CN102816040B - Oxidative coupling preparation method of phenanthrene, binaphthol and biphenyl derivatives under participation of manganese dioxide or m-chloroperoxybenzoic acid - Google Patents
Oxidative coupling preparation method of phenanthrene, binaphthol and biphenyl derivatives under participation of manganese dioxide or m-chloroperoxybenzoic acid Download PDFInfo
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Abstract
The invention relates to an oxidative coupling preparation method of phenanthrene, binaphthol and biphenyl derivatives under participation of manganese dioxide or m-chloroperoxybenzoic acid. The preparation method includes dissolving (E)-1,2-bis(substituted phenyl)ethylene derivative, (Z)-1,2-bis(substituted phenyl)ethylene derivative, or mixture thereof at any ratio with organic solvent; one-step adding manganese dioxide or m-chloroperoxybenzoic acid (m-CPBA); reacting under stirring at (-30)-80 DEG C; adding water and separating; drying the organic layer to remove solvent and obtain phenanthrene derivatives; and optionally recrystallizing to obtain pure product. With the same method, binaphthol derivatives can be prepared from 2-naphthol, and biphenyl derivatives can be prepared from substituted benzene.
Description
Technical field
The present invention relates to the luxuriant and rich with fragrance and dinaphthol of oxidative coupling preparation that Manganse Dioxide or metachloroperbenzoic acid participate in and biphenyl derivatives.
Background technology
WO03070166 disclose phenanthroindolizididerivative pyridine and phenanthro-quinoline in the preparation method of western piperidine derivatives and they are in application pharmaceutically.CN101189968 disclose phenanthroindolizididerivative pyridine and phenanthro-quinoline in western piperidine derivatives and the application of salt on agricultural chemicals thereof.Wherein, the synthesis of phenanthrene ring be synthesis phenanthroindolizididerivative pyridine and phenanthro-quinoline in the committed step of western piperidine derivatives, the method for current bibliographical information mainly contains: Pschorr cyclisation method, illumination coupling method, iodobenzene diacetate (PIDA), thallium trifluoroacetate coupling method, plumbic acetate coupling method, trifluoro vanadyl and vanadium oxytrichloride coupling method are (see document: 1.Pschorr, R.Chem.Ber.1896,29,496-501.2.Jin, Z.; Wang, Q.M.; Huang, R.Q.Syn.Commun.2004,34,119-128.3.Floyd, A.J.; Dyke, S.F.; Ward, S.E.Chem.Rev.1976,76,509-562.4. river Rong Ying, local records are outstanding, Gao Junfeng.Applied chemistry, 2006,23,1419.).Dinaphthol and derivative thereof are widely used in asymmetric synthesis as chiral catalyst, the method of bibliographical information mainly contains: Fe (III), Cu (II), Mn (III), Ti (IV), the metallic compounds such as V (V), Ru (III) (see document: 1.Toda, F.; Tanaka, K.; Lwata, S.J.Org.Chem.1989,54,3007-3009.2.Ding, K.L.; Wang, Y.; Zhang, L.J.; Wu, Y.J.Tetrahedron 1996,52,1005-1010.3.Smrcina, M.; Polakova, J.; Vyskocil, S.; Kocovsky, P.J.Org.Chem.1993,58,4534-4538.4.Sakamoto, T.; Yonehara, H.; Pac, C.J.Org.Chem.1994,59,6859-6861.).There is following defect in these methods above: toxicity is large, severe reaction conditions, catalyzer and product separation are difficult, reactions steps is long, reaction yield is low.
Summary of the invention
The object of this invention is to provide the oxidative coupling preparation phenanthrene of Manganse Dioxide or metachloroperbenzoic acid participation and the novel method of dinaphthol and biphenyl derivatives.
The oxidative coupling that Manganse Dioxide of the present invention or metachloroperbenzoic acid participate in prepares the synthetic route following (equation 1) of phenanthrene derivative.
