CN101041648B - Inverse type-1,2-cyclopropane derivative and preparation method thereof - Google Patents

Inverse type-1,2-cyclopropane derivative and preparation method thereof Download PDF

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CN101041648B
CN101041648B CN2007100399399A CN200710039939A CN101041648B CN 101041648 B CN101041648 B CN 101041648B CN 2007100399399 A CN2007100399399 A CN 2007100399399A CN 200710039939 A CN200710039939 A CN 200710039939A CN 101041648 B CN101041648 B CN 101041648B
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cyclopropane
dicyano
phenyl
thenoyl
furancarbonyl
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CN101041648A (en
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曹卫国
赵云辉
张慧
胡吉嵘
孙汝淑
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Nantong Shengda Chemical Industry Co., Ltd.
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University of Shanghai for Science and Technology
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Abstract

The invention discloses a making method of trans-1, 2-cyclopropane derivant with structural formula as formula I (X is O, S; Ar is phenyl or single-substituted phenyl), which comprises the following steps: dissolving furan bromide formyl methyl tripara-arsenic or thiofuran bromide formyl methyl tripara-arsenic as well as the 2-arylidene methyl malononitrile in the chloroform; using KF.2H2O as alkaline to improve the receiving rate of product.

Description

Anti-form-1,2-cyclopropane derivative and preparation method thereof
Technical field
The present invention relates to a kind of anti-form-1,2-cyclopropane derivative and preparation method thereof.
Background technology
Some compound with cyclopropane structure is important biological metabolism intermediate, extensively is present in the microbies such as many plant moulds and bacterium, and is the fine bioactive structural unit of a kind of tool.By can synthesizing many very useful organic compound to the transformation of cyclopropane ring, so the synthetic of cyclopropane derivative is the research direction that organic chemist is extremely paid close attention to always.But the method for common synthetic cyclopropanes is comparatively complicated, and stereoselectivity is bad.The cyclopropanes compound property is more special in addition, though its tension force greatly still has certain stability, cloud density is abundanter, and many and carbon-carbon double bond can take place similarly to react, as cationoid reaction, reduction reaction, rearrangement reaction etc.But because the electron rich of cyclopropane, it is difficult for and the nucleophilic reagent reaction, and this has just limited the application of cyclopropanes compound on synthesizing.The electron-deficient cyclopropane compound is meant a plurality of electron-withdrawing substituents, the compound that the cloud density of ring is lower on the ternary carbocyclic ring.And the bibliographical information of synthetic this compounds is few.
The cyclopropanes compound is implemented in one of focus of organic chemist research, so because their ring strain they in biological organic synthesis, play an important role.Recently, the organic chemical reactions of water as solvent is now just by extensive studies, and particularly stereoselectivity is reacted.Though alkaline aqueous solution is made the organic chemical reactions of solvent and obtained significant success, this field is explored as yet completely.
Summary of the invention:
One of purpose of the present invention is to provide a class anti-form-1,2-cyclopropane derivative.
Two of purpose of the present invention is to provide this anti-form-1, the preparation method of 2-cyclopropane derivative.
For achieving the above object, reaction mechanism of the present invention is:
Figure GSB00000072312900011
Wherein, X is O, S;
Ar is 4-NO 2C 6H 4, 3-NO 2C 6H 4, 4-ClC 6H 4, 2-ClC 6H 4, C 6H 5, 4-CH 3OC 6H 4, 3-BrC 6H 4, 3-FC 6H 4, 3-ClC 6H 4
According to above-mentioned reaction mechanism, the present invention adopts following technical scheme:
A kind of anti-form-1, the 2-cyclopropane derivative is characterized in that the structural formula of this derivative is:
Figure GSB00000072312900021
Wherein, X is O or S; Ar is phenyl or monosubstituted phenyl.
