CN103214491B - The preparation method of [2,7,12,18-tetramethyl--3,8-diethyl-13,17-dicarboxyethyl]-porphyrin - Google Patents
The preparation method of [2,7,12,18-tetramethyl--3,8-diethyl-13,17-dicarboxyethyl]-porphyrin Download PDFInfo
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Abstract
The present invention relates to [2,7,12,18-tetramethyl--3,8-diethyl-13,17-dicarboxyethyl] preparation method of-porphyrin, realize according to following synthetic method: be dissolved in by protohemine in acids solvent, under 90 ~ 140 DEG C of conditions, gradation is reacted after the reducing metal of quality such as adding.Question response terminates rear cooling, filters, and filtrate is collected in washing, regulates pH, leaves standstill a few hours, collected by filtration, and washing is dried, by thick product recrystallization, obtained [2,7,12,18-tetramethyl--3,8-diethyl-13,17-dicarboxyethyl]-porphyrin.The present invention compared with prior art, its remarkable advantage: (<b>1</bGreatT.Gr eaT.GT) scheme of the present invention cheaper starting materials used is easy to get, avoid the use of noble metal catalyst, preparation cost reduces greatly; (<b>2</bGreatT.Gr eaT.GT) scheme method step of the present invention is simple, a step is only needed to synthesize target product, the product loss can effectively avoiding step increase to cause, substantially increases the yield of target product; (<b>3</bGreatT.Gr eaT.GT) experimental program operational safety of the present invention, aftertreatment is easy, is applicable to carrying out multiple batches of, production in enormous quantities.
Description
Technical field
The invention belongs to organic synthesis field, particularly the preparation method of [2,7,12,18-tetramethyl--3,8-diethyl-13,17-dicarboxyethyl]-porphyrin (also known as a porphyrin).
Background technology
The chemical structural formula of [2,7,12,18-tetramethyl--3,8-diethyl-13,17-dicarboxyethyl]-porphyrin is as follows:
Porphyrin is the organic compound of the important 18 pi-conjugated structures of a class, as common a kind of bionic enzyme model, has been widely used in multiple fields such as medical science, biological chemistry, materials chemistry and medical science.Two ethyl deuteroporphyrin due to its stable physical and chemical performance more close with natural bionic enzyme model active center, become the first-selection at metalloporphyrin bionic catalysis applied research center, obtain the extensive concern of vast chemist in recent years.
1934, Fischer proposed the synthetic method of two ethyl deuteroporphyrin first, and with protohemine and formic acid for raw material, adopt palladium metal as catalyzer, under high temperature, shortening has synthesized two ethyl deuteroporphyrin.But what obtained by the method is not single product, and target product productive rate is very low.Baker etc. improve this method, take PtO2 as catalyzer, and to the two ethyl deuteroporphyrin of Catalysis by Hemin hydrogenation synthesis under alkaline normal temperature condition, productive rate reaches 80%.But this method long reaction time (more than 20h), post-processing operation complexity is loaded down with trivial details.Above-mentioned synthetic method is all based on shortening method, and catalyzer is expensive, often needs to adopt high temperature or condition of high voltage in experiment, and post-processing operation is complicated, and the hydrogen used in reaction is flammable explosive gas.In order to find two synthetic route that ethyl deuteroporphyrin derivates cost is low, experimental implementation is simple, reaction conditions is gentle, this seminar was once raw material with protohemine, through deferrization, esterification, added metal and at CoCl
2-NaBH
4the two ethyl deuteroporphyrin dimethyl ester of metalloporphyrin autocatalysis hydrogenation synthesis is passed through in system.But prepare two ethyl deuteroporphyrin with two ethyl deuteroporphyrin dimethyl ester, obviously unreasonable.
Summary of the invention
The object of the present invention is to provide the preparation method of [2,7,12,18-tetramethyl--3,8-diethyl-13,17-dicarboxyethyl]-porphyrin that a kind of cost is low, experimental implementation is simple, reaction conditions is gentle.
The technical solution realizing the object of the invention is:
The preparation method of [2,7,12,18-tetramethyl--3,8-diethyl-13,17-dicarboxyethyl]-porphyrin, realizes according to following synthetic method:
Be dissolved in by protohemine in acids solvent, gradation is reacted after the reducing metal of quality such as adding; Question response terminates rear cooling, filters, acids solvent wash, collects filtrate, regulates pH, leaves standstill, collected by filtration, distilled water wash, dries, by thick product recrystallization, obtains [2,7,12,18-tetramethyl--3,8-diethyl-13,17-dicarboxyethyl]-porphyrin.
