CN101519384A - Chiral oxazoline and synthesis method thereof - Google Patents

Chiral oxazoline and synthesis method thereof Download PDF

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CN101519384A
CN101519384A CN200810020198A CN200810020198A CN101519384A CN 101519384 A CN101519384 A CN 101519384A CN 200810020198 A CN200810020198 A CN 200810020198A CN 200810020198 A CN200810020198 A CN 200810020198A CN 101519384 A CN101519384 A CN 101519384A
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benzene
chiral
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metal chloride
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罗梅
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Hefei University of Technology
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Hefei University of Technology
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Abstract

A chiral oxazoline is characterized by a 1,4-(4S)-2R base-2-oxazolinyl benzene which is taken as the chemical name thereof and is expressed by the following chemical formula; as indicated in the picture, R in the formula is selected from -CH2CH(CH3)2, or -CH(CH3)2, or -ph or -CH2ph. A para-position di-nitrile-benzene or meta-position di-nitrile-benzene or ortho-position di-nitrile-benzene is respectively reacted with chiral amino alcohol for 20 hours to 30 hours at the temperature of110 DEG C to 145 DEG C in organic solvent under the condition of catalyst, and then target products are respectively obtained after separation and purification, namely the chiral oxazolines (I), (II) and (III). The method can be used for synthesizing the chiral oxazoline at one step, and the metal-organic complex thereof shows good catalytic activity and high enantioselectivity in the asymmetric synthesis of mandelic acid.

Description

A kind of chiral oxazoline and synthetic method thereof
One, technical field
The present invention relates to a kind of new compound and preparation method thereof, particularly a kind of chipal compounds and preparation method thereof exactly is a kind of chiral oxazoline and synthetic method thereof.
Two, background technology
The title complex of chiral oxazoline and metal shows the active and high enantioselectivity of good asymmetry catalysis in many reactions such as Diels-Alder (Di Le-Ai and spy) diene cycloaddition reaction, Michael (Mi Xieer) condensation reaction, Friedel-Crafts (Fu Ruide-carat Buddhist now) condensation reaction, Aldol (alcohol aldehyde) condensation reaction, thereby is subjected to paying close attention to widely.
The applicant is engaged in the development of asymmetric compound for a long time, once developing with hexahydropyridine propionitrile and chiral amino alcohol is the synthetic chiral oxazoline 1-[2-(4S) of raw material-R base-4,5-dihydro-2-oxazoline-ethyl] piperidines, and applied for patent of invention CN1939911A.
Three, summary of the invention
The present invention is intended to provide a kind of chiral catalyst efficiently for the asymmetric synthesis field particularly prepares chiral drug, and technical problem to be solved is to select corresponding raw material and set up corresponding method synthesis of chiral catalyzer.
(1) the alleged chiral oxazoline of the present invention is the compound shown in the following chemical formula (I):
Figure A200810020198D00041
R is selected from isobutyl-(CH in the formula 2CH (CH 3) 2) or sec.-propyl (CH (CH 3) 2) or phenyl is (ph) or benzyl (CH 2Ph).
Four kinds of chiral oxazolines that are made of above group claim 1a, 1b, 1c, 1d, its chemical name successively: 1, and 4-(4S)-two R base-2 — oxazolinyl benzene.
(2) second kind of alleged chiral oxazoline of the present invention is the compound shown in the following chemical formula (II):
Figure A200810020198D00042
R is selected from isobutyl-(CH in the formula 2CH (CH 3) 2) or sec.-propyl (CH (CH 3) 2) or phenyl is (ph) or benzyl (CH 2Ph).
Four kinds of chiral oxazolines that are made of above group claim 2a, 2b, 2c, 2d, its chemical name successively: 1, and 3-(4S)-two R base-2 — oxazolinyl benzene.
(3) the third alleged chiral oxazoline of the present invention is the compound shown in the following chemical formula (III):
Figure A200810020198D00051
R is selected from isobutyl-(CH in the formula 2CH (CH 3) 2) or sec.-propyl (CH (CH 3) 2) or phenyl is (ph) or benzyl (CH 2Ph).
