CN104592284B - 1,2 pairs of trimethylsiloxy group cyclohexene and its preparation technology - Google Patents
1,2 pairs of trimethylsiloxy group cyclohexene and its preparation technology Download PDFInfo
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- CN104592284B CN104592284B CN201310521068.XA CN201310521068A CN104592284B CN 104592284 B CN104592284 B CN 104592284B CN 201310521068 A CN201310521068 A CN 201310521068A CN 104592284 B CN104592284 B CN 104592284B
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- trimethylsiloxy group
- cyclohexene
- group cyclohexene
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Abstract
Preparation field is produced the present invention relates to chemical materials, more particularly to a kind of 1,2 couples of trimethylsiloxy group cyclohexene and its preparation technologies.A kind of chemical equation for preparing of 1,2 pairs of trimethylsiloxy group cyclohexene is：
Description
Technical field
Produce preparation field the present invention relates to chemical materials, more particularly to 1,2- of one kind pair trimethylsiloxy group cyclohexene and
Its preparation technology.
Background technology
Organosilicon reagent is initially mainly used for a kind of protection reagent of the compound containing hydroxyl and is applied to organic conjunction
Into.In the last few years, developing rapidly with organosilicon chemistry application technical research, makes organo-silicon compound as pharmaceutical synthesis
Research in terms of reagent and drug synthesis intermediate has obtained great achievement.Many organo-silicon compound, for example：Enol silicon
Ether, alkenyl silanes, Iodotrimethylsilane, phenyl silane etc., the entirely organic synthesis reagent with a variety of reactivity worth, they
Indispensable reagent and important intermediate are had become in modern medicines synthesis.
Dienol silicon ether is exactly the highly useful reagent of a class and important intermediate.Using dienol silicon ether, pass through
Cyclization, can synthesize a variety of pharmaceutical intermediates containing aromatic rings or heteroaromatic for not easily passing through other method synthesis,
All improved a lot in terms of the speed and yield of reaction, selectivity and space efficiency.The application of dienol silica-ether compound and
Development, has undoubtedly given important support to the medicine containing aromatic rings or heteroaromatic on new synthetic technology is studied.
The overwhelming majority directly used metallic sodium as the organic reaction of reagent in the past, all in the presence of following potential safety hazard：Just
It is that in production, without simple and feasible analysis method, whether all take part in instead for the metallic sodium input by judging
Should.Then in postprocessing working procedures, it is frequently run onto and does not react thoroughly residual metal sodium, brought greatly to postprocessing working procedures
Potential safety hazard.In order to avoid residual metal sodium, the generally excessive reaction substrate raw material of input.It was verified that such production exercise
Make, in addition to increasing cost, equally whether can not all take part in reaction with regard to the input metallic sodium of this judgement, so that
Avoid the potential safety hazard in postprocessing working procedures.
The content of the invention
The present invention has researched and developed the double trimethylsiloxy group cyclohexene of 1,2- of one kind and its preparation technology, it is therefore intended that：Carry
For a kind of double trimethylsiloxy group cyclohexene of safe and reliable, efficiency high 1,2- and its preparation technology.
This hair technical scheme：
1,2- double trimethylsiloxy group cyclohexene and its preparation technology, it is characterised in that comprise the following steps：
1）, under the protection of dry nitrogen, to equipped with reaction substrate 1, imported successively in the reactor of 6- diethylene adipates
Dry dry toluene, trace benzophenone and put into metallic sodium, after being sufficiently stirred for, navy blue is presented in reaction solution；
2）And then be warming up to after 50 DEG C, sequentially dropwise addition or simultaneously dropwise reaction substrate 1,6- adipic acids into reactor
The trim,ethylchlorosilane of 4 times of diethylester and 1,6- diethylene adipates mole；
3）, drop finish, insulated and stirred react 3-4 hours, when after the dark blue decoloration of reaction solution, being stirred for 1 hour, mistake
Filter insoluble matter NaCl；
4）, filtrate concentration, accessory substance trimethylethoxysilane and solvent toluene are distilled out successively；
5）, vacuum distillation afterwards, collect 102-105 DEG C/10-12mmHg cut, obtain product 1, the double trimethyl silicanes of 2-
Epoxide cyclohexene.
The step 1）Middle dry toluene is corresponding 2L solvents per molar reactive substrate with the addition of trace benzophenone,
The addition of metallic sodium is 4 times of reaction substrate mole.
The step 3）Middle insoluble matter NaCl is 4 times of reaction substrate 1,6- diethylene adipate moles.
The step 4）The chemical formula of accessory substance trimethylethoxysilane is TMSOEt, and mole is 1,6- adipic acids two
2 times of ethyl ester.
