CN104230797A - Preparation method of quinolone, isoquinoline and methylquinolines - Google Patents
Preparation method of quinolone, isoquinoline and methylquinolines Download PDFInfo
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- CN104230797A CN104230797A CN201410416474.4A CN201410416474A CN104230797A CN 104230797 A CN104230797 A CN 104230797A CN 201410416474 A CN201410416474 A CN 201410416474A CN 104230797 A CN104230797 A CN 104230797A
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- toluquinoline
- quinoline
- inclusion compound
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
- C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
- C07D215/04—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to the ring carbon atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
- C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D217/00—Heterocyclic compounds containing isoquinoline or hydrogenated isoquinoline ring systems
- C07D217/02—Heterocyclic compounds containing isoquinoline or hydrogenated isoquinoline ring systems with only hydrogen atoms or radicals containing only carbon and hydrogen atoms, directly attached to carbon atoms of the nitrogen-containing ring; Alkylene-bis-isoquinolines
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Abstract
The invention discloses a preparation method of quinolone, isoquinoline and methylquinolines, aiming to be short in process flow and low in cost. The preparation method comprises the following steps: placing rectified residual liquor obtained from extraction of quinolone into a urea coronary inclusion complex, and carrying quinolone and isoquinoline in a solution into the urea coronary inclusion complex according to molecule sizes; according to difference of crystallization points, separating the quinolone from isoquinoline; separating multiple solid-phase monomethylquinolone from a liquid-state mixed solvent; placing the separated multiple solid-phase monomethylquinoline and solid-phase 2,4-dimethylquinoline into a thiourea water solution for dipping to form a thiourea coronary inclusion complex; spraying anhydrous methanol, propanol, butanone and pentanone mixed solvent through a peristaltic pump; crystalizing 2,4-dimethylquinolone dissolved in the mixed solvent, separating from other trace polymethylquinolone impurities, and refining to obtain 2,4-dimethylquinoline products; and according to the difference of crystallization points, placing the thiourea coronary inclusion complex into a crystallization kettle for heating and separation.
Description
Technical field
The invention belongs to petrochemical industry, be specifically related to the preparation method of a kind of quinoline, isoquinoline 99.9 and multiple toluquinoline.
Background technology
Coal tar is the main source of China's quinoline, isoquinoline 99.9 and multiple toluquinoline.In the last few years, on medicine industry, the newtype drug of quinoline, isoquinoline 99.9 and multiple toluquinoline was increasingly developed out.From initial antimalarial agent to local anesthetic, from antibacterium, antifungal drug to antitumor, infection medicine; Agriculturally from weedicide to sterilant, sterilant, not only effectively and toxicity and residual lower.In addition, quinoline, isoquinoline 99.9 and toluquinoline or rubber anti-ageing agent, photosensitive agent, anticorrosive metal agent etc., of many uses.But in isoquinoline 99.9 raffinate, extract quinoline and multiple toluquinoline, obtain simultaneously quinoline, isoquinoline 99.9 product Method and process very limited, major cause is that physicochemical property is too close.Such as: the boiling point of 2-toluquinoline and 8-toluquinoline only differs from 0.5 DEG C, the boiling point of isoquinoline 99.9 and 8-toluquinoline also only differs from 5 DEG C, is difficult to by rectification method in addition separation and Extraction.And 6-toluquinoline fusing point-22 DEG C, 2-toluquinoline fusing point-2 DEG C, the proximity of the fusing point-8 DEG C of quinoline, 3-toluquinoline fusing point 15 DEG C, 4-toluquinoline fusing point 9-10 DEG C disturbs again freezing and crystallizing partition method.Therefore, species abundance in Baosteel in Shanghai chemical company once adopted rectification method separating quinoline, isoquinoline 99.9 (Zhou Xiaping, Wang Delong, He Yanqing, Wang great Fang, Wang Weiguo, Lv Miao, Zhang Haiping, Zhou Jie, Li Naimin. the separation of isoquinoline and its homologue. process engineering journal 2003(3)); Anshan iron and steel plant chemical general factory adopts mineral acid addition crystallization process, the physicochemical property distinguishing isoquinoline 99.9 and toluquinoline obtain 2-toluquinoline (Li Jian, Zhang Xianqiang, Hao Ying. from isoquinoline 99.9 still slag, extract 2 toluquinolines, fuel and chemical industry, 2002,33 (2): 99); Shanghai Xinming High-tech. Development Co., Ltd., adopts Steppecd crystallization purifying isoquinoline (granted patent 200910200498.5).Shanghai Xumin Chemical Technology Development Co., Ltd. adopts urea adduct method to be separated and obtains 2-toluquinoline (application number 201110332077.5), adopt solvent and reaction-crystallization method be separated 1-toluquinoline (application for a patent for invention number 201110332052.5).A kind of method (application number 201110190801.5) extracting high-purity 4-methylquinoline, solvent distillation is adopted to extract 6-toluquinoline (application number 201310044393.1) and 8-toluquinoline (application number 201310044468.6) with sulfuric acid reaction crystallization process, but many toluquinoline extraction process long flow paths, easily produce waste acid water.