Four kinds of chiral oxazolines that are made of above group claim 3a, 3b, 3c, 3d, its chemical name successively: 1, and 2-(4S)-two R base-2 — oxazolinyl benzene.
Chiral oxazoline (I), (II) and (III) synthetic respectively with contraposition, a position and adjacent dinitrile benzene and chiral amino alcohol in organic solvent under the condition that catalyzer exists synthetic, chemical equation is as follows:
Figure A200810020198D00052
R is selected from isobutyl-(CH in the formula 2CH (CH 3) 2) or sec.-propyl (CH (CH 3) 2) or phenyl is (ph) or benzyl (CH 2Ph).
This chiral oxazoline (I), (II) with the synthetic method of (III) comprise synthetic, separate and purifying, reacted 20～30 hours in 110～145 ℃ under the described synthetic condition that to be exactly contraposition or a position or ortho position dinitrile benzene have catalyzer to exist in organic solvent with chiral amino alcohol, catalyst levels is the 1～3wt% (weight percent, down together) of material quantity.
Preferred 120～140 ℃ of reactions 22～28 hours, catalyst levels is the 2wt% of material quantity
The organic solvent that described organic solvent selects inert, its boiling point and temperature of reaction to adapt is such as picoline or chlorobenzene or dichlorobenzene or ethylbenzene or dimethylbenzene or propyl benzene or alkane or halogenated alkane etc.At this moment synthetic can under refluxad carrying out.
Described catalyzer is selected from rare-earth metal chloride (trichlorine rare earth) or transition metal chloride (ZnCl 2, CuCl 2, NiCl 2, CoCl 2, FeCl 3, MnCl 2Deng) or AlCl 3Or alkoxide compound (tetraisopropoxy titanium, dimethyl dichloro stannane etc.).Preferred trichlorine rare earth or transition metal chloride.
Present method one-step synthesis chiral oxazoline 1a～1d, 2a～2d, 3a～3d, they are warp respectively 1HNMR, IR, MS characterizes, and its a metal-organic complex shows good catalytic activity and high enantioselectivity in the amygdalic acid asymmetric synthesis.
Four, description of drawings
Fig. 1,3,5,7,9,11,13,15,17,19,21,23 is catalyzer 1a, 1b, 1c, 1d, 2a, 2b, 2c, 2d, 3a, 3b, 3c, 3d successively 1HNMR figure.
Fig. 2,4,6,8,10,12,14,16,18,20,22,24 is catalyzer 1a, 1b, 1c, 1d, 2a, 2b, 2c, 2d, 3a, 3b, 3c, 3d successively 13CNMR figure.
Five, embodiment
1,1a:1, the preparation of 4-(4S)-diisobutyl-2 — oxazolinyl benzene
1，4-{bis-4(S)-butyloxazolin-2-yl]}benzene
In the 100mL two-mouth bottle, under the anhydrous and oxygen-free condition, add anhydrous ZnCl 260mg (0.37mmol), the 40ml chlorobenzene, 1,4-dinitrile benzene 1.0g (5.6mmol), L-leucinol 2g, with the mixture 24h that at high temperature refluxes, stopped reaction, decompression is desolvated to remove,,, and use CHCl with the residuum water dissolution 3(20mL x 2) extraction, the organic phase anhydrous sodium sulfate drying, rotation removes and desolvates, and thick product with sherwood oil/methylene dichloride (4:1) column chromatography, is got white solid 0.92g, productive rate 50%; Fusing point: 36～38 ℃, [a] 5 D=-107.14 ° of (c=0.112, CHCl 3); 1HNMR (500MHz, CDCl 3, 27 ℃), δ (ppm)=7.97 (s, 4H), 4.49～4.55 (m, 2H), 4.32～4.37 (m, 2H), 3.98～4.03 (t, J=4.75), 1.68～1.88 (m, 4H), 1.35～1.44 (m, 2H), 0.96～1.00 (m, 12H). 13CNMR 22.89,23.08, and 25.69,45.73,65.48,73.44,128.33,130.55,162.92.IR:3431,2955,2926,2905,2870,1641,1514,1470,1449,1409,1372,1360,1324,1273,1245,1131,1085,1073,1034,1020,971,861,691.HRMS (EI): m/z (%): calcd for C 20H 28N 2O 2: 328.2148; Found:328.2151.
