CN1120152C - Beta-halogamma-hydroxypyrrolidone and its synthesis process - Google Patents

Beta-halogamma-hydroxypyrrolidone and its synthesis process Download PDF

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CN1120152C
CN1120152C CN 00125758 CN00125758A CN1120152C CN 1120152 C CN1120152 C CN 1120152C CN 00125758 CN00125758 CN 00125758 CN 00125758 A CN00125758 A CN 00125758A CN 1120152 C CN1120152 C CN 1120152C
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benzyl
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CN1293189A (en
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麻生明
谢贺新
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Shanghai Institute of Organic Chemistry of CAS
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Shanghai Institute of Organic Chemistry of CAS
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Abstract

The present invention relates to beta-halogenated gamma-hydroxypyrrole ketone and a synthetic method thereof. The molecular formula of the beta-halogenated gamma-hydroxypyrrole ketone is disclosed in the formula, wherein R<1> is H, an alkyl group, an aryl group and a benzyl group; R<3> is H, an alkyl group and a benzyl group; R<4> is H, an alkyl group and a benzyl group; R<5> is OH and an alkyl group. The beta-halogenated gamma-hydroxypyrrole ketone is prepared by that CuX<2> reacts with 2, 3-combined diene amide in mixed solvent of organic solvent and water under the condition of the temperature of 40 to 150 DEG C, wherein X is Cl and Br. The yield is from 47 to 94%. In the method, water containing solvent is used as a reaction medium, and the environment is friendly; a ring is formed by one-step halogenating reaction, and is directly hydroxylated by using oxygen in air. The reaction has the advantages of simple operation, low cost and high universality. The method of the present invention is suitable for various kinds of substituted combined diene amide, and is convenient for industrialized production.

Description

A kind of beta-halogamma-hydroxypyrrolidone and synthetic method thereof
The present invention relates to a kind of unsaturated lactone heterocyclic compounds and synthetic method thereof, i.e. beta-halogamma-hydroxypyrrolidone compound and catalytic 2, the method for synthetic this compound of 3-divinyl acid amides cyclization by copper halide.
γ-hydroxy pyrrolidone tool is one of structure component common in the natural product, and multiple important physical activity is arranged.For example, have anti-tumor activity, can be used as thrombocyte stopper or the like.Aspect medical, huge value of exploiting and utilizing is arranged.The efficient succinct synthetic of this compounds is the focus of people's common concern always.And β-halo-γ-hydroxy pyrrolidone is the synthetic above-mentioned very important intermediate of physiologically active compound that has.Document J.C.S.Perkin I 1973,2046; Collect.Czech.Chem.Commun.1976,41,3113; Heterocycles.1984 discloses synthetic β-halo-γ-hydroxy pyrrolidone method in 22,1733, and common traditional synthetic method mainly contains: the amination of (1) corresponding furanone; The reduction of (2) 3,4-dibrom furan ketone; (3) 2,5-pyrroledione Yu Geshi reagent reacts.The shortcoming of these methods is: 1) raw material is not easy to obtain; 2) the reaction needed anhydrous and oxygen-free condition that has, operation inconvenience is unfavorable for mass production; 3) productive rate is generally not high.In view of this still consider it all is worthless from experimental implementation safety and environment aspect from the angle of economy.Therefore explore the synthetic of this compounds and will have actual using value.
Purpose of the present invention just provides a kind of β-halo-γ-hydroxy pyrrolidone compound, and its molecular formula is:
Figure C0012575800041
Wherein: R 1=H, alkyl, aryl, benzyl; R 3=H, alkyl, benzyl; R 4=H, alkyl, benzyl; R 5=OH, alkyl; X=Cl, Br; Condition is to work as R 1=4-pentyloxy phenyl, R 3=H, R 5=OH, during X=Br, R 4Be benzyl only, and work as R 1, R 3=H, R 5=OH, when X=Cl, Br, R 4Only be alkyl, benzyl.
