CN103130650A - Oxidative coupling preparation of phenanthrene derivative under catalysis of sodium nitrite - Google Patents
Oxidative coupling preparation of phenanthrene derivative under catalysis of sodium nitrite Download PDFInfo
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- CN103130650A CN103130650A CN2011103768781A CN201110376878A CN103130650A CN 103130650 A CN103130650 A CN 103130650A CN 2011103768781 A CN2011103768781 A CN 2011103768781A CN 201110376878 A CN201110376878 A CN 201110376878A CN 103130650 A CN103130650 A CN 103130650A
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- sodium nitrite
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Abstract
The invention relates to an oxidative coupling preparation of a phenanthrene derivative under catalysis of sodium nitrite. A product phenanthrene derivative (B) can be obtained by the steps of adding a (E)-1,2-bis(substituted phenyl)-vinyl derivative or a (Z)-1,2-bis(substituted phenyl)-vinyl derivative or a mixture with any ratio of E/Z mixture in an organic solvent, dissolving the above material, then adding a certain amount of trifluoroacetic acid, adding a catalytic amount of sodium nitrite added in one time, stirring at a temperature ranging from -30 DEG C to 80 DEC C until the raw materials are reacted completely, adding water, separating liquid, drying an organic layer and distilling off the solvent. A pure product can be obtained through recrystallization of the product.
Description
Technical field
The oxidative coupling that the present invention relates to Sodium Nitrite catalysis prepares phenanthrene derivative.
Background technology
WO03070166 disclose phenanthroindolizididerivative pyridine and phenanthro-quinoline in the preparation method of western piperidine derivatives and they in pharmaceutically application.CN101189968 disclose phenanthroindolizididerivative pyridine and phenanthro-quinoline in western piperidine derivatives and the application of salt on agricultural chemicals thereof.Wherein, phenanthrene ring synthetic be synthetic phenanthroindolizididerivative pyridine and phenanthro-quinoline in the committed step of western piperidine derivatives, the method for bibliographical information mainly contains at present: Pschorr cyclisation method, illumination coupling method, iodobenzene diacetate (PIDA), the thallium trifluoroacetate coupling method, the plumbic acetate coupling method, trifluoro vanadyl and vanadium oxytrichloride coupling method (are seen 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, high army peak applied chemistry, 2006,23,1419.).CN101348483 discloses the preparation of phenanthroindolizididerivative derivative.CN101747126A discloses oxidative coupling preparation phenanthrene and dinaphthol and the biphenyl derivatives of Manganse Dioxide or metachloroperbenzoic acid participation.The oxidative coupling that CN101747201A discloses ferric trichloride catalytic prepares phenanthrene derivative.Above these methods have following defective: toxicity is large, severe reaction conditions, catalyzer is difficult with product separation, reaction yield is low, and metal residual is difficult to eliminate from product.
Summary of the invention
The oxidative coupling that the purpose of this invention is to provide Sodium Nitrite catalysis prepares the novel method of phenanthrene derivative.
The synthetic route that the oxidative coupling of Sodium Nitrite catalysis of the present invention prepares phenanthrene derivative following (equation 1).
Equation 1:
Wherein, R
1And R
2Represent respectively hydrogen, one to four halogen atom, one to four C
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, COMe, CO
nBu, CH
2OH, CH
3, CH
2OCH
3, CH
2OCOCH
3Deng.
Method of the present invention is: (E)-1,2-two (substituted-phenyl) ethene derivatives or (Z)-1, the mixture (A) of 2-two (substituted-phenyl) ethene derivatives or any ratio E/Z adds organic solvent that it is dissolved, then add a certain amount of trifluoroacetic acid, property adds the Sodium Nitrite of catalytic amount again, be stirred to raw material reaction complete in-30-80 ℃ scope, add entry, separatory, organic layer is dry, boil off solvent, can obtain product phenanthrene derivative (B), product also can obtain sterling through recrystallization.
In this reaction 1, the mol ratio of 2-two (substituted-phenyl) ethene derivatives and Sodium Nitrite is 1: 0.01-0.4.Temperature of reaction can be carried out in-30-80 ℃ scope, and best temperature of reaction is 0-20 ℃.
