CN103772314A - Preparation method of carbene dipolymer - Google Patents
Preparation method of carbene dipolymer Download PDFInfo
- Publication number
- CN103772314A CN103772314A CN201410006387.1A CN201410006387A CN103772314A CN 103772314 A CN103772314 A CN 103772314A CN 201410006387 A CN201410006387 A CN 201410006387A CN 103772314 A CN103772314 A CN 103772314A
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- China
- Prior art keywords
- carbene
- cabbeen
- dipolymer
- condition
- compound
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- 0 CC(C(C)S1)N(C)C1=*1SC(C)=*(C)N1C Chemical compound CC(C(C)S1)N(C)C1=*1SC(C)=*(C)N1C 0.000 description 3
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
- C07D277/02—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings
- C07D277/20—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D277/22—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
- C07D277/24—Radicals substituted by oxygen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
- C07D277/02—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings
- C07D277/20—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D277/22—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Thiazole And Isothizaole Compounds (AREA)
- Plural Heterocyclic Compounds (AREA)
Abstract
The invention provides a preparation method of a carbene dipolymer. The method comprises the following steps: generating N-heterocyclic carbene on field from substituted biphenyl under an anhydrous pure-oxygen condition by taking dry oxygen-dissolvable acetonitrile as a solvent under an alkaline condition; reversing the polarity of an aldehyde group in the substituted biphenyl; reacting under the room temperature condition for 3 hours; synthesizing the carbene dipolymer (3a or 3b) at one step. A novel method for directly synthesizing the carbene dipolymer through a one-pot method by taking substituted biphenyl as a reaction substrate with the participation of organic small molecular N-heterocyclic carbene is provided. By adopting the method, a biaryl heptabasic lactone compound can be synthesized. The method has the advantages of easiness in operation, one-step reaction, mild condition, avoidance of the use of metal catalyst and strict conditions, and environmental friendliness. By adopting the method, a new way is provided for the synthesis of a carbene pre-catalyst, and a key substrate or intermediate is provided for the research of the carbene dimerization mechanism. The structural formula of the related carbene dipolymer is shown in the specifications.
Description
Technical field
The invention belongs to the preparation method of compound, relate generally to the dimeric preparation method of Cabbeen.
Background technology
Cabbeen dimer is Cabbeen participating in the process of various types of reactions as catalyzer or promotor, the by product producing after the polymerization of Cabbeen generation bimolecular.Cabbeen dimer itself can be used as procatalyst (precatalyst), participate in various types of reactions (referring to Francisco, L.C.; Josep, C.; Laura, D.; Josep, M.; Josep, B.
heterocycles 1994,
37,1579-97); On the other hand, in research Cabbeen dimerization mechanism process, Cabbeen dimer can be used as crucial substrate or intermediate (referring to David, C. G; Kingsley, J. C.; Brian, F. Y.
journal of Physical Organic Chemistry2005,
18, 298-309.), the research of dimerization mechanism can improve the catalytic efficiency of Cabbeen in various reactions, effectively improves reaction yield.
Summary of the invention
The object of this invention is to provide the dimeric preparation method of a kind of Cabbeen, related compound is:
Reaction formula is as follows:
Realize by following steps: substituted biphenyl (compound
1) under anhydrous pure oxygen condition, to be dried dissolved oxygen acetonitrile as solvent, the on-the-spot N-heterocycle carbine that generates under alkaline condition, and with this to substituted biphenyl (
1) in aldehyde radical carry out reversal of poles, react at ambient temperature 3h, stopped reaction, with Rotary Evaporators solvent evaporated, with column chromatography (ethyl acetate: sherwood oil=1:40) separate, one-step synthesis obtains Cabbeen dimer (compound
3aor compound
3b).
Compound
3abe 2,3-dihydro-2-[5-(2-hydroxyethyl)-4-methyl-3-benzyl-2 (3H)-Ya thiazole]-4-methyl-3-benzyl-5-thiazoleethanol.Compound
3bbe 2,3-dihydro-3,4,5-trimethylammonium-2-(3,4,5-trimethylammonium-2 (3
h)-Ya thiazole)-thiazole.
Substituted biphenyl (compound
1) precursor salt and the organic bases of raw material, N-heterocycle carbine (NHC) can be buied by commodity, in this reaction, the acetonitrile of reaction use is analytical reagent, under High Purity Nitrogen protection, adds CaH
2after refluxing, distillation is collected, and passes into while stirring oxygen 24 h and make dry dissolved oxygen acetonitrile under room temperature.Alkali used is selected sodium hydride or potassium tert.-butoxide.
Feature of the present invention is: using substituted biphenyl as reaction substrate, at organic molecule
nunder the participation of-heterocycle carbine, provide with the directly synthetic dimeric novel method of Cabbeen of one kettle way.The inventive method is also synthesized seven yuan of lactone compounds of dibenzyl simultaneously.That present method has is simple to operate, single step reaction, mild condition, and avoids using metal catalyst and severe condition, to environmental facies to advantages such as close friends.The inventive method provides a new way for synthetic Cabbeen procatalyst, and provides crucial substrate or intermediate for the research of Cabbeen dimerization mechanism.