Wherein, acids solvent is one or more in formic acid, acetic acid, dilute sulphuric acid; Temperature of reaction is 90 ~ 140 DEG C, and the reaction times is 1 ~ 4h; Filtrate pH to 4 ~ 5 are regulated with basic solution; Reducing metal is any one in sodium powder, magnesium powder, aluminium powder, iron powder, glass putty; The mol ratio of protohemine and metal is 1:3 ~ 15; Recrystallization solvent selects acetone, ethanol or methyl alcohol.
The present invention compared with prior art, its remarkable advantage:
(1) cheaper starting materials that scheme of the present invention is used is easy to get, and avoid the use of noble metal catalyst, preparation cost reduces greatly;
(2) scheme method step of the present invention is simple, and only need a step to synthesize target product, the product loss can effectively avoiding step increase to cause, substantially increases the yield of target product;
(3) experimental program operational safety of the present invention, aftertreatment is easy, is applicable to carrying out multiple batches of, production in enormous quantities.
Below in conjunction with accompanying drawing, the present invention is described in further detail.
Accompanying drawing explanation
Preparation technology's schema of Fig. 1 [2,7,12,18-tetramethyl--3,8-diethyl-13,17-dicarboxyethyl]-porphyrin;
The hydrogen nuclear magnetic resonance spectrogram of Fig. 2 [2,7,12,18-tetramethyl--3,8-diethyl-13,17-dicarboxyethyl]-porphyrin;
The mass spectrum of Fig. 3 [2,7,12,18-tetramethyl--3,8-diethyl-13,17-dicarboxyethyl]-porphyrin;
The infrared spectrum of Fig. 4 [2,7,12,18-tetramethyl--3,8-diethyl-13,17-dicarboxyethyl]-porphyrin.
Embodiment
The following examples can make the present invention of those skilled in the art comprehend, but do not limit the present invention in any way.
The preparation method of [2,7,12,18-tetramethyl--3,8-diethyl-13,17-dicarboxyethyl]-porphyrin, realizes according to following synthetic method:
Be dissolved in by protohemine in acids solvent, gradation is reacted after the reducing metal of quality such as adding; Question response terminates rear cooling, filters, acids solvent wash, collects filtrate, regulates pH, leaves standstill, collected by filtration, distilled water wash, dries, by thick product recrystallization, obtains [2,7,12,18-tetramethyl--3,8-diethyl-13,17-dicarboxyethyl]-porphyrin.
Wherein, acids solvent is one or more in formic acid, acetic acid, dilute sulphuric acid; Temperature of reaction is 90 ~ 140 DEG C, and the reaction times is 1 ~ 4h; Filtrate pH to 4 ~ 5 are regulated with basic solution; Reducing metal is any one in sodium powder, magnesium powder, aluminium powder, iron powder, glass putty; The mol ratio of protohemine and metal is 1:3 ~ 15; Recrystallization solvent selects acetone, ethanol or methyl alcohol.
Embodiment 1: in there-necked flask, adds 1g protohemine respectively, and 30mL formic acid is heated to 100 DEG C under oil bath condition, divides and add 0.909g reduced iron powder 3 times in 15min, reaction 4h.Question response terminates rear cooling, filters, washs 3 times with formic acid, collect filtrate, in filtrate, slowly drip sodium hydroxide solution regulation system pH=4 ~ 5 of 6mol/L, leave standstill a few hours, collected by filtration, with distilled water wash, is placed in baking oven and dries, product acetone recrystallization, obtains [2,7,12,18-tetramethyl--3,8-diethyl-13,17-dicarboxyethyl]-porphyrin, productive rate is 53.3%.Its nuclear-magnetism characterization data is as follows:
1hNMR (500MHz, DMSO-d6), δ: 12.24 (s, 2H, 13-, 17-COOH), 10.29 (s, 1H, 20-H), 10.22 (s, 1H, 5-H), 10.20 (s, 1H, 15-H), 10.19 (s, 1H, 10-H), 4.36 (t, 4H, J
hH=7.5Hz, 13-, 17-β-CH
2, α tocarbonyl), 4.12,4.10 (2q, 4H, J
hH=7.5Hz, 3,8-CH
2cH
3), 3.65,3.64,3.63 (3s, 12H, 2-, 7-, 12-, 18-CH
3), 3.20 (t, 4H, J
hH=7.5Hz, 13-, 17-α-CH
2, α tocarbonyl), 1.81 (t, 6H, J
hH=7.5Hz, 3,8-CH
2cH
3) ,-4.00 (s, 2H, NH).