The organic solvent that uses in the present invention can be aromatic hydrocarbons, as toluene, benzene, dimethylbenzene etc.; Alkane or naphthenic hydrocarbon are as hexanaphthene, normal hexane, Skellysolve A, normal heptane, sherwood oil, gasoline etc.; Ether is as ether, tetrahydrofuran (THF) etc.; Chloroparaffin is as methylene dichloride, trichloromethane, tetracol phenixin, 1,2-ethylene dichloride etc.Best organic solvent is methylene dichloride, trichloromethane, 1, the 2-ethylene dichloride.
Reaction times in this reaction is 0.5-12 hour, and the best reaction times is 0.5-2 hour.
Of the present invention 2,3,6,7-tetramethoxy-9-phenanthrenecarboxylic acid methyl esters (D) can be with following method preparation (equation 2).Specifically comprise the steps: (E)-2,3-two (3 ', 4 '-Dimethoxyphenyl) methyl acrylate (C) joins in methylene dichloride and trifluoroacetic acid its dissolving, property adds the Sodium Nitrite of catalytic amount again, stirring at room, TLC monitors to raw material reaction complete, adds entry, separatory, organic layer is dry, and the decompression precipitation namely gets 2,3,6,7-tetramethoxy-9-phenanthrenecarboxylic acid methyl esters (D).(E)-2 in this reaction, 3-two (3 ', 4 '-Dimethoxyphenyl) mol ratio of methyl acrylate (C) and Sodium Nitrite is 1: 0.2, and temperature of reaction is room temperature, and namely 0-20 ℃, the reaction times is 1 hour.
Equation 2:
The 9-phenanthrenecarboxylic acid methyl esters (F) of methoxy substitution of the present invention can prepare (equation 3) with following method.Specifically comprise the steps: (E)-2,3-two (substituted-phenyl) methyl acrylate (E) joins in methylene dichloride and trifluoroacetic acid its dissolving, property adds the Sodium Nitrite of catalytic amount again, stirring at room, TLC monitors to raw material reaction complete, adds entry, separatory, organic layer is dry, and the decompression precipitation namely gets the 9-phenanthrenecarboxylic acid methyl esters (F) of methoxy substitution.(E)-2 in this reaction, the mol ratio of 3-two (substituted-phenyl) methyl acrylate (E) and Sodium Nitrite is 1: 0.2, and temperature of reaction is room temperature, and namely 0-20 ℃, the reaction times is 1 hour.
Equation 3:
The reactivity of table 1 Sodium Nitrite catalytically oxidative coupling system to different substrates
Of the present invention 2,3,6,7-tetramethoxy-9-phenanthrene derivative (H) can be with following method preparation (equation 4).Specifically comprise the steps: (E)-1,2-two (3 ', 4 '-Dimethoxyphenyl) ethene derivatives (G) adds in methylene dichloride and trifluoroacetic acid its dissolving, property adds the Sodium Nitrite of catalytic amount again, stirring at room, TLC monitors to raw material reaction complete, adds entry, separatory, organic layer is dry, and the decompression precipitation namely gets 2,3,6,7-tetramethoxy-9-phenanthrene derivative (H).(E)-1 in this reaction, 2-two (3 ', 4 '-Dimethoxyphenyl) mol ratio of ethene derivatives (G) and Sodium Nitrite is 1: 0.2, temperature of reaction is room temperature, namely 0-20 ℃.
Equation 4:
The not isomorphism type of table 2 pair key and different the replacement reactive impact
Embodiment
In following embodiment, fusing point is not calibrated, and yield is without optimization.
Embodiment 1:2,3,6,7-tetramethoxy-9-phenanthrenecarboxylic acid methyl esters synthetic:
Take 0.5mmol (E)-2,3-two (3 ', 4 '-Dimethoxyphenyl) methyl acrylate is in the four neck flasks of 100mL, add 30mL methylene dichloride and 3mL trifluoroacetic acid that it is dissolved, with reaction flask stopper jam-pack, property adds the 0.1mmol Sodium Nitrite again, stirring at room, and TLC monitors to raw material reaction complete, add again 50mL water, separatory, the organic layer anhydrous sodium sulfate drying, the decompression precipitation gets 2,3,6,7-tetramethoxy-9-phenanthrenecarboxylic acid methyl esters, it is 99% that HPLC detects productive rate.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).
