CN105367596A - Preparation methods of tert-butyl dimethyl siloxy ethanol and tert-butyl dimethyl siloxy acetaldehyde - Google Patents
Preparation methods of tert-butyl dimethyl siloxy ethanol and tert-butyl dimethyl siloxy acetaldehyde Download PDFInfo
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- CN105367596A CN105367596A CN201410389218.0A CN201410389218A CN105367596A CN 105367596 A CN105367596 A CN 105367596A CN 201410389218 A CN201410389218 A CN 201410389218A CN 105367596 A CN105367596 A CN 105367596A
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- Prior art keywords
- butyl dimethyl
- tert
- tertiary butyl
- preparation
- acetaldehyde
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- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title abstract 10
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 title abstract 5
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 title abstract 5
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 title abstract 5
- NABIUKOOBGHKIX-UHFFFAOYSA-N 2-dimethylsilyloxy-3,3-dimethylbutanal Chemical compound C[SiH](C)OC(C=O)C(C)(C)C NABIUKOOBGHKIX-UHFFFAOYSA-N 0.000 title abstract 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000000047 product Substances 0.000 claims abstract description 18
- 239000000706 filtrate Substances 0.000 claims abstract description 14
- BCNZYOJHNLTNEZ-UHFFFAOYSA-N tert-butyldimethylsilyl chloride Chemical compound CC(C)(C)[Si](C)(C)Cl BCNZYOJHNLTNEZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000010992 reflux Methods 0.000 claims abstract description 11
- 239000002904 solvent Substances 0.000 claims abstract description 10
- 239000003960 organic solvent Substances 0.000 claims abstract description 7
- 239000011230 binding agent Substances 0.000 claims abstract description 5
- 150000007524 organic acids Chemical class 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims abstract description 3
- 125000005233 alkylalcohol group Chemical group 0.000 claims description 28
- -1 alkyl acetaldehyde, Chemical compound 0.000 claims description 16
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical group CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 15
- 238000004821 distillation Methods 0.000 claims description 13
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Natural products CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 claims description 8
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 8
- 239000012074 organic phase Substances 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 4
- IFPHDUVGLXEIOQ-UHFFFAOYSA-N ortho-iodosylbenzoic acid Chemical group OC(=O)C1=CC=CC=C1I=O IFPHDUVGLXEIOQ-UHFFFAOYSA-N 0.000 claims description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 4
- 238000000638 solvent extraction Methods 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract 1
- 238000001914 filtration Methods 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 239000007800 oxidant agent Substances 0.000 abstract 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- 238000009835 boiling Methods 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
Abstract
The present invention discloses preparation methods of tert-butyl dimethyl siloxy ethanol and tert-butyl dimethyl siloxy acetaldehyde. The tert-butyl dimethyl siloxy ethanol preparation comprises: adding tert-butyl dimethyl chlorosilane to an organic solvent, dissolving, adding ethylene glycol in a dropwise manner, adding an organic acid binding agent, carrying out a reflux reaction at a temperature of 45-55 DEG C, collecting the product, filtering, collecting the filtrate, carrying out normal pressure rectification at a temperature of 90-110 DEG C to evaporate the solvent, carrying out pressure reducing rectification, and collecting the distillate with a temperature 130 DEG C so as to obtain the tert-butyl dimethyl siloxy ethanol product. The tert-butyl dimethyl siloxy acetaldehyde preparation comprises that the tert-butyl dimethyl siloxy acetaldehyde is prepared from the tert-butyl dimethyl siloxy ethanol under the effect of an oxidizing agent. According to the present invention, the industrial production is achieved, the yield is high, and the purity can be more than or equal to 99%.
Description
Technical field
The invention belongs to organosilicon chemistry technical field, particularly the preparation method of tertiary butyl dimethyl Si alkyl alcohol and tertiary butyl dimethyl Si alkyl acetaldehyde.
Background technology
Tertiary butyl dimethyl Si alkyl alcohol, No. CAS is 102229-10-7, and molecular formula is C
6h
15o
2si, tertiary butyl dimethyl Si alkyl acetaldehyde, No. CAS is 102191-92-4, and molecular formula is C
6h
14o
3si, the two is protective material conventional in organic reaction, and at present, existing production method is only limitted to laboratory scale, and be difficult to amplificationization, yield is low, and product purity is not high.
Summary of the invention
The object of the present invention is to provide the preparation method of tertiary butyl dimethyl Si alkyl alcohol and tertiary butyl dimethyl Si alkyl acetaldehyde, to solve the above-mentioned problems in the prior art.