Embodiment 2: in there-necked flask, adds 1g protohemine respectively, and 30mL acetic acid is heated to 100 DEG C under oil bath condition, divides and add 0.909g reduced iron powder 3 times in 15min, reaction 4h.Question response terminates rear cooling, filters, washs 3 times with acetic acid, collect filtrate, in filtrate, slowly drip sodium hydroxide solution regulation system pH=4 ~ 5 of 6mol/L, leave standstill a few hours, collected by filtration, with distilled water wash, is placed in baking oven and dries, product acetone recrystallization, obtains [2,7,12,18-tetramethyl--3,8-diethyl-13,17-dicarboxyethyl]-porphyrin, productive rate is 31.9%.
Embodiment 3: in there-necked flask, adds 1g protohemine respectively, and 30mL dilute sulphuric acid is heated to 100 DEG C under oil bath condition, divides and add 0.909g reduced iron powder 3 times in 15min, reaction 4h.Question response terminates rear cooling, filters, washs 3 times with dilute sulphuric acid, collect filtrate, in filtrate, slowly drip sodium hydroxide solution regulation system pH=4 ~ 5 of 6mol/L, leave standstill a few hours, collected by filtration, with distilled water wash, is placed in baking oven and dries, product acetone recrystallization, obtains [2,7,12,18-tetramethyl--3,8-diethyl-13,17-dicarboxyethyl]-porphyrin, productive rate is 11.6%.
Embodiment 4: in there-necked flask, adds 1g protohemine respectively, and 30mL formic acid and acetic acid mixed solvent, be heated to 100 DEG C under oil bath condition, divides and add 0.909g reduced iron powder 3 times in 15min, reaction 4h.Question response terminates rear cooling, filters, washs 3 times with dilute sulphuric acid, collect filtrate, in filtrate, slowly drip sodium hydroxide solution regulation system pH=4 ~ 5 of 6mol/L, leave standstill a few hours, collected by filtration, with distilled water wash, is placed in baking oven and dries, product acetone recrystallization, obtains [2,7,12,18-tetramethyl--3,8-diethyl-13,17-dicarboxyethyl]-porphyrin, productive rate is 27.8%.
Embodiment 5: in there-necked flask, adds 1g protohemine respectively, and 30mL formic acid is heated to 100 DEG C under oil bath condition, divides and adds 0.390g reduction magnesium powder for 3 times, reaction 4h in 15min.Question response terminates rear cooling, filters, washs 3 times with formic acid, collect filtrate, in filtrate, slowly drip sodium hydroxide solution regulation system pH=4 ~ 5 of 6mol/L, leave standstill a few hours, collected by filtration, with distilled water wash, is placed in baking oven and dries, product acetone recrystallization, obtains [2,7,12,18-tetramethyl--3,8-diethyl-13,17-dicarboxyethyl]-porphyrin, productive rate is 11.2%.
Embodiment 6: in there-necked flask, adds 1g protohemine respectively, and 30mL formic acid is heated to 100 DEG C under oil bath condition, divides and adds 0.438g reduction aluminium powder for 3 times, reaction 4h in 15min.Question response terminates rear cooling, filters, washs 3 times with formic acid, collect filtrate, in filtrate, slowly drip sodium hydroxide solution regulation system pH=4 ~ 5 of 6mol/L, leave standstill a few hours, collected by filtration, with distilled water wash, is placed in baking oven and dries, product with methylalcohol recrystallization, obtains [2,7,12,18-tetramethyl--3,8-diethyl-13,17-dicarboxyethyl]-porphyrin, productive rate is 9.6%.
