CN106748949A - One kind synthesis α, the method for β unsaturated acyl amines - Google Patents
One kind synthesis α, the method for β unsaturated acyl amines Download PDFInfo
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- CN106748949A CN106748949A CN201710025520.1A CN201710025520A CN106748949A CN 106748949 A CN106748949 A CN 106748949A CN 201710025520 A CN201710025520 A CN 201710025520A CN 106748949 A CN106748949 A CN 106748949A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D207/18—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member
- C07D207/22—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D207/24—Oxygen or sulfur atoms
- C07D207/26—2-Pyrrolidones
- C07D207/263—2-Pyrrolidones with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to other ring carbon atoms
- C07D207/267—2-Pyrrolidones with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to other ring carbon atoms with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to the ring nitrogen atom
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Abstract
One kind synthesis α, the method for β unsaturated acyl amines is related to α, β unsaturated amides.It is raw material, a kind of efficiency synthesis α higher, the method for β unsaturated acyl amines to provide a kind of cyclic tertiary amide being easy to get with stabilization.By teritary amide add halogenated hydrocarbon solvent in, after carrying out condensation reaction with Trifluoromethanesulfonic anhydride, organic base, aromatic aldehyde, through extraction, dry, concentration, after purification, obtain final product α, β unsaturated acyl amines.It is raw material with the cyclic tertiary amide that stabilization is easy to get, expeditiously synthesizes class α, β a unsaturated acyl amines；Operation, separation are simple, and reagent used is common agents, cheap and easy to get.
Description
Technical field
The present invention relates to α, β unsaturated amides, more particularly, to one kind synthesis α, the method for β unsaturated acyl amines.
Background technology
At present, the synthesis of α, β unsaturated amides is compared to α, and the synthesis of β unsaturated aldehydes, ketone and ester, relevant document is less,
And lack very effective one-step method for synthesizing.Before, the use of more method is by Huo Naer-Wordsworth-Ai Mengsi
Reaction and the gloomy reaction of Peter, but these methods still have that some are insurmountable.Such as these methods are from one
α-phosphorus substitution and α-silicon substrate substitution acid amides goes out to send synthesis α, β unsaturated amides, it is impossible to be free of these functional groups from one
General amide set out synthesis this compound；In addition, some methods are because low yield is restricted its application.This and α, β
The importance of unsaturated amides is compared and forms very big contrast.α, β unsaturated amides unsaturated amides are prevalent in naturally
In product structure, these natural products have compared with Johnson ＆ Johnson's thing and insecticidal activity, such as and (±)-Isoanantine and (±)-
anantine.Meanwhile, α, β unsaturated amides are also useful organic synthesis stripping and slicing.
1989, M.K.Tay groups were reported to be reacted by phosphate and isocyanates or carbonic acid esteramides and build chain
Synthesize α, β unsaturated amides with aldehyde reaction again after alpha-phosphate esteramides.The method has good substrate applicability, but can only use
In structure chain α, β unsaturated amides.Compound is write a Chinese character in simplified form：LDA is lithium diisopropylamine.
2000, Satoshi Kojima groups reported α-silicon substrate acid amides and obtain α with aldehyde reaction, β unsaturated amides
Method, the method for aldehyde substrate have stronger substrate applicability, but for amide substrate substrate applicability compared with
It is low, the acid amides and aldehyde reaction for only having silicon substrate to replace on acid amides α carbon are only reported in text, thus the method can only be built in double bond
Dibasic α, β unsaturated amides.Above both approaches and all carried out in strong basicity system, for having in substrate
The substrate of the functional group that strong basicity system is not tolerated is also not suitable for.Compound is write a Chinese character in simplified form：LDA is lithium diisopropylamine, and base is
Organic base, Ar is aryl, and Alkyl is alkyl, and Alkenyl is alkenyl.
Chinese patent CN1561326A1 discloses a kind of method for preparing alpha-haloenamine, and the method is included teritary amide and five
Valency phosphorus halide mixes to form α-halogen inferior amine salt in a solvent, and the α-halogen inferior amine salt then is changed into α-halogen alkene with alkali
Amine, the pentavalent phosphorus halide has at least two halogen atoms being keyed on pentavalent phosphorous atom.
