CN105503794A - Method for synthesizing five-membered ring lactone compound from carbon dioxide in air - Google Patents

Method for synthesizing five-membered ring lactone compound from carbon dioxide in air Download PDF

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Publication number
CN105503794A
CN105503794A CN201510981882.9A CN201510981882A CN105503794A CN 105503794 A CN105503794 A CN 105503794A CN 201510981882 A CN201510981882 A CN 201510981882A CN 105503794 A CN105503794 A CN 105503794A
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China
Prior art keywords
air
membered ring
equivalents
lactone compound
ring lactone
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CN201510981882.9A
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Chinese (zh)
Inventor
潘英明
崔飞虎
梁英
苏世霞
王恒山
蒋邦平
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Guangxi Normal University
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Guangxi Normal University
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members 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
    • C07D307/58—One oxygen atom, e.g. butenolide
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
    • C07D409/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Furan Compounds (AREA)

Abstract

The invention discloses a method for synthesizing a five-membered ring lactone compound from carbon dioxide in air. 1 mmol of terminal alkyne and 5-10 folds of anhydrous tetrahydrofuran are added to a dry flask under protection of nitrogen gas, 1.0 equivalent weight of n-butylithium is added at the temperature of subzero 78 DEG C, air dried by anhydrous calcium chloride is pumped into a reaction liquid by a pressure pump after 1 h and is stopped from pumping in 8-10 h, 1.0 equivalent weight of an alpha-halogenate carbonyl compound and 2.0 equivalent weight of potassium carbonate are added under protection of nitrogen gas, the mixture reacts for 3-10 h at the temperature of 100 DEG C, and the reaction is tracked through TLC (thin layer chromatography). After the mixture sufficiently reacts, the mixture is cooled to the room temperature and filtered, a solvent is removed under reduced pressure, and a product is obtained through quick silica column chromatographic purification. According to the novel method for synthesizing the five-membered ring lactone compound, carbon dioxide in the air can be absorbed, the greenhouse effect is reduced, and a series of serious problems such as global climate warming and the like caused by the greenhouse effect can be reduced. Raw materials required in the experiment are easy to obtain, the yield is high, and the application prospect is wide.

