation
Hexamethyldisilazan/Hexamethyldisilazane /
Trimethylchlorsilan ')
Hexamethyldisilazan/HvSO4 2)
HexamethyldisilazanTrimethylchlorosilane ')
Hexamethyldisilazane / HvSO 4 2 ) hexamethyldisilazane
') äquimolare Mischung
2) l,( MoI-% H2SO4 ') equimolar mixture
2 ) l, (MoI-% H 2 SO 4
Umwandlungconversion
1919th
35 335 3
Beispiel 7 Trimethylsilyl-bis(trimethylsilyl)-sulfatExample 7 Trimethylsilyl bis (trimethylsilyl) sulfate
[(CH3)3SiLNSO2-O-Si(CH3)3 wird nach der Methode von Becke-Goehring et al., Annalen, Bd. 618, S. 43 bis 52 (1958) hergestellt. 4,70 g (0,015 Mol) dieser Verbindung und 1,82 g (0,010 MeI) 2,6-Dl-sek.-butylphenol werden in einem bei 24° C gehaltenen verschlossenen Kolben miteinander vermischt. Es bildet sich sofort ein weißer Niederschlag. Nach 15 Minuten wird das Reaktionsgemisch durch Gasflüssigkeitschromatographie untersucht, wofür eine 183 χ 0,64 cm messende Säule verwendet wird, die mit einem hochviskosen Diorganopolyslloxan auf Diatopart S. als Träger gefüllt Ist. Die chromatographische Säule wird mit einer Geschwindigkeit von 20°C/Minute von 700C auf 300° C erwärmt. Dabei wird eine einzige Spitze mit einer Verweilzeit von 8,90 Minuten, die dem 2,6-Di-sek.-butylphenoxytrimethylsilan entspricht, erhalten, woraus sich ergibt, daß die Siiylierung innerhalb von 15 Minuten praktisch vollständig ist.[(CH 3 ) 3 SiLNSO 2 -O-Si (CH 3 ) 3 is prepared according to the method of Becke-Goehring et al., Annalen, Vol. 618, pp. 43 to 52 (1958). 4.70 g (0.015 mol) of this compound and 1.82 g (0.010 mol) 2,6-Dl-sec-butylphenol are mixed with one another in a sealed flask kept at 24 ° C. A white precipitate forms immediately. After 15 minutes, the reaction mixture is examined by gas-liquid chromatography, for which a column measuring 183 χ 0.64 cm is used, which is filled with a highly viscous diorganopolyslloxane on Diatopart S. as a carrier. The chromatographic column is heated at a rate of 20 ° C / minute from 70 0 C to 300 ° C. A single peak with a residence time of 8.90 minutes, which corresponds to 2,6-di-sec-butylphenoxytrimethylsilane, is obtained, from which it follows that the silylation is practically complete within 15 minutes.
Unter den gleichen Bedingungen wird mit Hexamethyldisilazan eine Silyllerung von 8» und mit einer Mischung von Hexamethyldisilazan mit 10 Gew.-°6 (CH3)3SiCl eine Siiylierung von 4-f<- erzielt.Under the same conditions, a silylation of 8% is achieved with hexamethyldisilazane and a silylation of 4-f <- with a mixture of hexamethyldisilazane with 10% by weight 6 (CH 3 ) 3 SiCl.
Claims (1)
worin die einzelnen Reste
R Methyl- oder Äthylgruppen,
die einzelnen ResteRTl 2 SiNSO 3 SiRTl 2 ,
in which the individual residues
R methyl or ethyl groups,
the individual remains
In der Im Anspruch angegebenen allgemeinen Formel der erflndungsg^mäß als Silylierungsmittel einzusetzenden Sulfamatverbindungen kann jeder der Reste R' und R" Wasserstoff, eine Alkyigruppe mit bis zu S Kohlenstoffatomen, z. B. Methyl, Äthyl, tert.-Butyl, Hexyl und 2,4,4-Trimethylpentyl oder R' eine Phenylgruppe sein. R" kann außerdem eine Gruppe RTl2Si- z. B. (CHj)3Si-, (CH2=CH) (CHj)2SK (C6HsXCHj)2Sl- oder H(CHj)2Si- sein. Die Herstellung solcher Sulfamatverbindungen wird beispielsweise In Chem. Ber. Bd. 90, S. 1235 (1957) und Annalen, Bd. 618, S. 43 bis 52The invention thus relates to the use of a nitrogen-containing organosilicon compound as a silylating agent, as indicated in the preceding claim.
In the general formula given in the claim of the sulfamate compounds to be used as silylating agents according to the invention, each of the radicals R 'and R "can be hydrogen, an alkyl group with up to S carbon atoms, e.g. methyl, ethyl, tert-butyl, hexyl and 2 , 4,4-trimethylpentyl or R 'be a phenyl group. R "can also be a group RTl 2 Si z. B. (CHj) 3 Si-, (CH 2 = CH) (CHj) 2 SK (C 6 HsXCHj) 2 Sl- or H (CHj) 2 Si-. The production of such sulfamate compounds is described, for example, in Chem. Ber. Vol. 90, p. 1235 (1957) and Annalen, Vol. 618, p. 43 to 52
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB1108376A GB1511436A (en) | 1976-03-19 | 1976-03-19 | Silylation process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| DE2711092A1 DE2711092A1 (en) | 1977-09-22 |
| DE2711092C2 true DE2711092C2 (en) | 1984-08-02 |
Family
ID=9979728
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE19772711092 Expired DE2711092C2 (en) | 1976-03-19 | 1977-03-14 | Use of a nitrogen-containing organosilicon compound as a silylating agent |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JPS52139025A (en) |
| DE (1) | DE2711092C2 (en) |
| ES (1) | ES456995A1 (en) |
| GB (1) | GB1511436A (en) |
| NL (1) | NL7702279A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4459421A (en) * | 1981-06-12 | 1984-07-10 | The United States Of America As Represented By The United States Department Of Energy | Method of preparing (CH3)3 SiNSO and byproducts thereof |
| CN114524839B (en) * | 2022-01-12 | 2024-06-25 | 湖北江瀚新材料股份有限公司 | Preparation method of stearoxy trimethylsilane |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB760059A (en) * | 1953-06-16 | 1956-10-31 | Midland Silicones Ltd | A process of silylating organic compounds |
| US3397220A (en) * | 1964-05-28 | 1968-08-13 | Gen Electric | Silylating process and agent |
-
1976
- 1976-03-19 GB GB1108376A patent/GB1511436A/en not_active Expired
-
1977
- 1977-03-03 NL NL7702279A patent/NL7702279A/en not_active Application Discontinuation
- 1977-03-14 DE DE19772711092 patent/DE2711092C2/en not_active Expired
- 1977-03-18 JP JP2934677A patent/JPS52139025A/en active Granted
- 1977-03-18 ES ES456995A patent/ES456995A1/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| DE2711092A1 (en) | 1977-09-22 |
| JPS52139025A (en) | 1977-11-19 |
| NL7702279A (en) | 1977-09-21 |
| GB1511436A (en) | 1978-05-17 |
| ES456995A1 (en) | 1978-02-01 |
| JPS56439B2 (en) | 1981-01-08 |
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