CN104592288A - 1-(trimethylsiloxy)cyclopentene, and preparation method thereof - Google Patents
1-(trimethylsiloxy)cyclopentene, and preparation method thereof Download PDFInfo
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- CN104592288A CN104592288A CN201310521122.0A CN201310521122A CN104592288A CN 104592288 A CN104592288 A CN 104592288A CN 201310521122 A CN201310521122 A CN 201310521122A CN 104592288 A CN104592288 A CN 104592288A
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- China
- Prior art keywords
- trimethylsiloxy group
- cyclopentanone
- group cyclopentenes
- preparation technology
- cyclopentenes
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- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- UBMYYGXGMPGCBO-UHFFFAOYSA-N cyclopenten-1-yloxy(trimethyl)silane Chemical compound C[Si](C)(C)OC1=CCCC1 UBMYYGXGMPGCBO-UHFFFAOYSA-N 0.000 title abstract 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 53
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000002904 solvent Substances 0.000 claims abstract description 10
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 claims description 34
- 150000001941 cyclopentenes Chemical class 0.000 claims description 24
- 238000005516 engineering process Methods 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 239000000047 product Substances 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 7
- 239000000758 substrate Substances 0.000 claims description 6
- 239000012141 concentrate Substances 0.000 claims description 5
- 238000004821 distillation Methods 0.000 claims description 5
- 239000000706 filtrate Substances 0.000 claims description 5
- 238000009413 insulation Methods 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 239000005051 trimethylchlorosilane Substances 0.000 claims description 5
- 230000008676 import Effects 0.000 claims description 3
- 238000004817 gas chromatography Methods 0.000 claims description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 abstract description 11
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 abstract description 8
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 abstract description 4
- 239000002253 acid Substances 0.000 abstract description 3
- 239000011230 binding agent Substances 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 2
- 239000003513 alkali Substances 0.000 abstract 1
- -1 silyl enol ether Chemical class 0.000 description 8
- 239000003153 chemical reaction reagent Substances 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000000543 intermediate Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 150000007530 organic bases Chemical class 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 2
- CSRZQMIRAZTJOY-UHFFFAOYSA-N trimethylsilyl iodide Chemical compound C[Si](C)(C)I CSRZQMIRAZTJOY-UHFFFAOYSA-N 0.000 description 2
- 208000005623 Carcinogenesis Diseases 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000005575 aldol reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000036952 cancer formation Effects 0.000 description 1
- 231100000504 carcinogenesis Toxicity 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000002140 halogenating effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- PARWUHTVGZSQPD-UHFFFAOYSA-N phenylsilane Chemical compound [SiH3]C1=CC=CC=C1 PARWUHTVGZSQPD-UHFFFAOYSA-N 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 231100000004 severe toxicity Toxicity 0.000 description 1
Abstract
The invention belongs to the field of chemical material production, and especially relates to 1-(trimethylsiloxy)cyclopentene, and a preparation method thereof. Preparation chemical equation of 1-(trimethylsiloxy)cyclopentene is represented by a formula in the invention. According to the preparation method, low-toxic safe methylbenzene is taken as solvent instead of benzene, so that production operation is more safe; and relatively cheap triethylamine is taken as an acid-binding agent instead of organic alkali pyridine, so that production cost is reduced greatly.
Description
Technical field
The present invention relates to chemical materials manufacture field, particularly a kind of 1-trimethylsiloxy group cyclopentenes and preparation technology thereof.
Background technology
What organosilicon reagent was mainly used for compound containing hydroxyl at first a kind ofly protects reagent and is applied to organic synthesis.In the last few years, along with the develop rapidly of organosilicon chemistry application technical research, silicoorganic compound are made to obtain great achievement as the research of pharmaceutical synthesis reagent and medicinal intermediates aspect.A lot of silicoorganic compound, such as: silyl enol ether, alkenyl silanes, Iodotrimethylsilane, phenyl silane etc., be all the organic synthesis reagent with multiple reactivity worth, they have become indispensable reagent and important intermediate in modern medicines synthesis.