Equation 1:
Wherein, R
1and R
2represent hydrogen, one to four halogen atom, one to four C respectively
1-C
6alkoxyl group, one to four hydroxyl, one to four ester group, one to two methylene-dioxy (OCH
2o), one to two ethylenedioxy (OCH
2cH
2o); R
3represent H, CN, NO
2, CHO, COOH, COOMe, COOEt, COOPr, CONH
2, CH
2oH, CH
2oCH
3, CH
2oCOCH
3deng.
Method of the present invention is: (E)-1,2-bis-(substituted-phenyl) ethene derivatives or (Z)-1, the mixture (A) of 2-bis-(substituted-phenyl) ethene derivatives or any ratio E/Z adds organic solvent and is dissolved, property adds Manganse Dioxide or metachloroperbenzoic acid (m-CPBA) again, raw material reaction is stirred to complete within the scope of-30-80 DEG C, add water, separatory, organic layer is dry, boil off solvent, can obtain product phenanthrene derivative (B), product also can be passed through recrystallization and obtains sterling.
In this reaction, the mol ratio of 1,2-bis-(substituted-phenyl) ethene derivatives (A), Manganse Dioxide or metachloroperbenzoic acid (m-CPBA) is 1: 0.8-2.Temperature of reaction can be carried out within the scope of-30-80 DEG C, and best temperature of reaction is 0-20 DEG C.
Organic solvent used in the present invention can be aromatic hydrocarbons, as toluene, benzene, dimethylbenzene etc.; Alkane or naphthenic hydrocarbon, as hexanaphthene, normal hexane, Skellysolve A, normal heptane, sherwood oil, gasoline etc.; Ether, as ether, tetrahydrofuran (THF) etc.; Chloroparaffin, as methylene dichloride, trichloromethane, tetracol phenixin, 1,2-ethylene dichloride etc.; Trifluoroacetic acid, trichoroacetic acid(TCA), tribromoacetic acid, methanesulfonic, tosic acid, hydrochloric acid, sulfuric acid.Best organic solvent is trifluoroacetic acid.
Reaction times in this reaction is 0.5-12 hour.
The oxidative coupling that Manganse Dioxide of the present invention or metachloroperbenzoic acid participate in prepares the synthetic route following (equation 2) of binaphthol derivative.
Equation 2:
Wherein, R represents hydrogen, one to six chlorine atom, one to six bromine atoms, one to six C
1-C
6alkyl, one to six C
1-C
6alkoxyl group, one to six hydroxyl, one to six COOMe, COOEt, COOPr, CONH
2deng.
Method of the present invention is: beta naphthal (C) adds organic solvent and dissolved, property adds Manganse Dioxide or metachloroperbenzoic acid (m-CPBA) again, raw material reaction is stirred to complete within the scope of-30-80 DEG C, add water, separatory, organic layer is dry, boils off solvent, can obtain product binaphthol derivative (D), product also can be passed through recrystallization and obtains sterling.
In this reaction, the mol ratio of beta naphthal (C), Manganse Dioxide or metachloroperbenzoic acid (m-CPBA) is 1: 0.8-2.Temperature of reaction can be carried out within the scope of-30-80 DEG C, and best temperature of reaction is 0-20 DEG C.
Organic solvent used in the present invention can be aromatic hydrocarbons, as toluene, benzene, dimethylbenzene etc.; Alkane or naphthenic hydrocarbon, as hexanaphthene, normal hexane, Skellysolve A, normal heptane, sherwood oil, gasoline etc.; Ether, as ether, tetrahydrofuran (THF) etc.; Chloroparaffin, as methylene dichloride, trichloromethane, tetracol phenixin, 1,2-ethylene dichloride etc.; Trifluoroacetic acid, trichoroacetic acid(TCA), tribromoacetic acid, methanesulfonic, tosic acid, hydrochloric acid, sulfuric acid.Best organic solvent is trifluoroacetic acid.
Reaction times in this reaction is 0.5-12 hour.
