CN102464613B - Synthetic method of quinoline derivative - Google Patents
Synthetic method of quinoline derivative Download PDFInfo
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- CN102464613B CN102464613B CN201010539144.6A CN201010539144A CN102464613B CN 102464613 B CN102464613 B CN 102464613B CN 201010539144 A CN201010539144 A CN 201010539144A CN 102464613 B CN102464613 B CN 102464613B
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Abstract
The invention provides a synthetic method of a quinoline derivative of formula (C), characterized by: using a phenyl amine compound of formula (A) and an aldehyde compound of formula (B) as raw materials, using Lewis acid or protonic acid as a catalyst, adding an organic solvent and an oxidizing agent for reaction to obtain the quinoline derivative of formula (C), wherein, n represents the number of substituent on the benzene ring, and n can be 1, 2 or 3; X represents one or more of -H, C1-C10 straight chain or branched chain alkyl, C1-C10 alkoxy, -OH, -NH2, alkoxyamino, Cl-, Br-, and -NO2, and X is at the ortho position, meta-position, or para-position of amino; and R represents C1-C18 aryl or aliphatic hydrocarbon. The synthetic method of the quinoline derivative has the advantages of low cost, low reaction temperature, fast reaction speed, short reaction time, and high yield.
Description
Technical field
The present invention relates to a kind of synthetic method of quinoline, belong to organic synthesis field.
Background technology
Quinoline and its derivates is the very important heterogeneous ring compound of a class, extensively to be present in alkaloid and to show the biological activity of highly significant, there is anti-asthma, antibacterial, antiviral, hypermnesis, hypertension, antidepressant, antianaphylaxis, anti-malarial and the effect such as antitumor.In addition, they or important fine chemical material, be widely used in medicine, dyestuff chemistry auxiliary agent, the synthesis of agricultural chemicals and the preparation of sensitive materials, also can be used as solvent and extraction agent, be applied to the industries such as plating, METAL EXTRACTION, smelting.
Up to now, occurred the synthetic method of tens of kinds of quinolines, such as traditional Doebner-Miller method, it adopts aromatic primary amine and aldehyde under concentrated hydrochloric acid exists, are total to heat to generate corresponding substd quinolines;
method, it adopts o-Aminobenzaldehyde or ketone and one to contain
the compound of structural unit is obtained by reacting 2-, 3-or 4-bit strip has substituent quinoline compound; Skraup method, it is employing aniline, the mixture of glycerine heats generation quinoline with oil of mirbane together with the vitriol oil; Meanwhile, have also appeared the synthetic method much these traditional methods improved.
The synthesis condition of various synthetic method, raw material type, reactions steps, catalyzer, solvent have very large difference, also there is various shortcoming, such as target product yield compared with low, by product is many, raw material is difficult to obtain, long reaction time, synthesis step are many, temperature of reaction is high, severe reaction conditions, catalyzer are expensive or unfriendly etc. to environment.These shortcomings all can cause the production efficiency of quinoline to decline directly or indirectly, so people are constantly seeking the synthetic method improving quinoline productive rate, Reaction time shorten.
Summary of the invention
For solving the problem, the object of the present invention is to provide a kind of synthetic method of quinoline, adopting common cheap oxygenant synthesis of quinoline derivatives under the synthesis condition of gentleness, there is reaction times short, productive rate high.
For achieving the above object, the invention provides the synthetic method of the quinoline shown in a kind of formula (C), it comprises:
With the aldehyde compound shown in the amino benzenes compounds shown in formula (A), formula (B) for raw material, with Lewis acid or protonic acid for catalyzer, add organic solvent and oxygenant and carry out the quinoline shown in the formula that is obtained by reacting (C);
Wherein, n is substituent number on phenyl ring, and n is 1,2 or 3, namely phenyl ring can have more than one substituting group, and correspondingly, X can comprise X
1, X
2and/or X
3;
X can be-H, C
1-C
10straight or branched alkyl, C
1-C
10alkoxyl group ,-OH ,-NH
2, alkoxyamino, Cl-, Br-and-NO
2in one or more, and, X (i.e. X
1, X
2and/or X
3) can at the ortho position of amino, a position and/or contraposition;
R can be aryl or the aliphatic group of C1-C18.