Summary of the invention
The present invention seeks to the deficiency overcoming above-mentioned prior art, the preparation method of quinoline, isoquinoline 99.9 and the multiple toluquinoline that a kind of technical process is short, cost is lower, products therefrom quality is high is provided.
The present invention carries out according to the following steps:
(1) by extract the distillation residual liquid after quinoline be placed in temperature 10-26 DEG C, the aqueous solution of urea of mass concentration 2-15%, soak 0.5-3.5h, form the crown inclusion compound of urea of <500pm, according to molecular scale, the quinoline in solution, isoquinoline 99.9 are brought in the crown inclusion compound of urea, and 2,4-dimethyl quinolines of multiple monomethyl quinoline and two side chain are stayed urea clathration beyond the region of objective existence; Adopt the peristaltic pump of flow velocity 0.004-0.04ml/s, be that 1:0.3:0.6:0.1 sprays methyl alcohol, propyl alcohol, butanone, pentanone four kinds without water mixed solvent to crown inclusion compound according to methyl alcohol, propyl alcohol, butanone, pentanone mass ratio, the liquid-solid mass ratio of crown inclusion compound is made to be 3-5:0.5-1.5, according to the difference of quinoline, isoquinoline 99.9 inclusion compound and multiple toluquinoline solubleness in methyl alcohol, propyl alcohol, butanone, pentanone mixture solvent, the quinoline stayed in inclusion compound, isoquinoline 99.9 solid phase and many toluquinolines liquid phase of being dissolved in mixed solvent are separated;
(2) the ctystallizing point difference of foundation quinoline and isoquinoline 99.9, put by crown for urea inclusion compound and be heated to 26 DEG C in a kettle., isoquinoline 99.9 is solid-state, quality purity >99%, and quinoline feed circuit got back to by the remaining quinoline be in a liquid state; Quinoline ctystallizing point is-12, and isoquinoline 99.9 ctystallizing point is 26 DEG C;
(3) the multiple monomethyl quinoline and 2 in mixed solvent will be dissolved in, 4-dimethyl quinoline liquid phase freezing 2-5h at 5-10 DEG C, multiple monomethyl quinoline and 2 outside the crown inclusion compound of Separation of Urea, 4-dimethyl quinoline and mixed solvent, by the difference of ctystallizing point, the multiple monomethyl quinoline of solid phase and 2,4-dimethyl quinoline are separated with the mixed solvent of liquid state;
(4) isolated multiple monomethyl quinoline and 2,4-dimethyl quinoline solid phase are placed in temperature 10-25 DEG C, the thiourea solution of mass concentration 1-10%, soak 0.5-3.5h, form the crown inclusion compound of thiocarbamide of <700pm; According to molecular scale by 2 in solution, 3,4,6-toluquinoline brings in the crown inclusion compound of thiocarbamide, and stayed by 2 of two side chain, 4-dimethyl quinolines outside the crown inclusion compound of thiocarbamide, make 2,3,4,6 four kind of monomethyl quinoline and 2,4-dimethyl quinoline be separated;
