CN1252053C - Method for synthesizing N-substitution pyrrole in ion liquid - Google Patents
Method for synthesizing N-substitution pyrrole in ion liquid Download PDFInfo
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- CN1252053C CN1252053C CN 200410026556 CN200410026556A CN1252053C CN 1252053 C CN1252053 C CN 1252053C CN 200410026556 CN200410026556 CN 200410026556 CN 200410026556 A CN200410026556 A CN 200410026556A CN 1252053 C CN1252053 C CN 1252053C
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- substituted azole
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Abstract
The present invention discloses a method for synthesizing N-substituted pyrrole in ionic liquid, which comprises the following steps: step (1), 1 to 3 mmol of pyrrole, 2 to 6 mmol of electrophilic reagent, and 2 to 4 mmol alkali are added to 1 to 4mL of ionic liquid to react for 1 to 2 hours at 40 to 80 DEG C; step (2), a product obtained from step (1) is extracted; after being concentrated, the product is treated with reduced pressure distillation or recrystallization to obtain N-substituted pyrrole. The present invention has the characteristics of mild reaction, high reaction speed, high yield, etc., and especially has the wide application range of the reaction. By using the method of the present invention, alkylation reaction, acylation reaction, sulfonylation reaction and micheal reaction can be effectively carried out, and the selectivity of the reaction is increased; in addition, the N-substituted product can be obtained selectively and specially.
Description
Technical field
The present invention relates to-method of kind of synthetic N-substituted azole.
Background technology
To be raw material from inexpensive agents, development synthetic method gentle, efficient, highly selective is one of significant challenge of organic synthesis.The history in existing more than 100 year of synthetic and relevant reaction of pyrroles and derivative thereof is because it has wide biological activity, is alkaloidal chief component, extensively is present in the natural product.The N-substituted azole mainly is to obtain with different alkylating reagent, acylting agent, alkylsulfonyl reagent generation nucleophilic substitution reaction by pyrroles's positive ion.Yet, can be on nitrogen and carbon atom because the position of nucleophilic substitution reaction takes place, N-substituted azole product is mixed with C-substituted azole product usually.And these methods often need compare exacting terms, long reaction times, lower productive rate and use disagreeableness reagent of environment and catalyzer sometimes.Therefore gentle, efficient, highly selective of development and eco-friendly synthetic N-substituted azole method are very necessary.
Summary of the invention
The objective of the invention is to the shortcoming that exists at prior art, provide a kind of reaction temperature and, speed of response is fast, productive rate is high, the synthetic method of highly selective and eco-friendly N-substituted azole.
For achieving the above object, the present invention has taked following technical scheme:
A kind of method of in ionic liquid, synthesizing the N-substituted azole, specific as follows:
(1), 1～3mmol pyrroles, 2～6mmol electrophilic reagent and 2～4mmol alkali are joined in 1～4mL ionic liquid reaction 1～2h under 40～80 ℃;
(2), product extraction that step (1) is obtained, concentrate back underpressure distillation or recrystallization, promptly obtain the N-substituted azole.
Described electrophilic reagent is alkylating reagent, acylting agent or alkylsulfonyl reagent;
Described alkylating reagent can be tert.-butyl bromide;
Described alkali is potassium hydroxide;
Described ionic liquid is [Bmim] [PF
6] or [Bmim] [BF
4], by document preparation (G.S.Owensand M.M.Abu-Omer, J.Mol.Cata.A:Chem., 2002,187,211).
Compared with the prior art, the present invention has following beneficial effect:
The present invention have reaction temperature and, characteristics such as fast, the productive rate height of speed of response; particularly react applied widely: not only effectively take place alkylation, acylations, can also sulfonylation and micheal reaction, select high: can highly selective in addition specificity obtain the N-substitution product.
Embodiment
The present invention is described further below in conjunction with specific embodiment.
Embodiment 1～14
Electrophilic reagent, reaction conditions and productive rate are as shown in table 1.
Embodiment 3,10,12 uses ionic liquid [Bmim] [BF simultaneously
4], all the other are [Bmim] [PF
6], ion liquid consumption is 2ml.
Embodiment 1 and 12 used alkali are calcium hydroxide, and embodiment 4,5 and 10 used alkali are sodium hydroxide, and all the other are potassium hydroxide.