Description

By the method for the carbonic acid gas synthesizing five-membered ring lactone compound in air
Technical field
The present invention relates to five-ring lactone, the method for the carbonic acid gas synthesizing five-membered ring lactone compound specifically in a kind of air.
Background technology
Five-ring lactone compound is of many uses; a lot of people is in research; Zou Kaihua etc. study discovery: bilobalide has certain anti-oxidant, scavenging free radicals, expansion of cerebral vascular; and the ability of learning and memory of vascular dementia mouse can be improved; significantly protection and therapeutic action (" Shanghai medicine " is had to the infringement of fourth ventricle in mice with vascular dementia central nervous system; 2008,29 (8): 365-367).Cheng Lijiao etc. study discovery: natural Podophyllum lignans is the natural product (" external Medicinal Plants medicine fascicle ", 2006,21 (3): 93-100) that a class has remarkable anti-tumor activity.Deng Lulu etc. report cardiac glycoside compounds-periplocoside etc. in multiple, late period cancer pain have good analgesic effect (" Chinese experimental pharmacology of traditional Chinese medical formulae magazine ", 2015,21 (17): 116-120).Cai Mingyi etc. point out, 7-alkyl-gamma-butyrolactone is five-ring lactone compound, can be widely used in preparation food flavour and daily essence, and are used as (" Jiangxi chemical industry ", 2002,4,5-10) such as the intermediates of synthetic perfume, medicine and agricultural chemicals.But the carbonic acid gas in air all do not used by the raw material of synthesis.
Summary of the invention
The object of the invention is to utilize the carbonic acid gas in air, non-Terminal Acetylenes and α-halogenatedcarbonylcompounds to be raw material, under the effect of alkali, synthesize the five-ring lactone compound played an important role to industrial production, the method raw material is easy to get, and productive rate is considerable.
The technical scheme realizing the object of the invention is:
A method for carbonic acid gas synthesizing five-membered ring lactone compound in air, its synthetic method general formula is as follows:
R 1=H, aromatic base, fatty group
R 2=aromatic base, fatty group
X＝Cl,Br
Its synthetic method comprises the steps:
(1) add 1mmol end alkynes, the anhydrous tetrahydro furan of 5-10 times amount to dry propping up in mouth bottle under nitrogen protection, at-78 DEG C, add the n-Butyl Lithium of 1.0 equivalents;
(2) in reaction solution, pump into the air through Calcium Chloride Powder Anhydrous drying with force (forcing) pump after 1h, stop after 8-10h pumping into air;
(3) add the α-halogenatedcarbonylcompounds of 1.0 equivalents and the salt of wormwood of 2.0 equivalents under nitrogen protection, at 100 DEG C, react 3 ~ 10h, TLC follow the tracks of reaction;
(4) question response completely after, cool to room temperature, filters, removal of solvent under reduced pressure, through Flash silica column chromatography purification (ethyl acetate/petroleum ether=1:15 ~ 40) product.
Simultaneous test: in order to better illustrate that carbonic acid gas in reaction is from air, we have done simultaneous test, under rare gas element (as nitrogen, argon gas) protection, repeats above experiment, does not have product to generate.
The invention provides the novel method of a synthesizing five-membered ring lactone compound, importantly it can absorb the carbonic acid gas in air, reduces Greenhouse effect, reduces a series of serious problems such as the global warming caused due to Greenhouse effect.Experiment desired raw material is easy to get, and output is high, and application prospect is extensive.
Embodiment
Embodiment 1:
The preparation of 4,5-phenylbenzene furans-2 (5H)-one
0.8mmol (81.6mg) phenylacetylene is added under nitrogen protection to dry propping up in mouth bottle; the anhydrous tetrahydro furan of 25mL; the n-Butyl Lithium (2.5mol/L) of 1.0 equivalents (0.32mL) is added at-78 DEG C; in reaction solution, the air through Calcium Chloride Powder Anhydrous drying is pumped into force (forcing) pump after 1h; stop after 8h pumping into air; add the 2-bromoacetophenone of 1.0 equivalents (159mg) and the salt of wormwood of 2.0 equivalents (221mg) under nitrogen protection, at 100 DEG C, react 5h.After question response thing cool to room temperature, filter, removal of solvent under reduced pressure, obtain faint yellow solid 1a137.8mg through Flash silica column chromatography purification (ethyl acetate/petroleum ether=1:15 ~ 40), productive rate 73%.
1HNMR(500MHz,CDCl 3)δ7.44–7.39(m,2H),7.37–7.31(m,8H),6.55(d,J＝1.4Hz,1H),6.33(d,J＝1.4Hz,1H)ppm. 13CNMR(125MHz,CDCl 3)δ172.7,165.9,135.0,131.3),127.0(2C),129.2,129.0,127.9(s),127.6,114.6,84.4ppm.
Embodiment 2:
The preparation of 4-phenyl-5-p-methylphenyl furans-2 (5H)-one
0.8mmol (81.6mg) phenylacetylene is added under nitrogen protection to dry propping up in mouth bottle; the anhydrous tetrahydro furan of 25mL; the n-Butyl Lithium (2.5mol/L) of 1.0 equivalents (0.32mL) is added at-78 DEG C; in reaction solution, the air through Calcium Chloride Powder Anhydrous drying is pumped into force (forcing) pump after 1h; stop after 8h pumping into air; add the chloro-4 '-methyl acetophenone of 2-of 1.0 equivalents (135mg) and the salt of wormwood of 2.0 equivalents (221mg) under nitrogen protection, at 100 DEG C, react 7h.After question response thing cool to room temperature, filter, removal of solvent under reduced pressure, obtain faint yellow solid 1a315mg through Flash silica column chromatography purification (ethyl acetate/petroleum ether=1:15 ~ 40), productive rate 82%.