(5) peristaltic pump of flow velocity 0.004-0.04ml/s is adopted, be that 2:0.7:0.8:0.5 sprays methyl alcohol, propyl alcohol, butanone, pentanone four kinds without water mixed solvent to crown inclusion compound according to methyl alcohol, propyl alcohol, butanone, pentanone mass ratio, make inclusion compound liquid-solid ratio be 6-2:1-5; According to 2,3,4, the difference of 6-toluquinoline and 2,4-dimethyl quinoline solubleness in a solvent ,-10 ~ 0 DEG C by stay 2 in the crown inclusion compound of thiocarbamide, 3,4,6-toluquinoline solid phase be dissolved in 2,4-dimethyl quinoline liquid phases in mixed solvent and separate; ;
(6) be dissolved in 2 in mixed solvent, 4-dimethyl quinoline refrigerate 3-6h crystallization at 0-5 DEG C, separate with other the micro-many toluquinolines impurity be dissolved in methyl alcohol, propyl alcohol, butanone, pentanone mixed solvent, be refined into 2,4-dimethyl quinoline product;
(7) according to the difference of ctystallizing point, crown for thiocarbamide inclusion compound is placed in crystallization kettle, and temperature controls after 0-10 DEG C, 3-6h, 3-toluquinoline and 4-toluquinoline are solid phase, are separated with 2-toluquinoline and the 6-toluquinoline (boiling point 257.4-259 ° C) of liquid phase; Again the 3-toluquinoline of solid phase and 4-toluquinoline are placed in crystallization kettle, improve Tc to 10 DEG C, by 3-toluquinoline (fusing point 15 DEG C) and 4-toluquinoline (fusing point 9-10 DEG C) separating-purifying; 2-toluquinoline and 6-toluquinoline mixing solutions are improved temperature to 248 DEG C, utilizes boiling point difference to be separated with 6-toluquinoline by 2-toluquinoline.
Contain in distillation residual liquid after described extraction quinoline: quinoline 0.32-0.57Wt%, isoquinoline 99.9 70.33-78.80Wt%, 2,3,4,6-toluquinoline altogether 11.22-21.85Wt%, 2,4-dimethyl quinoline 5.18-7.55Wt%; Described 2,3,4,6-toluquinoline is: 2-toluquinoline, 3-toluquinoline, 4-toluquinoline and 6-toluquinoline.Described isoquinoline 99.9 ctystallizing point is 26 DEG C, and quinoline ctystallizing point is-12 DEG C; 2-toluquinoline fusing point-2 DEG C, boiling point 248 DEG C; 6-toluquinoline fusing point-22 DEG C, boiling point 259 ° of C; 3-toluquinoline fusing point 15 DEG C, 4-toluquinoline fusing point 9-10 DEG C.The peristaltic pump adopted is the model that Shanghai Pan Xing equipment company limited produces is the peristaltic pump of BT04F.
Advantage of the present invention is on the basis be separated according to molecular scale inclusion, utilize quinoline, isoquinoline 99.9, many toluquinolines physical property in conjunction with fractional crystallization, selectivity rectifying and obtain product respectively.Present invention process flow process is short, environmental protection, additional source material are few, and cost is lower, quality is high.