The oxidative coupling that Manganse Dioxide of the present invention or metachloroperbenzoic acid participate in prepares the synthetic route following (equation 3) of biphenyl derivatives.
Equation 3:
Wherein, R represents hydrogen, one to five halogen atom, one to five C
1-C
6alkyl, one to five C
1-C
6alkoxyl group, one to five hydroxyl, one to five ester group, one to two methylene-dioxy (OCH
2o), one to two ethylenedioxy (OCH
2cH
2o) etc.
Method of the present invention is: substituted benzene (E) adds organic solvent and dissolved, property adds Manganse Dioxide or metachloroperbenzoic acid (m-CPBA) again, raw material reaction is stirred to complete within the scope of-30-80 DEG C, add water, separatory, organic layer is dry, boils off solvent, can obtain product biphenyl derivatives (F), product also can be passed through recrystallization and obtains sterling.
In this reaction, the mol ratio of substituted benzene (E), Manganse Dioxide or metachloroperbenzoic acid (m-CPBA) is 1: 0.8-2.Temperature of reaction can be carried out within the scope of-30-80 DEG C, and best temperature of reaction is 0-20 DEG C.
Organic solvent used in the present invention can be aromatic hydrocarbons, as toluene, benzene, dimethylbenzene etc.; Alkane or naphthenic hydrocarbon, as hexanaphthene, normal hexane, Skellysolve A, normal heptane, sherwood oil, gasoline etc.; Ether, as ether, tetrahydrofuran (THF) etc.; Chloroparaffin, as methylene dichloride, trichloromethane, tetracol phenixin, 1,2-ethylene dichloride etc.; Trifluoroacetic acid, trichoroacetic acid(TCA), tribromoacetic acid, methanesulfonic, tosic acid, hydrochloric acid, sulfuric acid.Best organic solvent is trifluoroacetic acid.
Reaction times in this reaction is 0.5-12 hour.
Embodiment
In following embodiment, fusing point is not calibrated, and yield is without optimization.
The synthesis of embodiment 1:2,3,6,7-tetramethoxy-9-phenanthrenecarboxylic acid methyl esters:
0.179g (0.5mmol) (E)-2 is added in 25mL four-hole bottle, 3-bis-(3 ', 4 '-Dimethoxyphenyl) methyl acrylate, 5mL trifluoroacetic acid, stirring at room temperature makes material dissolution, adds 0.044g (0.5mmol) MnO
2, mixture stirring at room temperature 2 hours, adds 50mL methylene dichloride, washing, dry, and filter, namely precipitation obtains 2,3,6,7-tetramethoxy-9-phenanthrenecarboxylic acid methyl esters.Transformation efficiency (100%) and productive rate (100%) is measured through HPLC.m.p.202-203℃
1H NMR(CDCl
3，400MHz)δ：8.65(s，1H)，8.43(s，1H)，7.81(s，1H)，7.77(s，1H)，7.27(s，1H)，4.14(s，3H)，4.13(s，3H)，4.08(s，3H)，4.04(s，3H)，4.02(s，3H).
Use the same method and can synthesize following phenanthrene derivative, but do not limit the present invention.
Luxuriant and rich with fragrance acetonitrile: Yield 99%, the mp 266-268 DEG C of 2,3,6,7-tetramethoxy-9-;
1h NMR (CDCl
3, 400MHz) and δ: 8.05 (s, 1H), 7.78 (s, 1H), 7.75 (s, 1H), 7.57 (s, 1H), 7.22 (s, 1H), 4.15 (s, 3H), 4.14 (s, 3H) .4.10 (s, 3H), 4.05 (s, 3H).
2,3,6-trimethoxy-9-phenanthrenecarboxylic acid methyl esters: Yield 99%, mp 158-160 DEG C;
1h NMR (CDCl
3, 400MHz) δ: 8.93 (d,
3j
hH=9.2Hz, 1H), 8.30 (s, 1H), 7.88-7.85 (m, 2H), 7.27 (s, 1H), 7.26 (s, 1H), 4.12 (s, 3H), 4.04 (s, 3H), 4.02 (s, 3H), 4.01 (s, 3H).