In above-mentioned synthetic method provided by the invention, preferably, the aldehyde compound shown in formula (B) is the alkanoic or aromatic aldehyde etc. that α carbon have hydrogen.
In above-mentioned synthetic method provided by the invention, the value of n can be 1,2 or 3, and correspondingly, the amino benzenes compounds adopted can be a substituted aniline, disubstituted benzenes amine or trisubstituted benzene amine.When amino benzenes compounds be disubstituted benzenes amine or trisubstituted benzene amine time, each substituting group can be identical or different substituting group, i.e. each substituent X (X
1, X
2and/or X
3) can be identical, also can be different.When employing one substituted aniline, substituting group can be positioned at amino any ortho position, a position or contraposition; When adopting disubstituted benzenes amine, trisubstituted benzene amine, two amino ortho positions cannot be connected with substituting group simultaneously, otherwise the compound of synthesis does not belong to quinoline.
In above-mentioned synthetic method provided by the invention, preferably, the mol ratio of above-mentioned amino benzenes compounds and aldehyde compound is 1: 1 to 1: 4, is preferably 1: 3.
In above-mentioned synthetic method provided by the invention, preferably, above-mentioned Lewis acid comprises AlCl
3, TiCl
4, ZrCl
4, LaCl
3, MoCl
5, SnCl
4, FeCl
3, MgCl
2, CuCl
2, InCl
3, IrCl
3, CeNH
4(NO
3)
4and ZnCl
2deng in the combination of one or more, described protonic acid comprises the combination of one or more in p-methyl benzenesulfonic acid, phospho-molybdic acid, sulfuric acid, hydrochloric acid, phosphoric acid and acetic acid etc.
In above-mentioned synthetic method provided by the invention, preferably, above-mentioned organic solvent comprises the combination of one or more in methylene dichloride, ethylene dichloride, trichloromethane, glycol dimethyl ether, normal hexane, tetrahydrofuran (THF), ethyl acetate and acetonitrile etc.
In above-mentioned synthetic method provided by the invention, preferably, the temperature of reaction of above-mentioned reaction is-10 DEG C to 100 DEG C, and more preferably, temperature of reaction is 20 DEG C to 40 DEG C.
In above-mentioned synthetic method provided by the invention, preferably, the reaction times of above-mentioned reaction is 0.1-10 hour, is preferably 1-5 hour.
In above-mentioned synthetic method provided by the invention, preferably, above-mentioned oxygenant comprises H
2o
2, para benzoquinone, dichloro para benzoquinone, DDQ (DDQ), oxygen, SnCl
4, TiCl
4and FeCl
3deng in the combination of one or more.
In above-mentioned synthetic method provided by the invention, preferably, the mol ratio of above-mentioned oxygenant and amino benzenes compounds is 1: 3 to 3: 1, is preferably 1: 1.
Compared with existing synthetic method, the synthetic method tool of quinoline provided by the present invention has the following advantages:
1, cost is low: synthetic method provided by the invention directly with aniline and aldehyde for raw material, the catalyzer used and oxygenant are also all more common compounds, wide material sources, and price comparison is cheap;
2, temperature of reaction is low: the temperature of reaction of synthetic method provided by the invention is relatively low, even at normal temperatures just can synthetic product, and temperature variation is little on the impact of productive rate, does not need heating constant-temperature equipment, is conducive to energy efficient, reduce costs;
3, speed of response is fast, the time is short: the speed of response of synthetic method provided by the invention, than very fast, just can have been reacted, generate high-quality quinoline in several hours;
4, productive rate is high: in the synthesis of quinoline, mostly all relate to dehydrogenation oxidation process, the present invention improves in the use of oxygenant, by adopting several frequently seen oxygenant, the generation of by product can be suppressed well, and be oxidized two (or four) hydrogen quinoline, product yield can reach more than 80%, can improve 8 to 48% than the yield of the method for routine synthesis.
Embodiment
In order to there be understanding clearly to technical characteristic of the present invention, object and beneficial effect, existing following detailed description is carried out to technical scheme of the present invention, but can not be interpreted as to of the present invention can the restriction of practical range.
