CN101265211A - Ethyl (Z)-2-benzoylamino-4,4,4-trifluoro-2-crotonate, ethyl cis-1-benzoylamino-2-trifluoromethylcyclopropylformate and synthesis method thereof - Google Patents
Ethyl (Z)-2-benzoylamino-4,4,4-trifluoro-2-crotonate, ethyl cis-1-benzoylamino-2-trifluoromethylcyclopropylformate and synthesis method thereof Download PDFInfo
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Abstract
The invention relates to (Z)-2-benzoyl amino group-4, 4, 4-trifluoro-2-ethyl crotonic acid, cis form 1-benzoyl amino group-2-trifluoro methyl cyclopropane ethyl formate and a synthesis method thereof. The structural formula of the compound is shown in the above formula. The cis form 1-benzoyl amino group-2-trifluoro methyl cyclopropane ethyl formate prepared by the method can produce corresponding fluorine-containing cyclopropane amino acid after hydrolysis. Fluorine-containing Alpha, Beta unsaturated amino acid derivants can take place different reactions due to unsaturated double linkage thereof, for example new amino acid can be formed through oxidation reduction and Michael addition, etc. Therefore, the compound of the invention can be widely used as fluorine-containing building blocks, and can be used as a precursor for generating fluorine-containing tricyclic amino acid derivants in the reaction Compared with prior art, the method provided by the invention has the advantages that the raw material is cheap and easy to get; the reaction has stereoselectivity; no special demands are needed on the reaction device, so that the method has wider applicability on the preparation of the fluorine-containing cyclopropane amino acid and the derivants thereof.
Description
Technical field
The present invention relates to a kind of fluorine-containing α; β-unsaturated amino acid derivative and a kind of fluorine-containing triatomic ring amino acid derivative and synthetic method thereof; (Z)-2-benzoyl-amido-4 particularly; 4,4-three fluoro-2-butylene acetoacetic esters, cis 1-benzoyl-amido-2-trifluoromethyl cyclopropane-carboxylic acid ethyl ester and synthetic method thereof.
Background technology
Contain the amino acid of triatomic ring skeleton and derivative thereof because the activity that shows in physiologically active and the chemical reaction has caused scientist's extensive concern.They are integral parts of the non-natural compound of many natural compoundss and biologically active.They still are the integral part of biosynthetic intermediate of plant ripener and bacterium simultaneously.The amino acid and the derivative thereof that contain the triatomic ring skeleton also can be used as bioprobe, and enzyme inhibitors and the natural amino acid congener with rigid backbone are widely used.This class material, on the physiology and medicine on all very important.
In the pharmaceutical chemistry field, fluorine atom or a perfluoroalkyl are incorporated into and are considered to one of most effectual way that host compound is modified in the host molecule.Because the fluorine atom radius is little, has bigger electronegativity again, its formed C-F key bond energy is than big many of c h bond bond energy, the stability and the physiologically active of organofluorine compound have been increased significantly, fluorinated organic compound also has higher fat-soluble and hydrophobicity in addition, promote it to absorb in vivo and transmission speed, physiological action is changed.Have characteristics such as consumption is few, toxicity is low, drug effect is high, metabolic capacity is strong so a lot of fluorine-containing medicines and agricultural chemicals are relative on performance, this makes its proportion in the new pharmaceutical pesticide species more and more higher.
Cyclopropane amino acid is because of its higher value, and its synthetic method has also obtained broad research, and its general synthetic method is as follows:
1. through the cyclisation of carbanion nucleophilic: in the presence of alkali, utilize 1, the intermolecular cycloalkylation of 2-dihalo-ethane and glycine derivative is one of method for preparing cyclopropane amino acid and derivative thereof of using always.
(1) glycinate of N protection is biological reacts with 1-bromo-2-monochloroethane, generates α-cyclopropane amino acid behind the deprotection.
(2) reaction of isocyano-acetic ester and glycol dibromide generates α-cyclopropane amino acid derivative, obtains cyclopropane amino acid after the hydrolysis.
(3) with twice nucleophilic attack of propanedioic acid methyl esters, also can obtain cyclopropane amino acid to the epithio acid esters.