The content of the invention
It is raw material, a kind of efficiency conjunction higher it is an object of the invention to provide a kind of cyclic tertiary amide being easy to get with stabilization
Into α, the method for β unsaturated acyl amines.
Synthetic route of the invention is：
Wherein, R1=C3~C8 alkyl；R2,R3=H, C1~C5 alkyl or C6~C10 aromatic radicals；Compound 1 is tertiary acyl
Amine, compound 2 is α, β unsaturated acyl amines.
Synthetic method of the invention is comprised the following steps that：
By teritary amide add halogenated hydrocarbon solvent in, after carrying out condensation reaction with Trifluoromethanesulfonic anhydride, organic base, aromatic aldehyde,
Through extraction, dry, concentration, after purification, obtain final product α, β unsaturated acyl amines.
Temperature in the addition halogenated hydrocarbon solvent by teritary amide can be -78~0 DEG C；The structural formula of the teritary amide is：
Wherein, R1It can be C3~C8 alkyl；R2,R3Can be H, C1~C5 alkyl or C6~C10 aromatic radicals；The halogenated hydrocarbons
Solvent may be selected from the one kind in halogenated hydrocarbons of C1~C4 etc., preferably dichloromethane or 1,2- dichloroethanes etc.；The organic base can
From organic amine etc., the preferably one kind in diisopropyl ethyl amine, triethylamine etc.；The aromatic aldehyde can select heteroaromatic aldehyde or benzene
Benzaldehyde compound；The mol ratio that the tertiary acyl amine ︰ trifluoro Loprazolam acid anhydrides ︰ has machine alkali ︰ aromatic aldehydes can be the ︰ 3 of 1 ︰, 2 ︰ 2.
The cyclic tertiary amide that the present invention is easy to get with stabilization is raw material, expeditiously synthesizes class α, β a unsaturated acyl amine compounds
Thing.Operation of the invention, separation are simple, and reagent used is common agents, cheap and easy to get.
Specific embodiment
Below by embodiment, the present invention is further illustrated.
Embodiment 1
1- cyclohexyl pyrrolidones (being designated as compound 1a) (115mg, 0.69mmol) are dissolved in dichloromethane (6mL) solvent
In, benzene first is added dropwise in trifluoromethanesulfanhydride anhydride (0.23mL, 1.4mmol), -78 DEG C of stirring 45min is added under -78 DEG C and argon atmospher
Aldehyde (0.20mL, 2.0mmol), 0 DEG C is risen to after -78 DEG C of stirring 5min, and triethylamine (0.20mL, 1.4mmol), room temperature reaction is added dropwise
1h.After adding (1N) hydrochloric acid reaction of 10mL, a point liquid is stood, water is mutually extracted with dichloromethane (3 × 20mL).Merge organic
Phase, is washed with saturated sodium bicarbonate solution (30mL) and saturated aqueous common salt (20mL), through anhydrous sodium sulfate drying, filtering, decompression
Concentration, obtains 1- cyclohexyl -3- benzyls vinyl pyrrolidone (being designated as compound 2a) after purification, and gained compound 2a is colourless liquid
(74mg, 42%).IR(film)3051,2936,2855,1672,1643,1492,1448,1423,1296,1280,952,
764,694；1H NMR(400MHz,CDCl3)δ1.05-1.20(m,1H),1.35-1.52(m,4H),1.65-1.90(m,5H),
2.98-3.09 (m, 2H), 3.47 (t, J=6.5Hz, 2H), 4.05-4.21 (m, 1H), 7.24-7.43 (m, 4H), 7.43-7.51
(m,2H)；13C NMR(100MHz,CDCl3)δ24.5,25.4(2C),25.5,29.6,30.2(2C),40.4,51.2,128.1,
128.6(2C),129.4(2C),131.9,136.1,168.4；MS(ESI,m/z):256(M+H+, 100%).
