CN101747201B - Method for preparing ferric trichloride catalytic oxidative coupling phenanthrene derivative - Google Patents
Method for preparing ferric trichloride catalytic oxidative coupling phenanthrene derivative Download PDFInfo
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- CN101747201B CN101747201B CN 200810153623 CN200810153623A CN101747201B CN 101747201 B CN101747201 B CN 101747201B CN 200810153623 CN200810153623 CN 200810153623 CN 200810153623 A CN200810153623 A CN 200810153623A CN 101747201 B CN101747201 B CN 101747201B
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- MHYOPIANRZHZKR-XNTDXEJSSA-N COC(/C(/c(cc1OC)ccc1OC)=C/c(cc1OC)ccc1OC)=O Chemical compound COC(/C(/c(cc1OC)ccc1OC)=C/c(cc1OC)ccc1OC)=O MHYOPIANRZHZKR-XNTDXEJSSA-N 0.000 description 1
- RHMBLFABFWUWEP-UHFFFAOYSA-N COC(c(c1c2)cc(cc(c(OC)c3)OC)c3c1cc(OC)c2OC)=O Chemical compound COC(c(c1c2)cc(cc(c(OC)c3)OC)c3c1cc(OC)c2OC)=O RHMBLFABFWUWEP-UHFFFAOYSA-N 0.000 description 1
Abstract
The invention relates to a method for preparing a ferric trichloride catalytic oxidative coupling phenanthrene derivative, which comprises the following steps: adding a (E)-1 and 2-divinyl (substituted phenyl) derivative or a (Z)-1 and 2-divinyl (substituted phenyl) derivative or a E/Z mixture (A) with any proportions into organic solvent for dissolution, adding a catalytic amount of ferric trichloride again and adding organic solvent solution containing meta-chloroperoxybenzoic acid (m-CPBA); agitating at a temperature of minus 30-80 DEG C till raw materials are completely reacted; and adding water, separating liquid, drying an organic layer and steaming the solvent to obtain a product, namely the phenanthrene derivative (B). A pure product can be obtained through re-crystallizing the product.
Description
Technical field
The oxidative coupling that the present invention relates to ferric trichloride catalytic 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, Gao Junfeng.Applied chemistry, 2006,23,1419.) there is following defective in these methods: toxicity is large, severe reaction conditions, catalyzer is difficult with product separation, reaction yield is low.
Summary of the invention
The oxidative coupling that the purpose of this invention is to provide ferric trichloride catalytic prepares the novel method of phenanthrene derivative.
The synthetic route that the oxidative coupling of ferric trichloride catalytic 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, CH
2OH, 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 it is dissolved, the iron trichloride of property adding catalytic amount again, add again the organic solvent solution that contains metachloroperbenzoic acid (m-CPBA), it is complete to be stirred to raw material reaction 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, iron trichloride and m-CPBA is 1:0.02-0.40:0.5-1.5.Temperature of reaction can be carried out in-30-80 ℃ scope, and best temperature of reaction is 0-20 ℃.
Employed organic solvent can be aromatic hydrocarbons in the present invention, such as toluene, benzene, dimethylbenzene etc.; Alkane or naphthenic hydrocarbon are such as hexanaphthene, normal hexane, Skellysolve A, normal heptane, sherwood oil, gasoline etc.; Ether is such as ether, tetrahydrofuran (THF) etc.; Chloroparaffin is such as methylene dichloride, trichloromethane, tetracol phenixin, 1,2-ethylene dichloride etc.; Trifluoroacetic acid.Best organic solvent is methylene dichloride, trichloromethane, 1,2-ethylene dichloride.
Reaction times in this reaction is 0.5-12 hours, and the best reaction times is 0.5-2 hours.
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 the methylene dichloride its dissolving, the iron trichloride of property adding catalytic amount adds the dichloromethane solution that contains metachloroperbenzoic acid (m-CPBA), stirring at room more again, TLC monitors to raw material reaction complete, add entry, separatory, organic layer is dry, 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), iron trichloride and m-CPBA is 1:0.1:1, 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 the methylene dichloride its dissolving, the iron trichloride of property adding catalytic amount again, add again the dichloromethane solution that contains metachloroperbenzoic acid (m-CPBA), stirring at room, TLC monitors to raw material reaction complete, add 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), iron trichloride and m-CPBA is 1:0.15:1.1, and temperature of reaction is room temperature, and namely 0-20 ℃, the reaction times is 1 hour.
Equation 3:
Table 1 FeCl
3/ m-CPBA catalytically oxidative coupling system is to the reactivity of 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 the methylene dichloride its dissolving, the iron trichloride of property adding catalytic amount adds the dichloromethane solution that contains metachloroperbenzoic acid (m-CPBA), stirring at room more again, TLC monitors to raw material reaction complete, add entry, separatory, organic layer is dry, 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), iron trichloride and m-CPBA is 1:0.1:1, temperature of reaction is room temperature, namely 0-20 ℃.