(4) nineteen ninety, Salaun etc. have developed one by the initial amino acid whose variation route of synthetic α-cyclopropane of propenal, have used intramolecular nucleophilic cyclization dexterously.This method raw material is easy to get, the intermediate product separation is easy, and reaction yield is higher, has industrialized possibility, and its committed step is to derive cyclopropane by γ-chloro thing intramolecularly nucleophilic cyclisation.
2. synthetic by the alkene cycloaddition: synthetic at present cyclopropane amino acid method with the most use still is Cabbeen or class Cabbeen (as diazomethane and derivative, ylide etc.) to the addition of alkene, the different method that just produces Cabbeen.
(1) diazomethane and alkene take place one 1, and the 3-dipolar addition generates diazole compounds, and this compound is put denitrification gas under illumination, promptly obtain cyclopropane.
(2) use metal carbene and chiral ligand can be at an easy rate, and enantioselectivity ground synthesizes cyclopropane amino acid, and similarly report is a lot of recently.Charette etc. utilize the diazotization derivative of α-nitro ethyl ester and alkenes compounds to react under rhodium or copper complex formazan catalysis, have synthesized a series of cyclopropane amino acid.
(3) by with synthetic cyclopropane amino acid of various Ye Li Dehua compound reaction and derivative thereof also be one of method commonly used in recent years, and its reaction safety height next than diazonium compound.Charette etc. utilize the phenyl-iodide ylide derivative of α-nitro ethyl ester and alkenes compounds to react under rhodium or copper complex formazan catalysis equally, have synthesized a series of cyclopropane amino acid.
(4) Corey ylide (sulfur ylide, methyl-sulphoxide sulphur oxygen) is to use reagent very widely in the synthesis of ternary ring derivatives.As Najera etc., reported in 2000, itself and olefine reaction are generated the amino acid whose method of cyclopropane.
3. it is synthetic to be derived by cyclopropane compound: use diazotization reaction a carboxyl in α-carboxyl cyclopropane-carboxylic acid is converted into amino back acquisition α-cyclopropane amino acid.
Other: also can be from simple molecule, high productivity, Stereoselective synthesizes cyclopropane amino acid.
(1) Tadashi has reported the (O at Ti
t-Bu)
4, I
2Catalysis under, carbanion and olefine reaction also obtain cyclopropane, transform by simple functional group again, just can obtain cyclopropane amino acid.
Then compare less about the amino acid whose report of fluorine-containing cyclopropane.
1.2000 year, it is raw material that Kenji Uneyama adopts optically active trifluoromethyl oxyethane, intramolecular nucleophilic attack closes ring, has finished that optically active to contain trifluoromethyl α-cyclopropane amino acid whose synthetic.
3.2003 year, Biao Jiang etc. have also finished the synthetic of fluorine-containing ACC by a series of step.
Summary of the invention:
One of purpose of the present invention is to provide a kind of (Z)-2-benzoyl-amido-4,4,4-three fluoro-2-butylene acetoacetic ester compounds.
Two of purpose of the present invention is to provide a kind of cis 1-benzoyl-amido-2-trifluoromethyl cyclopropane-carboxylic acid ethyl ester.
Three of purpose of the present invention is to provide the synthetic method of above-claimed cpd.
