CN1206217C - Method for synthesizing aziridine compound - Google Patents
Method for synthesizing aziridine compound Download PDFInfo
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- CN1206217C CN1206217C CN 02150060 CN02150060A CN1206217C CN 1206217 C CN1206217 C CN 1206217C CN 02150060 CN02150060 CN 02150060 CN 02150060 A CN02150060 A CN 02150060A CN 1206217 C CN1206217 C CN 1206217C
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Abstract
The present invention discloses a method for synthesizing an ethylene imine compound. In the method, the ethylene imine compound is prepared by the reaction of an imine compound and a diazo compound in room-temperature ionic liquid. In the present invention, by adopting the room-temperature ionic liquid as a catalyst and a reaction medium, the process becomes a chemical process with environmental protection because of the properties of the ionic liquid; because organic solvent as a reaction medium is not used, the pollution for the environment is furthest reduced by using the present invention. The ionic liquid used as the reaction medium and the catalyst can be recycled, and the reactivity of the ionic liquid keeps unchanged.
Description
Technical field
The present invention relates to a kind of method of synthetic ethylene imine compound.
Background technology
The ethylene imine compound is a kind of very important organic synthesis intermediate.Can be by 1, the ring closure reaction of 2-amino alcohol synthesizes its derivative.Recently, (Chem.Comm.2002, p124), but the price of PhI=Ts is very expensive, has limited the use of this method to have become a kind of most important method by metal complexes catalyzed alkene and the synthetic ethylene imine compound of PhI=Ts.The synthetic ethylene imine compound of metal complexes and Lewis acid catalysis imines and diazonium compound also is a kind of most important method (J.Chem.Soc.Chem.Commun.1995, p1401; J.Org.Chem.1996,61, p8358), but exist by product many, product is difficult for the problem of purification; Simultaneously, these catalyzed reactions all with an organic solvent cause environmental pollution easily.
Summary of the invention
The objective of the invention is to overcome and with an organic solvent reach Lewis acid in the prior art, cause the deficiency of environmental pollution easily and a kind of ethylene imine compounds process for production thereof of providing.
The present invention can realize by following measure:
A kind of method of synthetic ethylene imine compound, it is characterized in that this method is is 1: 1 imines and diazonium compound by mol ratio, join by alkyl pyridine or 1,3 alkyl imidazole positively charged ion and Tetrafluoroboric acids, phosphofluoric acid, the ionic liquid of perchloric acid or anionic one of them composition of trifluoromethanesulfonic acid at room temperature reacted 1-5 hour, isolated resultant from reaction mixture.
The used imines of the present invention is by having that various substituent aniline or naphthylamine derivative and benzaldehyde derivative condensation reaction make and various alkylamine derivative and benzaldehyde derivative condensation reaction make.
The used diazonium compound of the present invention is ethyl diazoacetate, diazoacetic acid methyl esters, the diazoacetic acid tert-butyl ester, phenyldiazomethane, 2-phenyl diazoacetic acid methyl esters.
The chain length of alkyl pyridine or 1,3 alkyl imidazole kation alkyl is the integer of C1 to C8 in the used ionic liquid at room temperature of the present invention.
The amount of the ionic liquid at room temperature that the present invention is used is the ionic liquid of the substrate of 1mmol amount with 0.2～2mL.
Ionic liquid at room temperature is a kind of green reaction medium that development in recent years is got up, and it has non-volatile characteristic, generally ℃ all is in a liquid state in room temperature to 300.
The present invention adopts ionic liquid at room temperature as catalyzer and reaction medium, is a very green chemical process.Catalyzer of the present invention has very high catalytic activity and selectivity, and catalyzer is easy to separate with product, and catalyzer is reusable, and catalytic activity remains unchanged.Owing to not with an organic solvent, reduced pollution to greatest extent in the reaction to environment.
Advantage of the present invention is:
1. reaction preference height, product is up to 100% Cis formula selectivity.
2. product separates with ionic liquid simply;
3. it is reusable to react used ionic liquid, and catalytic activity is constant.
Embodiment
Embodiment 1:
10mmol imines 1a and 10mmol ethyl diazoacetate 2 are joined room-temperature ion [Bmim] PF of 10mL
6In (phosphofluoric acid butyl methyl imidazol ion liquid), at room temperature react 5h, after reaction finishes, mixed solution with sherwood oil and ethyl acetate (volume ratio=5/1) extracts product, get 1 after removing organic solvent, 3-phenylbenzene ethylene imine-2-carboxylic acid, ethyl ester 3a, isolated yield is 93%, all is cis-product cis-3a.Product is determined with GC-MS.
Embodiment 2:
With embodiment 1, room-temperature ion liquid [Bmim] BF
4(Tetrafluoroboric acid butyl methyl imidazol ion liquid) at room temperature reacts 5h, gets 1,3-phenylbenzene ethylene imine-2-carboxylic acid, ethyl ester 3a, and isolated yield is 82%, cis-3a/trans-3a=30.