Another object of the present invention just provides corresponding synthetic β-halo-γ-hydroxy pyrrolidone compound method.Reaction formula is as follows:
Figure C0012575800051
Wherein: R 1=H, alkyl, aryl, benzyl; R 2=H, alkyl; R 3=H, alkyl, benzyl; R 4=H, alkyl, benzyl; Work as R 2=H, R 5=OH, R 2=alkyl, R 5=R 2X=Cl, Br.
Concrete reactions steps of the present invention is in organic solvent-water blended solvent, copper halide CuX 2With 2,3-divinyl acid amides reacts under the certain temperature condition and obtains β-halo-γ-hydroxy pyrrolidone, wherein X=Cl, Br; 2,3-divinyl acid amides is (R 1R 2) C=C=C (R 3) CONHR 4, R 1=H, alkyl, aryl, benzyl; R 2=H, alkyl; R 3=H, alkyl, benzyl; R 4=H, alkyl, benzyl; Organic solvent is a polar solvent, and promptly ethanol, methylene dichloride, acetone, tetrahydrofuran (THF), methyl alcohol, dioxane, DMF are recommended as ethanol, tetrahydrofuran (THF); Temperature of reaction is 40-150 ℃, and recommended temperature is 50 ℃; Reaction times is 1-120 hour; 2, the mol ratio of 3-divinyl acid amides and copper halide is 1: 1-2 is recommended as 1: 2.
The present invention with compare with existing method, overcome the drawback of traditional method, have following characteristics: 1. use the low nontoxic relatively CuX of price 2As the source of halogen, its by product CuX is recyclable or be regenerated as CuX 2, help environment protection.2. react the not water funk oxygen of not being afraid of, use water-containing solvent to be reaction medium, environmental friendliness.3. this reaction one step halogenation becomes ring also directly by airborne oxygen hydroxylation, and operation is simple, and is with low cost.4. have higher ubiquity, be applicable to the divinyl acid amides of various replacements.5. conversion unit is simple, and is with low cost, is easy to suitability for industrialized production.
Following examples help to understand the present invention, but are not limited to content of the present invention:
Embodiment 1
0.28mmol N-benzyl 2-methyl-2,3-connection alkene decyl amide and 0.30mmol cupric bromide are dissolved in 8mL tetrahydrofuran (THF)-water, and in 40 ℃ of reactions 18.5 hours, cool to room temperature was with saturated ammonium chloride solution dilution, chloroform extraction five times.The organic phase anhydrous sodium sulfate drying.Obtain white solid product 4-bromo-1-benzyl-5-hydroxyl-5-n-hexyl-3-methyl-2 (5 hydrogen)-pyrrolidone 73mg, productive rate 72% through concentrated, column chromatography purification;
Fusing point: 119-119.5 ℃;
1H?NMR(300MHz，CDCl 3)：δ7.43-7.25(m，5H)，4.65(d，J＝15.00Hz，1H)，4.42(d，J＝15.11Hz，1H)，2.98(s，1H)，1.92(s，3H)，1.89-1.69(m，2H)，1.12-0.45(m，8H)，0.79(t，J＝7.14Hz，3H)；
13C?NMR(300MHz，CDCl 3)：δ168.8，139.2，137.9，134.1，128.8，128.5，127.5，92.5，42.7，34.3，31.4，28.5，22.6，22.4，14.0，10.5；
MS(m/e)：368(M +( 81Br)+1，22.17)，366(M +( 79Br)+1，23.76)，91(100)；
IR(KBr)：3303，1677，1072，1026cm -1；
Anal.Calcd?for?C 18H 24BrNO 2：
Calculated value: C 59.02, H 6.60, and N 3.82;
Measured value: C 59.15, H 6.74, and N 3.82.