Silyl enol ether is exactly the very useful reagent of a class and important intermediate.Application silyl enol ether, by halogenating reaction or aldol reaction, can synthesize the multiple hydroxyketone containing alpha-position or β-position not easily passing through additive method synthesis, the latter is the important intermediate of synthesis multi-medicament.The application and development of silyl enol ether compound, gives and important support in the new synthetic technology of research the medicine of the hydroxyketone structure containing alpha-position or β-position undoubtedly.
Be seen in the preparation method of 1-trimethylsiloxy group cyclopentenes of report in the past, and used organic bases pyridine as acid binding agent, and used benzene as reaction solvent; Due to severe toxicity and the carcinogenesis of benzole soln, make to be difficult to scale operation, organic bases pyridine is expensive in addition, also makes production cost remain high.
Summary of the invention
The present invention has researched and developed a kind of 1-trimethylsiloxy group cyclopentenes and preparation technology thereof, object is: providing a kind of safe and reliable, cost is low, efficiency is high 1-trimethylsiloxy group cyclopentenes and preparation technology thereof, is exactly silyl enol ether class organosilicon reagent and preparation technology thereof.
This technical scheme:
A kind of 1-trimethylsiloxy group cyclopentenes and preparation technology thereof, is characterized in that, comprise the steps:
1), under drying nitrogen protection, import successively in the reactor that reaction substrate cyclopentanone is housed solvent toluene and and triethylamine;
2) after, being then warmed up to 50 DEG C, the trimethylchlorosilane of dropping and cyclopentanone equimolar amount in reactor;
3), drip and finish, insulation reaction 3-4 hour, filters out insolubles Et
3nHCl;
4), filtrate concentrates, and distills out input solvent toluene and reclaims;
5), underpressure distillation afterwards, collect the cut of 72-74 DEG C/11-12mmHg, obtain product 1-trimethylsiloxy group cyclopentenes.
In described step 1), toluene add-on is the corresponding 0.2L toluene of every mole of cyclopentanone, and the add-on of triethylamine is identical with cyclopentanone molar weight.
In described step 3), insolubles is equal with reaction substrate cyclopentanone molar weight.
1-trimethylsiloxy group cyclopentenes in described step 5) obtains productive rate by GC analysis and is greater than 79%, and product chemistry purity is greater than 98%.
A kind of preparative chemistry equation of 1-trimethylsiloxy group cyclopentenes is:
。
The molecular formula of products therefrom is:
.
The invention has the beneficial effects as follows:
The present invention adopts safety low-poison toluene to substitute benzene as solvent, makes production operation safer, uses the triethylamine of relative low price to substitute organic bases pyridine as acid binding agent in addition, makes the reduction that production cost is able to by a relatively large margin.
Embodiment
Below in conjunction with embodiment, the present invention is described further.
Embodiment one:
A kind of 1-trimethylsiloxy group cyclopentenes and preparation technology thereof, comprise the steps:
1), under drying nitrogen protection, import successively in the reactor that reaction substrate cyclopentanone is housed solvent toluene and and triethylamine, wherein toluene add-on is the corresponding 0.2L toluene of every mole of cyclopentanone, and the add-on of triethylamine is identical with cyclopentanone molar weight;
2) after, being then warmed up to 50 DEG C, the trimethylchlorosilane of dropping and cyclopentanone equimolar amount in reactor;
3), drip and finish, insulation reaction 3-4 hour, filters out insolubles Et
3nHCl, wherein insolubles is equal with reaction substrate cyclopentanone molar weight;
4), filtrate concentrates, and distills out input solvent toluene and reclaims;
5), underpressure distillation afterwards, collect the cut of 72-74 DEG C/11-12mmHg, obtain product 1-trimethylsiloxy group cyclopentenes, 1-trimethylsiloxy group cyclopentenes is wherein analyzed by GC and is obtained productive rate and be greater than 79%, and product chemistry purity is greater than 98%.