Embodiment 7: in there-necked flask, adds 1g protohemine respectively, and 30mL formic acid is heated to 100 DEG C under oil bath condition, divides and add 1.055g reduction zinc powder 3 times in 15min, reaction 4h.Question response terminates rear cooling, filters, washs 3 times with formic acid, collect filtrate, in filtrate, slowly drip sodium hydroxide solution regulation system pH=4 ~ 5 of 6mol/L, leave standstill a few hours, collected by filtration, with distilled water wash, is placed in baking oven and dries, product acetone recrystallization, obtains [2,7,12,18-tetramethyl--3,8-diethyl-13,17-dicarboxyethyl]-porphyrin, productive rate is 7.9%.
Embodiment 8: in there-necked flask, adds 1g protohemine respectively, and 30mL formic acid is heated to 100 DEG C under oil bath condition, adds 1.932g reduction glass putty, reaction 4h in 15min in batches.Question response terminates rear cooling, filters, washs 3 times with formic acid, collect filtrate, in filtrate, slowly drip sodium hydroxide solution regulation system pH=4 ~ 5 of 6mol/L, leave standstill a few hours, collected by filtration, with distilled water wash, is placed in baking oven and dries, product acetone recrystallization, obtains [2,7,12,18-tetramethyl--3,8-diethyl-13,17-dicarboxyethyl]-porphyrin, productive rate is 10.7%.
Embodiment 9: in there-necked flask, adds 1g protohemine respectively, and 30mL formic acid is heated to 90 DEG C under oil bath condition, in 15min, add 0.909g reduced iron powder in batches, reaction 4h.Question response terminates rear cooling, filters, washs 3 times with formic acid, collect filtrate, in filtrate, slowly drip sodium hydroxide solution regulation system pH=4 ~ 5 of 6mol/L, leave standstill a few hours, collected by filtration, with distilled water wash, is placed in baking oven and dries, product acetone recrystallization, obtains [2,7,12,18-tetramethyl--3,8-diethyl-13,17-dicarboxyethyl]-porphyrin, productive rate is 39.7%.
Embodiment 10: in there-necked flask, adds 1g protohemine respectively, and 30mL formic acid is heated to 110 DEG C under oil bath condition, in 15min, add 0.909g reduced iron powder in batches, reaction 4h.Question response terminates rear cooling, filters, washs 3 times with formic acid, collect filtrate, in filtrate, slowly drip sodium hydroxide solution regulation system pH=4 ~ 5 of 6mol/L, leave standstill a few hours, collected by filtration, with distilled water wash, is placed in baking oven and dries, product acetone recrystallization, obtains [2,7,12,18-tetramethyl--3,8-diethyl-13,17-dicarboxyethyl]-porphyrin, productive rate is 62.3%.
Embodiment 11: in there-necked flask, adds 1g protohemine respectively, and 30mL formic acid is heated to 120 DEG C under oil bath condition, in 15min, add 0.909g reduced iron powder in batches, reaction 4h.Question response terminates rear cooling, filters, washs 3 times with formic acid, collect filtrate, in filtrate, slowly drip sodium hydroxide solution regulation system pH=4 ~ 5 of 6mol/L, leave standstill a few hours, collected by filtration, with distilled water wash, is placed in baking oven and dries, product acetone recrystallization, obtains [2,7,12,18-tetramethyl--3,8-diethyl-13,17-dicarboxyethyl]-porphyrin, productive rate is 80.2%.
Embodiment 12: in there-necked flask, adds 1g protohemine respectively, and 30mL formic acid is heated to 130 DEG C under oil bath condition, in 15min, add 0.909g reduced iron powder in batches, reaction 4h.Question response terminates rear cooling, filters, washs 3 times with formic acid, collect filtrate, in filtrate, slowly drip sodium hydroxide solution regulation system pH=4 ~ 5 of 6mol/L, leave standstill a few hours, collected by filtration, with distilled water wash, is placed in baking oven and dries, product acetone recrystallization, obtains [2,7,12,18-tetramethyl--3,8-diethyl-13,17-dicarboxyethyl]-porphyrin, productive rate is 71.5%.
Embodiment 13: in there-necked flask, adds 1g protohemine respectively, and 30mL formic acid is heated to 140 DEG C under oil bath condition, in 15min, add 0.909g reduced iron powder in batches, reaction 4h.Question response terminates rear cooling, filters, washs 3 times with formic acid, collect filtrate, in filtrate, slowly drip sodium hydroxide solution regulation system pH=4 ~ 5 of 6mol/L, leave standstill a few hours, collected by filtration, with distilled water wash, is placed in baking oven and dries, product acetone recrystallization, obtains [2,7,12,18-tetramethyl--3,8-diethyl-13,17-dicarboxyethyl]-porphyrin, productive rate is 66.9%.
