CN1293190A - Butenolide containing no substituent at beta position and its synthesis process - Google Patents

Butenolide containing no substituent at beta position and its synthesis process Download PDF

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CN1293190A
CN1293190A CN 00125757 CN00125757A CN1293190A CN 1293190 A CN1293190 A CN 1293190A CN 00125757 CN00125757 CN 00125757 CN 00125757 A CN00125757 A CN 00125757A CN 1293190 A CN1293190 A CN 1293190A
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butenolide
acid
substituent
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CN1106392C (en
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麻生明
俞瞻前
吴树林
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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

A butenolide containing no substituent at beta position is prepared through reaction of coprous halide on 2,3-dienoic acid in organic solvent under reflux condition. Its output rate is 77-97%. For the dienoic acid with optical activity, the ee value of obtained butenolide can reach 99%. Its advantages include gentle reaction condition, high yield, short period, and low cost.

Description

A kind of β position does not contain substituent butenolide and synthetic method thereof
The present invention relates to a kind of unsaturated lactone compounds and synthetic method thereof, promptly the β position does not have the butenolide compound of replacement and catalytic 2 by cuprous halide, the method for synthetic this compound of 3-di-olefin(e) acid cyclization.
The five-membered ring unsaturated lactone is one of modal structure component in the natural product, has multiple important physical activity.For example, antisepsis and anti-inflammation, antimycotic, antitumor, and regulate seed germination and plant-growth etc., at aspects such as medicine and agricultural chemicals huge value of exploiting and utilizing is arranged.2, the direct cyclisation of 3-connection olefin(e) acid generates β-nothing and replaces the existing report of butenolide.Document Tetrahedron 1978,54,461-465; J, Org.Chem.1997.62.367-371; Tetrahedron Lett.198526 (39), 4811-4814; The traditional synthetic method of butenolide that the β that reports among Liebigs Ann.Chem.1972 756 112-127-nothing replaces is: 1, connection olefin(e) acid or connection olefin(e) acid ester become ring under the effect of a large amount of hydrochloric acid or the vitriol oil; 2, use Silver Nitrate and make the direct Cheng Huan of catalyst connection olefin(e) acid.The shortcoming of these methods is: 1, use strong concentrated hydrochloric acid or the vitriol oil system of corrodibility, have a large amount of spent acid to produce, environment is unfriendly, lacks general suitability, and yield is medium usually; 2, use the Silver Nitrate system, its catalytic amount is bigger, this reagent costs an arm and a leg, corrodibility is strong, has economic aspect or experimental implementation safety and reagent storing stability problem, therefore still considers it all is worthless from experimental implementation safety and environment aspect from the angle of economy.The efficient succinct synthetic of this compounds is the focus of people's common concern always.
Purpose of the present invention just provides the butenolide of a kind of β position unsubstituted, and its molecular formula is: R wherein 1, R 3=H, C mH 2m+1, m=2-7, phenyl, naphthyl; R 2=H, C nH 2n+1, n=0-3, allyl group, benzyl;
Another object of the present invention just provide corresponding synthetic β position unsubstituted butenolide method.Reaction formula is as follows:
Figure 0012575700041
Concrete reactions steps of the present invention is in organic solvent, and cuprous halide CuX and 2,3-di-olefin(e) acid reaction under the condition that refluxes obtains β-nothing and replaces butenolide, wherein X=Cl, Br, I; 2,3-di-olefin(e) acid is optically-active or irrotational (R 1R 3) C=C=C (R 2) COOH, R 1, R 3=H, C mH 2m+1, m=2-7, phenyl, naphthyl; R 2=H, C nH 2n+1, n=0-3, allyl group, benzyl; Organic solvent is a polar solvent, and promptly ethanol, methylene dichloride, acetone, tetrahydrofuran (THF), methyl alcohol, dioxane, DMF, DMSO are recommended as methyl alcohol; Temperature of reaction is 40-150 ℃; Reaction times is 1-15 hour; 2, the mol ratio of 3-di-olefin(e) acid and cuprous halide is 1: 0.02-0.06 is recommended as 1: 0.04.
