CN102675150A - Preparation method and synthesis method of chiral compound - Google Patents
Preparation method and synthesis method of chiral compound Download PDFInfo
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- CN102675150A CN102675150A CN2012101307130A CN201210130713A CN102675150A CN 102675150 A CN102675150 A CN 102675150A CN 2012101307130 A CN2012101307130 A CN 2012101307130A CN 201210130713 A CN201210130713 A CN 201210130713A CN 102675150 A CN102675150 A CN 102675150A
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- chiral compound
- bromine
- phenylacetonitrile
- phenyl
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Abstract
The invention discloses a preparation method of chiral compound, wherein the chiral compound has the following chemical formula (I). A synthesis method of the chiral compound comprises the following steps of: taking 15mol% (S) alpha-phenylethylamine cupric acetate as catalyst, taking 2mmol of 4-bromobenzaldehydes, 6mmol of trimethyl silicon nitrile and 4mL of absolute methanol as solvent, reacting for 3days in a stirring way under room temperature, carrying out column chromatography separation, eluting by that the ratio of petroleum ether to methylene dichloride being 1:1, and naturally volatilizing a collected third component point, to obtain single crystal-ethylamino group phenyl-(4-bromine) phenyl acetonitrile.
Description
One, technical field
The present invention relates to a kind of preparation and compound method of chipal compounds, exactly is a kind of preparation and compound method of nitrogenous nitrile compounds.
Two, background technology
Ethylamino phenyl-phenylacetonitrile is important medicine intermediate, can be used to synthesizing heterocyclic class medicine arylpyrazines [1]
Reference:
1. Novel?Asymmetric?Synthesis?of?Atropisomeric?6-Aryl?Pyrazinones?via?an?Unusual?Chirality?Transfer?Process, Tulinsky,?John;?Cheney,?B.?Vernon;?Mizsak,?Stephen?A.;?Watt,?William;?Han,?Fusan;?Dolak,?Lester?A.;?Judge,?Thomas;?Gammill,?Ronald?B.?Journal?of?Organic?Chemistry?(1999),?64(1),?93-100.
The applicant in title complex (S)-α-Ben Yian venus crystals title complex asymmetry catalysis 4-bromobenzaldehyde nitrile silicification reaction process, obtained a kind of chipal compounds (S, S)-1-ethylamino phenyl-(4-bromine) phenylacetonitrile.
Three, summary of the invention
The present invention aim to provide chipal compounds (S, S)-1-ethylamino phenyl-(4-bromine) phenylacetonitrile.Technical problem to be solved is that one-step synthesis obtains title product.
The alleged chipal compounds of the present invention be by the preparation of 4-bromobenzaldehyde and trimethyl silicane nitrile by the compound shown in the following chemical formula:
(?I?)?。
Chemical name: (S, S)-1-ethylamino phenyl-(4-bromine) phenylacetonitrile, be called for short compound (I).
This compound method comprises synthetic and separates, and describedly syntheticly makees catalyzer with 15mol% (S)-α-Ben Yian venus crystals, 4-bromobenzaldehyde 2mmol; Trimethyl silicane nitrile 6 mmol make solvent with the 2mL anhydrous methanol, and room temperature reaction is after 3 days; Column chromatography for separation is with sherwood oil/methylene dichloride (1/1) wash-out, with the 3rd component point nature volatilization of collecting; Monocrystalline (S, S)-1-ethylamino phenyl-(2-bromine) phenylacetonitrile.
Building-up reactions is following:
One step of this compound method obtains title product, and technology is simple, and is easy to operate.
This compound has shown certain catalytic effect in the nitrile silicification reaction of phenyl aldehyde, its transformation efficiency reaches 62%
Its reaction mechanism can be inferred as follows:
4-bromobenzaldehyde and trimethyl silicane nitrile; Under the effect of catalyzer 15mol% (S)-α-Ben Yian venus crystals; At first generate product S-(-)-(α-trimethylsiloxy group) 4-bromobenzylcyanide, product again with catalyst action, the hydrogen proton in the phenylethylamine and trimethylsilyl ethers form trimethyl silanol and slough; Right formation chipal compounds (S, S)-1-ethylamino phenyl-(4-bromine) phenylacetonitrile.
Four, description of drawings
Fig. 1 be (S, S)-the X-diffraction analysis figure of 1-ethylamino phenyl-(4-bromine) phenylacetonitrile.