The step 5）Middle product 1, the double trimethylsiloxy group cyclohexene of 2- analyze yield by GC and are more than 83%, product
It is about 98% to learn purity.
The chemical equation for preparing of the double trimethylsiloxy group cyclohexene of 1,2- is：
。
Products therefrom chemical formula is：。
The beneficial effects of the invention are as follows:
The present invention has dexterously used benzophenone and metallic sodium to generate the property of blue compound in anhydrous solution
Matter, comes in Indicator Reaction mixture, if still has the complete metallic sodium of unreacted remaining, have found simple and feasible in production
Whether analytical reactions still have the method that metallic sodium is remained after terminating, so as to thoroughly avoid the potential safety hazard in postprocessing working procedures.
Embodiment
With reference to embodiment, the present invention is described further.
Embodiment one：
The double trimethylsiloxy group cyclohexene of 1,2- of one kind and its preparation technology, comprise the following steps：
1）, under the protection of dry nitrogen, to equipped with reaction substrate 1, imported successively in the reactor of 6- diethylene adipates
Dry dry toluene, trace benzophenone and put into metallic sodium, after being sufficiently stirred for, navy blue is presented in reaction solution；It is wherein anhydrous
Toluene is corresponding 2L solvents per molar reactive substrate with the addition of trace benzophenone, and the addition of metallic sodium is reaction substrate
4 times of mole;
2）And then be warming up to after 50 DEG C, sequentially dropwise addition or simultaneously dropwise reaction substrate 1,6- adipic acids into reactor
The trim,ethylchlorosilane of 4 times of diethylester and 1,6- diethylene adipates mole；
3）, drop finish, insulated and stirred react 3-4 hours, when after the dark blue decoloration of reaction solution, being stirred for 1 hour, mistake
Filter insoluble matter NaCl；Wherein insoluble matter NaCl is 4 times of reaction substrate 1,6- diethylene adipate moles；
4）, filtrate concentration, accessory substance trimethylethoxysilane and solvent toluene are distilled out successively；Wherein accessory substance front three
The chemical formula of base oxethyl silane is TMSOEt, and mole is 2 times of 1,6- diethylene adipates；
5）, vacuum distillation afterwards, collect 102-105 DEG C/10-12mmHg cut, obtain product 1, the double trimethyl silicanes of 2-
Epoxide cyclohexene, wherein product 1, the double trimethylsiloxy group cyclohexene of 2- analyze yield by GC and are more than 83%, product chemistry purity
About 98%.
Embodiment two：
A kind of chemical equation for preparing of the double trimethylsiloxy group cyclohexene of 1,2- is：
。
The double trimethylsiloxy group cyclohexene of 1,2- of one kind and its preparation technology, specifically include following steps：
1）, under the protection of dry nitrogen, sequentially added into 1000ml three-neck flasks 200ml drying solvent toluene,
After 0.05g benzophenone, put into 9.20g (0.40mol) metallic sodium in batches again；After being sufficiently stirred for, now solution is in reaction bulb
Navy blue；
2）And then be warming up to after 50 DEG C, 20.23g (0.1mol) 1,6- adipic acid diethyls are sequentially added dropwise into three-neck flask
Ester and 43.46g (0.40mol) trim,ethylchlorosilane；
3）, drop finish, at a temperature of 50 DEG C react 3 to 4 hours, when reaction solution navy blue thoroughly disappear after, then
Stir 1 hour；Stop stirring, filter out insoluble matter（NaCl, about 23.35g after drying）；
4）, filtrate concentration, accessory substance trimethylethoxysilane is distilled out successively（TMSOEt about 23.60g or so, boiling point
75-76℃）And solvent toluene；
5）, vacuum distillation afterwards, collect 102-105 DEG C/10-12mmHg cut, obtain product 1, the double trimethyl silicanes of 2-
Epoxide cyclohexene（Silyl enol ether）22.61g (0.087mol), yield 87.5%, purity 98%（GC is analyzed）.
Embodiment three：
1）, under the protection of dry nitrogen, sequentially added into 2000ml three-neck flasks 800ml drying solvent toluene,
After 0.1g benzophenone, put into 36.80g (1.6mol) metallic sodium in batches again；After being sufficiently stirred for, now solution is in deep in reaction bulb
Blueness；
2）And then be warming up to after 50 DEG C, 80.90g (0.4mol) 1,6- adipic acid diethyls are added dropwise simultaneously into three-neck flask
Ester and 130.37g (1.6mol) trim,ethylchlorosilane；
3）, drop finish, at a temperature of 50 DEG C react 3 to 4 hours, when reaction solution navy blue thoroughly disappear after, then
Stir 1 hour；Stop stirring, filter out insoluble matter NaCl (dry after about 93.56g）；
4）, filtrate concentration, accessory substance trimethylethoxysilane is distilled out successively（TMSOEt, about 94.55g, boiling point 75-
76℃）And solvent toluene；
5）, vacuum distillation afterwards, collect 102-105 DEG C/10-12mmHg cut, obtain product 1, the double trimethyl silicanes of 2-
Epoxide cyclohexene（Silyl enol ether）91.61g (0.35mol), yield 88.6%, purity 98%（GC is analyzed）.