The present invention compares with existing method, has overcome some drawbacks of traditional method, has following characteristics: the CuX that 1. uses the low relative non-environmental-pollution of price is as catalyzer.2. reaction conditions gentleness, the time is short, and the yield height is applicable to the di-olefin(e) acid of various replacements.3. product is single, is easy to separation and purification.4. conversion unit is simple, and cost is low, is easy to industrialization.This method is the effective ways that synthetic β-nothings replaces butenolide on the one hand, and the butenolide compound that also synthesizes some physiologically active for cheap highly-solid selectively provides real approach on the other hand.
Following examples help to understand the present invention, but are not limited to content of the present invention:
Embodiment 1
With 0.5 mmol 4-phenyl-2-methyl-2, the acid of 3-divinyl is dissolved in the 5ml methyl alcohol, adds the 0.02mmol cuprous chloride.This system is stirring reaction 2 hours under refluxad.Behind the cool to room temperature, column chromatography purification gets product 5-phenyl-3-methyl-2 (5 hydrogen)-furanone 84mg, and yield is 95%, colourless liquid.
1H?NMR(300MHz，CDCl 3)δ：7．49-7．28(m，5H)，7．18(d，J=3．14Hz，1H)，5．92(d，J=3．37Hz，1H)，2．04(s，3H)；
EIMS?m／z：175(M ++1，49．19)，174(M +，68．93)，105(100)；
IR(neat)：1748，1654，1492cm -1。
Embodiment 2
With 4-phenyl-2-propyl group-2,3-divinyl acid 0.5mmol is dissolved in the 5ml ethanol, adds the 0.02mmol cuprous bromide.This system is stirring reaction 2 hours under refluxad.Behind the cool to room temperature, except that after desolvating, column chromatography purification gets product 5-phenyl-3-propyl group-2 (5 hydrogen)-furanone 99mg, productive rate 97%; Colourless liquid;
1H?NMR(300MHz，CDCl 3)δ：7．4-7．22(m，5H)，7．09(d，J=1．54Hz，1H)，5．88(d，J=1．74Hz，1H)，2．34(t，J=5．15Hz，2H)，1．7-1．55(m，2H)，0．98(t，J=7．34Hz，3H)；
EIMS?m／z：203(M ++1，30．01)，202(M +，31．70)，105(100)；
IR(neat)：1756，1454cm -1。
HRMS(EI)calcd?for?C 13H 14O 2：
Calculated value: 202.099,
Measured value: 202.0978.
Embodiment 3
With 0.5mmol 4-phenyl-2-benzyl-2, the acid of 3-divinyl is dissolved in the 5ml methylene dichloride, adds the 0.02mmol cuprous iodide.This system is stirring reaction 2 hours under refluxad.Behind the cool to room temperature, except that after desolvating, column chromatography purification gets product 113mg 5-phenyl-3-benzyl-2 (5 hydrogen)-furanone, productive rate 90%; Colourless tabular crystal,
Fusing point 65-66 ℃;
1H?NMR(300MHz，CDCl 3)δ：7．4-7．18(m，10H)，6．91(d，J=1．3Hz，1H)，5．87(d，J=1．3Hz，1H)，3．66(s，2H)；
EIMS?m／z：250(M +，10．43)，205(100)；
IR(KBr)：1740，1644，1492，1452cm -1
Ultimate analysis C 17H 14O 2:
Calculated value: C81.58, H5.64;
Measured value: C81.79, H5.9.
Embodiment 4
With 0.5mmol 4-phenyl-2-allyl group-2, the acid of 3-divinyl is dissolved in the 5ml acetone, adds the 0.02mmol cuprous chloride.This system is stirring reaction 2 hours under refluxad.Behind the cool to room temperature, except that after desolvating, column chromatography purification gets product 5-phenyl-3-allyl group-2 (5 hydrogen)-furanone 102mg, productive rate 96%, colourless liquid;
1H?NMR(300MHz，CDCl 3)δ：7．45-7．11(m，6H)，5．82-6．00(m，2H)，5．26-5．13(m，2H)，3．11(d，J=5．39Hz，2H)；
EIMS?m／z：221(M ++1，69．97)，220(M +，58．34)，105(100)；
IR(neat)：1758，1636，1492，1452，1428cm -1。
HRMS(EI)calcd?for?C 13H 12O 2：
Calculated value: 200.0834,
Measured value: 200.0833.
