CN101089231A - Electrolytic oxidation coupling of aryl-1,3-dicarbonyl compound and oxolane type high efficient PAF antagonist (anti)-2-5 II (3,4,5 trimethoxyphenyl) oxolane and synthesis method of its analogue - Google Patents

Electrolytic oxidation coupling of aryl-1,3-dicarbonyl compound and oxolane type high efficient PAF antagonist (anti)-2-5 II (3,4,5 trimethoxyphenyl) oxolane and synthesis method of its analogue Download PDF

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CN101089231A
CN101089231A CN200710066039.3A CN200710066039A CN101089231A CN 101089231 A CN101089231 A CN 101089231A CN 200710066039 A CN200710066039 A CN 200710066039A CN 101089231 A CN101089231 A CN 101089231A
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aryl
tetrahydrofuran
thf
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朱洪友
刘复初
谢冰
雷泽
付正启
温晓江
木晓云
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Yunnan University YNU
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Abstract

This invention relates to electrolytic oxidation coupling of aryl-1, 3-dicarbonyl compounds. In this invention, aryl beta-keto ester and aryl beta-diketone are used as raw material, then electrolytic oxidation method is used for the coupling of above-mentioned two compounds. And then the coupling product is used as raw material; after procedures of: hydrolytic decarboxylating, NaBH4 reduction, CF3COOH ring-closing reaction to produce the inventive product tetrahydrofuran type high efficiency PAF agonist (trans)-2,5-di(3,4,5-trimethoxy) phenyl tetrahydrofuran and its analog (trans)-2,5-di(3,4-dimethoxyphenyl) terahydrofuran. This invention method is the first utilization of electrolytic coupling method to produce symmetric structure compounds.

Description

Aryl-1, the efficient PAF antagonist of the electrolytic oxidative coupling of 3-dicarbonyl compound and tetrahydrofuran derivatives (instead)-2, the synthetic method of 5-two (3,4, the 5-trimethoxyphenyl) tetrahydrofuran (THF) and analogue thereof
Technical field
The invention belongs to the organic synthesis field.
Background technology
1, aryl-1, the coupling of 3-dicarbonyl compound:
The coupling of activity methene compound is to form one of important method of C-C in the organic synthesis, and its product is generally symmetric polyfunctional compound, carries out structural modification by a plurality of reactive sites to this compounds and can synthesize the multiclass active substance.Its coupling is modal to be chemical coupling method, and available ether (glycol dimethyl ether) is a solvent, utilizes highly basic Na (NaH, NaOEt, LDA etc.) to make active methylene group generate carbanion, uses weak oxidant I again 2, CuBr 2And AgNO 3Obtain coupled product Deng dimerization after carbanion is converted into free radical.Because the coupled product of Polymethoxylated aryl β keto ester has the basic framework of natural Lignanoids compounds, in some have the natural lignanoid of symmetrical structure such as Jie dihydroguaiaretic acid and deoxyschizandrin synthetic, often with the linked reaction of Polymethoxylated aryl beta-ketoester as committed step.
Use electrochemical method, at KI-CH 3Can realize the coupling of diethyl malonate sodium salt in the CN system, can realize the coupling of malonic ester, cyanoacetate in KI (NaI)-ethanol (methyl alcohol) system, the coupling method of the aryl beta-ketoester of report is chemical coupling method.
2, about PAF and PAF antagonist
PAF is the abbreviation of platelet activation factor (Platelet Activating Factor), it is a kind of endogenous lipid medium that produces by thrombocyte and multiple inflammatory cell, rely on principle of dynamics to discharge by the basophilic leukocyte of immunoglobulin E, thrombocyte had strong activation and cohesion, it is the major incentive of blood pressure drops and bronchoconstriction, simultaneously can also cause Digestive tract and genital disease, cause ulcer.