Concrete principle is：In reaction solution, put into trace benzophenone, when metallic sodium put into reaction system, fully
After stirring, reaction solution is in navy blue；And be nearly completed when reaction, residual metal sodium total overall reaction it is complete after, hexichol first
Ketone disappears with the blue compound that metallic sodium is generated, and reaction solution system color recovers original state.
Claims (7)
1.1,2- double trimethylsiloxy group cyclohexene preparation technologies, it is characterised in that comprise the following steps：
1）, under the protection of dry nitrogen, to equipped with reaction substrate 1, drying is imported successively in the reactor of 6- diethylene adipates
Dry toluene, trace benzophenone simultaneously put into metallic sodium, after being sufficiently stirred for, and navy blue is presented in reaction solution；
2）And then be warming up to after 50 DEG C, sequentially dropwise addition or simultaneously dropwise reaction substrate 1,6- adipic acid diethyls into reactor
The trim,ethylchlorosilane of 4 times of ester and 1,6- diethylene adipates mole；
3）, drop finish, insulated and stirred react 3-4 hours, when after the dark blue decoloration of reaction solution, being stirred for 1 hour, filtering out
Insoluble matter NaCl；
4）, filtrate concentration, accessory substance trimethylethoxysilane and solvent toluene are distilled out successively；
5）, vacuum distillation afterwards, collect 102-105 DEG C/10-12mmHg cut, obtain product 1, the double trimethylsiloxy groups of 2-
Cyclohexene.
2. the double trimethylsiloxy group cyclohexene preparation technologies of 1,2- according to claim 1, it is characterised in that：The step
1）Middle dry toluene is corresponding 2L solvents per molar reactive substrate with the addition of trace benzophenone, and the addition of metallic sodium is
4 times of reaction substrate mole.
3. the double trimethylsiloxy group cyclohexene preparation technologies of 1,2- according to claim 1, it is characterised in that：The step
3）Middle insoluble matter NaCl is 4 times of reaction substrate 1,6- diethylene adipate moles.
4. the double trimethylsiloxy group cyclohexene preparation technologies of 1,2- according to claim 1, it is characterised in that：The step
4）The chemical formula of accessory substance trimethylethoxysilane is TMSOEt, and mole is 2 times of 1,6- diethylene adipates.
5. the double trimethylsiloxy group cyclohexene preparation technologies of 1,2- according to claim 1, it is characterised in that：The step
5）Middle product 1, the double trimethylsiloxy group cyclohexene of 2- analyze yield by GC and are more than 83%, and product chemistry purity is about 98%.
6. the double trimethylsiloxy group cyclohexene preparation technologies of 1,2- according to claim 1, it is characterised in that：The 1,2-
The chemical equation for preparing of double trimethylsiloxy group cyclohexene is：
。
7. the double trimethylsiloxy group cyclohexene preparation technologies of 1,2- according to claim 6, it is characterised in that：Products therefrom
Chemical formula is：。
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| CN111269255A (en) * | 2020-01-14 | 2020-06-12 | 浙江衢州硅宝化工有限公司 | Preparation method of isopropenyloxysilane |
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| CN101735261A (en) * | 2009-12-29 | 2010-06-16 | 浙江新和成股份有限公司 | Preparation method of 1,2-bi-trimethylsilyloxy cyclohexene |
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| CN101735261A (en) * | 2009-12-29 | 2010-06-16 | 浙江新和成股份有限公司 | Preparation method of 1,2-bi-trimethylsilyloxy cyclohexene |
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| Fancy bioisosteres: synthesis and dopaminergic properties of the endiyne FAUC 88 as a novel non-aromatic D3 agonist;Carola Lenz等，;《Bioorganic & Medicinal Chemistry》;20051231;第13卷;第185-191页，尤其是第186页方案1以及第188页实验部分3.1节 * |
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Address after: 223800 chemical industry zone (north area), Suyu Economic Development Zone, Jiangsu, Suqian Province, No. five, No. 3 Applicant after: Jilin Xinyaqiang Biochem Co., Ltd. Address before: 223800 chemical industry zone (north area), Suyu Economic Development Zone, Jiangsu, Suqian Province, No. five, No. 3 Applicant before: Xinyaqiang Silicon Chemistry Jiangsu Co.,Ltd. |
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