For achieving the above object, the reaction scheme that the inventive method has adopted is:
According to above-mentioned reaction mechanism, the present invention adopts following technical scheme;
A kind of (Z)-2-benzoyl-amido-4,4,4-three fluoro-2-butylene acetoacetic esters is characterized in that the structural formula of this compound is:
A kind of cis 1-benzoyl-amido-2-trifluoromethyl cyclopropane-carboxylic acid ethyl ester is characterized in that the structural formula of this compound is;
A kind of method for preparing cis 1-benzoyl-amido according to claim 2-2-trifluoromethyl cyclopropane-carboxylic acid ethyl ester is characterized in that the concrete steps of this method are:
A) in cryosel is bathed, with cis 2-amino-4,4,4-trifluoro 3-hydroxy ethyl butyrate and triethylamine are dissolved in the methylene dichloride, the dissolving back drips Benzoyl chloride, cis 2-amino-4,4 wherein, 4-trifluoro 3-hydroxy ethyl butyrate, triethylamine and Benzoyl chloride mol ratio are: 1: (2～4): (2～4); Stirring reaction 30 ± 10 minutes, adding the saturated aqueous ammonium chloride collection goes out, dichloromethane extraction, anhydrous magnesium sulfate drying, filter the back and remove the crude product that desolvates, this crude product obtains white solid cis 2-(N, N-dibenzyl amino)-3-phenylformic acid ester group-4 through column chromatography for separation, 4,4-trifluoroacetic acid ethyl ester;
B) under the inert atmosphere, with above-mentioned cis 2-(N, the N-dibenzyl amino)-3-phenylformic acid ester group-4,4,4-trifluoroacetic acid ethyl ester and potassium tert.-butoxide are dissolved in the tetrahydrofuran (THF), and stirring reaction is 30 ± 10 minutes under cryosel is bathed, cis 2-(N wherein, the N-dibenzyl amino)-and 3-phenylformic acid ester group-4,4,4-trifluoroacetic acid ethyl ester and potassium tert.-butoxide mol ratio are: 1: (1～3); Add the saturated aqueous ammonium chloride collection and go out, dichloromethane extraction, anhydrous magnesium sulfate drying filters the back and removes the crude product that desolvates, and this crude product obtains white solid (Z)-2-benzoyl-amido-4,4 through column chromatography for separation, 4-three fluoro-2-butylene acetoacetic esters;
C) in ice bath, with above-mentioned (Z)-2-benzoyl-amido-4,4,4-three fluoro-2-butylene acetoacetic esters are dissolved in the ether, the diethyl ether solution that adds excessive diazomethane again, stirred 3 ± 0.5 hours, and added Calcium Chloride Powder Anhydrous, filter back removal solvent and get yellow oily liquid to remove unnecessary diazomethane;
D) above-mentioned yellow oily liquid is dissolved in the toluene; and be transferred to the quartz reaction instrument; under the inert atmosphere; in cryosel is bathed; with lamp and high pressure mercury 3 ± 0.5 hours, the centre wavelength of high voltage mercury lamp was 254 nanometers, remove solvent after; after column chromatography for separation, obtain white solid, be the synthetic method of cis 1-benzoyl-amido-2-trifluoromethylation cyclopropane-carboxylic acid ethyl ester.
The cis 1-benzoyl-amido-2-trifluoromethylation cyclopropane-carboxylic acid ethyl ester of the present invention's preparation can generate corresponding fluorine-containing cyclopropane amino acid after hydrolysis, concrete grammar sees also Slama, J.T.; Satsangi, R.K.; Simmons, A.; Lynch, V.; Bolger, R.E.; Sutties, J.J.Med.Chem.1990,33,824.Fluorine-containing α, β-unsaturated amino acid derivative be because multiple reaction can take place in the existence of its unsaturated double-bond, as: hydro-reduction, Michael additions etc. form new amino acid (Enders, D.; Chen, Z.X.; Raabe, G.Synthesis.2005,2,306), therefore compound of the present invention can be widely used as fluoro-building block, can be used as the precursor that generates fluorine-containing triatomic ring amino acid derivative at this.
Compared with prior art, preparation method's raw material that this paper provided is cheap and easy to get, reaction has stereoselectivity, and conversion unit does not have particular requirement, the preparation of fluorine-containing cyclopropane amino acid and derivative thereof is had than extensive applicability.
Embodiment
Original raw material cis 2-amino-4,4 of the present invention, the preparation method of 4-trifluoro 3-hydroxy ethyl butyrate sees also Scolastico, C.; Coonca, E.; Prati, L.Synthesis.1985,9,850.