Embodiment 2:2,3,6,7-tetramethoxy-9-phenanthrenecarboxylic acid synthetic:
In the four-hole boiling flask of 100mL, add 0.5mmol (E)-2,3-two (3 ', 4 '-Dimethoxyphenyl) acrylic solid adds 30mL methylene dichloride and 3mL trifluoroacetic acid that substrate is dissolved.Property adds the 0.1mmol Sodium Nitrite again, stirring at room, and TLC monitors to raw material reaction complete, then adds 50mL water, separatory, the organic layer anhydrous sodium sulfate drying, the decompression precipitation gets 2,3,6,7-tetramethoxy-9-phenanthrenecarboxylic acid formic acid, and HPLC detects yield 91%.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).
Embodiment 3:2,3,6,7-tetramethoxy-9-phenanthrenecarboxylic acid methyl esters synthetic:
Take the mol ratio E of 1: 1, Z formula mixing 2,3-two-(3 ', 4 '-Dimethoxyphenyl) methyl acrylate 0.5mmol in the four neck flasks of 100mL, add the 30mL methylene dichloride that it is dissolved, property adds the 0.1mmol Sodium Nitrite again, stirring at room, TLC monitors to raw material reaction complete, then adds 50mL water, separatory, the organic layer anhydrous sodium sulfate drying, the decompression precipitation gets 2,3,6,7-tetramethoxy-9-phenanthrenecarboxylic acid methyl esters, it is 99% that HPLC detects productive rate.m.p.202-203℃。
Use the same method and to synthesize following phenanthrene derivative, but do not limit the present invention.
Luxuriant and rich with fragrance acetonitrile: the Yield 73% of 2,3,6,7-tetramethoxy-9-, mp 266-268 ℃;
1H NMR (CDCl
3, 400MHz) 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).
2,3,4,6,7-pentamethoxyl-9-phenanthrenecarboxylic acid methyl esters: mp 115-118 ℃;
1H NMR (400MHz, CDCl
3) δ 9.19 (s, 1H), 8.58 (s, 1H), 8.35 (s, 1H), 7.16 (s, 1H), 4.10 (s, 3H), 4.08 (s, 3H), 4.07 (s, 3H), (4.02 s, 3H), 4.02 (s, 3H), 4.00 (s, 3H); HRMS (ESI) calcd for C
21H
22O
7Na (M+Na)
+409.1258, found 409.1255.
201203 ℃ of luxuriant and rich with fragrance ethyl ketone: the mp of 2,3,6,7-tetramethoxy-9-;
1H NMR (400MHz, CDCl
3) δ 8.54 (s, 1H), 8.08 (s, 1H), 7.67 (s, 1H), 7.62 (s, 1H), 7.17 (s, 1H), 4.11 (s, 3H), 4.09 (s, 3H), (4.05 s, 3H), 4.03 (s, 3H), 2.79 (s, 3H); HRMS (ESI) calcd for C
20H
20O
5Na (M+Na)
+363.1203, found363.1205.
2,3-dimethoxy-6,7-methylene-dioxy-9-phenanthrenecarboxylic acid methyl esters: mp 209-210 ℃;
1H NMR (CDCl
3, 400MHz) 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-, two methylene-dioxies-9-phenanthrenecarboxylic acid: Yield 91.8%, mp＞300 ℃;
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 ℃.
2,3-dimethoxy-6,7-methylene-dioxy-9-phenanthrenecarboxylic acid: Yield 95%, mp＞300 ℃.
2,3-ethylenedioxy-6,7-dimethoxy-9-phenanthrenecarboxylic acid: Yield 94%, mp 281-284 ℃;
1H NMR (CDCl
3, 400MHz) 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-, two ethylenedioxies-9-phenanthrenecarboxylic acid: Yield 85%, mp 290-305 ℃;
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 ℃.
