SU715580A1 - Method of preparing silicon acetylenic carbonylic compounds - Google Patents
Method of preparing silicon acetylenic carbonylic compounds Download PDFInfo
- Publication number
- SU715580A1 SU715580A1 SU782654906A SU2654906A SU715580A1 SU 715580 A1 SU715580 A1 SU 715580A1 SU 782654906 A SU782654906 A SU 782654906A SU 2654906 A SU2654906 A SU 2654906A SU 715580 A1 SU715580 A1 SU 715580A1
- Authority
- SU
- USSR - Soviet Union
- Prior art keywords
- acetylenic
- preparing silicon
- oxidizing agent
- carbonylic compounds
- compounds
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 11
- 150000001875 compounds Chemical class 0.000 title description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title 1
- 229910052710 silicon Inorganic materials 0.000 title 1
- 239000010703 silicon Substances 0.000 title 1
- LEHBURLTIWGHEM-UHFFFAOYSA-N pyridinium chlorochromate Chemical compound [O-][Cr](Cl)(=O)=O.C1=CC=[NH+]C=C1 LEHBURLTIWGHEM-UHFFFAOYSA-N 0.000 claims description 8
- 239000007800 oxidant agent Substances 0.000 claims description 7
- 150000001728 carbonyl compounds Chemical class 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 2
- LSXBOJRQFRKOKI-UHFFFAOYSA-N 3-silylprop-2-yn-1-ol Chemical compound OCC#C[SiH3] LSXBOJRQFRKOKI-UHFFFAOYSA-N 0.000 claims 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 15
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- -1 silicon acetylene carbonyl compounds Chemical class 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- HJJSDJHRTMFJLP-UHFFFAOYSA-N 4-trimethylsilylbut-3-yn-2-ol Chemical compound CC(O)C#C[Si](C)(C)C HJJSDJHRTMFJLP-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- JWIPGAFCGUDKEY-UHFFFAOYSA-L O[Cr](Cl)(=O)=O.C1=CC=NC=C1 Chemical compound O[Cr](Cl)(=O)=O.C1=CC=NC=C1 JWIPGAFCGUDKEY-UHFFFAOYSA-L 0.000 description 1
- JGAOYYDLBBYVCT-UHFFFAOYSA-N [SiH3]C=CCO Chemical compound [SiH3]C=CCO JGAOYYDLBBYVCT-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- SRNLFSKWPCUYHC-UHFFFAOYSA-N ethynylsilane Chemical class [SiH3]C#C SRNLFSKWPCUYHC-UHFFFAOYSA-N 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000004809 thin layer chromatography Methods 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Description
Предлагаетс улучшенный способ получени кремнийацетиленовых карбонильных соединений общей формулыAn improved process for the preparation of silicon acetylene carbonyl compounds of the general formula
R SiC sCCORR SiC sCCOR
где R - алкйл; where R is an alkyl;
R- водород или алкйл,R is hydrogen or alcohol,
Силилацетиленовые альдегиды и ке тоны наход т широкое применение в органическом синтезе или вкачестве биологически активных веществ,Silylacetylene aldehydes and ketones are widely used in organic synthesis or as biologically active substances.
.Известен способ получени кремнийацетиленовых карбонильных соединений , например альдегидов, заклю-: чающийс в окислении силилэтинилкарбинолов хромовым ангидридом в серной кислоте 1.A known method for producing silicon acetylene carbonyl compounds, for example aldehydes, consists in the oxidation of silylethinylcarbinols with chromic anhydride in sulfuric acid 1.
Однако эта реакци протекает в жестких услови х. Исходные и синтезируемые силилацетилены легко осмол ютсн в услови х синтеза, а наличие агрессивной среды затрудн ет промышленное использование способа,However, this reaction proceeds under stringent conditions. The initial and synthesized silylacetylenes are easily osmolymed under synthesis conditions, and the presence of an aggressive medium makes it difficult to use the process
Целью изобретени вл етс упрощение способа синтеза кремнийацетиленовых карбонильных соединений.The aim of the invention is to simplify the process for the synthesis of silicon acetylene carbonyl compounds.
Указанна цель достигаетс за счет того, что силилэтинилкарбинол подвергают взаимодействию.с окислителем , а именно с хлорхроматомпиридини , в среде органического раствог рител , желательно хлористого метилена ,This goal is achieved due to the fact that the silylethenyl carbinol is reacted with an oxidizing agent, namely with chlorochromatompyridini, in an organic solvent medium, preferably methylene chloride,
Отличительным признаком способа вл етс использование в качестве окислител хлорхромата пиридини . Продукт выдел ют фильтрованием через окись алюмини и последующей перегонкой в вакууме.A distinctive feature of the process is the use of pyridinium chlorchromate as the oxidizing agent. The product is isolated by filtration through alumina and then distilled in vacuo.
00
Реакци протекает по след5пощей схемеThe reaction proceeds as follows.
WHCrO Ce WHCrO Ce
55.о55.o
SiHC-CHOHSiHC-CHOH
c H NHCrOjCeH NHCrOjCe
RR
C-CORC-COR
2-Триэтил.сй.пил-2-пропин-1-аль (R CaHj, R H), не описанный2-Triethyl.syp.-2-propyn-1-al (R CaHj, R H), not described
ранее, получен с выходом 86%, С высоким выходом этим способом могут быть получены и другие силилэтинилкарбонильные соединени .Earlier, it was obtained with a yield of 86%. Other silylethinylcarbonyl compounds can be obtained in a high yield by this method.