Above-mentioned anti-form-1, the preparation method of 2-cyclopropane derivative is characterized in that this method has following steps: with 2-arylidene methyl-prop dintrile, bromination furoyl ylmethyl TRIPHENYLARSINE or bromination thenoyl ylmethyl TRIPHENYLARSINE and KF2H 2O is dissolved in the chloroform by 1: 1～1.5: 3～4 mol ratio, and stirring reaction to 2-arylidene methyl-prop dintrile reacts completely under the room temperature, and after filtration, after the underpressure distillation, residuals uses column chromatography, and promptly obtains anti-form-1, the 2-cyclopropane derivative; The structural formula of described 2-arylidene methyl-prop dintrile is:
Figure GSB00000072312900022
Ar is phenyl or monosubstituted phenyl.
Think the anti-form-1 that the present invention obtains theoretically, the 2-cyclopropane derivative may have function:
(1) can be used for organic synthesis, is a kind of good organic synthesis intermediate;
(2) synthetic kind of the valid approach that provides of natural product is provided a kind of synthetic novel method.
Embodiment
Embodiment one: anti-form-1-furancarbonyl-2-p-nitrophenyl-3; synthesizing of 3-dicyano cyclopropane; 1; 1-dicyano-2-p-nitrophenyl propylene; bromination furancarbonyl-3-phenyl arsenic and two hydration Potassium monofluorides join chloroform with 1: 1～1.5: 3～4 and at room temperature stir; follow the tracks of reaction with thin-layer chromatography; question response is complete; insoluble substance is filtered; the solvent underpressure distillation; (sherwood oil: ethyl acetate=5: 1) separation can obtain product anti-form-1-furancarbonyl-2-p-nitrophenyl-3,3-dicyano cyclopropane to residuals with column chromatography.
Structure is:
Figure GSB00000072312900023
Molecular formula: C 16H 9O 4N 3
Chinese named: anti-form-1-furancarbonyl-2-p-nitrophenyl-3,3-dicyano cyclopropane
English name: trans-1-Furoyl-2-(4-nitrophenyl)-3,3-dicyanocyclopropane
Molecular weight: 317.2766
Outward appearance: solid
Proton nmr spectra (500MHz, CDCl 3, interior mark: TMS) δ (ppm): 4.22 (1H, d, J=8.24), 4.86 (1H, d, J=8.24), 6.90 (1H, dd, J=1.65,3.57), 8.15-8.27 (6H, m);
Infrared absorption (KBr disc) υ (cm -1): 3032,2247,1670.5,1388;
Mass spectrum m/z:240 (8.42), 185 (2.24), 160 (14.16), 95 (50.57), 89 (8.29), 77 (28.53), 39 (23.20);
Ultimate analysis: C:62.76, H:3.03, N:13.69.
Embodiment two: anti-form-1-furancarbonyl-2-m-nitro base-3; synthesizing of 3-dicyano cyclopropane; 1; 1-dicyano-2-m-nitro base propylene; bromination furancarbonyl-3-phenyl arsenic and two hydration Potassium monofluorides join chloroform with 1: 1～1.5: 3～4 and at room temperature stir; follow the tracks of reaction with thin-layer chromatography; question response is complete; insoluble substance is filtered; the solvent underpressure distillation; (sherwood oil: ethyl acetate=5: 1) separation can obtain product anti-form-1-furancarbonyl-2-m-nitro base-3,3-dicyano cyclopropane to residuals with column chromatography.Structure is:
Figure GSB00000072312900031
Molecular formula: C 16H 9O 4N 3
Chinese named: anti-form-1-furancarbonyl 2-m-nitro base-3,3-dicyano cyclopropane
English name: trans-1-Furoyl-2-(3-nitrophenyl)-3,3-dicyanocyclopropane
Molecular weight: 317.2766
Outward appearance: solid
Proton nmr spectra (500MHz, CDCl 3, interior mark: TMS) δ (ppm): 4.00 (1H, d, J=7.97), 4.18 (1H, d, J=7.97), 6.78 (1H, J=1.65,3.57), 7.57-8.24 (6H, m);
Infrared absorption (KBr disc) υ (cm -1): 3060,2247,1663,1533,1352;
Ultimate analysis: C:62.66, H:3.01, N:13.59;
Mass spectrum m/z:307 (0.52), 185 (0.71), 165 (2.36), 139 (2.62), 95 (100), 89 (1.51), 77 (2.25), 63 (2.90), 51 (3.54), 39 (12.35).