Embodiment 2
0.34mmol N-benzyl 2-methyl-2,3-connection alkene decyl amide and 0.37mmol CuCl 22H 2O is dissolved in 10mL tetrahydrofuran (THF)-water, back flow reaction 21 hours, and cool to room temperature is with saturated ammonium chloride solution dilution, chloroform extraction.The organic phase anhydrous sodium sulfate drying.Obtain white solid product 4-chloro-1-benzyl-5-hydroxyl-5-n-hexyl-3-methyl-2 (5 hydrogen)-pyrrolidone 61mg, productive rate 57% through concentrated, column chromatography purification;
Fusing point: 101-102 ℃;
1H?NMR(300MHz，CDCl 3)：δ7.42-7.25(m，5H)，4.65(d，J＝15.11Hz，1H)，4.43(d，J＝15.12Hz，1H)，2.81(s，1H)，1.90(s，3H)，1.97-1.68(m，2H)，1.13-0.50(m，8H)，0.79(t，J＝7.15Hz，3H)；
MS(m/e)：324(M +( 37Cl)+1，0.48)，322(M +( 35Cl)+1，1.46)，91(100)；
IR(KBr)：3310，1673，1092，1031cm -1；
Anal.Calcd?for?C 18H 24ClNO 2：
Calculated value: C 67.17, H 7.52, and N 4.35;
Measured value: C 67.13, H 7.65, and N 4.19.
Embodiment 3
0.47mmol N-benzyl 2-methyl-2,3-connection alkene butyramide and 0.93mmol cupric bromide are dissolved in the 5mL alcohol-water, are heated to 50 ℃ of reactions 19 hours, and cool to room temperature is with saturated ammonium chloride solution dilution, chloroform extraction five times.The organic phase anhydrous sodium sulfate drying.Obtain white solid product 4-bromo-1-benzyl-5-hydroxy-3-methyl-2 (5H)-pyrrolidone 102mg, productive rate 78% through concentrated, column chromatography purification;
Fusing point: 113-114 ℃;
1H?NMR(300MHz，CDCl 3)δ：7.32-7.28(m，5H)，5.07(d，J＝10.26Hz，1H)，4.97(d，J＝14.84Hz，1H)，4.25(d，J＝14.86Hz，1H)，4.09(d，J＝10.44Hz，1H)，1.86(s，3H)；
MS(m/e)：283(M +( 81Br)，2.09)，281(M +( 79Br)，2.30)，106(100)；
IR(KBr)：3294，1665，1065，1023cm -1；
Anal.Calcd?for?C 12H 12BrNO 2：
Calculated value: C 51.09, H 4.29, and N 4.96;
Measured value: C 50.75, H 4.03, and N 4.85.
Embodiment 4
0.52mmol N-benzyl 2-methyl-2,3-connection alkene butyramide and 1.04mmol CuCl 22H 2O is dissolved in the 5mL alcohol-water, is heated to 50 ℃ of reactions 22 hours, and cool to room temperature is with saturated ammonium chloride solution dilution, chloroform extraction five times.The organic phase anhydrous sodium sulfate drying.Obtain white solid product 4-chloro-1-benzyl-5-hydroxy-3-methyl-2 (5H)-pyrrolidone 74mg, productive rate 60% through concentrated, column chromatography purification;
Fusing point: 99-100.5 ℃;
1H?NMR(300MHz，CDCl 3)δ：7.31-7.25(m，5H)，5.03-4.93(m，2H)，4.23(d，J＝14.88Hz，1H)，3.23(d，J＝10.37Hz，1H)，1.86(s，3H)；
MS(m/e)：239(M +( 37Cl)，1.37)，237(M +( 35Cl)，4.04)，106(100)；
IR(KBr)：3418，1670，1079，1044cm -1；
Anal.Calcd?for?C 12H 12ClNO 2：
Calculated value: C 60.64, H 5.09, and N 5.89;
Measured value: C 60.59, H 5.07, and N 5.81.