Embodiment one: (Z)-2-benzoyl-amido-4,4, the preparation method of 4-three fluoro-2-butylene acetoacetic esters and cis 1-benzoyl-amido-2-trifluoromethyl cyclopropane-carboxylic acid ethyl ester.Concrete steps are as follows:
A) in 25 milliliters two mouthfuls of flasks, add 10 milliliters of methylene dichloride and cis 2-amino-4,4,4-trifluoro 3-hydroxy ethyl butyrate 0.267 gram (1.33 mmole) and 0.77 milliliter of triethylamine (5.32 mmole), cooling (18 degrees centigrade) in cryosel is bathed drips 0.62 milliliter of Benzoyl chloride (5.32 mmole).Stir about 30 minutes, adding 5 milliliters of collections of saturated aqueous ammonium chloride goes out, 3 * 8 milliliters of extractions of methylene dichloride, anhydrous magnesium sulfate drying removes by filter to remove on Rotary Evaporators behind the siccative and desolvates, crude product obtains cis 2-(N by column chromatography for separation, the N-dibenzyl amino)-and 3-phenylformic acid ester group-4,4,473 milligrams of 4-trifluoroacetic acid ethyl ester white solids, developping agent is: sherwood oil: ethyl acetate 6: 1, productive rate: 87%.
B) in 25 milliliters the there-necked flask; under nitrogen protection; cis 2-(N; the N-dibenzyl amino)-3-phenylformic acid ester group-4; 4; 4-trifluoroacetic acid ethyl ester 127 milligrams of (0.31 mmole) and 104 milligrams of potassium tert.-butoxides (0.93 mmole); be dissolved in 12 milliliters of tetrahydrofuran (THF)s; (18 degrees centigrade) reaction in cryosel is bathed, stir about 30 minutes adds 5 milliliters of collections of saturated aqueous ammonium chloride and goes out; 3 * 8 milliliters of extractions of methylene dichloride; anhydrous magnesium sulfate drying removes by filter to remove on Rotary Evaporators behind the siccative and desolvates, and crude product obtains (Z)-2-benzoyl-amido-4 by column chromatography for separation; 4; 73 milligrams of 4-three fluoro-2-butylene acetoacetic ester white solids, developping agent is: sherwood oil: ethyl acetate 6: 1, productive rate: 82%.
C) in 50 milliliters the there-necked flask; in ice bath; with 10 milliliters of ether is solvent; add (Z)-2-benzoyl-amido-4,4, after 50 milligrams of (0.17 mmole) dissolvings of 4-three fluoro-2-butylene acetoacetic esters; the diethyl ether solution that adds excessive diazomethane; stirred about 3 hours, add Calcium Chloride Powder Anhydrous with remove more than diazomethane, solvent evaporate to dryness on Rotary Evaporators is obtained yellow oily liquid after removing by filter calcium chloride.
D) this yellow oily liquid is transferred to 25 milliliters of quartz reaction instrument; add 10 milliliters of toluene; under nitrogen protection; in cryosel is bathed (18 degrees centigrade); with the lamp and high pressure mercury of 125 watts of power after about 3 hours (centre wavelength is about 254 nanometers) with solvent evaporate to dryness on Rotary Evaporators; obtain 23 milligrams of cis 1-benzoyl-amidos-2-trifluoromethylation cyclopropane-carboxylic acid ethyl ester white solid after column chromatography for separation, developping agent is: sherwood oil: ethyl acetate 6: 1, productive rate: 45%.
(Z)-and 2-benzoyl-amido-4,4, the structural formula of 4-three fluoro-2-butylene acetoacetic esters is:
Molecular formula: C
13H
12F
3NO
3
Molecular weight: 287.08
Outward appearance: white solid
Infrared spectra (pressed disc method): υ max (centimetre
-1): 3270; 2923; 1732; 1680; 1654; 1510; 1259; 1189; 1116; 712.
Proton nmr spectra (500 megahertzes, deuterochloroform, ppm): δ=1.35 (t, 3H, J=7.2 hertz); (4.35 q, 2H, J=7.2 hertz); (6.07 q, 1H, J=8.0 hertz), and 7.49-7.86 (m, 5H); 7.99 (s, 1H).
Carbon-13 nmr spectra (125 megahertzes, deuterochloroform, ppm): δ=14.08; 63.01; 111.79 (q,
2J
C-C-F=35.0 hertz); 122.68 (q,
1J
C-F=268.8 hertz); 127.78; 129.07; 132.30; 133.11; 135.25 (q,
3J
C-C-C-F=5.0 hertz); 163.16; 165.74.