Embodiment 3:
With embodiment 1, room-temperature ion liquid [Bmim] ClO
4(perchloric acid butyl methyl imidazol ion liquid) at room temperature reacts 5h, gets 1,3-phenylbenzene ethylene imine-2-carboxylic acid, ethyl ester 3a, and isolated yield is 60%, cis-3a/trans-3a=13.
Embodiment 4:
With embodiment 1, room-temperature ion liquid [Bmim] OTf (trifluoromethanesulfonic acid butyl methyl imidazol ion liquid) at room temperature reacts 5h, gets 1,3-phenylbenzene ethylene imine-2-carboxylic acid, ethyl ester 3a, and isolated yield is 90%, cis-3a/trans-3a=40.
Embodiment 5:
With embodiment 1, imines is changed to 1b, with room-temperature ion [Bmim] PF of ethyl diazoacetate 2 at 10mL
6In reaction 5h, productive rate is 1-phenyl-3-(4-methyl)-phenyl-ethylene imine-2-carboxylic acid, ethyl ester 3b of 85%, all be cis-product cis-3b.
Embodiment 6:
With embodiment 1, imines is changed to 1c, with room-temperature ion [Bmim] PF of ethyl diazoacetate 2 at 10mL
6In reaction 5h, productive rate is 1-(4-methyl)-phenyl-3-(4-methyl)-phenyl-ethylene imine-2-carboxylic acid, ethyl ester 3c of 91%, all be cis-product cis-3c.
Embodiment 7:
With embodiment 1, imines is changed to 1d, with room-temperature ion [Bmim] PF of ethyl diazoacetate 2 at 10mL
6In reaction 5h, productive rate is 1-phenyl-3-(2-methoxyl group)-phenyl-ethylene imine-2-carboxylic acid, ethyl ester 3d of 85%, all be cis-product cis-3d.
Embodiment 8:
With embodiment 1, imines is changed to 1e, with room-temperature ion [Bmim] PF of ethyl diazoacetate 2 at 10mL
6In reaction 5h, productive rate is 1-phenyl-3-(4-chlorine)-phenyl-ethylene imine-2-carboxylic acid, ethyl ester 3e of 98%, all be cis-product cis-3e.
Embodiment 9:
With embodiment 1, imines is changed to 1f, with room-temperature ion [Bmim] PF of ethyl diazoacetate 2 at 10mL
6In reaction 5h, productive rate is 1-phenyl-3-(2-chlorine)-phenyl-ethylene imine-2-carboxylic acid, ethyl ester 3f of 97%, all be cis-product cis-3f.
Embodiment 10:
With embodiment 1, imines is changed to 1g, with room-temperature ion [Bmim] PF of ethyl diazoacetate 2 at 10mL
6In reaction 5h, productive rate is 1-phenyl-3-(2-bromine)-phenyl-ethylene imine-2-carboxylic acid, ethyl ester 3g of 97%, all be cis-product cis-3g.
Embodiment 11:
With embodiment 1, imines is changed to 1h, with room-temperature ion [Bmim] PF of ethyl diazoacetate 2 at 10mL
6In reaction 5h, productive rate is 1-phenyl-3-(4-bromine)-phenyl-ethylene imine-2-carboxylic acid, ethyl ester 3h of 97%, all be cis-product cis-3h.
Embodiment 12:
With embodiment 1, embodiment 1 used ionic liquid [Bmim] PF
6The second time use, productive rate be 93%1,3-phenylbenzene ethylene imine-2-carboxylic acid, ethyl ester 3a all is cis-product cis-3a.
Embodiment 13:
With embodiment 1, embodiment 1 used ionic liquid [Bmim] PF
6Use for the third time, productive rate be 93%1,3-phenylbenzene ethylene imine-2-carboxylic acid, ethyl ester 3a all is cis-product cis-3a.
Embodiment 14:
With embodiment 1, embodiment 1 used ionic liquid [Bmim] PF
6Use for the 4th time, productive rate be 94%1,3-phenylbenzene ethylene imine-2-carboxylic acid, ethyl ester 3a all is cis-product cis-3a.
Embodiment 15:
With embodiment 1, embodiment 1 used ionic liquid [Bmim] PF
6Use for the 5th time, productive rate be 91%1,3-phenylbenzene ethylene imine-2-carboxylic acid, ethyl ester 3a all is cis-product cis-3a.
Embodiment 16:
With embodiment 1, be changed to 1-methyl-3-n-hexyl-imidazoles phosphofluoric acid drone salt [Hmim] PF as the ionic liquid of reaction medium and catalyzer
6, getting productive rate is 85%1,3-phenylbenzene ethylene imine-2-carboxylic acid, ethyl ester 3a all is cis-product cis-3a.