Embodiment 1
Present embodiments provide the synthetic method of 3-ethyl-2-propyl group quinoline (C1), it comprises the following steps:
0.5038g (3.778mmol) aluminum chloride and 20mL methylene dichloride are uniformly mixed, after temperature remains on about 30 DEG C, add 344 μ L (3.778mmol) aniline, 1.02mL (11.334mmol) butyraldehyde-n, then 191 μ L (1.889mmol) hydrogen peroxide are added, reaction process is monitored with gas-chromatography and TLC, react 1 hour, productive rate reaches the highest.
Reaction product is through the cancellation of 0.3N ammoniacal liquor, and extracted with diethyl ether, with water, 20% saturated NaHCO
3, water and saturated common salt water washing, with ether, sherwood oil, normal hexane for eluent, after pressure reducing and steaming solvent, chromatography column is separated and obtains product C 1, and chromatogram yield is 84%, and separation yield is that 70%, MS, NMR identify structure.
The nuclear magnetic data of product C 1 (3-ethyl-2-propyl group quinoline) is:
1h NMR (CDCl
3, Me
4si): δ 1.07 (t, J=7.5Hz, 3H), 1.33 (t, J=7.5Hz, 3H), 1.77-1.87 (m, 2H), 2.83 (q, J=7.4Hz, 2H), 2.96 (t, J=7.8Hz, 2H), 7.43 (t, J=7.4Hz, 1H), 7.60 (t, J=7.7Hz, 1H), 7.71 (d, J=8.1Hz, 1H), 7.85 (s, 1H), 8.02 (d, J=8.4Hz, 1H).
13c NMR (CDCl
3me
4si): δ 14.3,14.4,22.8,25.1,37.7,125.5,126.9,127.3,128.3,128.4,133.9,135.3,146.3,162.0.
Comparative example 1
This comparative example provides the synthetic method of 3-ethyl-2-propyl group quinoline (C1), and it comprises the following steps:
0.5038g (3.778mmol) aluminum chloride and 20mL methylene dichloride are uniformly mixed, after temperature remains on about 30 DEG C, add 344 μ L (3.778mmol) aniline, 1.02mL (11.334mmol) butyraldehyde-n, do not add hydrogen peroxide, reaction process is monitored with gas-chromatography and TLC, react 3 hours, collect product.
Product is through the cancellation of 0.3N ammoniacal liquor, and extracted with diethyl ether, with water, 20% saturated NaHCO
3, water and saturated common salt water washing, with ether, sherwood oil, normal hexane for eluent, after pressure reducing and steaming solvent, chromatography column is separated and obtains product C 1, chromatogram yield 64%, and nuclear magnetic data is identical with embodiment 1.
Can find by the present embodiment and comparative example 1 are carried out contrast, add hydrogen peroxide and productive rate can be made to improve 20%, and the reaction process of the present embodiment only needs reaction just can reach the highest productive rate in 1 hour, there is larger shortening in the reaction times than comparative example 1.
Embodiment 2
Present embodiments provide the synthetic method of 3-ethyl-2-propyl group quinoline (C1), it comprises the following steps:
0.5038g (3.778mmol) aluminum chloride and 20mL dichloromethane solvent are uniformly mixed, after temperature remains on about 30 DEG C, add 344 μ L (3.778mmol) aniline, 1.02mL (11.334mmol) butyraldehyde-n, add 382 μ L (3.778mmol) hydrogen peroxide, other step is identical with comparative example 1 with reaction conditions, monitors reaction process with gas-chromatography and TLC.
Product is through the cancellation of 0.3N ammoniacal liquor, and extracted with diethyl ether, with water, 20% saturated NaHCO
3, water and saturated common salt water washing, with ether, sherwood oil, normal hexane for eluent, after pressure reducing and steaming solvent, chromatography column is separated and obtains product C 1, chromatogram yield 82%, and nuclear magnetic data is identical with embodiment 1.
Can find by the present embodiment and comparative example 1 are carried out contrast, add hydrogen peroxide and productive rate can be made to improve 18%, and the reaction process of the present embodiment only needs reaction just can reach the highest productive rate in 1 hour, there is larger shortening in the reaction times than comparative example 1.