Nucleus magnetic resonance fluorine spectrum (470 megahertzes, deuterochloroform, interior mark: the fluoro chloroform, ppm): δ=-59.44 (d, 3F,
3J
H-C-C-F=8.0 hertz).
The structural formula of cis 1-benzoyl-amido-2-trifluoromethyl cyclopropane-carboxylic acid ethyl ester is:
Molecular formula: C
14H
14F
3NO
3
Molecular weight: 301.09
Outward appearance: white solid
Infrared spectra (pressed disc method): υ max (centimetre
-1): 3432; 3289; 3061; 2923; 1734; 1655; 1525; 1275; 1148; 1082; 694.
Proton nmr spectra (500 megahertzes, deuterochloroform, ppm): δ=1.27 (t, 3H, J=7.2 hertz); (1.88 t, 1H, J=7.0 hertz); (2.15 dd, 1H, J=9.0 hertz, 7.0 hertz); 2.54-2.62 (m, 1H); (4.22 q, 2H, J=7.2 hertz); 6.65 (s, 1H); 7.46-7.78 (m, 5H).
Carbon-13 nmr spectra (125 megahertzes, deuterochloroform, ppm): δ=14.20; 19.17; 27.72 (q,
2J
C-C-F=36.3 hertz); 36.60; 62.66; 124.56 (q,
1J
C-F=271.3 hertz); 127.28; 128.89; 132.30; 133.83; 168.79; 169.71.
Nucleus magnetic resonance fluorine spectrum (470 megahertzes, deuterochloroform, interior mark: the fluoro chloroform, ppm): δ=-61.24 (d, 3F,
3J
H-C-C-F=6.5 hertz).
Embodiment two: (Z)-2-benzoyl-amido-4,4, the preparation method of 4-three fluoro-2-butylene acetoacetic esters and cis 1-benzoyl-amido-2-trifluoromethyl cyclopropane-carboxylic acid ethyl ester.Concrete steps are as follows:
A) in 1 liter two mouthfuls of flasks, add 400 milliliters of methylene dichloride and cis 2-amino-4,4,4-trifluoro 3-hydroxy ethyl butyrate 10.05 gram (50 mmole) and 14.43 milliliters of triethylamines (100 mmole), cooling (18 degrees centigrade) in cryosel is bathed drips 11.71 milliliters of Benzoyl chlorides (100 mmole).Stir about 30 minutes, adding 60 milliliters of collections of saturated aqueous ammonium chloride goes out, 3 * 80 milliliters of extractions of methylene dichloride, anhydrous magnesium sulfate drying removes by filter to remove on Rotary Evaporators behind the siccative and desolvates, crude product obtains cis 2-(N by column chromatography for separation, the N-dibenzyl amino)-and 3-phenylformic acid ester group-4,4,4-trifluoroacetic acid ethyl ester white solid 18.41 grams, developping agent is: sherwood oil: ethyl acetate 6: 1, productive rate: 90%.
B) in 1 liter the there-necked flask; under nitrogen protection; cis 2-(N; the N-dibenzyl amino)-3-phenylformic acid ester group-4; 4; 4-trifluoroacetic acid ethyl ester 6.14 grams (15 mmole) and potassium tert.-butoxide 1.68 grams (15 mmole); be dissolved in 400 milliliters of tetrahydrofuran (THF)s; (18 degrees centigrade) reaction in cryosel is bathed, stir about 30 minutes adds 60 milliliters of collections of saturated aqueous ammonium chloride and goes out; 3 * 80 milliliters of extractions of methylene dichloride; anhydrous magnesium sulfate drying removes by filter to remove on Rotary Evaporators behind the siccative and desolvates, and crude product obtains (Z)-2-benzoyl-amido-4 by column chromatography for separation; 4; 4-three fluoro-2-butylene acetoacetic ester white solids 3.75 grams, developping agent is: sherwood oil: ethyl acetate 6: 1, productive rate: 87%.