Embodiment two:
A kind of preparative chemistry equation of 1-trimethylsiloxy group cyclopentenes is:
。
A kind of 1-trimethylsiloxy group cyclopentenes and preparation technology thereof, comprise the steps:
1), under drying nitrogen protection, in 250ml three-necked bottle, 50ml dry toluene and 20.74g triethylamine (0.205mol) is added successively;
2), after, being then warmed up to 50 DEG C, in reactor, order drips 16.82g cyclopentanone (0.20mol), 22.27g trimethylchlorosilane (0.205mol);
3), drip and finish, insulation reaction 3 hours, filters out insolubles (Et
3nHCl, about 28.20g after drying);
4), filtrate concentrates, and distills out input solvent toluene and reclaims;
5), underpressure distillation afterwards, collect the cut of 72-74 DEG C/11-12mmHg, obtain product 1-trimethylsiloxy group cyclopentenes (silyl enol ether) 24.63g(0.157mol), productive rate 78.8%, product chemistry purity 98%(GC analyzes).
Embodiment three:
1), under drying nitrogen protection, in 5L reactor, 1000ml dry toluene and 511.01g triethylamine (5.05mol) is added successively;
2), after, being then warmed up to 50 DEG C, in reactor, drip 420.60g cyclopentanone (5.00mol), 554.14g trimethylchlorosilane (5.05mol) simultaneously;
3), drip and finish, insulation reaction 4 hours, filters out insolubles (Et
3nHCl, about 685g after drying);
4), filtrate concentrates, and distills out input solvent toluene and reclaims;
5), underpressure distillation afterwards, collect the cut of 72-74 DEG C/11-12mmHg, obtain product 1-trimethylsiloxy group cyclopentenes (silyl enol ether) 620.50g(3.97mol), productive rate 79.4%, product chemistry purity 98%(GC analyzes).
Claims (6)
1.1-trimethylsiloxy group cyclopentenes and preparation technology thereof, is characterized in that, comprises the steps:
1), under drying nitrogen protection, import successively in the reactor that reaction substrate cyclopentanone is housed solvent toluene and and triethylamine;
2) after, being then warmed up to 50 DEG C, the trimethylchlorosilane of dropping and cyclopentanone equimolar amount in reactor;
3), drip and finish, insulation reaction 3-4 hour, filters out insolubles Et
3nHCl;
4), filtrate concentrates, and distills out input solvent toluene and reclaims;
5), underpressure distillation afterwards, collect the cut of 72-74 DEG C/11-12mmHg, obtain product 1-trimethylsiloxy group cyclopentenes.
2. 1-trimethylsiloxy group cyclopentenes according to claim 1 and preparation technology thereof, is characterized in that: in described step 1), toluene add-on is the corresponding 0.2L toluene of every mole of cyclopentanone, and the add-on of triethylamine is identical with cyclopentanone molar weight.
3. 1-trimethylsiloxy group cyclopentenes according to claim 1 and preparation technology thereof, is characterized in that: in described step 3), insolubles is equal with reaction substrate cyclopentanone molar weight.
4. 1-trimethylsiloxy group cyclopentenes according to claim 1 and preparation technology thereof, is characterized in that: the 1-trimethylsiloxy group cyclopentenes in described step 5) obtains productive rate by GC analysis and is greater than 79%, and product chemistry purity is greater than 98%.
The preparative chemistry equation of 5.1-trimethylsiloxy group cyclopentenes is:
。
6. the preparative chemistry equation of 1-trimethylsiloxy group cyclopentenes according to claim 5, is characterized in that: the molecular formula of products therefrom is:
.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310521122.0A CN104592288A (en) | 2013-10-30 | 2013-10-30 | 1-(trimethylsiloxy)cyclopentene, and preparation method thereof |
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| CN201310521122.0A CN104592288A (en) | 2013-10-30 | 2013-10-30 | 1-(trimethylsiloxy)cyclopentene, and preparation method thereof |
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| CN104592288A true CN104592288A (en) | 2015-05-06 |
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
-
2013
- 2013-10-30 CN CN201310521122.0A patent/CN104592288A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Non-Patent Citations (1)
| Title |
|---|
| 黄慧琴等，: "邻叔丁基环己酮的合成", 《香料香精化妆品 》 * |
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Application publication date: 20150506 |