The fusing point instrument of compound shows the fusing point instrument with numeral, and thermometer is not proofreaied and correct.Infrared spectrometer is the VECTOR22 of Bruker.Nuclear magnetic resonance analyser is the AVANCEDMX 400 of Bruker.Reagent is homemade analytical pure.
Table 1
| Embodiment | Electrophilic reagent 2 | Reaction conditions | Pyrroles: electrophilic reagent: alkali (mmolmmolmmol) | Productive rate |
| 1 2 3 4 5 6 7 8 9 10 11 12 13 14 | CH 3I i-C 3H 7Br n-C 4H 2Br n-C 4H 9Cl t-C 4H 9Br CH 2＝CHCH 2Br C 6H 5CH 2Br C 6H 5CH 2Cl CH 2＝CHCN CH 2＝CHCOOCH 3 CH 2＝CHCOCH 3 C 6H 5SO 2Cl p-CH 3C 6H 5SO 2Cl C 6H 5COCl | 2h，40℃ 2h，60℃ 1h，80℃ 2H，80℃ 2h，70℃ 1h，70℃ 1h，80℃ 1h，80℃ 1h，80℃ 1h，80℃ 1h，80℃ 1h，80℃ 1h，80℃ 1h，80℃ | 1∶2∶2 2∶4∶4 2∶4∶4 2∶4∶4 2∶4∶4 2∶5∶4 2∶4∶4 3∶3∶4 3∶6∶4 1∶2∶4 2∶4∶4 3∶6∶2 2∶4∶4 2∶4∶4 | 82 70 98(95a) 76 57 100 100 99 82 78(70a) 80 100 (100a) 100 100 |
aFor at ionic liquid [Bmim] [BF
4] the middle productive rate that obtains that reacts, all the other are at ionic liquid [Bmim] [PF
6] the middle productive rate that obtains that reacts.
Present method has more advantage than traditional method as can be seen from Table 1: comprise that selectivity is good, productive rate is high, simple to operate, environmental friendliness etc.And ionic liquid can reuse, and the experimental result basically identical of triplicate, table 2 are embodiment 1～3 intermediate ion liquid [Bmim] [PF
6] recycle the result.
Table 2
| Cycle index | N-butyl pyrroles's productive rate (%) | |
| 1 2 3 | 1 2 3 | 98 96 97 |
Claims (3)
1, a kind of method of synthesizing the N-substituted azole in ionic liquid comprises the steps:
(1), 1～3mmol pyrroles, 2～6mmol electrophilic reagent and 2～4mmol alkali are joined in 1～4mL ionic liquid reaction 1～2h under 40～80 ℃;
(2), product extraction that step (1) is obtained, concentrate back underpressure distillation or recrystallization, promptly obtain the N-substituted azole;
Described electrophilic reagent is alkylating reagent, acylting agent or alkylsulfonyl reagent;
Described ionic liquid is [Bmim] [PF
6] or [Bmim] [BF
4].
2, a kind of method of synthesizing the N-substituted azole in ionic liquid according to claim 1 is characterized in that described electrophilic reagent is a tert.-butyl bromide.
3, according to each described a kind of method of in ionic liquid, synthesizing the N-substituted azole in claim 1 or 2, it is characterized in that described alkali is potassium hydroxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410026556 CN1252053C (en) | 2004-03-22 | 2004-03-22 | Method for synthesizing N-substitution pyrrole in ion liquid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410026556 CN1252053C (en) | 2004-03-22 | 2004-03-22 | Method for synthesizing N-substitution pyrrole in ion liquid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1562968A CN1562968A (en) | 2005-01-12 |
| CN1252053C true CN1252053C (en) | 2006-04-19 |
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| CN 200410026556 Expired - Fee Related CN1252053C (en) | 2004-03-22 | 2004-03-22 | Method for synthesizing N-substitution pyrrole in ion liquid |
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Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101400173B1 (en) * | 2006-09-12 | 2014-05-27 | 술저 켐테크 악티엔게젤샤프트 | Method of purifying ionic liquids |
| CN107840966B (en) * | 2016-09-21 | 2020-06-12 | 天津大学 | Pentaerythritol triacrylate-dopamine-pyrrole polymer and application thereof |
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