Equation 4:
The not isomorphism type of table 2 pair key and different replacements are on reactive impact
Embodiment
Among the 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 by weighing 0.5mmol (E)-2,3-two (3 ', 4 '-Dimethoxyphenyl) methyl acrylate is in the four neck flasks of 100mL, adding the 30mL methylene dichloride dissolves it, with reaction flask stopper jam-pack, property adding 0.05mmol iron trichloride adds the dichloromethane solution 20mL that contains the 0.5mmol metachloroperbenzoic acid more again, stirring at room, TLC monitors to raw material reaction complete, adds 50mL water, separatory again, 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 2L, add 68.8g (0.2mol) (E)-2,3-two (3 ', 4 '-Dimethoxyphenyl) acrylic solid adds 1200mL CH
2Cl
2And stirring makes the substrate dissolving.Property adding 4.88g (0.03mol) FeCl again
3Solid adds the CH that is dissolved with 36g (0.22mol) metachloroperbenzoic acid again after adding
2Cl
2Solution 100mL, mixture at room temperature stirs, and TLC monitors to raw material reaction complete, adds 200mL water again, separatory, the mixture precipitation, solid gets colorless solid 62g with recrystallizing methanol, 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 by weighing the E of mol ratio 1:1, the Z formula mixes 2,3-two-(3 ', 4 '-Dimethoxyphenyl) methyl acrylate 0.5mmol is in the four neck flasks of 100mL, add the 30mL methylene dichloride it is dissolved, property adding 0.05mmol iron trichloride adds the dichloromethane solution 20mL that contains the 0.5mmol metachloroperbenzoic acid more again, stirring at room, TLC monitors to raw material reaction complete, adds 50mL water, separatory again, 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 99% 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).
2,3,6-trimethoxy-9-phenanthrenecarboxylic acid methyl esters: Yield 99%, mp 158-160 ℃;
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 ℃;
1H NMR (CDCl
3, 400MHz) 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 ℃;
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 ℃;
1H NMR (CDCl
3, 400MHz) 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 calcdfor 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 ℃;
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 (10)
1. the oxidative coupling of ferric trichloride catalytic prepares the method for phenanthrene derivative, (E)-1 that it is characterized in that 1 equivalent, 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 it is dissolved, the iron trichloride of property adding 0.02-0.40 equivalent again, the organic solvent solution that adds again the metachloroperbenzoic acid (m-CPBA) that contains the 0.5-1.5 equivalent, it is complete to be stirred to raw material reaction 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) ,-individual 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
3
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, iron trichloride and metachloroperbenzoic acid is 1: 0.02-0.40: 0.5-1.5.
3. according to synthetic method claimed in claim 1, it is characterized in that described organic solvent is toluene, benzene, dimethylbenzene, hexanaphthene, normal hexane, Skellysolve A, normal heptane, sherwood oil, gasoline, ether, tetrahydrofuran (THF), methylene dichloride, trichloromethane, tetracol phenixin, 1,2-ethylene dichloride, trifluoroacetic acid.
4. according to synthetic method claimed in claim 3, it is characterized in that best organic solvent is methylene dichloride, trichloromethane, 1, the 2-ethylene dichloride.
5. according to synthetic method claimed in claim 1, it is characterized in that best temperature of reaction is 0-20 ℃.
6. according to synthetic method claimed in claim 1, it is characterized in that the described reaction times is 0.5-12 hour.
7. according to synthetic method claimed in claim 6, it is characterized in that the best reaction times is 0.5-2 hour.
8. according to synthetic method claimed in claim 1, it is characterized in that synthetic for the phenanthrenecarboxylic acid derivative of Polymethoxylated replacement.
9. according to synthetic method claimed in claim 8, it is characterized in that being 2,3,6,7-tetramethoxy-9-phenanthrenecarboxylic acid methyl esters synthetic.
10. according to synthetic method claimed in claim 8, it is characterized in that being the synthetic of 2,3,6,7-tetramethoxy-9-phenanthrenecarboxylic acid.
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|---|---|---|---|---|
| CN101189968A (en) * | 2006-11-23 | 2008-06-04 | 南开大学 | Phenanthroindolizidine and phenanthroquinolizidine derivatives and applications of salts in pesticides |
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| CN101189968A (en) * | 2006-11-23 | 2008-06-04 | 南开大学 | Phenanthroindolizidine and phenanthroquinolizidine derivatives and applications of salts in pesticides |
Non-Patent Citations (5)
| Title |
|---|
| .2008,第64卷(第32期),7504-7510. * |
| Kai-Liang Wang等.Iron(III) chlroide-based mild wynthesis of phenanthrene and its application to total synthesis of phenanthroindolizidine alkaloids.< * |
| Kai-Liang Wang等.Iron(III) chlroide-based mild wynthesis of phenanthrene and its application to total synthesis of phenanthroindolizidine alkaloids.<TETRAHEDRON>.2008,第64卷(第32期),7504-7510. |
| TETRAHEDRON> * |
| 张育川.间氯过氧化苯甲酸.《精细与专用化学品》.2004,(第07期), * |
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Assignee: Jiangsu Lanfeng Biochemical Co., Ltd. Assignor: Nankai University Contract record no.: 2012320000742 Denomination of invention: Method for preparing ferric trichloride catalytic oxidative coupling phenanthrene derivative License type: Exclusive License Open date: 20100623 Record date: 20120607 |
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