Embodiment 5
0.14mmol N-normal-butyl 2-methyl-4-phenyl-2,3-connection alkene butyramide and 0.29mmol cupric bromide are dissolved in 4mL tetrahydrofuran (THF)-water, back flow reaction 24 hours, and cool to room temperature is with saturated ammonium chloride solution dilution, chloroform extraction five times.The organic phase anhydrous sodium sulfate drying.Obtain yellow solid product 4-bromo-1-normal-butyl-5-hydroxy-3-methyl-5-phenyl-2 (5 hydrogen)-pyrrolidone 44mg, productive rate 94% through concentrated, column chromatography purification;
Fusing point: 99-100 ℃;
1H?NMR(300MHz，CDCl 3)δ：7.36(s，5H)，3.46(s，1H)，3.41-3.31(m，1H)，2.98-2.88(m，1H)，1.91(s，3H)，1.44-1.13(m，4H)，0.77(t，J＝7.24Hz，3H)；
MS(m/e)：325(M +( 81Br)，26.02)，323(M +( 79Br)，25.86)，253(100)；
IR(KBr)：3283，1638，1069，1027cm -1；
Anal.Calcd?for?C 15H 18BrNO 2：
Calculated value: C 55.57, H 5.60, and N 4.32;
Measured value: C 55.55, H 5.60, and N 4.31.
Embodiment 6
0.31mmol N-normal-butyl 2-methyl-4-phenyl-2,3-connection alkene butyramide and 1.22mmolCuCl 22H 2O is dissolved in 8mL tetrahydrofuran (THF)-water, back flow reaction 5 days, and cool to room temperature is with saturated ammonium chloride solution dilution, chloroform extraction five times.The organic phase anhydrous sodium sulfate drying.Obtain yellow solid product 4-chloro-1-normal-butyl-5-hydroxy-3-methyl-5-phenyl-2 (5 hydrogen)-pyrrolidone 61mg, productive rate 71% through concentrated, column chromatography purification;
Fusing point: 89-90 ℃;
1H?NMR(300MHz，CDCl 3)δ：7.44-7.39(m，5H)，3.40(s，1H)，3.43-3.36(m，1H)，3.01-2.96(m，1H)，1.96(s，3H)，1.54-1.18(m，4H)，0.82(t，J＝7.25Hz，3H)；
MS(m/e)：281(M +( 37Cl)，7.89)，279(M +( 35Cl)，21.94)，207(100)；
IR(KBr)：3294，1683，1073，1037cm -1；
Anal.Calcd?for?C 15H 18ClNO 2：
Calculated value: C 64.40, H 6.48, and N 5.01;
Measured value: C 64.47, H 6.44, and N 4.93.
Embodiment 7
0.40mmol 2,3-connection alkene undecanoyl amine and 0.44mmol cupric bromide are dissolved in the 12mL methanol-water, are heated to 50 ℃ of reactions 22 hours, cool to room temperature is with saturated ammonium chloride solution dilution, chloroform extraction five times.The organic phase anhydrous sodium sulfate drying.Obtain white solid product 4-bromo-5-n-heptyl-5-hydroxyl-2 (5 hydrogen)-pyrrolidone 76mg, productive rate 69% through concentrated, column chromatography purification;
Fusing point: 89-90 ℃;
1H?NMR(300MHz，CDCl 3)：δ6.97(s，1H)，6.17(s，1H)，4.05(s，1H)，1.87-1.82(m，2H)，1.26-1.14(m，10H)，0.87(t，J＝5.23Hz，3H)；
MS(m/e)：278(M +( 81Br)+1，8.77)，276(M +( 79Br)+1，9.16)，258(100)；
IR(KBr)：3258，1687，1093，1039cm -1；
Anal.Calcd?for?C 11H 18BrNO 2：
Calculated value: C 47.84, H 6.57, and N 5.07;
Measured value: C 47.78, H 6.34, and N 4.94.
Embodiment 8
0.61mmol 2,3-connection alkene undecanoyl amine and 1.23mmol CuCl 22H 2O is dissolved in 10mL tetrahydrofuran (THF)-water, is heated to 50 ℃ of reactions 27.5 hours, and cool to room temperature is with saturated ammonium chloride solution dilution, chloroform extraction five times.The organic phase anhydrous sodium sulfate drying.Obtain white solid product 4-chloro-5-n-heptyl-5-hydroxyl-2 (5 hydrogen)-pyrrolidone 67mg, productive rate 47% through concentrated, column chromatography purification;
Fusing point: 118.5-120 ℃;
1H?NMR(300MHz，CDCl 3)δ：6.91(bs，1H)，5.97(s，1H)，4.08(bs，1H)，1.89-1.80(m，2H)，1.26-1.16(m，10H)，0.84(t，J＝6.59Hz，3H)；
MS(m/e)：234(M +( 37Cl)+1，5.74)，232(M +( 35Cl)+1，16.28)，132(100)；
IR(KBr)3226，1705，1094，1049cm -1；
Anal.Calcd?for?C 11H 18ClNO 2：
Calculated value: C 57.02, H 7.83, and N 6.04;
Measured value: C 57.09, H 7.84, and N 6.18.