2,3,6-trimethoxy-10-phenanthrenecarboxylic acid methyl esters: Yield 97%, mp 147-149 DEG C;
1h NMR (CDCl
3, 400MHz) and δ: 8.66 (s, 1H), 8.46 (s, 1H), 7.90 (s, 1H), 7.87 (d,
3j
hH=8.8Hz, 1H), 7.84 (d,
4j
hH=1.6Hz, 1H), 7.22 (dd,
3j
hH=8.8Hz,
4j
hH=2.4Hz, 1H), 4.12 (s, 3H), 4.09 (s, 3H), 4.04 (s, 3H), 4.02 (s, 3H).
2,3,7-trimethoxy-9-phenanthrenecarboxylic acid methyl esters: Yield 97%, mp 163-164 DEG C;
1h NMR (CDCl
3, 300MHz) δ: 8.59 (d,
4j
hH=2.7Hz, 1H), 8.50 (s, 1H), 8.47 (d,
3j
hH=9.3Hz, 1H), 7.89 (s, 1H), 7.32-7.27 (m, 2H), 4.13 (s, 3H), 4.04 (s, 3H), 4.02 (s, 3H), 4.00 (s, 3H).
2,3,7-trimethoxy-10-phenanthrenecarboxylic acid methyl esters: Yield 94%, mp 153-154 DEG C;
1h NMR (CDCl
3, 400MHz) and δ: 8.55 (s, 1H), 8.44 (d,
3j
hH=9.2Hz, 1H), 8.42 (s, 1H), 7.93 (s, 1H), 7.35 (dd,
3j
hH=9.10Hz,
4j
hH=2.80Hz, 1H), 7.29 (d,
4j
hH=2.80Hz, 1H), 4.12 (s, 3H), 4.08 (s, 3H), 4.03 (s, 3H), 3.96 (s, 3H) .HRMS (ESI) m/z calcd for C
19h
18o
5(M+H)
+327.1227, found 327.1226.
2,3-dimethoxy-6,7-methylene-dioxy-9-phenanthrenecarboxylic acid methyl esters: mp 209-210 DEG C;
1h NMR (CDCl
3, 400MHz) and δ: 8.47 (s, 1H), 8.36 (s, 1H), 7.87 (s, 1H), 7.72 (s, 1H), 7.24 (s, 1H), 6.12 (s, 2H), 4.12 (s, 3H), 4.03 (s, 3H), 4.01 (s, 3H); HRMS (ESI) m/z calcd.for C
19h
16o
6(M+Na)
+363.0839, found 363.0837.
2,3,6,7-bis-methylene-dioxy-9-phenanthrenecarboxylic acid: Yield 91.8%, mp > 300 DEG C;
1h NMR (400MHz, DMSO) δ: 13.00 (br, 1H), 8.36 (s, 1H), 8.35 (s, 1H), 8.23 (s, 1H), 8.20 (s, 1H), 7.52 (s, 1H), 6.18 (s, 2H), (6.17 s, 2H).
2,3-methylene-dioxy-6,7-dimethoxy-9-phenanthrenecarboxylic acid: Yield 96.5%, mp > 300 DEG C.
2,3-dimethoxy-6,7-methylene-dioxy-9-phenanthrenecarboxylic acid: Yield 95%, mp > 300 DEG C.
2,3-ethylenedioxy-6,7-dimethoxy-9-phenanthrenecarboxylic acid: Yield 96%, mp 281-284 DEG C;
1hNMR (CDCl
3, 400MHz) and δ: 8.67 (s, 1H), 8.52 (s, 1H), 7.95 (s, 1H), 7.83 (s, 1H), 7.43 (s, 1H), 4.44 (s, 2H), 4.42 (s, 2H), 4.12 (s, 3H), 4.09 (s, 3H).