2,1b:1, the preparation of 4-(4S)-di-isopropyl-2 — oxazolinyl benzene
1，4-{bis-[4(S)-isopropyloxazolin-2-yl]}benzene
Catalyst n iCl 2, solvent ethylbenzene, operation is with example 1.
Productive rate 45%; White crystal, fusing point: 48～50 ℃ [a] 5 D=-113.7 ° of (c=0.469, CHCl 3); 1HNMR (500MHz, CDCl 3, 27 ℃), δ (ppm)=7.97 (s, 4H), 4.39～4.43 (t, 3.18Hz, 1H), 4.09～4.15 (m, 2H), 1.85～1.86 (m, 1H), (d, J=6.24Hz, 6H), 0.86～0.96 (d, J=6.24Hz, 6H). 13CNMR18.13,19.03,32.85,70.26,72.76,128.10,128.16,130.32,162.82.IR:3273,2976,2960,2932,2889,2869,1643,1512,1469,1408,1382,1366,1350,1320,1296,1276,1214,1180,1108,1077,1047,1014,971,955,900,891,838,726,698,675,659,540.HRMS (EI): m/z (%): calcd for C 18H 24N 2O 2: 300.1838; Found:300.1835.
3,1c:1, the preparation of 4-(4S)-phenylbenzene-2 — oxazolinyl benzene
1，4-{bis-[4(S)-phenyloxazolin-2-yl]}benzene
Catalyzer trichlorine rare earth, solvent xylene, operation is with example 1.
Productive rate 40%; White solid, fusing point: 42～44 ℃, [a] 5 D=-61.3 ° of (c=0.04, CHCl 3); 1HNMR (500MHz, CDCl 3, 27 ℃), δ (ppm)=8.11～8.15 (t, 4H), 7.71～7.78 (t, J=2.89,4H), 7.23～7.40 (m, 8H), 5.40～5.46 (m, 2H), 4.82～4.87 (m, 2H), 4.30～4.35 (m, 2H). 13CNMR 70.36,75.28, and 114.99,118.32,126.75,127.95,128.94,129.07,132.24,141.69,163.17.IR:3420,3081,3054,3031,2988,2956,2893,2231,1647,1608,1497,1454,1406,1359,1343,1317,1293,1276,1262,1201,1174,1073,1046,1017,967,953,860,840,755,697,669,548,527.HRMS (EI): m/z (%): calcd for C 24H 20N 2O 2: 368.1525; Found:368.1518.
4,1d:1, the preparation of 4-(4S)-dibenzyl-2 — oxazolinyl benzene
1，4-{bis-[4(S)-benzyloxazolin-2-yl]}benzene
Catalyst A lCl 2, the solvent nitropropane, operation is with example 1.
Productive rate 43%; Faint yellow solid, fusing point: 40～42 ℃, [a] 5 D=38.2 ° of (c=0.098, CHCl 3); 1HNMR (500MHz, CDCl 3, 27 ℃), δ (ppm)=8.98 (s, 4H), 7.20～7.34 (m, 10H), 7.23～7.40 (m, 8H), 4.57～4.63 (m, 2H), 4.34～4.40 (t, J=5.1Hz, 2H), 4.13～4.18 (t, 2H). 13CNMR:44.95,68.19,72.21,126.78,128.43,128.79,129.00,129.45,130.49,138.01.IR:3420,3081,3054,3031,2988,2956,2893,2231,1647,1608,1497,1454,1406,1359,1343,1317,1293,1276,1262,1201,1174,1073,1046,1017,967,953,860,840,755,697,669,548,527.HRMS (EI): m/z (%): calcd for C 24H 20N 2O 2: 368.1525; Foumd:368.1518.