Embodiment 5
With 0.5mmol 4-naphthyl-2-methyl-2, the acid of 3-divinyl is dissolved in the 5ml tetrahydrofuran (THF), adds the 0.02mmol cuprous bromide.This system is stirring reaction 2 hours under refluxad.Behind the cool to room temperature, except that after desolvating, column chromatography purification gets product 3-methyl-5-naphthyl-2 (5 hydrogen)-furanone 91mg, productive rate 80%;
Colourless acicular crystal;
Fusing point: 91-92 ℃;
1H?NMR(300MHz，CDCl 3)δ：8．06(d，J=8?Hz，1H)，7．96-7．82(m，2H)，7．68-7．38(m，3H)，6．65(s，1H)，2．02(s，3H)；
EIMS?m／z：224(M +，100)；
IR(KBr)：1744，1650，1598，1506，1438cm -1；
Ultimate analysis C 15H 12O 2:
Calculated value: C80.34, H5.39;
Measured value: C80.23, H5.45.
Embodiment 6
With 0.5 mmol 4-naphthyl-2-propyl group-2, the acid of 3-divinyl is dissolved in the 5ml alcohol, adds the 0.02mmol cuprous iodide.This system is stirring reaction 2 hours under refluxad.Behind the cool to room temperature, except that after desolvating, column chromatography purification gets product 3-propyl group-5-naphthyl-2 (5 hydrogen)-furanone 122mg, productive rate 96%;
Clear crystal;
Fusing point: 84-85 ℃;
1H?NMR(300MHz，CDCl 3)δ：8．08(d，J=7．83Hz，1H)，7．9-7．8(m，2H)，7．6-7．5(m，2H)，7．45-7．3(m，3H)，6．66(d，J=1．63Hz，1H)，2．36(t，J=7．12Hz，2H)，1．7-1．56(m，2H)，0．99(t，J=7．36Hz，3H)；
EIMS?m／z：252(M +，4．55)，177(100)；
IR(KBr)：1744，1650，1596，1540，1453，1436cm -1。
Ultimate analysis C 17H 16O 2:
Calculated value: C80.93, H6.39;
Measured value: C80.54, H6.18.
Embodiment 7
With 0.6mmol 2-methyl-2, the 3-heptadienoic acid is dissolved in the 5ml dioxane, adds the 0.02mmol cuprous halide.This system is stirring reaction 2 hours under refluxad.Behind the cool to room temperature, except that after desolvating, column chromatography purification gets product 5-propyl group-3-methyl-2 (5 hydrogen)-furanone 73mg, productive rate 87%;
Colourless liquid;
1H?NMR(300MHz，CDCl 3)δ：7．04(s，1H)，4．92-4．86(m，1H)，1．92(s，3H)，1．75-1．4(m，4H)，0．97(t，J=7．45Hz，3H)；
EIMS?m／z：141(M ++1，100)；
IR(neat)：1748，1654，1464cm -1。
Embodiment 8
With 0.51mmol 2-benzyl-2, the 3-heptadienoic acid is dissolved among the 5ml DMF, adds the 0.02mmol cuprous iodide.This system is stirring reaction 2 hours under refluxad.Behind the cool to room temperature, except that after desolvating, column chromatography purification gets product 3-benzyl-5-propyl group-2 (5 hydrogen)-furanone 93mg, productive rate 93%;
Colourless liquid;
1H?NMR(300MHz，CDCl 3)δ：7．36-7．19(m，5H)，6．81(d，J=3．03Hz，1H)，4．88(ddd，J=8．1，3．43，1．72Hz，1H)，3．57(s，2H)，1．71-1．51(m，2H)，1．5-1．35(m，2H)，0．93(t，J=2．87Hz，3H)；
EIMS?m／z：217(M ++1，33．06)，216(M +，21．90)，129(100)；
IR(neat)：1748，1600，1492，1452cm -1。
HRMS(EI)?calcd?for?C 14H 16O 2：
Calculated value: 216.1146,
Measured value: 216.1183.