Embodiment 2
By 1- benzyl-pyrroles alkanone (1b) 121mg, 0.69mmol) be dissolved in dichloromethane (6mL) solvent, in -78 DEG C and
Addition trifluoromethanesulfanhydride anhydride (0.23mL, 1.4mmol) under argon atmospher, -78 DEG C of stirring 45min, dropwise addition benzaldehyde (0.20mL,
2.0mmol), 0 DEG C is risen to after -78 DEG C of stirring 5min, triethylamine (0.20mL, 1.4mmol), room temperature reaction 1h is added dropwise.Add
After (1N) hydrochloric acid reaction of 10mL, a point liquid is stood, water is mutually extracted with dichloromethane (3 × 20mL).Merge organic phase, with full
Washed with sodium bicarbonate solution (30mL) and saturated aqueous common salt (20mL), through anhydrous sodium sulfate drying, filtering is concentrated under reduced pressure, pure
After change 1- benzyls -3- benzyls vinyl pyrrolidone (being designated as compound 2b), gained compound 2b be colourless liquid (109mg,
60%).IR (film) 3082,3028,2923,2850,1674,1645,1495,1448,1434,1422,1295,1282,
1255,1120,1076,763,696；1H NMR(400MHz,CDCl3) δ 2.99-3.08 (m, 2H), 3.38 (t, J=6.4Hz,
2H),4.62(s,2H),7.22-7.45(m,9H),7.45-7.52(m,2H)；13C NMR(100MHz,CDCl3)δ24.3,
44.0,47.3,127.6,128.3(2C),128.4,128.6(2C),128.7(2C),129.5(2C),130.4,130.8,
135.8,136.4,169.1；MS(ESI,m/z):264(M+H+, 100%).
Embodiment 3
1- (1- phenylethyls) pyrrolidones (1c) (131mg, 0.69mmol) is dissolved in dichloromethane (6mL) solvent,
Benzaldehyde is added dropwise in trifluoromethanesulfanhydride anhydride (0.23mL, 1.4mmol), -78 DEG C of stirring 45min is added under -78 DEG C and argon atmospher
(0.20mL, 2.0mmol), 0 DEG C is risen to after -78 DEG C of stirring 5min, and triethylamine (0.20mL, 1.4mmol), room temperature reaction is added dropwise
1h.After adding (1N) hydrochloric acid reaction of 10mL, a point liquid is stood, water is mutually extracted with dichloromethane (3 × 20mL).Merge organic
Phase, is washed with saturated sodium bicarbonate solution (30mL) and saturated aqueous common salt (20mL), through anhydrous sodium sulfate drying, filtering, decompression
Concentration, obtains 1- (1- phenylethyls) -3- benzyls vinyl pyrrolidone (being designated as compound 2c) after purification, and gained compound 2c is colourless
Liquid (88mg, 46%).IR(film)3084,3023,2978,2919,1670,1645,1491,1437,1418,1281,
1212,1182,1069,1028,926,784,763,688；1H NMR(400MHz,CDCl3) δ 1.60 (d, J=7.1Hz, 3H),
2.86-3.15 (m, 3H), 3.38-3.50 (m, 1H), 5.70 (q, J=7.1Hz, 1H), 7.22-7.43 (m, 9H), 7.43-7.51
(m,2H)；13C NMR(100MHz,CDCl3)δ16.1,24.2,29.6,39.7,49.7,127.2(2C),127.5,128.3,
128.5(2C),128.6(2C),129.4(2C),130.2,131.4,135.9,140.0,168.6；MS(ESI,m/z):278(M
+H+, 100%).
Claims (10)
1. a kind of synthesis α, the method for β unsaturated acyl amines, it is characterised in that its synthetic route is：
Wherein, R1=C3~C8 alkyl；R2,R3=H, C1~C5 alkyl or C6~C10 aromatic radicals；Compound 1 is teritary amide, is changed
Compound 2 is α, β unsaturated acyl amines.
2. it is a kind of as claimed in claim 1 to synthesize α, the method for β unsaturated acyl amines, it is characterised in that its synthetic method
Comprise the following steps that：
By teritary amide add halogenated hydrocarbon solvent in, after carrying out condensation reaction with Trifluoromethanesulfonic anhydride, organic base, aromatic aldehyde, through extraction
Take, dry, concentrating, after purification, obtaining final product α, β unsaturated acyl amines.