C) in 500 milliliters the there-necked flask, in ice bath, with 50 milliliters of ether is solvent, add (Z)-2-methyl-phenoxide base amino-4,4, after 2.3 gram (8 mmole) dissolvings of 4-three fluoro-2-butylene acetoacetic esters, the diethyl ether solution that adds excessive diazomethane, stirred about 3 hours, add Calcium Chloride Powder Anhydrous with remove more than diazomethane, solvent evaporate to dryness on Rotary Evaporators is obtained yellow oily liquid after removing by filter calcium chloride.
D) this yellow oily liquid is transferred to 250 milliliters of quartz reaction instrument; add 150 milliliters of toluene; under nitrogen protection; in cryosel is bathed (18 degrees centigrade); with the lamp and high pressure mercury of 125 watts of power after about 3 hours (centre wavelength is about 254 nanometers) with solvent evaporate to dryness on Rotary Evaporators; obtain cis 1-benzoyl-amido-2-trifluoromethylation cyclopropane-carboxylic acid ethyl ester white solid 1.16 grams after column chromatography for separation, developping agent is: sherwood oil: ethyl acetate 6: 1, productive rate: 48%.
Claims (3)
1. (Z)-2-benzoyl-amido-4,4,4-three fluoro-2-butylene acetoacetic esters is characterized in that the structural formula of this compound is:
2. cis 1-benzoyl-amido-2-trifluoromethyl cyclopropane-carboxylic acid ethyl ester is characterized in that the structural formula of this compound is;
3. method for preparing cis 1-benzoyl-amido according to claim 2-2-trifluoromethyl cyclopropane-carboxylic acid ethyl ester is characterized in that the concrete steps of this method are:
A. in cryosel is bathed, with cis 2-amino-4,4,4-trifluoro 3-hydroxy ethyl butyrate and triethylamine are dissolved in the methylene dichloride, the dissolving back drips Benzoyl chloride, cis 2-amino-4,4 wherein, 4-trifluoro 3-hydroxy ethyl butyrate, triethylamine and Benzoyl chloride mol ratio are: 1: (2～4): (2～4); Stirring reaction 30 ± 10 minutes, adding the saturated aqueous ammonium chloride collection goes out, dichloromethane extraction, anhydrous magnesium sulfate drying, filter the back and remove the crude product that desolvates, this crude product obtains white solid cis 2-(N, N-dibenzyl amino)-3-phenylformic acid ester group-4 through column chromatography for separation, 4,4-trifluoroacetic acid ethyl ester;
B. under the inert atmosphere, with above-mentioned cis 2-(N, the N-dibenzyl amino)-3-phenylformic acid ester group-4,4,4-trifluoroacetic acid ethyl ester and potassium tert.-butoxide are dissolved in the tetrahydrofuran (THF), and stirring reaction is 30 ± 10 minutes under cryosel is bathed, cis 2-(N wherein, the N-dibenzyl amino)-and 3-phenylformic acid ester group-4,4,4-trifluoroacetic acid ethyl ester and potassium tert.-butoxide mol ratio are: 1: (1～3); Add the saturated aqueous ammonium chloride collection and go out, dichloromethane extraction, anhydrous magnesium sulfate drying filters the back and removes the crude product that desolvates, and this crude product obtains white solid (Z)-2-benzoyl-amido-4,4 through column chromatography for separation, 4-three fluoro-2-butylene acetoacetic esters;
C. in ice bath, with above-mentioned (Z)-2-benzoyl-amido-4,4,4-three fluoro-2-butylene acetoacetic esters are dissolved in the ether, the diethyl ether solution that adds excessive diazomethane again, stirred 3 ± 0.5 hours, and added Calcium Chloride Powder Anhydrous, filter back removal solvent and get yellow oily liquid to remove unnecessary diazomethane;
D. above-mentioned yellow oily liquid is dissolved in the toluene; and be transferred to the quartz reaction instrument; under the inert atmosphere; in cryosel is bathed; with lamp and high pressure mercury 3 ± 0.5 hours, the centre wavelength of high voltage mercury lamp was 254 nanometers, remove solvent after; after column chromatography for separation, obtain white solid, be the synthetic method of cis 1-benzoyl-amido-2-trifluoromethylation cyclopropane-carboxylic acid ethyl ester.
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