Embodiment 9
With 0.58mmol 2-propyl group-2, the 3-pentadienoic acid is dissolved among the 5ml DMSO, adds the 0.02mmol cuprous chloride.This system is stirring reaction 2 hours under refluxad.Behind the cool to room temperature, except that after desolvating, column chromatography purification gets product 3-propyl group-5-methyl-2 (5 hydrogen)-furanone 63mg, productive rate 77%;
Colourless liquid;
1H?NMR(300MHz，CDCl 3)δ：6．99(d，J=1．22Hz，1H)，4．99(dq，J=1．52，6．88Hz，1H)，2．23(t，J=7．34Hz，2H)，1．65-1．51(m，2H)，1．39(d，J=6．86Hz，3H)，0．94(t，J=7．45Hz，3H)；
EIMS?m／z：141(M ++1，17．44)，140(M +，47．70)，97(100)；
IR(neat)：1746，1650，1454cm -1。
Embodiment 10
With 0.55mmol 2-methyl-2, the 3-decadienoic acid is dissolved in the 5ml methyl alcohol, adds the 0.02mmol cuprous iodide.This system is stirring reaction 2 hours under refluxad.Behind the cool to room temperature, except that after desolvating, column chromatography purification gets product 3-methyl-5-n-hexyl-2 (5 hydrogen)-furanone 85mg, productive rate 85%;
Colourless liquid;
1H?NMR(300MHz，CDCl 3)δ：7．04(d，J=3Hz，1H)，4．88(ddd，J=7．32，3．61，1．79Hz，1H)，1．92(s，3H)，1．76-1．58(m，2H)，1．5-1．24(m，8H)，0．88(t，J=3．03Hz，3H)；
EIMS?m／z：183(M ++1，3．43)，182(M +，2．62)，43(100)；
IR(neat)：1752，1464cm -1。
Embodiment 11
With 0.52mmol 4-phenyl-2-methyl-2, the 3-Sorbic Acid is dissolved in the 5ml methyl alcohol, adds the 0.02mmol cuprous chloride.This system is stirring reaction 2 hours under refluxad.Behind the cool to room temperature, except that after desolvating, column chromatography purification gets 5-phenyl-3-methyl-5-ethyl-2-furanone, 99mg productive rate 93%;
Colourless liquid;
1H?NMR(300MHz，CDCl 3)δ：7．61-7．22(m，6H)，2．21-2．06(m，1H)，2．04-1．89(m，4H)，0．86(t，J=5．55Hz，3H)；
EIMS?m／z：202(M +，2．51)，173(100)；
IR(neat)：1758，1660，1494，1448cm -1。
Embodiment 12
With 0.54mmol 2,3-11 diolefinic acids are dissolved in the 5ml ethanol, add the 0.02mmol cuprous bromide.This system is stirring reaction 2 hours under refluxad.Behind the cool to room temperature, except that after desolvating, column chromatography purification gets product 5-heptyl-2-(5 hydrogen)-furanone 79mg, productive rate 81%;
Colourless liquid;
1H?NMR(300MHz，CDCl 3)δ：7．46(d，J=5．61Hz，1H)，6．10(d，J=5．55Hz，1H)，5．04(t，J=6．37Hz，1H)，1．82-1．59(m，4H)，1．5-1．19(m，8H)，0．88(t，J=4．02Hz，3H)；
EIMS?m／z：183(M ++1，3．63)，182(M +，6．85)，111(100)；
IR(neat)：1747，1599，1465cm -1。
Embodiment 13
With 0.52mmol 3-allyl group-2, the 3-heptadienoic acid is dissolved in the 5ml acetone, adds the 0.02mmol cuprous chloride.This system is stirring reaction 2 hours under refluxad.Behind the cool to room temperature, except that after desolvating, column chromatography purification gets product 5-propyl group-3-allyl group-2 (5 hydrogen)-furanone 78mg, productive rate 91%;
Colourless liquid;
1H?NMR(300MHz，CDCl 3)δ：7．02(s，1H)，5．93-5．79(m，1H)，5．2-5．19(m，2H)，4．91(d，J=4．85Hz，2H)，3．0(d，J=5．79Hz，2H)，1．75-1．38(m，4H)，0．94(t，J=7．25Hz，3H)；
EIMS?m／z：167(M ++1，3．21)，166(M +，7．09)，95(100)；
IR(neat)：1747，1636，1465，1430cm -1；
HRMS(EI)?calcd?for?C 10H 14O 2：
Calculated value: 166.099,
Measured value: 166.09573.