Использование в качестве окислител хлорхромата пиридини позвол ет получать искомые карбонильные соединени с высоким выходом в м гких услови х.The use of pyridinium chlorochromate as an oxidizing agent makes it possible to obtain the desired carbonyl compounds with a high yield under mild conditions.
Описываемый способ имеет р д преимуществ: .The described method has several advantages:.
хлорхромат пиридини - легкодоступный , устойчивый при длительном хранении окислитель;Pyridinium chlorochromate is an easily available oxidizing agent that is stable during long-term storage;
ОКИ ел ени е хл ор хррмат OWtrfipH ди ни притекает в-м гких услови х (хлористый -метилен, комнатна температурка ) , исключающих агрессивную среду, что особенно важно при использовании этого способа в пррмпишенности;OCIs e chl o hrrmat OWtrfipH of di при ay flows under m-h conditions (methylene chloride, room temperature), which exclude an aggressive environment, which is especially important when using this method in prichishennosti;
сокращаетс врем реакции (если окисление хромовым, ангидридом в серной кислоте осуществл етс в течение 2-6 ч, то согласно данны-м тонкослойной хроматографии предлагаемый процесс заканчиваетс за 2 ч; tt flSteHHe окислител от продукта реакции производите фильтрованием через слой окиси алюмини , при этом одновременно происходит очистка карбонильйого соединени 6твЪзй65кных смолистых примесей, а послеудалени растворител получаетс хроматогра фически чистый продукт реакции почти с количественным выходом, несколько понижающимс в результате вакуумной разгонки. the reaction time is reduced (if oxidation with chromic, anhydride in sulfuric acid takes 2-6 hours, according to thin-layer chromatography, the proposed process ends in 2 hours; tt flSteHHe oxidant from the reaction product is filtered through a layer of alumina, at the same time, purification of the carbonyl compound 6 of hr65 of resinous impurities takes place, and after removing the solvent, the chromatographically pure product of the reaction is obtained in almost quantitative yield, somewhat decreasing Tate vacuum distillation.
Пример 1, К суспензии 16,5г хлорхромата пиридини в 100 мл сухсэго хлористого метилена в токе артона прибавл ют по капл м раствор 6,5 г 3-трйэтилсйлил-2-пр6пин-1-ола в 10 мл сухого хлористого метилена, Реакционную смесь перемешивают в течение 2 ч, приливают 100 мл сухого серногоэфира, раствор декантируют и фильтруют через 10-сантйметровый столбик окиси алюмини , РастворительExample 1 A solution of 6.5 g of 3-triethylsyl-2-pr6pin-1-ol in 10 ml of dry methylene chloride is added dropwise to a suspension of 16.5 g of pyridinium chlorochromate in 100 ml of suhsego methylene chloride in a stream of arton in 10 ml of dry methylene chloride, the reaction mixture is stirred within 2 h, poured 100 ml of dry sulfuric ester, the solution is decanted and filtered through a 10-cm aluminum oxide column, Solvent
отгон ют на вод ной бане, остаток разгон ют в вакууме .The mixture is distilled off in a water bath, the residue is distilled in vacuo.
Получают 5,5 г (86%) З-триэтилси-. лил-2-пропин-1-ал , т,кип, 7172 С/10 мм рт.ст.; 1,4658. 5.5 g (86%) of 3-triethylsis are obtained. lil-2-propyne-1-al, t, kip, 7172 C / 10 mm Hg; 1.4658.
9,74; Найдено,: С 64,26; 64,32; Н9.74; Found: C, 64.26; 64.32; H
9,74; Si 16,50; 16,58,9.74; Si 16.50; 16.58,
C H e-OSiC e-OSi
Вычислено,%: С 64,22; Н 9,59; Si 16,69.Calculated,%: C 64.22; H 9.59; Si 16.69.
ИК-спектр 1240 . (C Hj-Si), 1670 (), 2160 () ,IR spectrum 1240. (C Hj-Si), 1670 (), 2160 (),
.Пример 2, Аналогично получают 3-триметилсилил-2-пропин-1-апь с выходом 75%, т.кип, 42°С/ :Example 2, Similarly, receive 3-trimethylsilyl-2-propyne-1-ap with a yield of 75%, so Kip, 42 ° C /:
/16 мм рт,ст; п|,°. 1,4420,/ 16 mm Hg, St; n |, °. 1.4420,
-Пример 3, Окислением 4-триметилсилил-З-бутин-2-ола в тех же услови х.синтезируют 4-триметилсилил-З-бутин-2-он с выходом 8%, 48с/15 мм рт,ст,; Пщ° 1,4432,-Example 3, by oxidation of 4-trimethylsilyl-3-butyn-2-ol under the same conditions, 4-trimethylsilyl-3-butin-2-one is synthesized with a yield of 8%, 48s / 15 mm Hg, Art .; PC ° 1,4432,
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| SU782654906A SU715580A1 (en) | 1978-08-07 | 1978-08-07 | Method of preparing silicon acetylenic carbonylic compounds |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| SU782654906A SU715580A1 (en) | 1978-08-07 | 1978-08-07 | Method of preparing silicon acetylenic carbonylic compounds |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| SU715580A1 true SU715580A1 (en) | 1980-02-15 |
Family
ID=20781424
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| SU782654906A SU715580A1 (en) | 1978-08-07 | 1978-08-07 | Method of preparing silicon acetylenic carbonylic compounds |
Country Status (1)
| Country | Link |
|---|---|
| SU (1) | SU715580A1 (en) |
-
1978
- 1978-08-07 SU SU782654906A patent/SU715580A1/en active
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