Embodiment
The present invention is further described in conjunction with the embodiments.Following embodiment is that explanation is of the present invention, rather than limits by any way the present invention.
embodiment 12,3-dihydro-2-[5-(2-hydroxyethyl)-4-methyl-3-benzyl-2 (3H)-Ya thiazole]-4-methyl-3-benzyl-5-thiazoleethanol (compound
3a) synthetic method
To add successively in dry reaction tubes 2 '-(brooethyl) xenyl-2-formaldehyde (
1a) 55 mg (0.2 mmol), the acetonitrile that 2mL is dry, 31.4 mg (0.1 mmol) thiazole salt
i, stir and treat that thiazole salt dissolves completely, add 16.0 mg(0.4 mmol) sodium hydride, room temperature reaction approximately 3 h, stopped reaction, with Rotary Evaporators solvent evaporated, column chromatography (ethyl acetate: sherwood oil=1:40) separates, and obtains compound
3a8.4 mg, yield is 9%.
1H NMR (400 MHz, CDCl
3)δ7.38 -7.30 (m, 6H), 7.24 -7.21 (m, 4H), 4.95 (s, 4H), 3.77 (t,
J = 6.6 Hz, 4H), 2.74 (t,
J = 6.2 Hz, 4H), 2.01 (s, 6H)。
embodiment 22,3-dihydro-3,4,5-trimethylammonium-2-(3,4,5-trimethylammonium-2 (3
h)-Ya thiazole)-thiazole (compound
3b) synthetic
In dry reaction tubes, add successively 2 '-(brooethyl) xenyl-2-formaldehyde (compound
1) 55 mg (0.2 mmol), the acetonitrile that 2mL is dry, 25.5 mg (0.1 mmol) thiazole salt
iI, stir and treat that thiazole salt dissolves completely, add 44.9 mg(0.4 mmol) potassium tert.-butoxide, room temperature reaction approximately 3 h, stopped reaction, with Rotary Evaporators solvent evaporated, dry method loading separates with column chromatography (ethyl acetate: sherwood oil=1:40), obtains compound
3b6.9 mg, yield 14%.
1H NMR (400 MHz, CDCl
3) δ 3.25 (s, 6H), 2.10 (s, 6H), 2.06 (s, 6H)。
embodiment 3biphenyl [c, e] oxa--5 (7
h)-one (compound
2) synthetic and
n-heterocycle carbine dimer (compound
3aand compound
3b) synthetic method
According to the inventive method, also synthesize biphenyl [c, e] oxa--5 (7 simultaneously
h)-one (compound
2), this compound has antiarrhythmic activity, and fascioliasis hepatica is also had to certain therapeutic action.Net reaction is as follows:
(1) reaction formula:
To add successively in dry reaction tubes 2 '-(brooethyl) xenyl-2-formaldehyde (
1a) 55 mg (0.2 mmol), the acetonitrile that 2mL is dry, 31.4 mg (0.1 mmol) thiazole salt
i, stir and treat that thiazole salt dissolves completely, add 16.0 mg(0.4 mmol) sodium hydride, room temperature reaction approximately 3 h, stopped reaction, with Rotary Evaporators solvent evaporated, column chromatography (ethyl acetate: sherwood oil=1:40) separates, and obtains product
213.5 mg, yield is 33%, column chromatography (methylene dichloride: methyl alcohol=30:1) obtains simultaneously
n-heterocycle carbine dimer
3a8.4 mg, yield is 9%.
2 1H NMR (400 MHz, CDCl
3) δ 8.02 (dd,
J = 7.8, 1.2 Hz, 1H), 7.73-7.62 (m, 3H), 7.60 -7.52 (m, 2H), 7.51 – 7.43 (m, 2H), 5.05 (d,
J = 24.0 Hz, 2H). LRMS: [M]
+, 210.1；
3a 1H NMR (400 MHz, CDCl
3)δ7.38 -7.30 (m, 6H), 7.24 -7.21 (m, 4H), 4.95 (s, 4H), 3.77 (t,
J = 6.6 Hz, 4H), 2.74 (t,
J = 6.2 Hz, 4H), 2.01 (s, 6H)。
(2) reaction formula:
To add successively in dry reaction tubes 2 '-(brooethyl) xenyl-2-formaldehyde (
1a) 55 mg (0.2 mmol), the acetonitrile that 2mL is dry, 25.5 mg (0.1 mmol) thiazole salt
iI, stir and treat that thiazole salt dissolves completely, add 44.9 mg(0.4 mmol) potassium tert.-butoxide, room temperature reaction approximately 3 h, stopped reaction, with Rotary Evaporators solvent evaporated, dry method loading separates with column chromatography (ethyl acetate: sherwood oil=1:40), obtains product
224.4 mg, yield is 58%, column chromatography (ethyl acetate: sherwood oil=1:4) obtains simultaneously
n-heterocycle carbine dimer
3b6.9 mg, yield 14%.