Embodiment 14
With 0.5mmol 5-naphthyl-2-allyl group-2, the acid of 3-divinyl is dissolved in the 5ml methyl alcohol, adds the 0.02mmol cuprous halide.This system is stirring reaction 2 hours under refluxad.Behind the cool to room temperature, except that after desolvating, column chromatography purification gets product 5-naphthyl-3-allyl group-2 (5 hydrogen)-furanone 115mg, productive rate 92%;
Colourless liquid;
1H?NMR(300MHz，CDCl 3)δ：8．05(d，J=8．26Hz，1H)，7．98-7．76(m，2H)，7．6-7．5(m，2H)，7．48-7．3(m，3H)，6．67(s，1H)，6．0-5．8(m，1H)，5．25-5．10(m，2H)，3．12(d，J=6．66Hz，2H)；
ElMS?m／z：250(M +，100)；
IR(neat)：1758，1635，1597，1507cm -1；
HRMS(EI)?calcd?for?C 17H 14O 2：
Calculated value: 250.099,
Measured value: 250.10291.
Embodiment 15
With 0.4mmol (S)-(+)-4-phenyl-2-methyl-2, the acid of 3-divinyl is dissolved in the 4ml ethanol, adds the 0.016mmol cuprous bromide.This system stirring reaction 2 hours under 60 ℃ of conditions.Behind the cool to room temperature, except that after desolvating, column chromatography purification gets product (+)-3-methyl-5 phenyl-2 (5 hydrogen)-furanone 65mg, productive rate 94%, and ee 98.6%,
Clear crystal
Fusing point: 57-58 ℃;
[α]=+226．7°(C=1．025，EtOH)；
1H?NMR(300MHz，CDCl 3)δ：7．4-7．25(m，5H)，7．13(d，J=1．58Hz，1H)，5．87(s，1H)，1．99(d，J=1．47Hz，3H)。
Embodiment 16
With 0.4mmol (R)-(-)-4-phenyl-2-methyl-2, the acid of 3-divinyl is dissolved among the 4ml DMF, adds the 0.016mmol cuprous chloride.This system stirring reaction 2.5 hours under 60 ℃ of conditions.Behind the cool to room temperature, except that after desolvating, column chromatography purification gets product (-)-3-methyl-5 phenyl-2 (5 hydrogen)-furanone 58mg, productive rate 83%, and ee 97.6%;
Clear crystal;
Fusing point: 57-58 ℃;
[α]=-211．8°(C=1．05，EtOH)；
1H?NMR(300MHz，CDCl 3)δ：7．41-7．2(m，5H)，7．12(d，J=1．58Hz，1H)，5．86(s，1H)，1．98(s，3H)。
Embodiment 17
With 0.4mmol (+)-4-phenyl-2-propyl group-2, the acid of 3-divinyl is dissolved in the 4ml methyl alcohol, adds the 0.016mmol cuprous iodide.This system stirring reaction 2 hours under 60 ℃ of conditions.Behind the cool to room temperature, except that after desolvating, column chromatography purification gets product (+)-5-phenyl-3-propyl group-2 (5 hydrogen)-furanone 70mg, productive rate 85%, and ee 99.8%;
Colourless liquid;
1HNMR(300MHz，CDCl 3)δ7.46-7.19(m，5H)，7.09(s，1H)，5.87(s，1H)，2.4-2.28(br，2H)，1.7-1.55(br，2H)，1.08-0.91(br，3H)。
Embodiment 18
With 0.4mmol (-)-4-phenyl-2-propyl group-2, the acid of 3-divinyl is dissolved in the 4ml methyl alcohol, adds the 0.016mmol cuprous iodide.This system stirring reaction 2 hours under 60 ℃ of conditions.Behind the cool to room temperature, except that after desolvating, column chromatography purification gets product (-)-5-phenyl-3-propyl group-2 (5 hydrogen)-furanone 73mg, productive rate 90%, and ee 96.5%;
Colourless liquid;