Embodiment 14: in there-necked flask, adds 1g protohemine respectively, and 30mL formic acid is heated to 120 DEG C under oil bath condition, in 15min, add 0.909g reduced iron powder in batches, reaction 1h.Question response terminates rear cooling, filters, washs 3 times with formic acid, collect filtrate, in filtrate, slowly drip sodium hydroxide solution regulation system pH=4 ~ 5 of 6mol/L, leave standstill a few hours, collected by filtration, with distilled water wash, is placed in baking oven and dries, product acetone recrystallization, obtains [2,7,12,18-tetramethyl--3,8-diethyl-13,17-dicarboxyethyl]-porphyrin, productive rate is 62.4%.
Embodiment 15: in there-necked flask, adds 1g protohemine respectively, and 30mL formic acid is heated to 120 DEG C under oil bath condition, in 15min, add 0.909g reduced iron powder in batches, reaction 2h.Question response terminates rear cooling, filters, washs 3 times with formic acid, collect filtrate, in filtrate, slowly drip sodium hydroxide solution regulation system pH=4 ~ 5 of 6mol/L, leave standstill a few hours, collected by filtration, with distilled water wash, is placed in baking oven and dries, product acetone recrystallization, obtains [2,7,12,18-tetramethyl--3,8-diethyl-13,17-dicarboxyethyl]-porphyrin, productive rate is 83.3%.
Embodiment 16: in there-necked flask, adds 1g protohemine respectively, and 30mL formic acid is heated to 120 DEG C under oil bath condition, in 15min, add 0.909g reduced iron powder in batches, reaction 3h.Question response terminates rear cooling, filters, washs 3 times with formic acid, collect filtrate, in filtrate, slowly drip sodium hydroxide solution regulation system pH=4 ~ 5 of 6mol/L, leave standstill a few hours, collected by filtration, with distilled water wash, is placed in baking oven and dries, product acetone recrystallization, obtains [2,7,12,18-tetramethyl--3,8-diethyl-13,17-dicarboxyethyl]-porphyrin, productive rate is 67.4%.
Embodiment 17: in there-necked flask, adds 1g protohemine respectively, and 30mL dilute sulphuric acid is heated to 120 DEG C under oil bath condition, in 15min, add 0.273g reduced iron powder in batches, reaction 2h.Question response terminates rear cooling, filters, washs 3 times with formic acid, collect filtrate, in filtrate, slowly drip sodium hydroxide solution regulation system pH=4 ~ 5 of 6mol/L, leave standstill a few hours, collected by filtration, with distilled water wash, is placed in baking oven and dries, product acetone recrystallization, obtains [2,7,12,18-tetramethyl--3,8-diethyl-13,17-dicarboxyethyl]-porphyrin, productive rate is 6.8%.
Embodiment 18: in there-necked flask, adds 1g protohemine respectively, and 30mL formic acid and dilute sulphuric acid are heated to 120 DEG C under oil bath condition, in 15min, add 0.456g reduced iron powder in batches, reaction 2h.Question response terminates rear cooling, filters, washs 3 times with formic acid, collect filtrate, in filtrate, slowly drip sodium hydroxide solution regulation system pH=4 ~ 5 of 6mol/L, leave standstill a few hours, collected by filtration, with distilled water wash, is placed in baking oven and dries, product acetone recrystallization, obtains [2,7,12,18-tetramethyl--3,8-diethyl-13,17-dicarboxyethyl]-porphyrin, productive rate is 12.7%.
Embodiment 19: in there-necked flask, adds 1g protohemine respectively, and 30mL acetic acid and dilute sulphuric acid are heated to 120 DEG C under oil bath condition, in 15min, add 1.364g reduced iron powder in batches, reaction 2h.Question response terminates rear cooling, filters, washs 3 times with formic acid, collect filtrate, in filtrate, slowly drip sodium hydroxide solution regulation system pH=4 ~ 5 of 6mol/L, leave standstill a few hours, collected by filtration, with distilled water wash, is placed in baking oven and dries, product ethyl alcohol recrystallization, obtains [2,7,12,18-tetramethyl--3,8-diethyl-13,17-dicarboxyethyl]-porphyrin, productive rate is 82.1%.