Compound with paf receptor antagonistic activity is broadly divided into three classes such as PAF analog (as SRI63-119), natural PAF antagonist (as ginkgolide B) and the non-PAF compounds of synthetic.In the non-PAF compounds of synthetic 2,5-diaryl tetrahydrofuran derivatives PAF antagonist synthetic easily because it is simple in structure, to its structure activity relationship more deep research.
People have finished the synthetic of a series of lignanoids based on natural compounds veraguensin, and its structure activity study shows:
Figure A20071006603900031
(1) number that methoxyl group replaces on the aromatic ring is with active relevant, and the activity of trimethoxy is higher than the activity of dimethoxy;
(2) activity of transconfiguration is higher than the activity of cis-configuration on the furan nucleus;
(3) when 2, the 5-position is trans, and is 3,4 when not having methyl, active high when its activity has methyl than 3,4.Wherein screen the most representative compound and be (instead)-2,5-two (3,4, the 5-trimethoxyphenyl) tetrahydrofuran (THF) (its code name is L-652731) shows good anti-PAF activity, suppresses people and rabbit platelet accumulative IC 50=2 * 10 -8Mol/L.
3, tetrahydrofuran derivatives PAF antagonist is synthetic
Because this compounds has the active and simple structure of significant PAF, its synthetic extensive concern of people that caused wherein representative mainly contains following two kinds of synthetic methods: the one, and be raw material with the 2,3 dihydro furan, introduce aryl to furan nucleus; The 2nd, with 1, the 4-dimethyl diketone is a raw material, through the synthetic target molecule of steps such as reduction, closed loop.
(1), the diaryl reaction of 2,3 dihydro furan
a：2.5％Pd(OAc) 2，2.5％Ph 3P，1N?n-BuNCl，3N?KOAc，DMF，rt～80℃；b：3～4％Pd(OAc) 2，9％Ph 3P，2N?Ag 2CO 3，CH 3CN，80℃.
(2), 1, the ring-closure reaction of 4-butyleneglycol
Figure A20071006603900042
The step of this method most critical is how to construct 1, the skeleton of 4-diaryl dimethyl diketone, and the construction method of skeleton mainly contains following several:
The alkylated reaction of a, arone
Figure A20071006603900043
The linked reaction of b, arone
Figure A20071006603900044
Synthesizing of c, aromatic aldehyde and aryl methyl ketone
Figure A20071006603900045
The reaction of d, aromatic aldehyde and aryl ethylene ketone
Figure A20071006603900046
Above-mentioned synthetic method respectively has characteristics, but has severe reaction conditions more, separation difficulty, and raw material is rare, and yield is lower, is difficult to shortcomings such as industrialization.
Summary of the invention
The objective of the invention is to utilize the method high productivity realization aryl beta-ketoester of electrolytic oxidative coupling and the linked reaction of aryl beta-diketon, and be raw material with the coupled product, through hydrolysis decarboxylation, construct 1 easily, the basic framework of 4-diaryl dimethyl diketone, realize the synthetic of efficient PAF antagonist of tetrahydrofuran derivatives and analogue thereof through reduction, the acid ring that closes again, for tetrahydrofuran derivatives PAF antagonist synthetic provides new synthetic thinking.
The present invention is a raw material with aryl beta-ketoester (1a-1d) and aryl beta-diketon (1e), realized the coupling (2a-2e) of aryl beta-ketoester and aryl beta-diketon with the mode of electrolytic oxidation, and be raw material with coupled product (2c-2d) wherein, through hydrolysis decarboxylation, NaBH 4Reduction, CF 3COOH closes ring, has synthesized the efficient PAF antagonist of tetrahydrofuran derivatives (instead)-2,5-two (3,4, the 5-trimethoxy) phenyl tetrahydrofuran (THF) (5d) and analogue (instead)-2 thereof, 5-two (3, the 4-Dimethoxyphenyl) tetrahydrofuran (THF) (5c).Concrete synthetic route is as follows:
Figure A20071006603900051
The present invention is by following step synthetic:
(1), the coupling of aryl beta-ketoester and aryl beta-diketon: with aryl beta-ketoester (1a-1d) and aryl beta-diketon (1e) is raw material, with KI-NaI is indirect electrolytic matter, acetone is solvent, with platinum electrode electrolysis under-5 ℃ of conditions, control current is 1A, about 5～the 6h of electrolysis, reaction is finished after simple aftertreatment gets white crystal (2a-2e), and yield is 80.1～94.8%.