Claims (8)
1. the oxidative coupling of Sodium Nitrite catalysis prepares the novel method of phenanthrene derivative, it is characterized in that (E)-1,2-two (substituted-phenyl) ethene derivatives or (Z)-1, the mixture (A) of 2-two (substituted-phenyl) ethene derivatives or any ratio E/Z adds organic solvent that it is dissolved, then add a certain amount of trifluoroacetic acid, property adds the Sodium Nitrite of catalytic amount again, be stirred to raw material reaction complete in-30-80 ℃ scope, add entry, separatory, organic layer is dry, boil off solvent, can obtain product phenanthrene derivative (B), product also can obtain sterling through recrystallization.
Wherein, R
1And R
2Represent respectively hydrogen, one to four halogen atom, one to four C
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, COMe, CO
nBu, CH
2OH, CH
3, CH
2OCH
3, CH
2OCOCH
3Deng.
2. according to synthetic method claimed in claim 1, it is characterized in that describedly 1, the mol ratio of 2-two (substituted-phenyl) ethene derivatives and Sodium Nitrite is 1: 0.01-0.2.
3. according to synthetic method claimed in claim 1, it is characterized in that described organic solvent can be aromatic hydrocarbons, as toluene, benzene, dimethylbenzene etc.; Alkane or naphthenic hydrocarbon are as hexanaphthene, normal hexane, Skellysolve A, normal heptane, sherwood oil, gasoline etc.; Ether is as ether, tetrahydrofuran (THF) etc.; Chloroparaffin is as methylene dichloride, trichloromethane, tetracol phenixin, 1,2-ethylene dichloride etc.Best organic solvent is methylene dichloride, trichloromethane, 1, the 2-ethylene dichloride.
4. according to synthetic method claimed in claim 1, it is characterized in that described temperature of reaction can carry out in-30-80 ℃ scope, best temperature of reaction is 0-20 ℃.
5. according to synthetic method claimed in claim 1, it is characterized in that the described reaction times is 0.5-12 hour, the best reaction times is 0.5-2 hour.
6. according to synthetic method claimed in claim 1, it is characterized in that the phenanthrene derivative (B) that synthesizes is the phenanthrenecarboxylic acid derivative of Polymethoxylated replacement.
7. according to the phenanthrenecarboxylic acid derivative of Polymethoxylated replacement claimed in claim 6, it is characterized in that preferred phenanthrenecarboxylic acid derivative is 2,3,6,7-tetramethoxy-9-phenanthrenecarboxylic acid methyl esters.
8. according to the phenanthrenecarboxylic acid derivative of Polymethoxylated replacement claimed in claim 6, it is characterized in that preferred phenanthrenecarboxylic acid derivative is 2,3,6,7-tetramethoxy-9-phenanthrenecarboxylic acid.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108586310A (en) * | 2018-04-17 | 2018-09-28 | 浙江工业大学 | The catalysis oxidation synthetic method of 3- sulfydryl indole class compounds |
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| US20050222418A1 (en) * | 2002-02-15 | 2005-10-06 | Baker David C | Novel tyloindicines and related processes, pharmaceutical compositions and methods |
| CN101747201A (en) * | 2008-11-28 | 2010-06-23 | 南开大学 | Method for preparing ferric trichloride catalytic oxidative coupling phenanthrene derivative |
| CN101747126A (en) * | 2008-11-28 | 2010-06-23 | 南开大学 | Manganese dioxide or m-chloroperoxybenzoic acid-participated oxidative coupling-prepared phenanthrene, dinaphthol and biphenyl derivative |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US20050222418A1 (en) * | 2002-02-15 | 2005-10-06 | Baker David C | Novel tyloindicines and related processes, pharmaceutical compositions and methods |
| CN101747201A (en) * | 2008-11-28 | 2010-06-23 | 南开大学 | Method for preparing ferric trichloride catalytic oxidative coupling phenanthrene derivative |
| CN101747126A (en) * | 2008-11-28 | 2010-06-23 | 南开大学 | Manganese dioxide or m-chloroperoxybenzoic acid-participated oxidative coupling-prepared phenanthrene, dinaphthol and biphenyl derivative |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108586310A (en) * | 2018-04-17 | 2018-09-28 | 浙江工业大学 | The catalysis oxidation synthetic method of 3- sulfydryl indole class compounds |
| CN108586310B (en) * | 2018-04-17 | 2020-06-12 | 浙江工业大学 | Catalytic oxidation synthesis method of 3-mercaptoindole compounds |
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Application publication date: 20130605 |