For achieving the above object, technical scheme of the present invention is as follows:
Prepare a method for tertiary butyl dimethyl Si alkyl alcohol, comprise the steps:
TERT-BUTYL DIMETHYL CHLORO SILANE is joined in organic solvent, after dissolving, drip ethylene glycol;
Add organic acid binding agent, at 45 ~ 55 DEG C, carry out back flow reaction, collect product and filter;
Collect filtrate and at 90 ~ 110 DEG C, carry out atmospheric distillation with solvent evaporated;
Carry out rectification under vacuum, collect 130 DEG C of cuts, i.e. tertiary butyl dimethyl Si alkyl alcohol product.
Preferably, the mol ratio of described TERT-BUTYL DIMETHYL CHLORO SILANE and ethylene glycol is 1:(1 ~ 10).
Preferably, described organic acid binding agent is triethylamine or pyridine.
Preferably, the vacuum tightness that described rectification under vacuum reaches is 10 ~ 20mmHg.
Preferably, the mol ratio of described TERT-BUTYL DIMETHYL CHLORO SILANE and ethylene glycol is 1:(1 ~ 5).
Prepare a method for tertiary butyl dimethyl Si alkyl acetaldehyde, comprise the steps:
Above-mentioned tertiary butyl dimethyl Si alkyl alcohol is dissolved in organic solvent;
Add oxygenant, after refluxing, add organic solvent extraction;
Get organic phase to filter, collect filtrate and carry out atmospheric distillation, with solvent evaporated;
Under the vacuum tightness of 10 ~ 20mmHg, carry out rectification under vacuum, get 60 ~ 80 DEG C of cuts, be i.e. tertiary butyl dimethyl Si alkyl acetaldehyde product.
Preferably, described oxygenant is 2-iodosobenzoic acid, and the mol ratio of described 2-iodosobenzoic acid and tertiary butyl dimethyl Si alkyl alcohol is 1:1.
Preferably, described oxygenant for wearing this Martin, described in wear this Martin and tertiary butyl dimethyl Si alkyl alcohol mol ratio be 1:4.
Preferably, the temperature of described backflow is 50 ~ 70 DEG C.
The invention has the advantages that, achieve suitability for industrialized production, yield is higher, and purity can reach more than 99%.
Embodiment
Below in conjunction with embodiment, the invention will be further described, but protection scope of the present invention is not only confined to embodiment.
The preparation method of embodiment 1 tertiary butyl dimethyl Si alkyl alcohol, comprises following operation:
151kg TERT-BUTYL DIMETHYL CHLORO SILANE is dissolved in sherwood oil, be added dropwise to 62kg ethylene glycol, add triethylamine again, reflux at 45 DEG C after 32h and filter, collect filtrate and at 90 ~ 110 DEG C, carry out atmospheric distillation with solvent evaporated, under the vacuum tightness of then 10 ~ 20mmHg, carry out rectification under vacuum, collect 130 DEG C of cuts, obtain tertiary butyl dimethyl Si alkyl alcohol product, yield is 75%, and purity is 99.95%.
The preparation method of embodiment 2 tertiary butyl dimethyl Si alkyl alcohol, comprises following operation:
151kg TERT-BUTYL DIMETHYL CHLORO SILANE is dissolved in sherwood oil, be added dropwise to 248kg ethylene glycol, add pyridine again, reflux at 45 DEG C after 36h and filter, collect filtrate and at 90 ~ 110 DEG C, carry out atmospheric distillation with solvent evaporated, under the vacuum tightness of then 10 ~ 20mmHg, carry out rectification under vacuum, collect 130 DEG C of cuts, obtain tertiary butyl dimethyl Si alkyl alcohol product, yield is 70%, and purity is 99.96%.
The preparation method of embodiment 3 tertiary butyl dimethyl Si alkyl alcohol, comprises following operation:
151kg TERT-BUTYL DIMETHYL CHLORO SILANE is dissolved in sherwood oil, be added dropwise to 310kg ethylene glycol, add triethylamine again, reflux at 55 DEG C after 38h and filter, collect filtrate and at 90 ~ 110 DEG C, carry out atmospheric distillation with solvent evaporated, under the vacuum tightness of then 10 ~ 20mmHg, carry out rectification under vacuum, collect 130 DEG C of cuts, obtain tertiary butyl dimethyl Si alkyl alcohol product, yield is 76%, and purity is 99.97%.