Five, embodiment
In the 25mL two-mouth bottle, under the anhydrous and oxygen-free condition, add the 4mL anhydrous methanol, 4-bromobenzaldehyde 2mmol; Trimethyl silicane nitrile 6 mmol, catalyzer (S)-α-Ben Yian venus crystals 0.134g (0.30 mmol) at room temperature stirred reactant 3 days; Stopped reaction, column chromatography for separation is with sherwood oil/methylene dichloride (1/1) wash-out; With the 3rd component point nature volatilization of collecting, must monocrystalline (S, S)-1-ethylamino phenyl-(4-bromine) phenylacetonitrile.Productive rate 30 %; [a]
5 D=-16.44o (c=0.0304 CH
2Cl
2):
1HNMR (300MHz, CDCl
3, 27 ℃), δ (ppm)=7.55～7.59 (m, 2H), 7.32～7.53 (m, 9H), 4.34 (s, 1H), 4.23 (d, 5Hz, 1H), 1.56 (s, 1H), 1.44 (d, J=5 Hz, 1H),
13CNMR (100MHz, CDCl
3, 27 ℃) and 132.0,129.0,128.9,128.0,126.9,119.9,56.9,58.19; 51.8,24.8. IR (KBr): 3245,2970,2546,1607,1527,1457,1368,1228; 1149,1090,856,785,766,716,698,611; HRMS:m-CH
3/ z (%): calcd for C
15H
12N
2Br, 301.0163; Found:301.0185.
The nitrile silicification reaction is used
2-phenyl-2-(three silyloxies) acetonitrile
0.2 the mmol compound I, phenyl aldehyde 0.1mL, TMSCN 0.3 ml (3.3mmol); The 2mL methylene dichloride adds under 20 ~ 30C in succession, after 5 days, adds the shrend (sherwood oil/methylene dichloride: 5/1) behind the post layer that goes out; Get colourless oil liquid, transformation efficiency rate: 62 %;
1H NMR (300MHz, CDCl3) 7.56 – 7.59 (m, 0.9 Hz, 2H), 7.31 – 7.34 (m, 3H), 5.43 (s, 1H), 0.16 (s, 9H).
13C NMR (75 MHz, CDCl3) 136.1,128.8 (x2), 126.2 (x2), 119.1,63.5 ,-0.39 (x3).
Claims (2)
- The preparation of a chipal compounds be by the preparation of 4-bromobenzaldehyde and trimethyl silicane nitrile by the compound shown in the following chemical formula:(?I?)?。
- 2. by the compound method of the described compound of claim 1 (I), comprise and synthesize and separate, it is characterized in that the compound method of chirality 1-ethylamino phenyl-(4-bromine) phenylacetonitrile; Describedly syntheticly make catalyzer with 15mol% (S) α-Ben Yian venus crystals, 4-bromobenzaldehyde 2mmol, trimethyl silicane nitrile 6mmol; Make solvent with the 4mL anhydrous methanol; The stirring at room reaction is after 3 days, and column chromatography for separation is with sherwood oil/methylene dichloride=1/1 wash-out; The 3rd component point nature volatilization with collecting gets monocrystalline 1-ethylamino phenyl-(4-bromine) phenylacetonitrile.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103396341A (en) * | 2013-08-05 | 2013-11-20 | 罗梅 | Synthesis method of chiral hydroxy nitrile |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102069014A (en) * | 2010-09-15 | 2011-05-25 | 罗梅 | Chiral zinc complex and copper complexes of alpha-phenylethylamine |
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2012
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102069014A (en) * | 2010-09-15 | 2011-05-25 | 罗梅 | Chiral zinc complex and copper complexes of alpha-phenylethylamine |
Non-Patent Citations (1)
| Title |
|---|
| JOHN TULINSKY, ET AL: "Novel Asymmetric Synthesis of Atropisomeric 6-Aryl Pyrazinones via an Unusual Chirality Transfer Process", 《J. ORG. CHEM.》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103396341A (en) * | 2013-08-05 | 2013-11-20 | 罗梅 | Synthesis method of chiral hydroxy nitrile |
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Effective date of registration: 20191211 Address after: Room 207, main office building, No.118 Longxing Road, Haining Economic Development Zone, Haining City, Jiaxing City, Zhejiang Province Patentee after: Haining Economic Development Industrial Park Development and Construction Co., Ltd Address before: 230009 Tunxi Road, Anhui, China, No. 193, No. Patentee before: Luo Mei |