Embodiment 3
Present embodiments provide the synthetic method of 3-ethyl-2-propyl group quinoline (C1), it comprises the following steps:
0.5038g (3.778mmol) aluminum chloride and 20mL methylene dichloride are uniformly mixed, after temperature remains on about 30 DEG C, add 344 μ L (3.778mmol) aniline, 1.02mL (11.334mmol) butyraldehyde-n, add 0.4288g (1.889mmol) DDQ (2 again, 3-bis-chloro-5,6-dicyan para benzoquinone), react 3 hours, monitor reaction process with gas-chromatography and TLC.
Product is through the cancellation of 0.3N ammoniacal liquor, and extracted with diethyl ether, with water, 20% saturated NaHCO
3, water and saturated common salt water washing, with ether, sherwood oil, normal hexane for eluent, after pressure reducing and steaming solvent, chromatography column is separated and obtains product C 1, and chromatogram yield reaches 77%, and nuclear magnetic data is identical with embodiment 1.
The products collection efficiency of the present embodiment improves 13% relative to comparative example 1.
Embodiment 4
Present embodiments provide the synthetic method of 3-ethyl-2-propyl group quinoline (C1), it comprises the following steps:
0.6498g (3.778mmol) p-methyl benzenesulfonic acid and 12mL methylene dichloride, 8mL acetonitrile are uniformly mixed, after temperature remains on about 30 DEG C, add 344 μ L (3.778mmol) aniline, 1.02mL (11.334mmol) butyraldehyde-n, add 0.4288g (1.889mmol) DDQ (2 again, chloro-5, the 6-dicyan para benzoquinone of 3-bis-), react 3 hours, collect product, monitor reaction process with gas-chromatography and TLC.
Product is through the cancellation of 0.3N ammoniacal liquor, and extracted with diethyl ether, with water, 20% saturated NaHCO
3, water and saturated common salt water washing, with ether, sherwood oil, normal hexane for eluent, after pressure reducing and steaming solvent, chromatography column is separated and obtains product C 1, and chromatogram yield reaches 76%, and nuclear magnetic data is identical with embodiment 1.
Comparative example 2
This comparative example provides the synthetic method of 3-ethyl-2-propyl group quinoline (C1), and it comprises the following steps:
0.6498g (3.778mmol) p-methyl benzenesulfonic acid and 12mL methylene dichloride, 8mL acetonitrile are uniformly mixed, after temperature remains on about 30 DEG C, add 344 μ L (3.778mmol) aniline, 1.02mL (11.334mmol) butyraldehyde-n, do not add DDQ, react 6 hours, collect product, monitor reaction process with gas-chromatography and TLC.
Product is through the cancellation of 0.3N ammoniacal liquor, and extracted with diethyl ether, with water, 20% saturated NaHCO
3, water and saturated common salt water washing, with ether, sherwood oil, normal hexane for eluent, after pressure reducing and steaming solvent, separatory after cancellation reaction, pressure reducing and steaming solvent, chromatography column is separated and obtains product C 1, and chromatogram yield reaches 51%, and nuclear magnetic data is identical with embodiment 1.
The products collection efficiency of embodiment 4 improves 25% relative to comparative example 2.
Embodiment 5
Present embodiments provide the synthetic method of 3-ethyl-2-propyl group-6-bromoquinoline (C2), it comprises the following steps:
0.5038g (3.778mmol) aluminum chloride and 20mL methylene dichloride are uniformly mixed, after temperature remains on about 30 DEG C, add 344 μ L (3.778mmol) para-bromoaniline, 1.02mL (11.334mmol) butyraldehyde-n, add 382 μ L (3.778mmol) hydrogen peroxide again, react 3 hours, collect product, monitor reaction process with gas-chromatography and TLC.
Product is through the cancellation of 0.3N ammoniacal liquor, and extracted with diethyl ether, with water, 20% saturated NaHCO
3, water and saturated common salt water washing, with ether, sherwood oil, normal hexane for eluent, after pressure reducing and steaming solvent, chromatography column is separated and obtains product C 2, and chromatogram yield reaches 67%.
The nuclear magnetic data of product C 2 (3-ethyl-2-propyl group-6-bromoquinoline) is:
1h NMR (CDCl
3, Me
4si): δ 1.06 (t, J=7.4Hz, 3H), 1.33 (t, J=7.4Hz, 3H), 1.80-1.86 (m, 2H), 2.82 (q, J=7.5Hz, 2H), 2.92 (t, J=7.8Hz, 2H), 7.64 ~ 7.67 (m, 1H), 7.74 (s, 1H), 7.85-7.87 (m, 2H).