Embodiment
(1) will through rectifying enrichment containing quinoline 0.32-0.57Wt%, isoquinoline 99.9 70.33-78.80Wt%, 2,3,4,6-toluquinoline 11.22-21.85Wt%, 2, the solution of the 5.18-7.55Wt% of 4-dimethyl quinoline be put in temperature 15-26 DEG C, in the aqueous solution of urea of mass concentration 2-15%, form the crown inclusion compound of <500pm urea, according to molecular scale, the quinoline in solution, isoquinoline 99.9 are brought in crown inclusion compound, and 2,4-dimethyl quinolines of multiple monomethyl quinoline and two side chain are stayed urea clathration beyond the region of objective existence.Adopt the peristaltic pump of flow velocity 0.004-0.04ml/s, according to methyl alcohol, propyl alcohol, butanone, pentanone mass ratio is 1:0.3:0.6:0.1, total concn quality 3.6% sprays methyl alcohol to crown inclusion compound, propyl alcohol, butanone, pentanone four kinds is without water mixed solvent, the liquid-solid mass ratio of crown inclusion compound is made to be 3-5:0.5-1.5, according to quinoline, isoquinoline 99.9 inclusion compound and multiple toluquinoline are at methyl alcohol, propyl alcohol, butanone, the difference of solubleness in pentanone mixture solvent, quinoline in inclusion compound will be stayed, isoquinoline 99.9 solid phase is separated with the many toluquinolines liquid phase be dissolved in mixed solvent, (2) the ctystallizing point difference of foundation quinoline and isoquinoline 99.9, put by crown for urea inclusion compound and be heated to 26 DEG C in a kettle., isoquinoline 99.9 is solid-state, enrichment isoquinoline 99.9, obtain solid-state isoquinoline 99.9, quality purity >99%, quinoline feed circuit got back to by the remaining quinoline be in a liquid state,
(3) by 2 of the 21.80Wt% that is dissolved in outside crown for urea inclusion compound in mixed solvent, 3,4, the multiple monomethyl quinoline such as 6-toluquinoline and 5.20Wt% 2, freezing 2-5h at 4-dimethyl quinoline solution is put in temperature 5-10 DEG C, multiple monomethyl quinoline and 2 outside the crown inclusion compound of Separation of Urea, 4-dimethyl quinoline and mixed solvent, by the difference of ctystallizing point, the multiple monomethyl quinoline of solid phase and 2,4-dimethyl quinoline are separated with the mixed solvent of liquid state;
(4) isolated multiple monomethyl quinoline and 2,4-dimethyl quinoline solid phase are placed in temperature 10-25 DEG C, the thiourea solution of mass concentration 1-10%, soak 0.5-3.5h, form the crown inclusion compound of thiocarbamide of <700pm; According to molecular scale by 2 in solution, 3,4,6-toluquinoline brings in the crown inclusion compound of thiocarbamide, and stayed by 2 of two side chain, 4-dimethyl quinolines outside the crown inclusion compound of thiocarbamide, make 2,3,4,6 four kind of monomethyl quinoline and 2,4-dimethyl quinolines are separated; Make 2,3,4, toluquinoline more than 6 and 2,4-dimethyl quinoline be separated.
(5) peristaltic pump of flow velocity 0.004-0.04ml/s is adopted, be that 2:0.7:0.8:0.5 sprays methyl alcohol, propyl alcohol, butanone, pentanone four kinds without water mixed solvent to the crown inclusion compound of thiocarbamide according to methyl alcohol, propyl alcohol, butanone, pentanone mass ratio, make the crown inclusion compound liquid-solid ratio of thiocarbamide be 6-2:1-5; According to 2,3,4, the difference of 6-toluquinoline and 2,4-dimethyl quinoline solubleness in a solvent ,-10 ~ 0 DEG C by stay 2 in inclusion compound, 3,4,6-toluquinoline solid phase be dissolved in 2,4-dimethyl quinoline liquid phases in mixed solvent and separate;
(6) be dissolved in 2 in mixed solvent, 4-dimethyl quinoline refrigerate 3-6h crystallization at 0-5 DEG C, separate with other the micro-many toluquinolines impurity be dissolved in methyl alcohol, propyl alcohol, butanone, pentanone mixed solvent, be refined into 2,4-dimethyl quinoline product;
(7) according to the difference of ctystallizing point, crown for thiocarbamide inclusion compound is placed in crystallization kettle, and temperature controls after 0-10 DEG C, 3-6h, and 3-toluquinoline and 4-toluquinoline are solid phase, is separated with 6-toluquinoline with the 2-toluquinoline of liquid phase; Again the 3-toluquinoline of solid phase and 4-toluquinoline are placed in crystallization kettle, improve Tc to 10 DEG C, by 3-toluquinoline and 4-toluquinoline separating-purifying; 2-toluquinoline and 6-toluquinoline mixing solutions are improved temperature to 248 DEG C, utilizes boiling point difference to be separated with 6-toluquinoline by 2-toluquinoline.