Embodiment three: anti-form-1-furancarbonyl-2-rubigan-3; synthesizing of 3-dicyano cyclopropane; 1; 1-dicyano-2-rubigan propylene; bromination furancarbonyl-3-phenyl arsenic and two hydration Potassium monofluorides join chloroform with 1: 1～1.5: 3～4 and at room temperature stir; follow the tracks of reaction with thin-layer chromatography; question response is complete; insoluble substance is filtered; the solvent underpressure distillation; (sherwood oil: ethyl acetate=5: 1) separation can obtain product anti-form-1-furancarbonyl-2-rubigan-3,3-dicyano cyclopropane to residuals with column chromatography.Structure is:
Molecular formula: C 16H 9O 2N 2Cl
Chinese named: anti-form-1-furancarbonyl-2-rubigan-3,3-dicyano cyclopropane
English name: trans-1-Furoyl-2-(4-chlorophenyl)-3,3-dicyanocyclopropane
Molecular weight: 296.0353
Outward appearance: solid
Proton nmr spectra (500MHz, CDCl 3, interior mark: TMS) δ (ppm): 3.84 (1H, d, J=7.97), 4.04 (1H, d, J=7.97), 6.74 (1H, dd, J=1.65,3.57), 7.54 (1H, dd, J=0.55,3.57), 7.79 (1H, dd, J=0.55,1.65), 7.32 (2H, d, J=8.79), 7.44 (2H, d, J=8.79);
Infrared absorption (KBr disc) υ (cm -1): 3037,2251,1670;
Mass spectrum m/z:298 (0.08), 296 (0.24), 201 (0.25), 174 (2.52), 165 (2.94), 139 (2.75), 95 (100), 89 (1.16), 67 (2.52), 51 (1.90), 39 (7.94);
Ultimate analysis: C:64.76, H:3.23, N:9.29.
Embodiment four: anti-form-1-furancarbonyl-2-Chloro-O-Phenyl-3; synthesizing of 3-dicyano cyclopropane; 1; 1-dicyano-2-Chloro-O-Phenyl propylene; bromination furancarbonyl-3-phenyl arsenic and two hydration Potassium monofluorides join chloroform with 1: 1～1.5: 3～4 and at room temperature stir; follow the tracks of reaction with thin-layer chromatography; question response is complete; insoluble substance is filtered; the solvent underpressure distillation; (sherwood oil: ethyl acetate=5: 1) separation can obtain product anti-form-1-furancarbonyl-2-Chloro-O-Phenyl-3,3-dicyano cyclopropane to residuals with column chromatography.Structure is:
Figure GSB00000072312900042
Molecular formula: C 16H 9O 2N 2Cl
Chinese named: anti-form-1-furancarbonyl-2-Chloro-O-Phenyl-3,3-dicyano cyclopropane
English name: trans-1-Furoyl-2-(2-chlorophenyl)-3,3-dicyanocyclopropane
Molecular weight: 296.0353
Outward appearance: solid
Proton nmr spectra (500MHz, CDCl 3, interior mark: TMS) δ (ppm): 3.91 (1H, d, J=7.97), 4.05 (1H, d, J=7.97), and 6.76 (1H, dd, J=1.65,3.57), 7.55 (1H, dd, J=0.55,3.57), 7.79 (1H, dd, J=0.55,1.65), 7.26-7.57 (4H, m);
Infrared absorption (KBr disc) υ (cm -1): 3063,2247,1671;
Mass spectrum m/z:202 (0.21), 174 (1.74), 165 (1.90), 139 (2.32), 95 (100), 89 (1.07), 51 (2.43), 39 (10.12);
Ultimate analysis: C:64.70, H:3.25, N:9.39.