13c NMR (CDCl
3, Me
4si): δ 14.3,14.4,22.7,25.2,37.8,119.3,128.6,129.0,130.4,131.7,132.8,136.5,145.0,162.6.
Comparative example 3
This comparative example provides the synthetic method of 3-ethyl-2-propyl group-6-bromoquinoline (C2), and it comprises the following steps:
0.5038g (3.778mmol) aluminum chloride and 20mL methylene dichloride are uniformly mixed, after temperature remains on about 30 DEG C, add 344 μ L (3.778mmol) para-bromoaniline, 1.02mL (11.334mmol) butyraldehyde-n, do not add hydrogen peroxide, react 3 hours, collect product, monitor reaction process with gas-chromatography and TLC.
Product is through the cancellation of 0.3N ammoniacal liquor, and extracted with diethyl ether, with water, 20% saturated NaHCO
3, water and saturated common salt water washing, be eluent with ether, sherwood oil, normal hexane, after pressure reducing and steaming solvent, chromatography column is separated and obtains product C 2, and chromatogram yield reaches 53%, and nuclear magnetic data is identical with embodiment 5.
The products collection efficiency of embodiment 5 improves 14% relative to comparative example 3.
Embodiment 6
Present embodiments provide the synthetic method of 3-hexyl-2-heptyl quinoline (C3), it comprises the following steps:
0.5038g (3.778mmol) aluminum chloride and 20mL methylene dichloride are uniformly mixed, after temperature remains on about 30 DEG C, add 344 μ L (3.778mmol) aniline, add n-octaldehyde 1.77mL (3.778mmol) again, add 382 μ L (3.778mmol) hydrogen peroxide again, react 1 hour, collect product, monitor reaction process with gas-chromatography and TLC.
Product is through the cancellation of 0.3N ammoniacal liquor, and extracted with diethyl ether, with water, 20% saturated NaHCO
3, water and saturated common salt water washing, with ether, sherwood oil, normal hexane for eluent, after pressure reducing and steaming solvent, chromatography column is separated and obtains product C 3, and chromatogram yield reaches 73%.
The nuclear magnetic data of product C 3 (3-hexyl-2-heptyl quinoline) is:
1h NMR (CDCl
3, Me
4si): δ 0.89-0.91 (m, 6H), 1.30-1.50 (m, 14H), 1.65-1.70 (m, 2H), 1.76-1.82 (m, 2H), 2.77 (t, J=7.9Hz, 2H), 2.97 (t, J=8.3Hz, 2H), 7.42 (t, J=7.2Hz, 1H), 7.59 (t, J=8.1Hz, 1H), 7.69 (d, J=8.3Hz, 1H), 7.82 (s, 1H), 8.02 (d, J=8.3Hz, 1H).
13c NMR (CDCl
3, Me
4si): δ 14.2,22.7,22.8,29.3,29.4,29.9,30.0,30.6,31.8,31.9,32.5,36.0,125.6,126.9,127.3,128.3,128.6,134.2,134.9,146.6,162.4.
Comparative example 4
This comparative example provides the synthetic method of 3-hexyl-2-heptyl quinoline (C3), and it comprises the following steps:
0.5038g (3.778mmol) aluminum chloride and 20mL methylene dichloride are uniformly mixed, after temperature remains on about 30 DEG C, add 344 μ L (3.778mmol) aniline, add 1.77mL (3.778mmol) n-octaldehyde again, react 3 hours, collect product, monitor reaction process with gas-chromatography and TLC.
Product is through the cancellation of 0.3N ammoniacal liquor, and extracted with diethyl ether, with water, 20% saturated NaHCO
3, water and saturated common salt water washing, with ether, sherwood oil, normal hexane for eluent, after pressure reducing and steaming solvent, chromatography column is separated and obtains product C 3, chromatogram yield reaches 53%, and nuclear magnetic data is identical with embodiment 6, and the products collection efficiency of embodiment 6 improves 20% relative to comparative example 4.
The building-up process of above-described embodiment and comparative example all can be carried out in stone Ranque tube.