Contain in distillation residual liquid after described extraction quinoline: quinoline 0.32-0.57Wt%, isoquinoline 99.9 70.33-78.80Wt%, 2,3,4,6-toluquinoline altogether 11.22-21.85Wt%, 2,4-dimethyl quinoline 5.18-7.55Wt%; Described 2,3,4,6-toluquinoline is: 2-toluquinoline, 3-toluquinoline, 4-toluquinoline and 6-toluquinoline.Percentage composition in the distillation residual liquid of described 2,4-dimethyl quinolines after extracting quinoline is 5.18-7.55Wt%.2-toluquinoline fusing point is-2 DEG C, boiling point 247 DEG C; 3-toluquinoline fusing point is 15 DEG C; 4-toluquinoline fusing point is 9-10 DEG C; 6-toluquinoline fusing point is-22 DEG C, and liquid 6-toluquinoline boiling point is 257.4 ~ 258.6; Isoquinoline 99.9 ctystallizing point is 26 DEG C, and quinoline ctystallizing point is-12 DEG C.Gained isoquinoline 99.9 quality purity >99%, 2,3,4, the quality purity of 6-toluquinoline all can reach 92-95%, wherein 2-toluquinoline purity >99.19%.
Claims (2)
1. a preparation method for quinoline, isoquinoline 99.9 and multiple toluquinoline, comprises the steps:
(1) by extract the distillation residual liquid after quinoline be placed in temperature 10-26 DEG C, the aqueous solution of urea of mass concentration 2-15%, soak 0.5-3.5h, form the crown inclusion compound of urea of <500pm, according to molecular scale, the quinoline in solution, isoquinoline 99.9 are brought in the crown inclusion compound of urea, and 2,4-dimethyl quinolines of multiple monomethyl quinoline and two side chain are stayed urea clathration beyond the region of objective existence, adopt the peristaltic pump of flow velocity 0.004-0.04ml/s, according to methyl alcohol, propyl alcohol, butanone, pentanone mass ratio is that 1:0.3:0.6:0.1 sprays methyl alcohol to crown inclusion compound, propyl alcohol, butanone, pentanone four kinds is without water mixed solvent, the liquid-solid mass ratio of crown inclusion compound is made to be 3-5:0.5-1.5, according to quinoline, isoquinoline 99.9 inclusion compound and multiple monomethyl quinoline are at methyl alcohol, propyl alcohol, butanone, the difference of solubleness in pentanone mixture solvent, quinoline in inclusion compound will be stayed, isoquinoline 99.9 solid phase be dissolved in 2 of multiple monomethyl quinoline in mixed solvent and two side chain, 4-dimethyl quinoline liquid phase separately,
(2) the ctystallizing point difference of foundation quinoline and isoquinoline 99.9, put by crown for urea inclusion compound and be heated to 26 DEG C in a kettle., isoquinoline 99.9 is solid-state;
(3) the multiple monomethyl quinoline and 2 in mixed solvent will be dissolved in, 4-dimethyl quinoline liquid phase freezing 2-5h at 5-10 DEG C, multiple monomethyl quinoline and 2 outside the crown inclusion compound of Separation of Urea, 4-dimethyl quinoline and mixed solvent, by the difference of ctystallizing point, the multiple monomethyl quinoline of solid phase and 2,4-dimethyl quinoline are separated with the mixed solvent of liquid state;
(4) isolated multiple monomethyl quinoline and 2,4-dimethyl quinoline solid phase are placed in temperature 10-25 DEG C, the thiourea solution of mass concentration 1-10%, soak 0.5-3.5h, form the crown inclusion compound of thiocarbamide of <700pm; According to molecular scale by 2 in solution, 3,4,6-toluquinoline brings in the crown inclusion compound of thiocarbamide, and stayed by 2 of two side chain, 4-dimethyl quinolines outside the crown inclusion compound of thiocarbamide, make 2,3,4,6 four kind of monomethyl quinoline and 2,4-dimethyl quinolines are separated;