Embodiment five: anti-form-1-furancarbonyl-2-phenyl-3; synthesizing of 3-dicyano cyclopropane; 1; 1-dicyano-2-phenyl propylene; bromination furancarbonyl-3-phenyl arsenic and two hydration Potassium monofluorides join chloroform with 1: 1～1.5: 3～4 and at room temperature stir; follow the tracks of reaction with thin-layer chromatography; question response is complete; insoluble substance is filtered; the solvent underpressure distillation; (sherwood oil: ethyl acetate=5: 1) separation can obtain product anti-form-1-furancarbonyl-2-phenyl-3,3-dicyano cyclopropane to residuals with column chromatography.Structure is:
Figure GSB00000072312900051
Molecular formula: C 16H 10O 2N 2
Chinese named: anti-form-1-furancarbonyl-2-phenyl-3,3-dicyano cyclopropane
English name: trans-1-Furoyl-2-phenyl-3,3-dicyanocyclopropane
Molecular weight: 262.0742
Outward appearance: solid
Proton nmr spectra (500MHz, CDCl 3, interior mark: TMS) δ (ppm): 3.86 (1H, d, J=7.97), 4.08 (1H, d, J=7.97), and 6.74 (1H, dd, J=1.65,3.57), 7.54 (1H, dd, J=0.55,3.57), 7.79 (1H, dd, J=0.55,1.65), 7.36-7.48 (5H, m);
Infrared absorption (KBr disc) υ (cm -1): 3062,2248,1675;
Mass spectrum m/z:167 (0.27), 140 (4.13), 95 (100), 89 (1.31), 77 (3.00), 63 (2.01), 51 (3.27), 39 (9.02);
Ultimate analysis: C:73.46, H:3.83, N:10.49.
Embodiment six: anti-form-1-furancarbonyl-2-p-methoxyphenyl-3; synthesizing of 3-dicyano cyclopropane; 1; 1-dicyano-2-p-methoxyphenyl propylene; bromination furancarbonyl-3-phenyl arsenic and two hydration Potassium monofluorides join chloroform with 1: 1～1.5: 3～4 and at room temperature stir; follow the tracks of reaction with thin-layer chromatography; question response is complete; insoluble substance is filtered; the solvent underpressure distillation; (sherwood oil: ethyl acetate=5: 1) separation can obtain product anti-form-1-furancarbonyl-2-p-methoxyphenyl-3,3-dicyano cyclopropane to residuals with column chromatography.Structure is:
Molecular formula: C 17H 12O 3N 2
Chinese named: anti-form-1-furancarbonyl-2-p-methoxyphenyl-3,3-dicyano cyclopropane
English name: trans-1-Furoyl-2-(4-methoxylphenyl)-3,3-dicyanocyclopropane
Molecular weight: 292.0848
Outward appearance: solid
Proton nmr spectra (500MHz, CDCl 3, interior mark: TMS) δ (ppm): 3.80 (1H, d, J=7.97), 4.02 (1H, d, J=7.97), 3.83 (3H, s), 6.73 (1H, dd, J=1.65,3.57), 7.51 (1H, dd, J=0.55,3.57), 7.78 (1H, dd, J=0.55,1.65), 6.96 (2H, d, J=8.79), 7.30 (2H, d, J=8.79);
Infrared absorption (KBr disc) υ (cm -1): 3059,2247,1668,1259;
Mass spectrum m/z:292 (1.39), 197 (3.20), 170 (2.30), 165 (0.96), 139 (0.91), 95 (100), 89 (1.78), 77 (1.71), 63 (1.75), 51 (1.82), 39 (5.68);
Ultimate analysis: C:69.76, H:4.23, N:9.39.
Embodiment seven: bromophenyl between anti-form-1-furancarbonyl-2--3; synthesizing of 3-dicyano cyclopropane; 1; bromophenyl propylene between 1-dicyano-2-; bromination furancarbonyl-3-phenyl arsenic and two hydration Potassium monofluorides join chloroform with 1: 1～1.5: 3～4 and at room temperature stir; follow the tracks of reaction with thin-layer chromatography; question response is complete; insoluble substance is filtered; the solvent underpressure distillation; (sherwood oil: ethyl acetate=5: 1) separation can obtain bromophenyl between product anti-form-1-furancarbonyl-2--3,3-dicyano cyclopropane to residuals with column chromatography.