1HNMR(400MHz,DMSO)δ7.62(dd,J＝7.6,1.8Hz,2H),7.39(d,J＝7.1Hz,3H),7.27(d,J＝8.1Hz,2H),7.17(d,J＝8.0Hz,2H),6.92(d,J＝1.3Hz,1H),6.77(d,J＝1.5Hz,1H),2.25(s,3H)ppm. 13CNMR(100MHz,DMSO)δ173.02(s),166.79(s),139.31(s),133.15(s),131.59(s),130.11(d,J＝12.6Hz),129.32(s),128.37(s),128.09(s),114.67(s),83.40(s),21.19(s)ppm.
Embodiment 3:
The preparation of 5-(3-bromophenyl)-4-benzofurane-2 (5H)-one
0.8mmol (81.6mg) phenylacetylene is added under nitrogen protection to dry propping up in mouth bottle; the anhydrous tetrahydro furan of 25mL; the n-Butyl Lithium (2.5mol/L) of 1.0 equivalents (0.32mL) is added at-78 DEG C; in reaction solution, the air through Calcium Chloride Powder Anhydrous drying is pumped into force (forcing) pump after 1h; stop after 8h pumping into air; add 2,4 of 1.0 equivalents (221mg) under nitrogen protection ,the salt of wormwood of-dibromobenzene ethyl ketone and 2.0 equivalents (221mg), reacts 5h at 100 DEG C.After question response thing cool to room temperature, filter, removal of solvent under reduced pressure, through Flash silica column chromatography purification (ethyl acetate/petroleum ether=1:15 ~40) faint yellow solid 1a137.8mg is obtained, productive rate 73%.
1HNMR(400MHz,DMSO)δ7.73–7.53(m,4H),7.37(m,5H),7.03–6.87(m,1H),6.83(s,1H)ppm； 13CNMR(100MHz,DMSO)δ172.34(s),166.04(s),135.09(s),132.06(s),131.30(s),129.89(s),129.43(s),128.95(s),127.90(s),122.66(s),114.41(s),82.07(s)ppm.
Embodiment 4:
The preparation of 5-(4-chloro-phenyl-)-4-p-methylphenyl furans-2 (5H)-one
0.8mmol (92.8mg) 4-tolyl acetylene is added under nitrogen protection to dry propping up in mouth bottle; the anhydrous tetrahydro furan of 25mL; the n-Butyl Lithium (2.5mol/L) of 1.0 equivalents (0.32mL) is added at-78 DEG C; in reaction solution, the air through Calcium Chloride Powder Anhydrous drying is pumped into force (forcing) pump after 1h; stop after 8h pumping into air; add the alpha-brominated-4-chloro-acetophenone of 1.0 equivalents (186mg) and the salt of wormwood of 2.0 equivalents (221mg) under nitrogen protection, at 100 DEG C, react 8h.After question response thing cool to room temperature, filter, removal of solvent under reduced pressure, obtain faint yellow solid 1a185mg through Flash silica column chromatography purification (ethyl acetate/petroleum ether=1:15 ~ 40), productive rate 81%.
1HNMR(400MHz,CDCl 3)δ7.31–7.21(m,7H),7.13(d,J＝8.0Hz,2H),6.48(d,J＝0.8Hz,1H),6.28(s,1H),2.31(s,3H)ppm； 13CNMR(100MHz,CDCl 3)δ172.7(s),165.7(s),142.3(s),135.6(s),133.8(s),129.9(s),129.4(d,J＝9.7Hz),127.6(s),126.7(s),113.8(s),83.40(s),21.6(s)ppm.
Embodiment 5:
The preparation of 5-(4-chloro-phenyl-)-4-(thiophene-2-base) furans-2 (5H)-one
0.8mmol (86.4mg) 2-acetylene thiophene is added under nitrogen protection to dry propping up in mouth bottle; the anhydrous tetrahydro furan of 25mL; the n-Butyl Lithium (2.5mol/L) of 1.0 equivalents (0.32mL) is added at-78 DEG C; in reaction solution, the air through Calcium Chloride Powder Anhydrous drying is pumped into force (forcing) pump after 1h; stop after 8h pumping into air; add the alpha-brominated-4-chloro-acetophenone of 1.0 equivalents (186mg) and the salt of wormwood of 2.0 equivalents (221mg) under nitrogen protection, at 100 DEG C, react 9h.After question response thing cool to room temperature, filter, removal of solvent under reduced pressure, obtain faint yellow solid 1a142mg through Flash silica column chromatography purification (ethyl acetate/petroleum ether=1:15 ~ 40), productive rate 61%.
1HNMR(400MHz,DMSO)δ7.81(d,J＝4.0Hz,1H),7.51–7.43(m,5H),7.39(dd,J＝3.7,1.0Hz,1H),7.12(dd,J＝5.0,3.8Hz,1H),6.71(d,J＝1.5Hz,1H),6.64(d,J＝1.5Hz,1H)ppm； 13CNMR(101MHz,DMSO)δ172.1(s),159.4(s),134.6(s),134.3(s),132.1(2C),131.1(s),129.9(s),129.2(s),128.6(s),111.8(s),82.0(s)ppm。
Embodiment 6:
The preparation of 5-(4-chloro-phenyl-)-4-cyclopropyl furans-2 (5H)-one
0.8mmol (52.9mg) cyclopropyl acethlene is added under nitrogen protection to dry propping up in mouth bottle; the anhydrous tetrahydro furan of 25mL; the n-Butyl Lithium (2.5mol/L) of 1.0 equivalents (0.32mL) is added at-78 DEG C; in reaction solution, the air through Calcium Chloride Powder Anhydrous drying is pumped into force (forcing) pump after 1h; stop after 8h pumping into air; add the alpha-brominated-4-chloro-acetophenone of 1.0 equivalents (186mg) and the salt of wormwood of 2.0 equivalents (221mg) under nitrogen protection, at 100 DEG C, react 10h.After question response thing cool to room temperature, filter, removal of solvent under reduced pressure, obtain faint yellow solid 6a132mg through Flash silica column chromatography purification (ethyl acetate/petroleum ether=1:15 ~ 40), productive rate 66%.
1HNMR(400MHz,DMSO)δ7.53–7.48(m,2H),7.43–7.32(m,2H),6.18(s,1H),5.89(d,J＝1.0Hz,1H),1.40–1.32(m,1H),1.05–0.87(m,2H),0.80–0.67(m,2H)ppm. 13CNMR(100MHz,DMSO)δ177.1(s),173.0(s),134.2(s),133.9(s),129.0(2C),109.5(s),83.65(s),11.8(s),11.1(s),9.7(s)ppm。