5,2a:1, the preparation of 3-(4S)-diisobutyl-2 — oxazolinyl benzene
1，3-{bis-[4(S)-butyloxazolin-2-yl]}benzene
In the 100mL two-mouth bottle, under the anhydrous and oxygen-free condition, add anhydrous ZnCl 260mg (0.37mmol), the 40ml chlorobenzene, 1,3-dinitrile benzene 1.0g (5.6mmol), L-leucinol 2g, with the mixture 24h that at high temperature refluxes, stopped reaction, decompression is desolvated to remove,,, and use CHCl with the residuum water dissolution 3(20mL x 2) extraction, the organic phase anhydrous sodium sulfate drying, rotation removes and desolvates, and thick product with sherwood oil/methylene dichloride (4:1) column chromatography, is got faint yellow solid 0.83g, productive rate 45%; Fusing point: 20～22 ℃ [a] 5 D=-129.9 ° of (c=0.404, CHCl 3); 1HNMR (500MHz, CDCl 3, 27 ℃), and δ (ppm)=8.48 (s, 1H), 8.03～8.06 (m, 2H), 7.41～7.46 (t, J=0.021,1H) 4.48～4.54 (m, 2H), 4.31～4.39 (m, 2H), 3.96～4.02 (t, J=0.17), 1.75～1.88 (m, 2H), 1.66～1.73 (m, 2H), 1.33～1.42 (m, 2H), 0.96～0.99 (m, 12H). 13CNMR:22.72,25.40,45.55,65.20,73.13,127.95,128.21,130.68,162.48.IR:2956,2927,2899,2870,1652,1600,1581,1468,1438,1367,1306,1284,1243,1168,1081,1061,1034,979,950,924,812,702.HRMS (EI): m/z (%): calcd for C 20H 28N 2O 2: 328.2151; Found:328.2160.
6,2b:1, the preparation of 3-(4S)-di-isopropyl-2 — oxazolinyl benzene
1，3-{bis-[4(S)-isopropyloxazolin-2-yl]}benzene
Catalyzer trichlorine rare earth, the solvent octane, operation is with example 5.
Productive rate 46%; White solid, 18～20 ℃ of fusing points, [a] 5 D=-136.6 ° of (c=0.26, CHCl 3); 1HNMR (500MHz, CDCl 3, 27 ℃), δ (ppm)=8.49 (s, 1H), 8.03～8.07 (m, 2H), 7.40～7.46 (m, 1H), 4.38～4.45 (m, 2H) 4.06～4.16 (m, 4H), 1.79～1.90 (m, 2H), 1.01～1.03 (d, J=6.9Hz, 6H), 0.86～0.96 (d, J=6.9Hz, 6H). 13CNMR 18.14,18.92, and 32.85,70.22,72.70,128.07,128.21,128.34,130.85,130.92,162.72.IR:2961,2897,2869,1650,1597,1475,1464,1362,1327,1314,1269,1103,1066,1040,1020,975,955,935,925,900,818,701HRMS (EI): m/z (%): calcd for C 18H 24N 2O 2: 300.1838; Found:300.1834.
7,2c:1, the preparation of 3-(4S)-phenylbenzene-2 — oxazolinyl benzene
1，3-{bis-[4(S)-butyloxazolin-2-yl]}benzene
CATALYST Co Cl 2, the solvent ethylene dibromide, operation is with example 5.
Productive rate 42%; Yellow solid, fusing point: 34～36 ℃, [a] 5 D=-59.7 ° of (c=0.148, CHCl 3); 1HNMR (500MHz, CDCl 3, 27 ℃), δ (ppm)=8.69 (s, 1H), 8.19～8.21 (m, 1H), 7.51～7.54 (t, J=0.05,2H), 7.23～7.40 (m, 2H), 7.29～7.38 (m, 7H), 5.40-5.46 (m, 2H), 4.82～4.87 (m, 2H), 4.30～4.35 (m, 2H). 13CNMR 70.39,75.18,126.88,126.94,127.88,128.14 .128.72,128.79,128.98,129.05,129.08,131.59,142.37.164.26., IR:3280,3082,3062,3028,2978,2900,2231,1651,1601,1581,1494,1454,1298,1267,1237,1206,1166,1080,1067,1030,980,960,914,890,807,761,734,699,671,612,542.HRMS (EI): m/z (%): calcd for C 24H 20N 2O 2: 368.1525; Found:368.1520.