Structure is:
Molecular formula: C 16H 9O 2N 2Br
Chinese named: bromophenyl between anti-form-1-furancarbonyl-2--3,3-dicyano cyclopropane
English name: trans-1-Furoyl-2-(3-bromophenyl)-3,3-dicyanocyclopropane
Molecular weight: 339.9847
Outward appearance: solid
Proton nmr spectra (500MHz, CDCl 3, interior mark: TMS) δ (ppm): 3.84 (1H, d, J=7.97), 4.05 (1H, d, J=7.97), 6.74 (1H, dd, J=1.65,3.57), 7.26-7.81 (6H, m);
Infrared absorption (KBr disc) υ (cm -1): 3030,2246,1660;
Mass spectrum m/z:218 (0.20), 165 (2.54), 139 (4.09), 95 (100), 89 (1.06), 51 (2.34), 39 (10.30);
Ultimate analysis: C:56.46, H:2.33, N:8.39.
Embodiment eight: fluorophenyl between anti-form-1-furancarbonyl-2--3; synthesizing of 3-dicyano cyclopropane; 1; fluorophenyl propylene bromination furancarbonyl-3-phenyl arsenic and two hydration Potassium monofluorides join chloroform with 1: 1～1.5: 3～4 and at room temperature stir between 1-dicyano-2-; follow the tracks of reaction with thin-layer chromatography; question response is complete; insoluble substance is filtered; the solvent underpressure distillation; (sherwood oil: ethyl acetate=5: 1) separation can obtain fluorophenyl between product anti-form-1-furancarbonyl-2--3,3-dicyano cyclopropane to residuals with column chromatography.Structure is:
Figure GSB00000072312900072
Molecular formula: C 16H 9O 2N 2F
Chinese named: fluorophenyl between anti-form-1-furancarbonyl-2--3,3-dicyano cyclopropane
English name: trans-1-Furoyl-2-(4-fluorophenyl)-3,3-dicyanocyclopropane
Molecular weight: 280.0648
Outward appearance: solid
Proton nmr spectra (500MHz, CDCl 3, interior mark: TMS) δ (ppm): 3.85 (1H, d, J=7.97), 4.03 (1H, d, J=7.97), 6.74 (1H, dd, J=1.653.57), and 7.53 (1H, dd, J=0.55,3.57), 7.79 (1H, dd, J=0.55,1.65), 7.13-7.40 (4H, m);
Infrared absorption (KBr disc) υ (cm -1): 3065,2250,1662;
Mass spectrum m/z:184 (0.27), 158 (6.57), 165 (0.27), 139 (0.23), 95 (100), 77 (0.28), 63 (1.11), 39 (10.82);
Ultimate analysis: C:68.76, H:3.23, N:9.89.
Embodiment nine: anti-form-1-Thenoyl-2-p-nitrophenyl-3; synthesizing of 3-dicyano cyclopropane; 1; 1-dicyano-2-p-nitrophenyl propylene bromination Thenoyl-3-phenyl arsenic and two hydration Potassium monofluorides join chloroform with 1: 1～1.5: 3～4 and at room temperature stir; follow the tracks of reaction with thin-layer chromatography; insoluble substance is filtered; the solvent underpressure distillation; (sherwood oil: ethyl acetate=5: 1) separation can obtain product anti-form-1-Thenoyl-2-p-nitrophenyl-3,3-dicyano cyclopropane to residuals with column chromatography.Structure is:
Figure GSB00000072312900081
Molecular formula: C 16H 9O 3N 3S
Chinese named: anti-form-1-Thenoyl-2-p-nitrophenyl-3,3-dicyano cyclopropane
English name: trans-1-Thienoyl-2-(4-nitrophenyl)-3,3-dicyanocyclopropane
Molecular weight: 323.0365
Outward appearance: solid
Proton nmr spectra (500MHz, CDCl 3, interior mark: TMS) δ (ppm): 4.22 (1H, d, J=7.30), 5.10 (1H, d, J=7.30), 7.42 (1H, dd, J=3.81,4.90), 8.00 (2H, d, J=8.52), 8.25 (1H d, J=4.90), 8.32 (1H, d, J=3.81), 8.66 (2H, d, J=8.52);
Infrared absorption (KBr disc) υ (cm -1): 2247,1650,1605,1517,1342,1413,1347;
Mass spectrum m/z:323 (0.2), 308 (100), 212 (0.1), 165 (2), 111 (100), 105 (19), 89 (0.8);
Ultimate analysis: C:59.58, H:2.84, N:12.90.