3. it is a kind of as claimed in claim 2 to synthesize α, the method for β unsaturated acyl amines, it is characterised in that described by teritary amide
It is -78~0 DEG C to add the temperature in halogenated hydrocarbon solvent.
4. it is a kind of as claimed in claim 2 to synthesize α, the method for β unsaturated acyl amines, it is characterised in that the teritary amide
Structural formula is：
Wherein, R1It is C3~C8 alkyl；R2,R3It is H, C1~C5 alkyl or C6~C10 aromatic radicals.
5. it is a kind of as claimed in claim 2 to synthesize α, the method for β unsaturated acyl amines, it is characterised in that the halogenated hydrocarbons is molten
Agent is selected from the one kind in the halogenated hydrocarbons of C1~C4.
6. it is a kind of as claimed in claim 5 to synthesize α, the method for β unsaturated acyl amines, it is characterised in that the halogenated hydrocarbons is molten
Agent is selected from dichloromethane or 1,2- dichloroethanes.
7. it is a kind of as claimed in claim 2 to synthesize α, the method for β unsaturated acyl amines, it is characterised in that the organic base choosing
Use organic amine.
8. it is a kind of as claimed in claim 7 to synthesize α, the method for β unsaturated acyl amines, it is characterised in that the organic amine choosing
With diisopropyl ethyl amine or triethylamine.
9. it is a kind of as claimed in claim 2 to synthesize α, the method for β unsaturated acyl amines, it is characterised in that the aromatic aldehyde is selected
Heteroaromatic aldehyde or compound of benzaldehyde category.
10. it is a kind of as claimed in claim 2 to synthesize α, the method for β unsaturated acyl amines, it is characterised in that the tertiary acyl amine ︰
The mol ratio that trifluoro Loprazolam acid anhydride ︰ has machine alkali ︰ aromatic aldehydes is the ︰ 3 of 1 ︰, 2 ︰ 2.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113896648A (en) * | 2021-09-29 | 2022-01-07 | 浙江理工大学 | Preparation method of alpha, beta-unsaturated amide compound |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6112660A (en) * | 1984-06-27 | 1986-01-21 | Kanegafuchi Chem Ind Co Ltd | Novel 2-pyrrolidone derivative and antiinflammatory therefrom |
| JPS61218571A (en) * | 1985-03-23 | 1986-09-29 | Kanegafuchi Chem Ind Co Ltd | Novel lactam derivative, novel thiolactam derivative and anti-inflammatory agent |
| CN104262255A (en) * | 2014-09-22 | 2015-01-07 | 四川大学 | Method for asymmetric catalytic synthesis of gamma-nitropyrazole amide compound |
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2017
- 2017-01-13 CN CN201710025520.1A patent/CN106748949B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6112660A (en) * | 1984-06-27 | 1986-01-21 | Kanegafuchi Chem Ind Co Ltd | Novel 2-pyrrolidone derivative and antiinflammatory therefrom |
| JPS61218571A (en) * | 1985-03-23 | 1986-09-29 | Kanegafuchi Chem Ind Co Ltd | Novel lactam derivative, novel thiolactam derivative and anti-inflammatory agent |
| CN104262255A (en) * | 2014-09-22 | 2015-01-07 | 四川大学 | Method for asymmetric catalytic synthesis of gamma-nitropyrazole amide compound |
Non-Patent Citations (1)
| Title |
|---|
| OKIKO MIYATA,ET AL.: "Sulfanyl radical addition–cyclization and its synthetic application", 《C. R. ACAD. SCI. PARIS, CHIMIE / CHEMISTRY》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113896648A (en) * | 2021-09-29 | 2022-01-07 | 浙江理工大学 | Preparation method of alpha, beta-unsaturated amide compound |
| CN113896648B (en) * | 2021-09-29 | 2023-08-18 | 浙江理工大学 | Preparation method of alpha, beta-unsaturated amide compound |
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