8,2d:1, the preparation of 3-(4S)-dibenzyl-2 — oxazolinyl benzene
1，4-{bis-[4(S)-benzyloxazolin-2-yl]}benzene
The catalyzer tetraisopropoxy titanium, the solvent chlorobenzene, operation is with example 5.
Productive rate 47%; Yellow liquid, [a] 5 D=5.73 ° of (c=0.174, CHCl 3); 1HNMR (300MHz, CDCl 3, 27 ℃), δ (ppm)=8.12～8.19 (m, 3H), 7.84～7.91 (m, 2H), 7.69～7.72 (m, 2H), 7.47～7.52 (m, 2H), 7.20～7.30 (m, 5H), 4.56～4.61 (m, 2H), 4.33～4.39 (t, J=1Hz, 2H), 4.11～4.16 (t, J=1.5Hz, 2H). 13CNMR 41.4841.61,67.82,70.22,72.14,112.56,117.96,126.41,126.52,128.46,128.97,129.13,131.71,132.16,134.29,137.42,161.83.IR:3083,3064,3028,2923,2901,2232,1702,1652,1603,1578,1496,1475,1454,1439,1312,1291,1179,1088,1059,1030,924,808,754,706,681,574.HRMS (EI): m/z (%): calcd for C 24H 20N 2O 2: 368.1525; Found:368.1518.
9,3a1, the preparation of 2-(4S)-diisobutyl-2 — oxazolinyl benzene
1，2-{bis-[4(S)-butyloxazolin-2-yl]}benzene
In the 100mL two-mouth bottle, under the anhydrous and oxygen-free condition, add anhydrous ZnCl 260mg (0.37mmol), the 40ml chlorobenzene, 1,3-dinitrile benzene 1.0g (5.6mmol), L-leucinol 2g, with the mixture 24h that at high temperature refluxes, stopped reaction, decompression is desolvated to remove,,, and use CHCl with the residuum water dissolution 3(20mL x 2) extraction, the organic phase anhydrous sodium sulfate drying, rotation removes and desolvates, and thick product with sherwood oil/methylene dichloride (4:1) column chromatography, is got faint yellow viscous liquid 0.86g, productive rate 47%; [a] 5 D=-81.6 ° of (c=0177, CHCl 3); 1HNMR (500MHz, CDCl 3, 27 ℃), and δ (ppm)=7.70～7.21 (m, 2H), 7.44～7.45 (m, 2H), 4.44～4.48 (t, 2H), 4.32～4.37 (m, 2H), 3.90～3.93 (t, 2H), 1.83～1.85 (m, 2H), 1.69～1.73 (m, 2H), 1.36～1.40 (m, 2H), 0.94～0.98 (m, 12H). 13CNMR 22.66,22.88, and 25.38,45.27,65.40,73.49,128.53,129.74,130.23,163.46.IR:3426,2925,2870,1467,1449,1356,1310,1089,1049,1032,971,946,909,775,708.HRMS (EI): m/z (%): calcd for C 20H 28N 2O 2: 328.2148, found:328.2149.
10,3b:1, the preparation of 2-(4S)-di-isopropyl-2 — oxazolinyl benzene
1，2-{bis-[4(S)-isopropyloxazolin-2-yl]}benzene
Catalysts Cu Cl 2, solvent ethylbenzene, operation is with example 9.
Productive rate 43%; Faint yellow viscous liquid, [a] 5 D=-14.4 ° of (c=0.139, CH 2Cl 2); 1HNMR (500MHz, CDCl 3, 27 ℃), δ (ppm)=8.98 (s, 4H), 7.20～7.34 (m, 10H), 7.23～7.40 (m, 8H), 4.57～4.63 (m, 2H), 4.34～4.40 (t, J=5.1Hz, 2H), 4.13～4.18 (t, 2H). 13CNMR18.39,19.22,32.81,70.73,73.16,128.71,130.03,130.39,163.89.IR:3305,3273,3067,2959,2930,2898,1726,1713,1655,1576,1492,1468,1354,1309,1293,1288,1248,1178,1089,1053,1033,966,908,773,706.HRMS (EI): m/z (%): calcd for C 18H 24N 2O 2: 300.1838; Found:300.1833.