The preparation method of embodiment 4 tertiary butyl dimethyl Si alkyl alcohol, comprises following operation:
151kg TERT-BUTYL DIMETHYL CHLORO SILANE is dissolved in sherwood oil, be added dropwise to 496kg ethylene glycol, add triethylamine again, reflux at 50 DEG C after 40h and filter, collect filtrate and at 90 ~ 110 DEG C, carry out atmospheric distillation with solvent evaporated, under the vacuum tightness of then 10 ~ 20mmHg, carry out rectification under vacuum, collect 130 DEG C of cuts, obtain tertiary butyl dimethyl Si alkyl alcohol product, yield is 75%, and purity is 99.98%.
The preparation method of embodiment 5 tertiary butyl dimethyl Si alkyl alcohol, comprises following operation:
151kg TERT-BUTYL DIMETHYL CHLORO SILANE is dissolved in sherwood oil, be added dropwise to 620kg ethylene glycol, add pyridine again, reflux at 55 DEG C after 45h and filter, collect filtrate and at 90 ~ 110 DEG C, carry out atmospheric distillation with solvent evaporated, under the vacuum tightness of then 10 ~ 20mmHg, carry out rectification under vacuum, collect 130 DEG C of cuts, obtain tertiary butyl dimethyl Si alkyl alcohol product, yield is 74%, and purity is 99.96%.
The preparation method of embodiment 6 tertiary butyl dimethyl Si alkyl acetaldehyde, comprises following operation:
164kg tertiary butyl dimethyl Si alkyl alcohol is dissolved in sherwood oil, add the IBX of 282kg, extract with ether after normal temperature backflow 25h, get organic phase to filter, collection filtrate is heated to boiling and carries out atmospheric distillation except desolventizing, then under the vacuum tightness of 10 ~ 20mmHg, carries out rectification under vacuum, collect 60 ~ 80 DEG C of cuts, i.e. tertiary butyl dimethyl Si alkyl acetaldehyde product, yield is 80%, and purity is 99.96%.
The preparation method of embodiment 7 tertiary butyl dimethyl Si alkyl acetaldehyde, comprises following operation:
164kg tertiary butyl dimethyl Si alkyl alcohol is dissolved in sherwood oil, add the IBX of 282kg, reflux at 70 DEG C after 15h and extract with ether, get organic phase to filter, collection filtrate is heated to boiling and carries out atmospheric distillation except desolventizing, then under the vacuum tightness of 10 ~ 20mmHg, carries out rectification under vacuum, collect 60 ~ 80 DEG C of cuts, i.e. tertiary butyl dimethyl Si alkyl acetaldehyde product, yield is 82%, and purity is 99.97%.
The preparation method of embodiment 8 tertiary butyl dimethyl Si alkyl acetaldehyde, comprises following operation:
164kg tertiary butyl dimethyl Si alkyl alcohol is dissolved in sherwood oil, add the Dai Si-Martin reagent of 106kg, reflux at 50 DEG C after 20h and extract with ether, get organic phase to filter, collection filtrate is heated to boiling and carries out atmospheric distillation except desolventizing, then under the vacuum tightness of 10 ~ 20mmHg, carries out rectification under vacuum, collect 60 ~ 80 DEG C of cuts, i.e. tertiary butyl dimethyl Si alkyl acetaldehyde product, yield is 79%, and purity is 99.98%.
The preparation method of embodiment 9 tertiary butyl dimethyl Si alkyl acetaldehyde, comprises following operation:
164kg tertiary butyl dimethyl Si alkyl alcohol is dissolved in sherwood oil, add the Dai Si-Martin reagent of 106kg, reflux at 60 DEG C after 18h and extract with ether, get organic phase to filter, collection filtrate is heated to boiling and carries out atmospheric distillation except desolventizing, then under the vacuum tightness of 10 ~ 20mmHg, carries out rectification under vacuum, collect 60 ~ 80 DEG C of cuts, i.e. tertiary butyl dimethyl Si alkyl acetaldehyde product, yield is 80%, and purity is 99.99%.
Last it is noted that above embodiment only in order to illustrate the present invention and and unrestricted technical scheme described in the invention; Therefore, although this specification sheets with reference to each above-mentioned embodiment to present invention has been detailed description, those of ordinary skill in the art should be appreciated that and still can modify to the present invention or equivalent to replace; And all do not depart from technical scheme and the improvement thereof of the spirit and scope of the present invention, it all should be encompassed in right of the present invention.