Embodiment 20: in there-necked flask, adds 1g protohemine respectively, and 30mL formic acid, acetic acid and dilute sulphuric acid are heated to 120 DEG C under oil bath condition, in 15min, add 1.364g reduced iron powder in batches, reaction 2h.Question response terminates rear cooling, filters, washs 3 times with formic acid, collect filtrate, in filtrate, slowly drip potassium hydroxide solution regulation system pH=4 ~ 5 of 6mol/L, leave standstill a few hours, collected by filtration, with distilled water wash, is placed in baking oven and dries, product ethyl alcohol recrystallization, obtains [2,7,12,18-tetramethyl--3,8-diethyl-13,17-dicarboxyethyl]-porphyrin, productive rate is 96.9%.
Embodiment 21: in there-necked flask, adds 1g protohemine respectively, and 30mL formic acid is heated to 120 DEG C under oil bath condition, in 15min, add 1.364g reduced iron powder in batches, reaction 2h.Question response terminates rear cooling, filters, washs 3 times with formic acid, collect filtrate, in filtrate, slowly drip sodium hydroxide solution regulation system pH=4 ~ 5 of 6mol/L, leave standstill a few hours, collected by filtration, with distilled water wash, is placed in baking oven and dries, product acetone recrystallization, obtains [2,7,12,18-tetramethyl--3,8-diethyl-13,17-dicarboxyethyl]-porphyrin, productive rate is 97.6%.
Claims (5)
1. the preparation method of [2,7,12,18-tetramethyl--3,8-diethyl-13,17-dicarboxyethyl]-porphyrin, is characterized in that, realize according to following synthetic method:
Be dissolved in by protohemine in acids solvent, gradation is reacted after the reducing metal of quality such as adding at 90 ~ 140 DEG C; Question response terminates rear cooling, filters, acids solvent wash, collects filtrate, regulates pH, leaves standstill, collected by filtration, distilled water wash, dries, by thick product recrystallization, obtains [2,7,12,18-tetramethyl--3,8-diethyl-13,17-dicarboxyethyl]-porphyrin; Wherein, one or more in described acids solvent formic acid, acetic acid, dilute sulphuric acid; Reducing metal is any one in sodium powder, magnesium powder, aluminium powder, iron powder, glass putty.
2. the preparation method of [2,7,12,18-tetramethyl--3,8-diethyl-13,17-dicarboxyethyl]-porphyrin according to claim 1, the reaction times is 1 ~ 4h.
3. the preparation method of [2,7,12,18-tetramethyl--3,8-diethyl-13,17-dicarboxyethyl]-porphyrin according to claim 1, regulates filtrate pH to 4 ~ 5 with basic solution.
4. the preparation method of [2,7,12,18-tetramethyl--3,8-diethyl-13,17-dicarboxyethyl]-porphyrin according to claim 1, the mol ratio of protohemine and metal is 1:3 ~ 15.
5. the preparation method of [2,7,12,18-tetramethyl--3,8-diethyl-13,17-dicarboxyethyl]-porphyrin according to claim 1, recrystallization solvent selects acetone, ethanol or methyl alcohol.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080280934A1 (en) * | 2003-12-18 | 2008-11-13 | Johannis Lugtenburg | Method of Preparing Porphyrin Derivatives, Porphyrin Derivatives, Uses Thereof and Pharmaceutical Compositions |
| CN101573122A (en) * | 2006-10-04 | 2009-11-04 | 婴儿护理药品公司 | High-purity large-scale preparation of stannsoporfin |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080280934A1 (en) * | 2003-12-18 | 2008-11-13 | Johannis Lugtenburg | Method of Preparing Porphyrin Derivatives, Porphyrin Derivatives, Uses Thereof and Pharmaceutical Compositions |
| CN101573122A (en) * | 2006-10-04 | 2009-11-04 | 婴儿护理药品公司 | High-purity large-scale preparation of stannsoporfin |
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| 卟啉还原合成二氢卟吩及其光生物活性研究;方勇;《中国激光医学杂志》;20010531;第10卷(第2期);第83页左栏最后一段 * |
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