Figure 0012575700122
1HNMR(300MHz，CDCl 3)δ：7.42-7.2(m，?5H)，?6.98(s，1H)，5.88(d，J=1.46Hz，1H)，2.39-2.3(m，2H)，1.6-1.58(m，2H)，0.98(t，J=7.42Hz，3H)。

Claims (7)

1, a kind of β position does not contain substituent butenolide, it is characterized in that molecular formula is R wherein 1, R 3=H, C mH 2m+1, m=2-7, phenyl, naphthyl; R 2=H, C nH 2n+1, n=0-3, allyl group, benzyl.
2, a kind of synthetic β position does not contain the method for substituent butenolide, it is characterized in that in organic solvent CuX and 2,3-di-olefin(e) acid react under 40-150 ℃ reflux conditions and obtain, and reaction formula is as follows:
Figure 0012575700022
Wherein X=Cl, Br, I; 2,3-di-olefin(e) acid is optically-active or irrotational (R 1R 3) C=C=C (R 2) COOH, R 1, R 3=H, C mH 2m+1, m=2-7, phenyl, naphthyl; R 2=H, C nH 2n+1, n=0-3, allyl group, benzyl.
3, synthetic β as claimed in claim 1 or 2 position does not contain the method for substituent butenolide, it is characterized in that organic solvent is a polar solvent, comprises ethanol, methylene dichloride, acetone, tetrahydrofuran (THF), methyl alcohol, dioxane, DMF, DMSO.
4, synthetic β as claimed in claim 3 position does not contain the method for substituent butenolide, it is characterized in that organic solvent is a methyl alcohol.
5, synthetic β as claimed in claim 1 or 2 position does not contain the method for substituent butenolide, it is characterized in that the reaction times is 1-15 hour.
6, synthetic β as claimed in claim 1 or 2 position does not contain the method for substituent butenolide, it is characterized in that 2, and the mol ratio of 3-di-olefin(e) acid and cuprous halide is 1: 0.02-0.06.
7, synthetic β as claimed in claim 6 position does not contain the method for substituent butenolide, it is characterized in that 2, and the mol ratio of 3-di-olefin(e) acid and cuprous halide is for being 1: 0.04.
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CN101220012B (en) * 2008-01-09 2010-04-07 浙江大学 Method for synthesizing polysubstitution 4-fluorine-2(5H)-furanone
WO2020119549A1 (en) * 2018-12-12 2020-06-18 复旦大学 Method for directly constructing tetra-substituted allenic acid compound having high optical activity
JP2022511915A (en) * 2018-12-12 2022-02-01 フーダン ユニバーシティー A method for directly constructing a highly optically active tetrasubstituted allene carboxylic acid compound
JP7464234B2 (en) 2018-12-12 2024-04-09 フーダン ユニバーシティー Method for producing highly optically active allene carboxylic acid compounds having axial asymmetry
CN111233843A (en) * 2020-01-20 2020-06-05 中山大学 Gamma-butenolide derivative and preparation method and application thereof
CN111233843B (en) * 2020-01-20 2021-07-02 中山大学 Gamma-butenolide derivative and preparation method and application thereof

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