(2), 1, the preparation of 4-two (Polymethoxylated phenyl) dimethyl diketone (3c-3d): with coupled product (2c-2d) is raw material, the NaOH solution with 5% is heating hydrolysis, decarboxylation under 100 ℃ of conditions, reaction needs 6～7h approximately.Through chloroform extraction, the resistates behind the dry desolventizing gets white crystal through the chloroform recrystallization.Yield 43.3～48.5%.
(3), 1, the preparation of 4-two (Polymethoxylated phenyl) butyleneglycol (4c-4d): with 1,4-two (Polymethoxylated phenyl) dimethyl diketone (3c-3d) is a raw material, at room temperature, in THF-CH 3OH (V/V=3: 1) in batches add NaBH in the mixing solutions 4, after reaction is finished, decompose the intact NaBH of unreacted with rare cold hydrochloric acid 4, without purification process, be directly used in the next step through the thick product of aftertreatment gained.
(4), (instead)-2, the preparation of 5-diaryl-tetrahydrofuran (THF) (5c-5d): with 1,4-two (Polymethoxylated phenyl) butyleneglycol (4c-4d) is a raw material, with CHCl 3Be solvent, under the ice bath, slowly drip CF 3The CHCl of COOH 3Solution stirs, and the thick product after reaction finishes can get white crystal by ether or sherwood oil recrystallization purifying, yield 85.1%～90.0%.
Beneficial effect of the present invention:
The present invention use electrolysis link coupled method first high productivity realized the coupling of aryl beta-ketoester and aryl beta-diketon, realized constructing of symmetrical molecule skeleton easily, and as committed step, by the efficient PAF antagonist of tetrahydrofuran derivatives (instead)-2 has been synthesized in the further conversion of electrolysis coupled product, 5-two (3,4, the 5-trimethoxyphenyl) tetrahydrofuran (THF) and analogue (instead)-2 thereof, 5-two (3, the 4-Dimethoxyphenyl) tetrahydrofuran (THF).
The present invention provides new route of synthesis for the efficient PAF antagonist of natural lignanoid, tetrahydrofuran derivatives with symmetrical structure and the synthetic of analogue thereof, and step of the present invention is succinct, easy and simple to handle, product is easy to separation and purification, the yield height.
Below the present invention is described further by embodiment, this invention is not subjected to the limitation of illustrated embodiment.
Embodiment
Embodiment comprises the linked reaction of aryl beta-ketoester and aryl beta-diketon, the efficient PAF antagonist of tetrahydrofuran derivatives (instead)-2, and 5-two (3,4, the 5-trimethoxyphenyl) tetrahydrofuran (THF) and analogue thereof (instead)-2,5-two (3, the 4-Dimethoxyphenyl) tetrahydrofuran (THF) synthetic.
1: the coupling of aryl beta-ketoester and aryl beta-diketon
General method:
In the tubular undivided cell, add 50mmol aryl beta-ketoester (1a-1d) or aryl beta-diketon (1e), the 80mL anhydrous propanone, 1.0gKI and 0.5gNaI are with two Pt paper tinsels (5mm apart, area 2.5 * cm 2) be electrode, under-5 ℃ of conditions, controlling certain voltage, to make electric current be 1A, promptly current density is 80mA/cm 2, evenly stir, complete until the TLC detection reaction, need 5～6h approximately, boil off solvent, residue is dissolved in 50mL 1mol/L Na 2S 2O 3In the solution, use ether extraction, anhydrous Na 2SO 4Drying, the gained crude product gets white crystal (2a-2e) with acetone recrystallization behind the desolventizing, and yield is 80.1～94.8%.2,3-dibenzoyl-1,4-diethyl succinate (2a): C 22H 22O 6(M=382.41) white crystal, yield 80.1%, m.p.:77～79 ℃.