Above-described specific embodiment; object of the present invention, technical scheme and beneficial effect are further described; be understood that; the foregoing is only specific embodiments of the invention; the protection domain be not intended to limit the present invention; within the spirit and principles in the present invention all, any amendment made, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (7)
1. the synthetic method of the quinoline shown in formula (C), it comprises:
With the aldehyde compound shown in the amino benzenes compounds shown in formula (A), formula (B) for raw material, with Lewis acid or protonic acid for catalyzer, add organic solvent and oxygenant and carry out the quinoline shown in the formula that is obtained by reacting (C);
Wherein, n is substituent number on phenyl ring, n=1,2 or 3;
X is-H, C
1-C
10straight or branched alkyl, C
1-C
10alkoxyl group ,-OH ,-NH
2, alkoxyamino, Cl-, Br-and-NO
2in one or more, and, X at the ortho position of amino, a position and/or contraposition;
R is C
1-C
18aryl or aliphatic group;
Wherein, described Lewis acid is AlCl
3, described protonic acid is p-methyl benzenesulfonic acid;
Described organic solvent is methylene dichloride;
Described oxygenant is H
2o
2and/or DDQ.
2. synthetic method as claimed in claim 1, wherein, the aldehyde compound shown in described formula (B) is the alkanoic or the aromatic aldehyde that α carbon have hydrogen.
3. synthetic method as claimed in claim 1, wherein, described amino benzenes compounds is disubstituted benzenes amine or trisubstituted benzene amine, and each substituting group is identical or different substituting group.
4. synthetic method as claimed in claim 1, wherein, the mol ratio of described amino benzenes compounds and described aldehyde compound is 1:1 to 1:4.
5. synthetic method as claimed in claim 1, wherein, the temperature of reaction of described reaction is-10 DEG C to 100 DEG C.
6. synthetic method as claimed in claim 1, wherein, the reaction times of described reaction is 0.1-10 hour.
7. synthetic method as claimed in claim 1, wherein, the mol ratio of described oxygenant and described amino benzenes compounds is 1:3 to 3:1.
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| CN103524408A (en) * | 2013-10-16 | 2014-01-22 | 连云港市华伦化工有限公司 | Method for preparing 7-chloroquinaldine by use of phase-transfer catalytic reaction |
| CN106543078B (en) * | 2016-07-21 | 2019-01-11 | 中国科学院兰州化学物理研究所苏州研究院 | A kind of preparation method of quinoline |
| CN107602461A (en) * | 2017-09-25 | 2018-01-19 | 青岛农业大学 | A kind of synthetic method of quinolines |
| CN117069654A (en) * | 2023-10-11 | 2023-11-17 | 湖南工程学院 | Method for synthesizing 2-methylquinoline by taking paraldehyde as raw material |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1030231A (en) * | 1987-06-06 | 1989-01-11 | Basf公司 | The preparation method of quinoline |
| CN101429157A (en) * | 2008-06-05 | 2009-05-13 | 先尼科化工（上海）有限公司 | Process for producing 2-methyl-8-nitryl quinoline |
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2010
- 2010-11-10 CN CN201010539144.6A patent/CN102464613B/en active Active
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1030231A (en) * | 1987-06-06 | 1989-01-11 | Basf公司 | The preparation method of quinoline |
| CN101429157A (en) * | 2008-06-05 | 2009-05-13 | 先尼科化工（上海）有限公司 | Process for producing 2-methyl-8-nitryl quinoline |
Non-Patent Citations (3)
| Title |
|---|
| Catalytic Activity of Iron(III), Aluminum(III),Cobalt(II), and Magnesium(II) Chloride Crystal Hydrates in the Condensation of Aniline with Butyraldehyde;R. G. Bulgakov,et al.;《RUSSIAN JOURNAL OF ORGANIC CHEMISTRY》;20091231;956-957 * |
| LnCl3 · 6H2O Crystal Hydrates as Highly Effective Catalysts in the Synthesis of Alkyl-Substituted Quinolines and Phenanthrolines;R. G. Bulgakov,et al.;《Russian Journal of Organic Chemistry》;20061231;1583-1584 * |
| Practical and Simple Synthesis of Substituted Quinolines by an HCl-DMSO System on a Large Scale: Remarkable Effect of the Chloride Ion;Shin-ya Tanaka,et al.;《J. Org. Chem.》;20051202;800-803 * |
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