(5) peristaltic pump of flow velocity 0.004-0.04ml/s is adopted, be that 2:0.7:0.8:0.5 sprays methyl alcohol, propyl alcohol, butanone, pentanone four kinds without water mixed solvent to crown inclusion compound according to methyl alcohol, propyl alcohol, butanone, pentanone mass ratio, make inclusion compound liquid-solid ratio be 6-2:1-5; According to 2,3,4, the difference of 6-toluquinoline and 2,4-dimethyl quinoline solubleness in a solvent ,-10 ~ 0 DEG C by stay 2 in the crown inclusion compound of thiocarbamide, 3,4,6-toluquinoline solid phase be dissolved in 2,4-dimethyl quinoline liquid phases in mixed solvent and separate;
(6) by being dissolved in 2 in mixed solvent, 4-dimethyl quinoline refrigerates 3-6h crystallization at 0-5 DEG C, separates with other the micro-many toluquinolines impurity be dissolved in methyl alcohol, propyl alcohol, butanone, pentanone mixed solvent, is refined into 2,4-dimethyl quinoline product;
(7) according to the difference of ctystallizing point, crown for thiocarbamide inclusion compound is placed in crystallization kettle, and temperature controls after 0-10 DEG C, 3-6h, and 3-toluquinoline and 4-toluquinoline are solid phase, is separated with 6-toluquinoline with the 2-toluquinoline of liquid phase; Again the 3-toluquinoline of solid phase and 4-toluquinoline are placed in crystallization kettle, improve Tc to 10 DEG C, by 3-toluquinoline and 4-toluquinoline separating-purifying; 2-toluquinoline and 6-toluquinoline mixing solutions are improved temperature to 248 DEG C, utilizes boiling point difference to be separated with 6-toluquinoline by 2-toluquinoline.
2. the preparation method of a kind of quinoline according to claim 1, isoquinoline 99.9 and multiple toluquinoline, it is characterized in that: contain in the distillation residual liquid after described extraction quinoline: quinoline 0.32-0.57Wt%, isoquinoline 99.9 70.33-78.80Wt%, 2,3,4,6-toluquinoline 11.22-21.85Wt% altogether, 2,4-dimethyl quinoline 5.18-7.55Wt%; Described 2,3,4,6-toluquinoline is: 2-toluquinoline, 3-toluquinoline, 4-toluquinoline and 6-toluquinoline.
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| CN104788371A (en) * | 2015-04-20 | 2015-07-22 | 黄骅市信诺立兴精细化工股份有限公司 | Method for extracting 2-methylquinoline from isoquinoline stillage residual liquor |
| CN107382850A (en) * | 2017-09-25 | 2017-11-24 | 贾海亮 | A kind of 2 methylquinoline and its isomer and the separation method of isoquinolin |
| CN108393022A (en) * | 2017-02-08 | 2018-08-14 | 鞍钢股份有限公司 | A kind of isoquinolin deployment device and technique |
| CN111471008A (en) * | 2019-01-23 | 2020-07-31 | 安阳师范学院 | Preparation method of quinoline, isoquinoline and various methylquinolines |
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| CN103058923A (en) * | 2013-02-05 | 2013-04-24 | 上海煦旻化工科技发展有限公司 | Method for extracting high-purity 6-methylquinoline |
| CN103641778A (en) * | 2013-11-22 | 2014-03-19 | 徐广苓 | Method for extracting quinoline and isoquinoline from coal tar wash oil |
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| CN104788371A (en) * | 2015-04-20 | 2015-07-22 | 黄骅市信诺立兴精细化工股份有限公司 | Method for extracting 2-methylquinoline from isoquinoline stillage residual liquor |
| CN108393022A (en) * | 2017-02-08 | 2018-08-14 | 鞍钢股份有限公司 | A kind of isoquinolin deployment device and technique |
| CN108393022B (en) * | 2017-02-08 | 2021-04-02 | 鞍钢股份有限公司 | Isoquinoline blending device and process |
| CN107382850A (en) * | 2017-09-25 | 2017-11-24 | 贾海亮 | A kind of 2 methylquinoline and its isomer and the separation method of isoquinolin |
| CN111471008A (en) * | 2019-01-23 | 2020-07-31 | 安阳师范学院 | Preparation method of quinoline, isoquinoline and various methylquinolines |
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