IR(cm -1)：3000，1730，1680，1600，1580，1450.
1H?NMR(CDCl 3，500MHz)δ0.99(t，3H，CH 3)，1.17(t，3H，CH 3)，4.00(q，2H，CH 2)，4.17(q，2H，CH 2)，5.57(s，1H，CH)，5.64(s，1H，CH)，7.49-8.19(10H，2×C 6H 5).
2,3-two (4-methoxyl group-benzoyl)-1,4-diethyl succinate (2b): C 24H 26O 8(M=442.46) white crystal, yield 90.3%, m.p.:114～116 ℃.
1H?NMR(CDCl 3，500MHz)δ1.27(t，6H，2×CH 3)，3.89(s，6H，2×OCH 3)，4.25(q，4H，2×OCH 2)，5.60(s，2H，2×CH)，6.90-8.12(m，8H，2×C 6H 4).
2,3-two (3,4-dimethoxy-benzoyl)-1,4-diethyl succinate (2c): C 26H 30O 10(M=502.51) white crystal, yield 94.8%, m.p.:165～166 ℃.
IR(cm -1)：3030，1725，1658，1580，1520.
1H?NMR(CDCl 3，500MHz)δ1.02(t，6H，2×CH 3)，4.00(s，12H，4×OCH 3)，4.03(q，4H，2×OCH 2)，5.57(s，2H，2×CH)，6.98-7.96(m，6H，2×C 6H 3).
MS(EI，70ev)：502(M +)，484，457，411，165.
2,3-two (3,4,5-trimethoxy-benzoyl)-1,4-diethyl succinate (2d): C 28H 34O 12(M=562.56) white crystal, yield 93.4%, m.p.:164～165 ℃.
IR(cm -1)：3000，1730，1675，1585，1510.
1H?NMR(CDCl 3，500MHz)δ1.06(t，6H，2×CH 3)，3.95(s，18H，6×OCH 3)，4.03(q，4H，2×OCH 2)，5.54(s，2H，2×CH)，7.45(s，4H，2×C 6H 2).
MS(EI，70ev)：562(M +)，544，515，471，195，167.
2,3-dibenzoyl-1,4-dimethyl diketone (2e): C 20H 18O 4(M=322.35) white crystal, yield 89.7%.
IR(cm -1)：3450，1720，1670，1600，1580，1450.
1H?NMR(CDCl 3，500MHz)δ2.28(s，6H，2×CH 3)，5.91(s，2H，2×CH)，7.56-8.17(10H，2×C 6H 5).
MS(EI，70ev)：322(M +)，304，280，105，77.
2:1, the preparation of 4-two (Polymethoxylated phenyl) dimethyl diketone (3c-3d)
General method:
Get NaOH solution (15mmol) heated and stirred in 100 ℃ oil bath of aryl beta-ketoester electrolysis coupled product (2c-2d) 5mmol and 5%, TCL detection reaction process (v/v benzene: methylene dichloride: ethyl acetate=10: 3: 2), reaction is finished needs 6～7h approximately, after finishing, reaction uses chloroform extraction three times, anhydrous Na 2SO 4Drying, the resistates behind the desolventizing add an amount of chloroform and are back to fully dissolving, and the heat filter is separated out white crystal (3c-3d), yield 43.3～48.5% after cold.
1,4-two (3,4-dimethoxy-benzoyl)-1,4-dimethyl diketone (3c): C 20H 22O 6(M=358.39) white crystal, yield 43.3%, m.p.:183～184 ℃.
IR(cm -1)：3030，2900，1670，1590，1460，1440，1420.
1H?NMR(CDCl 3，500MHz)δ3.44(s，4H，2×CH 2)，3.96(s，6H，2×OCH 3)3.97(s，6H，2×OCH 3)，6.94-7.73(m，6H，2×C 6H 3).