2,3,6,7-bis-ethylenedioxy-9-phenanthrenecarboxylic acid: Yield 85%, mp 290-305 DEG C;
1h NMR (DMSO, 400MHz) δ: 12.92 (br, 1H), 8.34 (d, 1H), 8.22 (m, 1H), 8.04 (m, 2H), 7.47 (m, 1H), 4.32 (s, 8H).
2,3-dimethoxy-6,7-ethylenedioxy-9-phenanthrenecarboxylic acid: Yield 93%, mp 285-300 DEG C.
The synthesis of embodiment 2:2,3,6,7-tetramethoxy-9-phenanthrenecarboxylic acid:
Add 0.5mmol (E)-2,3-bis-(3 ', 4 '-Dimethoxyphenyl) vinylformic acid in 25mL four-hole bottle, 5mL trifluoroacetic acid, stirring at room temperature makes material dissolution, adds 0.5mmol MnO
2, mixture stirring at room temperature 2 hours, adds 50mL methylene dichloride, washing, dry, and filter, namely precipitation obtains 2,3,6,7-tetramethoxy-9-phenanthrenecarboxylic acid methyl esters.Transformation efficiency (100%) and productive rate (100%) is measured through HPLC.m.p.285-287℃；
1H NMR(DMSO，300MHz)δ：8.58(s，1H)，8.43(s，1H)，8.03(s，1H)，7.99(s，1H)，7.54(s，1H)，4.08(s，3H)，4.07(s，3H)，3.94(s，3H)，3.93(s，3H).
The synthesis of embodiment 3:2,3,6,7-tetramethoxy-9-phenanthrenecarboxylic acid methyl esters:
Take the E of mol ratio 1: 1, Z formula mixing 2,3-bis--(3 ', 4 '-Dimethoxyphenyl) methyl acrylate 0.5mmol is in the four neck flasks of 25mL, 5mL trifluoroacetic acid, stirring at room temperature makes material dissolution, adds 0.044g (0.5mmol) MnO
2, mixture stirring at room temperature 2 hours, adds 50mL methylene dichloride, washing, dry, and filter, namely precipitation obtains 2,3,6,7-tetramethoxy-9-phenanthrenecarboxylic acid methyl esters.Transformation efficiency (100%) and productive rate (100%) is measured through HPLC.m.p.202-203℃
The synthesis of embodiment 4:2,3,6,7-tetramethoxy-9-phenanthrenecarboxylic acid methyl esters:
0.179 gram of (0.5mmol) (E)-2,3-bis-(3 ', 4 '-Dimethoxyphenyl) methyl acrylate is added, 50mL CF in 100mL reaction flask
3cOOH, adds the m-CPBA solid of 0.152 gram of (0.75mmol) 85%.Mixture stirring at room temperature reacts 0.5 hour, adds 100mL CH
2cl
2, washing, anhydrous MgSO
4drying, filter, namely precipitation obtains 2,3,6,7-tetramethoxy-9-phenanthrenecarboxylic acid methyl esters.Its transformation efficiency 100% is detected, productive rate 99% through HPLC.m.p.202-203℃.
Embodiment 5:2, the synthesis of 2 '-dinaphthol:
In 50mL reaction flask, add 0.144 gram of (1mmol) beta naphthal, 10mL trifluoroacetic acid, stirring at room temperature is dissolved, then adds 0.088 gram of (1mmol) MnO
2, stirring at room temperature reacts 5.5 hours, then adds 20mL methylene dichloride, washing, anhydrous MgSO
4drying, filter, namely precipitation obtains 2,2 '-dinaphthol.Its transformation efficiency 100% is detected, productive rate 97% through HPLC.mp 216-218℃；
1H NMR(CDCl
3，400MHz)δ：7.98(s，1H)，7.95(s，1H)，7.90(s，1H)，7.89(s，1H)，7.36-7.40(m，4H)，7.29-7.33(m，2H)，7.17(s，1H)，7.15(s，1H)，5.06(s，2H).
Use the same method and can synthesize following binaphthol derivative, but do not limit the present invention.