Claims (9)
1. prepare a method for tertiary butyl dimethyl Si alkyl alcohol, it is characterized in that, comprise the steps:
TERT-BUTYL DIMETHYL CHLORO SILANE is joined in organic solvent, after dissolving, drip ethylene glycol;
Add organic acid binding agent, at 45 ~ 55 DEG C, carry out back flow reaction, collect product and filter;
Collect filtrate and at 90 ~ 110 DEG C, carry out atmospheric distillation with solvent evaporated;
Carry out rectification under vacuum, collect 130 DEG C of cuts, i.e. tertiary butyl dimethyl Si alkyl alcohol product.
2. preparation method according to claim 1, is characterized in that: the mol ratio of described TERT-BUTYL DIMETHYL CHLORO SILANE and ethylene glycol is 1:(1 ~ 10).
3. preparation method according to claim 1, is characterized in that: described organic acid binding agent is triethylamine or pyridine.
4. preparation method according to claim 1, is characterized in that: the vacuum tightness that described rectification under vacuum reaches is 10 ~ 20mmHg.
5. preparation method according to claim 2, is characterized in that: the mol ratio of described TERT-BUTYL DIMETHYL CHLORO SILANE and ethylene glycol is 1:(1 ~ 5).
6. prepare a method for tertiary butyl dimethyl Si alkyl acetaldehyde, it is characterized in that: comprise the steps:
Tertiary butyl dimethyl Si alkyl alcohol claim 1 prepared is dissolved in organic solvent;
Add oxygenant, after refluxing, add organic solvent extraction;
Get organic phase to filter, collect filtrate and carry out atmospheric distillation, with solvent evaporated;
Under the vacuum tightness of 10 ~ 20mmHg, carry out rectification under vacuum, get 60 ~ 80 DEG C of cuts, be i.e. tertiary butyl dimethyl Si alkyl acetaldehyde product.
7. preparation method according to claim 6, is characterized in that: described oxygenant is 2-iodosobenzoic acid, and the mol ratio of described 2-iodosobenzoic acid and tertiary butyl dimethyl Si alkyl alcohol is 1:1.
8. preparation method according to claim 6, is characterized in that: described oxygenant for wearing this Martin, described in wear this Martin and tertiary butyl dimethyl Si alkyl alcohol mol ratio be 1:4.
9. preparation method according to claim 6, is characterized in that: the temperature of described backflow is 50 ~ 70 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410389218.0A CN105367596A (en) | 2014-08-08 | 2014-08-08 | Preparation methods of tert-butyl dimethyl siloxy ethanol and tert-butyl dimethyl siloxy acetaldehyde |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410389218.0A CN105367596A (en) | 2014-08-08 | 2014-08-08 | Preparation methods of tert-butyl dimethyl siloxy ethanol and tert-butyl dimethyl siloxy acetaldehyde |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101575331A (en) * | 2008-05-05 | 2009-11-11 | 中国科学院上海药物研究所 | Preparation method of 5'-((5-methoxyl-2-phenyl indole-1-yl) methylene)-2'-oxo-3'-tetrahydrofurfuryl |
| CN103012357A (en) * | 2012-12-28 | 2013-04-03 | 中国农业大学 | 2-octenyllactone compounds, and preparation method and application thereof |
-
2014
- 2014-08-08 CN CN201410389218.0A patent/CN105367596A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101575331A (en) * | 2008-05-05 | 2009-11-11 | 中国科学院上海药物研究所 | Preparation method of 5'-((5-methoxyl-2-phenyl indole-1-yl) methylene)-2'-oxo-3'-tetrahydrofurfuryl |
| CN103012357A (en) * | 2012-12-28 | 2013-04-03 | 中国农业大学 | 2-octenyllactone compounds, and preparation method and application thereof |
Non-Patent Citations (4)
| Title |
|---|
| BURKHARDT I. WILKE等: ""Hexanes/acetonitrile: a binary solvent system for the efficient monosilylation of symmetric primary and secondary diols"", 《TETRAHEDRON LETTERS》 * |
| HIROFUMI TOHMA等: ""Hypervalent Iodine Reagents for the Oxidation of Alcohols and Their Application to Complex Molecule Synthesis"", 《ADVANCED SYNTHESIS & CATALYSIS》 * |
| VLADIMIR N. BELOV等: ""Syntheses of D-Labelled Oxidative Metabolites of Acrylamide and Acrylonitrile for the Quantification of Their Toxicities in Humans"", 《EUROPEAN JOURNAL OF ORGANIC CHEMISTRY》 * |
| 刘飞 等: ""依维莫司合成路线综述"", 《国外医药抗生素分册》 * |
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Application publication date: 20160302 |