MS(EI，70ev)：358(M +)，193，165，137，77，65.
1,4-two (3,4,5-trimethoxy-benzoyl)-1,4-dimethyl diketone (3d): C 22H 26O 8(M=418.44) white crystal, yield 48.5%, m.p.:202～204 ℃.
IR(cm -1)：3000，2900，1680，1590，1510，1470.
1H?NMR(CDCl 3，500MHz)δ3.44(s，4H，2×CH 2)，3.94(d，18H，6×OCH 3)7.32(s，4H，2×C 6H 2)MS(EI，70ev)：418(M +)，400，385，223，195，137，77，66.
3:1, the preparation of 4-two (Polymethoxylated phenyl) butyleneglycol (4c-4d)
Get 1,4-two (Polymethoxylated phenyl) dimethyl diketone (3c-3d) 3mmol is dissolved in 50mL THF-CH 3OH (V/V=3: 1) in the mixed solution, in batches add NaBH 46mmol stirs under the room temperature, and the TCL detection reaction is carried out journey (V/V sherwood oil: ethyl acetate: acetone: methylene dichloride=5: 2: 2: 1), after reaction is finished, add the rare cold hydrochloric acid of 10mL and decompose the intact NaBH of unreacted 4, and use dichloromethane extraction, washing organic phase, anhydrous Na 2SO 4Drying, the resistates behind the desolventizing is directly used in the next step.
4:(is anti-)-2, the preparation of 5-two (Polymethoxylated phenyl) tetrahydrofuran (THF) (5c-5d)
Get 1,4-two (Polymethoxylated phenyl) butyleneglycol (4c-4d) 1mmol is dissolved in 10mLCHCl 3In, ice bath slowly drips 10%CF down 3The CHCl of COOH (1mmol) 3Solution stirs, TCL detection reaction process (V/V sherwood oil: ethyl acetate=1: 1), wash organic phase with 5%NaOH after reaction is finished, use CHCl 3Extract three times, merge organic phase, washing, anhydrous Na 2SO 4Drying, the resistates behind the desolventizing gets white crystals 5c through the sherwood oil recrystallization, yield 90.0%; Through the ether recrystallization, get white crystals 5d, yield 85.1%.
(instead)-2,5-two (3, the 4-Dimethoxyphenyl) tetrahydrofuran (THF) (5c): C 20H 24O 5(M=344.40) white crystal, m.p.:113～114 ℃.
IR(cm -1)：2980，1610，1590，1515，1470，1455.
1H?NMR(CDCl 3，500MHz)δ2.05(m，2H，CH 2)，2.48(m，2H，CH 2)，3.97(2×s，12H，4×OCH 3)，5.22(t，2H，
2×CH)，6.90-6.99(m，6H，2×C 6H 3).
(instead)-2,5-two (3,4, the 5-trimethoxyphenyl) tetrahydrofuran (THF) (5d): C 22H 28O 7(M=404.45) white crystal, m.p.:128～129 ℃.
IR(cm -1)：3000，2900，1590，1510，1460.
1H?NMR(CDCl 3，500MHz)δ2.10(m，2H，CH 2)，2.50(m，2H，)，3.870(2×s，18H，6×OCH 3)，5.20(t，2H，
2×CH，)，6.654(s，2H，C 6H 2)，6.678(s，2H，C 6H 2).
MS(EI，70ev)：404(M +)，210，194，177，77，65.