6,6 '-two bromo-2,2 '-dinaphthol: Yield 85%, mp 200-202 DEG C;
1h NMR (CDCl
3, 400MHz) and δ: 8.05 (s, 2H), 7.90 (s, 1H), 7.88 (s, 1H), 7.36-7.40 (m, 4H), 6.97 (s, 1H), 6.95 (s, 1H), 5.04 (s, 2H).
3,3 '-dimethoxycarbonyl-2,2 '-dinaphthol: Yield 47%, mp 285-287 DEG C;
1h NMR (CDCl
3, 400MHz) and δ: 10.73 (s, 2H), 8.70 (s, 2H), 7.91-7.94 (m, 2H), 7.33-7.36 (m, 4H), 7.15-7.18 (m, 2H), 4.06 (s, 6H).
1,1 '-dinaphthalene-2,2 '-two sulphur: Yield 88%, mp 180-181 DEG C;
1h NMR (CDCl
3, 400MHz) and δ: 8.52 (s, 1H), 8.50 (s, 1H), 7.85 (s, 1H), 7.83 (s, 1H), 7.74-7.76 (m, 2H), 7.59-7.67 (m, 4H), 7.50-7.53 (m, 2H);
13c NMR (CDCl
3, 75MHz) and δ: 134.0,133.3,133.0,132.0,128.4,127.8,127.1,126.5,126.4,124.4; EI-MS m/z (%) 316 (M
+, 100), 271 (8), 115 (16), 57 (18), 43 (37); Anal.Calcdfor C
20h
12s
2: C, 75.91, H, 3.82; Found:C, 76.11, H, 3.72.
2,2 '-diaminostilbene, 1 '-dinaphthalene: Yield 88%, mp 189-191 DEG C.
Embodiment 6:2,2 '-dimethyl-4,4 ', 5, the synthesis of 5 '-tetramethoxy biphenyl:
In 50mL reaction flask, add 0.152 gram (1mmol) 3 ' 4-dimethoxy-p, 10mL trifluoroacetic acid, stirring at room temperature is dissolved, then adds 0.088 gram of (1mmol) MnO
2, stirring at room temperature reacts 1.2 hours, then adds 20mL methylene dichloride, washing, anhydrous MgSO
4drying, filter, namely precipitation obtains 2,2 '-dimethyl-4, and 4 ' 5,5 '-tetramethoxy biphenyl.Its transformation efficiency 100% is detected, productive rate 93% through HPLC.mp 121-122℃；
1H NMR(CDCl
3，400MHz)δ：6.77(s，2H)，6.65(s，2H)，3.91(s，6H)，3.83(s，6H)，2.02(s，6H).
Use the same method and can synthesize other biphenyl derivatives, but do not limit the present invention.
Claims (4)
1. the oxidative coupling that Manganse Dioxide participates in prepares the method for biphenyl derivatives, it is characterized in that substituted benzene (E) adds trifluoroacetic acid and dissolved, property adds Manganse Dioxide again, is stirred to raw material reaction complete, adds water within the scope of-30-80 DEG C, separatory, organic layer is dry, boils off solvent, can obtain product biphenyl derivatives (F), product also can be passed through recrystallization and obtains sterling
Wherein, R represents hydrogen, one to five halogen atom, one to five C
1-C
6alkyl, one to five C
1-C
6alkoxyl group, one to five hydroxyl, one to five ester group, one to two methylene-dioxy (OCH
2o), one to two ethylenedioxy (OCH
2cH
2o).
2., according to synthetic method according to claim 1, it is characterized in that described substituted benzene (E), the mol ratio of Manganse Dioxide is 1: 0.8-2.
3., according to synthetic method according to claim 1, it is characterized in that best temperature of reaction is 0-20 DEG C.
4., according to synthetic method according to claim 1, it is characterized in that the described reaction times is 0.5-12 hour.
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| CN102816040A (en) | 2012-12-12 |
| CN101747126B (en) | 2013-05-01 |
| CN101747126A (en) | 2010-06-23 |
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