1H NMR (400 MHz, CDCl
3) δ 8.02 (dd,
J = 7.8, 1.2 Hz, 1H), 7.73-7.62 (m, 3H), 7.60 -7.52 (m, 2H), 7.51 – 7.43 (m, 2H), 5.05 (d,
J = 24.0 Hz, 2H). LRMS: [M]
+, 210.1。
1H NMR (400 MHz, CDCl
3) δ 3.25 (s, 6H), 2.10 (s, 6H), 2.06 (s, 6H)。
Claims (4)
1. the dimeric preparation method of Cabbeen, is characterized in that, realizes: compound by following steps
1substituted biphenyl is under anhydrous pure oxygen condition, to be dried dissolved oxygen acetonitrile as solvent, under alkaline condition, generate N-heterocycle carbine, and with this, aldehyde radical in substituted biphenyl is carried out to reversal of poles, react at ambient temperature 3h, stopped reaction, with Rotary Evaporators solvent evaporated, with column chromatography for separation, one-step synthesis Cabbeen dimer compound 3a or compound 3b; Reaction formula is as follows:
2. the dimeric preparation method of a kind of Cabbeen according to claim 1, is characterized in that column chromatography condition: ethyl acetate: sherwood oil=1:40.
3. the dimeric preparation method of a kind of Cabbeen according to claim 1, is characterized in that, the acetonitrile of reaction use is analytical reagent, under High Purity Nitrogen protection, adds CaH
2after refluxing, distillation is collected, and passes into while stirring oxygen 24 h and make dry dissolved oxygen acetonitrile under room temperature.
4. the dimeric preparation method of a kind of Cabbeen according to claim 1, is characterized in that, alkali used is selected sodium hydride or potassium tert.-butoxide.
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| CN201410006387.1A CN103772314A (en) | 2014-01-07 | 2014-01-07 | Preparation method of carbene dipolymer |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105085463A (en) * | 2015-08-25 | 2015-11-25 | 浙江医学高等专科学校 | Method for quickly preparing polyaryls 7-membered lactone in microwave manner |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101506135A (en) * | 2006-08-18 | 2009-08-12 | 赢创德固赛有限责任公司 | Production of alpha hydroxy ketones via carbene catalyzed pole reversal reaction of aldehydes |
| CN102260129A (en) * | 2011-05-13 | 2011-11-30 | 华东理工大学 | Application of N-heterocyclic carbene in esterification reaction |
| JP2013122912A (en) * | 2011-11-08 | 2013-06-20 | Hodogaya Chem Co Ltd | Sensitizing dye for photoelectric conversion, photoelectric conversion element using the same, and dye-sensitized solar cell |
-
2014
- 2014-01-07 CN CN201410006387.1A patent/CN103772314A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101506135A (en) * | 2006-08-18 | 2009-08-12 | 赢创德固赛有限责任公司 | Production of alpha hydroxy ketones via carbene catalyzed pole reversal reaction of aldehydes |
| CN102260129A (en) * | 2011-05-13 | 2011-11-30 | 华东理工大学 | Application of N-heterocyclic carbene in esterification reaction |
| JP2013122912A (en) * | 2011-11-08 | 2013-06-20 | Hodogaya Chem Co Ltd | Sensitizing dye for photoelectric conversion, photoelectric conversion element using the same, and dye-sensitized solar cell |
Non-Patent Citations (3)
| Title |
|---|
| DAVID C. GRAHAM，等: "Dimerization mechanisms of heterocyclic carbenes", 《JOURNAL OF PHYSICAL ORGANIC CHEMISTRY》, vol. 18, no. 4, 30 April 2005 (2005-04-30), pages 298 - 309 * |
| 林璐: "N-杂环卡宾参与的芳香醛与卤代烃的亲核取代反应及其机理研究", 《华东理工大学硕士学位论文》, 15 November 2010 (2010-11-15), pages 51 - 52 * |
| 马亚军 等: "吡啶氮桥联三唑卡宾反应性质及其Pd(II)-配合物催化杂芳环与芳基溴的α-烷基化反应研究", 《有机化学》, vol. 31, no. 3, 31 March 2011 (2011-03-31), pages 368 - 373 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105085463A (en) * | 2015-08-25 | 2015-11-25 | 浙江医学高等专科学校 | Method for quickly preparing polyaryls 7-membered lactone in microwave manner |
| CN105085463B (en) * | 2015-08-25 | 2017-06-16 | 浙江医学高等专科学校 | A kind of microwave quickly prepares seven yuan of methods of lactone of biaryl |
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Application publication date: 20140507 |