Embodiment ten: anti-form-1-Thenoyl-2-m-nitro base-3; synthesizing of 3-dicyano cyclopropane; 1; 1-dicyano-2-m-nitro base propylene; bromination Thenoyl-3-phenyl arsenic and two hydration Potassium monofluorides join chloroform with 1: 1～1.5: 3～4 and at room temperature stir; follow the tracks of reaction with thin-layer chromatography; insoluble substance is filtered; the solvent underpressure distillation; (sherwood oil: ethyl acetate=5: 1) separation can obtain product anti-form-1-Thenoyl-2-m-nitro base-3,3-dicyano cyclopropane to residuals with column chromatography.Structure is:
Figure GSB00000072312900091
Molecular formula: C 16H 9O 3N 3S
Chinese named: anti-form-1-Thenoyl-2-m-nitro base-3,3-dicyano cyclopropane
English name: trans-1-Thienoyl-2-(3-nitrophenyl)-3,3-dicyanocyclopropane
Molecular weight: 323.0365
Outward appearance: solid
Proton nmr spectra (500MHz, CDCl 3, interior mark: TMS) δ (ppm): 3.96 (1H, d, J=8.00), 4.06 (1H, d, J=8.00), (7.32 1H, dd, J=4.89,3.80), and 7.70-7.80 (2H, m), 7.92 (1H, d, J=4.89), 8.08 (1H, d, J=3.80), 8.22-8.34 (2H, m);
Infrared absorption (KBr disc) υ (cm -1): 2249,1643,1526,1487,1440,1420,1354;
Mass spectrum m/z:323 (0.71), 212 (0.17), 165 (1.3), 111 (100), 89 (0.78), 83 (8), 63 (2.08);
Ultimate analysis: C:59.66, H:2.85, N:12.85.
Embodiment 11: anti-form-1-Thenoyl-2-rubigan-3; synthesizing of 3-dicyano cyclopropane; 1; 1-dicyano-2-rubigan propylene bromination Thenoyl-3-phenyl arsenic and two hydration Potassium monofluorides join chloroform with 1: 1～1.5: 3～4 and at room temperature stir; follow the tracks of reaction with thin-layer chromatography; insoluble substance is filtered; the solvent underpressure distillation; (sherwood oil: ethyl acetate=5: 1) separation can obtain product anti-form-1-Thenoyl-2-rubigan-3,3-dicyano cyclopropane to residuals with column chromatography.Structure is:
Figure GSB00000072312900092
Molecular formula: C 16H 9ON 2SCl
Chinese named: anti-form-1-Thenoyl-2-rubigan-3,3-dicyano cyclopropane
English name: trans-1-Thienoyl-2-(4-chlorophenyl)-3,3-dicyanocyclopropane
Molecular weight: 312.0124
Outward appearance: solid
Proton nmr spectra (500MHz, CDCl 3, interior mark: TMS) δ (ppm): 3.82 (1H, d, J=8.01), 3.84 (1H, d, J=8.01), 7.28-8.02 (7H, m);
Infrared absorption (KBr disc) υ (cm -1): 2247,165l, 1,515 1500,1430,1414,1355;
Mass spectrum m/z:323 (0.71), 212 (0.17), 165 (1.3), 111 (100), 89 (0.78), 83 (8), 63 (2.08), 202 (0.1), 165 (1.9), 111 (100), 83 (7), 89 (0.9), 63 (1.9);
Ultimate analysis: C:61.32, H:2.79, N:8.88.