Claims (4)

1, aryl-1, the efficient PAF antagonist of the electrolytic oxidative coupling of 3-dicarbonyl compound and tetrahydrofuran derivatives (instead)-2, the synthetic method of 5-two (3,4, the 5-trimethoxyphenyl) tetrahydrofuran (THF) and analogue thereof comprises following synthesis step:
(1) electrolytic oxidative coupling of aryl beta-ketoester and aryl beta-diketon: with aryl beta-ketoester and aryl beta-diketon is raw material, is indirect electrolytic matter with KI-NaI, and acetone is solvent, uses at a distance of 5mm area 2.5 * cm 2Platinum electrode electrolysis under-5 ℃ of conditions, control current is 1A, electrolysis 5～6h, wherein, the proportioning of raw material, catalyzer, solvent is: aryl beta-ketoester or aryl beta-diketon: KI: NaI: acetone=50mmo1: 1g: 0.5g: 80mL;
(2) the hydrolysis decarboxylation preparation 1,4-two (Polymethoxylated phenyl) dimethyl diketone: with the coupled product 2 of (1), 3-two (3,4,5-trimethoxy-benzoyl)-1,4-diethyl succinate and 2,3-two (3,4-dimethoxy-benzoyl)-1, the 4-diethyl succinate is a raw material, mix back heated and stirred in 100 ℃ oil bath with 5% NaOH solution, reaction needs 6～7h, and through chloroform extraction, the resistates behind the dry desolventizing gets white crystal through the chloroform recrystallization, wherein, raw material and NaOH mole proportioning are 1: 3;
(3) NaBH 4Reduction preparation 1,4-two (Polymethoxylated phenyl) butyleneglycol: with 1,4-two (3,4-dimethoxy-benzoyl)-1,4-dimethyl diketone and 1,4-two (3,4,5-trimethoxy-benzoyl)-1, the 4-dimethyl diketone is a raw material, and it is dissolved in THF-CH 3OH volume ratio V/V=3: in 1 mixed solution, in batches add NaBH 4, stir under the room temperature, after reaction is finished, add rare cold hydrochloric acid and decompose the intact NaBH of unreacted 4, through dichloromethane extraction, drying, the resistates behind the desolventizing is directly used in the next step, wherein, raw material, NaBH 4And THF-CH 3The proportioning of OH is 1mmol: 2mmol: 17mL;
(4) CF 3COOH closes ring preparation (instead)-2,5-diaryl-tetrahydrofuran (THF): with 1, and 4-two (3,4-dimethoxy-benzoyl)-1,4-butyleneglycol and 1,4-two (3,4,5-trimethoxy-benzoyl)-1, the 4-butyleneglycol is a raw material, and it is dissolved in CHCl 3In, ice bath slowly drips 10%CF down 3The CHCl of COOH 3Solution stirs, and the thick product after reaction is finished gets white crystal by purifying, and wherein, the proportioning of raw material, acid and solvent is: raw material: CF 3COOH: CHCl 3=1mmol: 1mmol: 10mL.
2, synthetic method as claimed in claim 1 is characterized in that the mixed solution after step (1) electrolysis, and the residue that boils off acetone is dissolved in an amount of 1mol/L Na 2S 2O 3In the solution, use ether extraction, anhydrous Na 2SO 4Drying, the thick product of gained gets purified white crystal with acetone recrystallization behind the desolventizing.
3, synthetic method as claimed in claim 1 is characterized in that the reaction product of step (2), with chloroform extraction three times, and anhydrous Na 2SO 4Drying, the resistates behind the desolventizing add an amount of chloroform and are back to it and dissolve fully, the heat filter, and crystallisation by cooling can get purified white crystal.
4, synthetic method as claimed in claim 1 is characterized in that the reaction product of step (4), washs organic phase with 5%NaOH, uses CHCl 3Extraction, (instead)-2 of gained behind drying, the desolventizing, 5-two (3,4, the 5-trimethoxy) the thick product of phenyl tetrahydrofuran (THF) gets white crystal with the ether recrystallization purifying; Gained (instead)-2,5-two (3, the 4-Dimethoxyphenyl) tetrahydrofuran (THF) crude product gets purified white crystal with the sherwood oil recrystallization.
CN200710066039.3A 2007-07-16 2007-07-16 Electrolytic oxidation coupling of aryl-1,3-dicarbonyl compound and oxolane type high efficient PAF antagonist (anti)-2-5 II (3,4,5 trimethoxyphenyl) oxolane and synthesis method of its analogue Pending CN101089231A (en)

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