11,3c:1, the preparation of 2-(4S)-phenylbenzene-2 — oxazolinyl benzene
1，2-{bis-[4(S)-phenyloxazolin-2-yl]}benzene
Catalyzer trichlorine rare earth, the solvent chlorobenzene, operation is with example 9.
Productive rate 45%; Faint yellow viscous liquid, [a] 5 D=-61.8 ° of (c=0.42, CHCl 3); 1HNMR (500MHz, CDCl 3, 27 ℃), and δ (ppm)=7.86～7.89 (m, 2H), 7.52～7.55 (m, 2H), 7.23～7.36 (m, 10H), 4.49～4.59 (m, 2H), 4.21～4.27 (t, J=0.61Hz, 2H), 3.99～4.03 (t, J=0.84Hz, 2H), 3.14～3.20 (dd, J=5.57,5.48Hz, 2H), 2.73～2.75 (dd, J=4.24,4.27Hz, 2H). 13CNMR, 41.23,67.89,72.03,126.27,128.24,128.32,129.06,129.20,129.61,130.19,137.83,163.92.IR:3061,3029,2956,2924,2897,2854,1651,1601,1494,1470,1454,1356,1313,1303,1236,1090,1054,1032,971,950,901,893,758,700.HRMS (EI): m/z (%): calcd for C 24H 20N 2O 2: 368.1525; Found:368.1475.
12,3d:1, the preparation of 2-(4S)-dibenzyl-2 — oxazolinyl benzene
1，2-{bis-[4(S)-benzyloxazolin-2-yl]}benzene
Catalyzer dimethyl dichloro stannane, the solvent chlorobenzene, operation is with example 9.
Productive rate 43%; Yellow liquid, [a] 5 D=-27.2 ° of (c=0.349, CH 2Cl 2); 1HNMR (500MHz, CDCl 3, 27 ℃), δ (ppm)=7.71～7.74 (m, 2H), 7.41～7.44 (m, 2H), 7.16～7.30 (m, 10H), 4.57～4.63 (m, 2H), 4.34～4.40 (t, J=5.1Hz, 2H), 4.13～4.18 (t, 2H). 13CNMR 41.2367.89,72.03,32.81,126.27,126.39,128.24,128.32,128.45,129.06,129.20,129.20,129.61,129.83,130.19,137.83,163.92.IR:3061,3027,2924,2895,1710,1650,1602,1494,1471,1452,1356,1354,1312,1288,1288,1252,1091,1053,1053,1031,965,918,752,702.HRMS (EI): m/z (%): calcd for C 26H 24N 2O 2: 396.1838; Found:396.1833.

Claims (9)

1, a kind of chiral oxazoline is characterized in that: by following chemical formulation, its chemical name is 1,4-(4S)-two R base-2 — oxazolinyl benzene:
Figure A200810020198C00021
R is selected from-CH in the formula 2CH (CH 3) 2Or-CH (CH 3) 2Or-ph or-CH 2Ph.
2, by the synthetic method of the described chiral oxazoline of claim 1, comprise synthetic, separation and purifying, it is characterized in that: described synthesizing is 1,4-dinitrile benzene and chiral amino alcohol under the condition that catalyzer exists in organic solvent, 110～145 ℃ of following back flow reaction 20～30 hours, catalyst levels is 1～3wt% of material quantity, and described catalyzer is selected from rare-earth metal chloride or transition metal chloride or AlCl 3Or alkoxide compound.
3, by the described synthetic method of claim 2, it is characterized in that: synthesize under the catalyzer condition in organic solvent, 120～140 ℃ of following back flow reaction 22～28 hours, catalyst levels is the 2wt% of material quantity, and described catalyzer is selected from rare earth metal oxychloride or transition metal chloride.
4, a kind of chiral oxazoline is characterized in that: by following chemical formulation, its chemical name is 1,3-(4S)-two R base-2 — oxazolinyl benzene:
R is selected from-CH in the formula 2CH (CH 3) 2Or-CH (CH 3) 2Or-ph or-CH 2Ph.