Embodiment 12: chloro-phenyl-between anti-form-1-Thenoyl-2--3; synthesizing of 3-dicyano cyclopropane; 1; chloro-phenyl-propylene bromination Thenoyl-3-phenyl arsenic and two hydration Potassium monofluorides join chloroform with 1: 1～1.5: 3～4 and at room temperature stir between 1-dicyano-2-; follow the tracks of reaction with thin-layer chromatography; insoluble substance is filtered; the solvent underpressure distillation; (sherwood oil: ethyl acetate=5: 1) separation can obtain chloro-phenyl-between product anti-form-1-Thenoyl-2--3,3-dicyano cyclopropane to residuals with column chromatography.Structure is:
Figure GSB00000072312900101
Molecular formula: C 16H 9ON 2SCl
Chinese named: chloro-phenyl-between anti-form-1-Thenoyl-2--3,3-dicyano cyclopropane
English name: trans-1-Thienoyl-2-(3-chlorophenyl)-3,3-dicyanocyclopropane
Molecular weight: 312.0124
Outward appearance: solid
Proton nmr spectra (500MHz, CDCl 3, interior mark: TMS) δ (ppm): 3.82 (1H, d, J=8.01), 3.84 (1H, d, J=8.01), 7.25-8.02 (7H, m);
Infrared absorption (KBr disc) υ (cm -1): 2252,1640,1601,1571,1517,1418,1355;
Mass spectrum m/z:313 (0.32), 202 (0.48), 165 (2.8), 111 (100), 89 (0.8), 83 (6.9), 63 (1.4);
Ultimate analysis: C:61.59, H:2.73, N:8.78.
Embodiment 13: anti-form-1-Thenoyl-2-Chloro-O-Phenyl-3; synthesizing of 3-dicyano cyclopropane; 1; 1-dicyano-2-Chloro-O-Phenyl propylene; bromination Thenoyl-3-phenyl arsenic and two hydration Potassium monofluorides join chloroform with 1: 1～1.5: 3～4 and at room temperature stir; follow the tracks of reaction with thin-layer chromatography; insoluble substance is filtered; the solvent underpressure distillation; (sherwood oil: ethyl acetate=5: 1) separation can obtain product anti-form-1-Thenoyl-2-Chloro-O-Phenyl-3,3-dicyano cyclopropane to residuals with column chromatography.Structure is:
Figure GSB00000072312900111
Molecular formula: C 16H 9ON 2SCl
Chinese named: anti-form-1-Thenoyl-2-Chloro-O-Phenyl-3,3-dicyano cyclopropane
English name: trans-1-Thienoyl-2-(2-chlorophenyl)-3,3-dicyanocyclopropane
Molecular weight: 312.0124
Outward appearance: solid
Proton nmr spectra (500MHz, CDCl 3, interior mark: TMS) 6 (ppm): 3.82 (1H, d, J=8.02), 3.86 (1H, d, J=8.02), 7.25-8.05 (7H, m);
Infrared absorption (KBr disc) υ (cm -1): 2251,1644,1510,1481,1420,1358;
Mass spectrum m/z:202 (0.1), 165 (2), 111 (100), 89 (1), 83 (7), 63 (2);
Ultimate analysis: C:59.46, H:2.69, N:12.70.