Embodiment 17:
With embodiment 1, be changed to 1-ethyl-3-n-octyl-imidazoles phosphofluoric acid drone salt [Oeim] PF as the ionic liquid of reaction medium and catalyzer
6, getting productive rate is 80%1,3-phenylbenzene ethylene imine-2-carboxylic acid, ethyl ester 3a all is cis-product cis-3a.
Embodiment 18:
With embodiment 1, diazonium compound is changed to the diazoacetic acid tert-butyl ester, and getting productive rate is 90%1, and 3-phenylbenzene ethylene imine-2-carboxylic acid tert-butyl ester all is a cis-product.
Embodiment 19:
With embodiment 1, the reaction times is 1h, obtains 1, and the isolated yield of 3-phenylbenzene ethylene imine-2-carboxylic acid, ethyl ester 3a is 68%, all is cis-product cis-3a.
Embodiment 20:
With embodiment 1, diazonium compound is changed to the diazoacetic acid methyl esters, and getting productive rate is 96%1, and 3-phenylbenzene ethylene imine-2-carboxylate methyl ester all is a cis-product.
Embodiment 21:
With embodiment 1, diazonium compound is changed to phenyldiazomethane, and getting productive rate is 90%1,2,3-triphenyl ethylene imine.
Embodiment 22:
With embodiment 1, diazonium compound is changed to the diazoacetic acid methyl esters, and getting productive rate is 96%1, and 3-phenylbenzene ethylene imine-2-carboxylate methyl ester all is a cis-product.
Embodiment 23:
With embodiment 1, imines is changed to 1i, with room-temperature ion [Bmim] PF of ethyl diazoacetate 2 at 10mL
6In reaction 5h, productive rate is 1-phenyl-3 normal-butyls-ethylene imine-2-carboxylic acid, ethyl ester 3i of 97%, cis-3i/trans-3i=10.
Embodiment 24:
With embodiment 1, imines is changed to 1j, with room-temperature ion [Bmim] PF of ethyl diazoacetate 2 at 10mL
6In reaction 5h, productive rate is 1-phenyl-3 t-butyl-ethylene imine-2-carboxylic acid, ethyl ester 3j of 91%, cis-3j/trans-3j=35.
Embodiment 25:
With embodiment 1, room-temperature ion liquid is changed to Tetrafluoroboric acid butyl-pyridinium ionic liquid, at room temperature reacts 5h, gets 1,3-phenylbenzene ethylene imine-2-carboxylic acid, ethyl ester 3a, and isolated yield is 79%, cis-3a/trans-3a=20.
Embodiment 26:
With embodiment 1, room-temperature ion liquid is changed to phosphofluoric acid butyl-pyridinium ionic liquid, at room temperature reacts 5h, gets 1,3-phenylbenzene ethylene imine-2-carboxylic acid, ethyl ester 3a, and isolated yield is 89%, cis-3a/trans-3a=35.
Claims (5)
1. the method for a synthetic ethylene imine compound, it is characterized in that this method is is 1: 1 imines and diazonium compound by mol ratio, join by alkyl pyridine or 1,3 alkyl imidazole positively charged ion and Tetrafluoroboric acids, phosphofluoric acid, the ionic liquid of perchloric acid or anionic one of them composition of trifluoromethanesulfonic acid at room temperature reacted 1-5 hour, isolated resultant from reaction mixture.
2. the method for claim 1 is characterized in that diazonium compound selects ethyl diazoacetate, the diazoacetic acid tert-butyl ester, diazoacetic acid methyl esters, phenyldiazomethane, 2-phenyl ethyl diazoacetate for use.
3. the method for claim 1 is characterized in that imine compound is selected for use and has various substituent aniline or naphthylamine derivative and benzaldehyde derivative condensation product and various alkylamine derivative and benzaldehyde derivative condensation product.
4. the method for claim 1, the chain length that it is characterized in that ion liquid kation alkyl is the integer of C1 to C8.
5. the method for claim 1 is characterized in that ion liquid consumption is 0.2～2mL/mmol substrate.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02150060 CN1206217C (en) | 2002-11-19 | 2002-11-19 | Method for synthesizing aziridine compound |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02150060 CN1206217C (en) | 2002-11-19 | 2002-11-19 | Method for synthesizing aziridine compound |
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| CN1412179A CN1412179A (en) | 2003-04-23 |
| CN1206217C true CN1206217C (en) | 2005-06-15 |
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| CN 02150060 Expired - Fee Related CN1206217C (en) | 2002-11-19 | 2002-11-19 | Method for synthesizing aziridine compound |
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| CN105130834B (en) * | 2015-09-30 | 2017-06-23 | 中国科学院兰州化学物理研究所 | A kind of preparation method of β amidos alpha amino acid ester derivative |
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