Embodiment 9
0.23mmol N-benzyl 2,3-connection alkene undecanoyl amine and 0.26mmol cupric bromide 57mg are dissolved in 10mL methylene dichloride-water, are heated to back flow reaction 32 hours, and cool to room temperature is with saturated ammonium chloride solution dilution, chloroform extraction five times.The organic phase anhydrous sodium sulfate drying.Obtain white solid product 4-bromo-1-benzyl-5-n-heptyl-5-hydroxyl-2 (5 hydrogen)-pyrrolidone 65mg, productive rate 78% through concentrated, column chromatography purification;
Fusing point: 120.5-122.5 ℃;
1H?NMR(300MHz，CDCl 3)δ：7.45-7.27(m，5H)，6.33(s，1H)，4.64(d，J＝15.11Hz，1H)，4.46(d，J＝15.14Hz，1H)，2.91(s，1H)，1.88-1.67(m，2H)，1.26-0.53(m，10H)，0.86(t，J＝7.13Hz，3H)；
MS(m/e)：368(M +( 81Br)+1，2.15)，366(M +( 79Br)+1，2.33)，106(100)；
IR(KBr)3258，1673，1095，1036cm -1；
Anal.Calcd?for?C 18H 24BrNO 2：
Calculated value: C 59.02, H 6.60, and N 3.82;
Measured value: C 58.94, H 6.44, and N 3.90.
Embodiment 10
0.23mmol N-benzyl 2,3-connection alkene undecanoyl amine and 0.46mmol CuCl 22H 2O is dissolved in the 10mL acetone-water, is heated to 50 ℃ of reactions 3 days, and cool to room temperature is with saturated ammonium chloride solution dilution, chloroform extraction five times.The organic phase anhydrous sodium sulfate drying.Obtain white solid product 4-chloro-1-benzyl-5-n-heptyl-5-hydroxyl-2 (5 hydrogen)-pyrrolidone 58mg, productive rate 78% through concentrated, column chromatography purification;
Fusing point: 120-120.5 ℃;
1H?NMR(300MHz，CDCl 3)δ：7.39-7.23(m，5H)，6.05(s，1H)，4.62(d，J＝15.10Hz，1H)，4.36(d，J＝15.15Hz，1H)，3.41(bs，1H)，1.86-1.69(m，2H)，1.19-0.53(m，10H)，0.82(t，J＝7.09Hz，3H)；
MS(m/e)：324(M +( 37Cl)+1，0.78)，322(M +( 35Cl)+1，2.19)，106(100)；
IR(KBr)：3264，1674，1096，1035cm -1；
Anal.Calcd?for?C 18H 24ClNO 2：
Calculated value: C 67.17, H 7.52, and N 4.35;
Measured value: C 67.23, H 7.49, and N 4.28.
Embodiment 11
0.21mmol N-benzyl 2-benzyl-4-methyl-2,3-connection alkene valeramide and 0.87mmol cupric bromide are dissolved in 8mL dioxane-water, and back flow reaction 1 hour is with saturated ammonium chloride solution dilution, chloroform extraction three times.The organic phase anhydrous sodium sulfate drying.Obtain yellow oil product 4-bromo-1,3-dibenzyl-5,5-dimethyl-2 (5 hydrogen)-pyrrolidone 70mg, productive rate 89% through concentrated, column chromatography purification;
1H?NMR(300MHz，CDCl 3)δ：7.48-7.22(m，10H)，4.51(s，2H)，3.70(s，2H)，1.48(s，6H)；
MS(m/e)：371(M +( 81Br)，52.32)，369(M +( 79Br)，54.98)，91(100)；
IR(neat)：1682cm -1；
Anal.Calcd?for?C 20H 20BrNO：
Calculated value: C 64.87, H 5.44, and N 3.78;
Measured value: C 64.75, H 5.50, and N 3.97.