Embodiment 14: anti-form-1-Thenoyl-2-phenyl-3; synthesizing of 3-dicyano cyclopropane; 1; 1-dicyano-2-phenyl propylene bromination Thenoyl-3-phenyl arsenic and two hydration Potassium monofluorides are with 1: 1～1.5: 3～4; with the chloroform is solvent; stirred under the room temperature 2～3 hours; follow the tracks of reaction with thin-layer chromatography; insoluble substance is filtered; the solvent underpressure distillation; (sherwood oil: ethyl acetate=5: 1) separation can obtain product anti-form-1-Thenoyl-2-phenyl-3,3-dicyano cyclopropane to residuals with column chromatography.Structure is:
Figure GSB00000072312900112
Molecular formula: C 16H 10ON 2S
Chinese named: anti-form-1-Thenoyl-2-phenyl-3,3-dicyano cyclopropane
English name: trans-1-Thienoyl-2-phenyl-3,3-dicyanocyclopropane
Molecular weight: 278.0514
Outward appearance: solid
Proton nmr spectra (500MHz, CDCl 3, interior mark: TMS) δ (ppm): 3.88 (1H, d, J=8.00), 3.90 (1H, d, J=8.00), 7.30 (1H, dd, J=3.81,4.91), 7.35-7.50 (5H, m), 7.88 (1H, dd, J=1.10,4.91), 8.02 (1H, dd, J=1.10,3.81);
Infrared absorption (KBr disc) υ (cm -1): 2255,1652,1518,1454,1421,1357;
Mass spectrum m/z:167 (0.42), 140 (3), 111 (100), 89 (1.7), 83 (7), 63 (2);
Ultimate analysis: C:69.17, H:3.69, N:10.63;
Embodiment 15: anti-form-1-Thenoyl-2-p-methoxyphenyl-3; synthetic 1 of 3-dicyano cyclopropane; 1-dicyano-2-p-methoxyphenyl propylene; bromination Thenoyl-3-phenyl arsenic and two hydration Potassium monofluorides join chloroform with 1: 1～1.5: 3～4 and at room temperature stir; follow the tracks of reaction with thin-layer chromatography; insoluble substance is filtered; the solvent underpressure distillation; (sherwood oil: ethyl acetate=5: 1) separation can obtain product anti-form-1-Thenoyl-2-p-methoxyphenyl-3,3-dicyano cyclopropane to residuals with column chromatography.Structure is:
Figure GSB00000072312900121
Molecular formula: C 17H 12O 2N 2S
Chinese named: anti-form-1-Thenoyl-2-p-methoxyphenyl-3,3-dicyano cyclopropane
English name: trans-1-Thienoyl-2-(4-methoxylphenyl)-3,3-dicyanocyclopropane
Molecular weight: 308.0619
Outward appearance: solid
Proton nmr spectra (500MHz, CDCl 3, interior mark: TMS) δ (ppm): 3.82 (3H, s), 3.86 (1H, d, J=8.01), 3.96 (1H, d, J=8.01), 6.94-8.02 (7H, m);
Infrared absorption (KBr disc) υ (cm -1): 2245,1652,1612,1519,1437,1415,1359;
Mass spectrum m/z:308 (0.14), 197 (0.77), 165 (0.44), 111 (100), 89 (1.4), 83 (4.8), 63 (2.3);
Ultimate analysis: C:66.42, H:3.85, N:9.15.

Claims (1)

1. anti-form-1, the preparation method of 2-cyclopropane derivative is characterized in that this method has following steps: with 2-arylidene methyl-prop dintrile, bromination furoyl ylmethyl TRIPHENYLARSINE or bromination thenoyl ylmethyl TRIPHENYLARSINE and KF2H 2O is dissolved in the chloroform by 1: 1～1.5: 3～4 mol ratio, and stirring reaction to 2-arylidene methyl-prop dintrile reacts completely under the room temperature, after filtration, after the underpressure distillation, residuals uses column chromatography, promptly obtain anti-form-1, the 2-cyclopropane derivative, the structural formula of this derivative is:
The structural formula of described 2-arylidene methyl-prop dintrile is: Wherein, X is O or S; Ar is phenyl or monosubstituted phenyl.
CN2007100399399A 2007-04-25 2007-04-25 Inverse type-1,2-cyclopropane derivative and preparation method thereof Expired - Fee Related CN101041648B (en)

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Ren, Zhongjiao, et al..Stereoselective synthesis ofcis-1-aryl-2-benzoyl-3,3-dicyanocyclopropanes in thepresence of KF·2H2O.Synthetic Communications34 20.2004,34(20),3785-3792. *
Satoshi Kojima, et al..Asymmetric synthesis of activated cyclopropanes catalyzedby cinchonidine as a chiral Bronsted base.Tetrahedron Letters47.2006,479061-9065,尤其是9061页第1栏、9063页Scheme 5、表2. *
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