Claims (4)

1., with the carbonic acid gas synthesizing five-membered ring lactone compound in air, it is characterized in that: synthetic method general formula is as follows:
R 1=H, aromatic base, fatty group
R 2=aromatic base, fatty group
X＝Cl,Br。
2., by a method for the carbonic acid gas synthesizing five-membered ring lactone compound in air, it is characterized in that: comprise the steps:
(1) add 1mmol end alkynes, the anhydrous tetrahydro furan of 5-10 times amount to dry propping up in mouth bottle under nitrogen protection, at-78 DEG C, add the n-Butyl Lithium of 1.0 equivalents;
(2) in reaction solution, pump into air with force (forcing) pump after 1h, stop after 8-10h pumping into air;
(3) add the α-halogenatedcarbonylcompounds of 1.0 equivalents and the salt of wormwood of 2.0 equivalents under nitrogen protection, at 100 DEG C, react 3 ~ 10h, TLC follow the tracks of reaction;
(4) question response completely after, cool to room temperature, filter, removal of solvent under reduced pressure, obtains product through Flash silica column chromatography purification.
3. method according to claim 2, is characterized in that: the purification by silica gel column chromatography described in step (4) is ethyl acetate/petroleum ether=1:15 ~ 40.
4. method according to claim 2, is characterized in that: the air pumped into described in step (2) is the air through Calcium Chloride Powder Anhydrous drying.
CN201510981882.9A 2015-12-24 2015-12-24 Method for synthesizing five-membered ring lactone compound from carbon dioxide in air Pending CN105503794A (en)

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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015060862A1 (en) * 2013-10-25 2015-04-30 Empire Technology Development Llc Methods of producing dicarbonyl compounds

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015060862A1 (en) * 2013-10-25 2015-04-30 Empire Technology Development Llc Methods of producing dicarbonyl compounds

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
GEORGE E. GRECO 等: "Palladium-Catalyzed [3+2] Cycloaddition of Carbon Dioxide and Trimethylenemethane under Mild Conditions", 《ORG. LETT.》 *
JORDAN D. GOODREID 等: "Amidation Reactions from the Direct Coupling of Metal Carboxylate Salts with Amines", 《J. ORG. CHEM.》 *
RENAN S. FERRARINI 等: "Tellurium in organic synthesis: a general approach to buteno- and butanolides", 《TETRAHEDRON》 *
YONG LEI 等: "Base-Mediated Tandem Reaction Consisting of an Acyl Shift Strategy Leading to 4,5-Disubstiuted Furan-2(5H)-ones", 《ADV. SYNTH. CATAL.》 *

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Application publication date: 20160420