5, by the synthetic method of the described chiral oxazoline of claim 4, comprise synthetic, separation and purifying, it is characterized in that: described synthesizing is 1,3-dinitrile benzene and chiral amino alcohol under the condition that catalyzer exists in organic solvent, 110～145 ℃ of following back flow reaction 20～30 hours, catalyst levels is 1～3wt% of material quantity, and described catalyzer is selected from rare-earth metal chloride or transition metal chloride or AlCl 3Or alkoxide compound.
6, synthetic method according to claim 5, it is characterized in that: synthesize under the condition that catalyzer exists in organic solvent, 120～140 ℃ of following back flow reaction 22～28 hours, catalyst levels is the 2wt% of material quantity, and described catalyzer is selected from rare-earth metal chloride or transition metal chloride.
7, a kind of chiral oxazoline is characterized in that: by following chemical formulation, its chemical name is 1,2-(4S)-two R base-2 — oxazolinyl benzene:
Figure A200810020198C00031
R is selected from-CH in the formula 2CH (CH 3) 2Or-CH (CH 3) 2Or-ph or-CH 2Ph.
8, by the synthetic method of the described chiral oxazoline of claim 7, comprise synthetic, separation and purifying, it is characterized in that: described synthesizing is 1,2-dinitrile benzene and chiral amino alcohol under the condition that catalyzer exists in organic solvent, 110～145 ℃ of following back flow reaction 20～30 hours, catalyst levels is 1～3wt% of material quantity, and described catalyzer is selected from rare-earth metal chloride or transition metal chloride or AlCl 3Or alkoxide compound.
9, synthetic method according to claim 8, it is characterized in that: synthesize under the condition that catalyzer exists in organic solvent, 120～140 ℃ of following back flow reaction 22～28 hours, catalyst levels is the 2wt% of material quantity, and described catalyzer is selected from rare-earth metal chloride or transition metal chloride.
CN200810020198A 2008-03-28 2008-03-28 Chiral oxazoline and synthesis method thereof Pending CN101519384A (en)

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Cited By (7)

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CN102127028A (en) * 2010-11-24 2011-07-20 罗梅 Chiral oxazoline and synthesis method thereof
CN102464657A (en) * 2010-11-07 2012-05-23 上海交通大学 Two-oxazoline-containing chiral binuclear ligand with pyridazine or phthalazines matrix framework, and synthetic method thereof
CN101773856B (en) * 2010-01-21 2012-06-27 北京理工大学 Oxazoline Schiff base ligand metal complex catalyst and application thereof
CN102675238A (en) * 2011-09-02 2012-09-19 罗梅 Synthetic method of chiral oxazoline
CN103012447A (en) * 2013-01-20 2013-04-03 罗梅 Chiral oxazoline zinc complex
CN107011281A (en) * 2017-05-07 2017-08-04 合肥祥晨化工有限公司 A kind of Preparation method and use of chiral oxazoline crystal
CN110448561A (en) * 2019-08-08 2019-11-15 合肥工业大学 A kind of purposes of chiral double oxazoline metal complexs

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101773856B (en) * 2010-01-21 2012-06-27 北京理工大学 Oxazoline Schiff base ligand metal complex catalyst and application thereof
CN102464657A (en) * 2010-11-07 2012-05-23 上海交通大学 Two-oxazoline-containing chiral binuclear ligand with pyridazine or phthalazines matrix framework, and synthetic method thereof
CN102127028A (en) * 2010-11-24 2011-07-20 罗梅 Chiral oxazoline and synthesis method thereof
CN102127028B (en) * 2010-11-24 2012-08-01 罗梅 Chiral oxazoline and synthesis method thereof
CN102675238A (en) * 2011-09-02 2012-09-19 罗梅 Synthetic method of chiral oxazoline
CN103012447A (en) * 2013-01-20 2013-04-03 罗梅 Chiral oxazoline zinc complex
CN107011281A (en) * 2017-05-07 2017-08-04 合肥祥晨化工有限公司 A kind of Preparation method and use of chiral oxazoline crystal
CN110448561A (en) * 2019-08-08 2019-11-15 合肥工业大学 A kind of purposes of chiral double oxazoline metal complexs

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