Embodiment 12
0.29mmol N-benzyl 2-benzyl-4-methyl-2,3-connection alkene valeramide and 0.56mmolCuCl 22H 2O is dissolved in the 8mL DMF-water, and room temperature reaction 35 hours is with saturated ammonium chloride solution dilution, chloroform extraction three times.The organic phase anhydrous sodium sulfate drying.Obtain yellow oil product 4-chloro-1,3-dibenzyl-5,5-dimethyl-2 (5 hydrogen)-pyrrolidone 75mg, productive rate 80% through concentrated, column chromatography purification;
1H?NMR(300MHz，CDCl 3)δ：7.43-7.24(m，10H)，4.64(s，2H)，3.75(s，2H)，1.53(s，6H)；
MS(m/e)：327(M +( 37Cl)，36.93)，325(M +( 35Cl)，84.57)，91(100)；
IR(neat)：1683cm -1；
Anal.Calcd?for?C 20H 20ClNO：
Calculated value: C 73.72, H 6.19, and N 4.30;
Measured value: C 73.36, H 6.09, and N 4.20.

Claims (8)

1, a kind of β-halo-γ-hydroxy pyrrolidone compound is characterized in that molecular formula is:
Figure C0012575800021
R wherein 1=H, alkyl, aryl, benzyl; R 3=H, alkyl, benzyl; R 4=H, alkyl, benzyl; R 5=OH, alkyl; X=Cl, Br; Condition is to work as R 1=4-pentyloxy phenyl, R 3=H, R 5=OH, during X=Br, R 4Be benzyl only, and work as R 1, R 3=H, R 5=OH, when X=Cl, Br, R 4Only be alkyl, benzyl.
2, a kind of composite structure general formula is
Figure C0012575800022
The method of β-halo-γ-hydroxy pyrrolidone compound, R in the formula 1=H, alkyl, aryl, benzyl; R 3=H, alkyl, benzyl; R 4=H, alkyl, benzyl; R 5=OH, alkyl; X=Cl, Br; It is characterized in that in organic solvent-water blended solvent CuX 2With 2,3-divinyl acid amides reacts under 40-150 ℃ of temperature condition and obtains β-halo-γ-hydroxy pyrrolidone, and reaction formula is as follows: R wherein 1=H, alkyl, aryl, benzyl; R 2=H, alkyl; R 3=H, alkyl, benzyl; R 4=H, alkyl, benzyl; Work as R 2=H, R 5=OH; R 2=alkyl, R 5=R 2X=Cl, Br.
3, the method for synthetic β-halo as claimed in claim 2-γ-hydroxy pyrrolidone compound is characterized in that organic solvent is a polar solvent, comprises ethanol, methylene dichloride, acetone, tetrahydrofuran (THF), methyl alcohol, dioxane, DMF.
4, the method for synthetic β-halo as claimed in claim 3-γ-hydroxy pyrrolidone compound is characterized in that organic solvent is ethanol, tetrahydrofuran (THF).
5, the method for synthetic β-halo as claimed in claim 2-γ-hydroxy pyrrolidone compound is characterized in that temperature of reaction is 50 ℃.
6, the method for synthetic β-halo as claimed in claim 2-γ-hydroxy pyrrolidone compound is characterized in that the reaction times is 1-120 hour.
7, the method for synthetic β-halo as claimed in claim 2-γ-hydroxy pyrrolidone compound is characterized in that 2, and the mol ratio of 3-divinyl acid amides and copper halide is 1: 1-2.
8, the method for synthetic β-halo as claimed in claim 7-γ-hydroxy pyrrolidone compound is characterized in that 2, and the mol ratio of 3-divinyl acid amides and copper halide is 1: 2.
CN 00125758 2000-10-24 2000-10-24 Beta-halogamma-hydroxypyrrolidone and its synthesis process Expired - Fee Related CN1120152C (en)

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