CN108658848B - Production process of 2,2' -bipyridine - Google Patents
Production process of 2,2' -bipyridine Download PDFInfo
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- CN108658848B CN108658848B CN201810422645.2A CN201810422645A CN108658848B CN 108658848 B CN108658848 B CN 108658848B CN 201810422645 A CN201810422645 A CN 201810422645A CN 108658848 B CN108658848 B CN 108658848B
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- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 13
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 claims abstract description 32
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims abstract description 27
- -1 bis (cyclopentadienyl) cobalt Chemical compound 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 17
- FFNVQNRYTPFDDP-UHFFFAOYSA-N 2-cyanopyridine Chemical compound N#CC1=CC=CC=N1 FFNVQNRYTPFDDP-UHFFFAOYSA-N 0.000 claims abstract description 16
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims abstract description 14
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims abstract description 14
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 7
- CVKFXBUVLBFHGO-UHFFFAOYSA-N cobalt 5,10,15,20-tetraphenyl-21,23-dihydroporphyrin Chemical compound [Co].c1cc2nc1c(-c1ccccc1)c1ccc([nH]1)c(-c1ccccc1)c1ccc(n1)c(-c1ccccc1)c1ccc([nH]1)c2-c1ccccc1 CVKFXBUVLBFHGO-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000003054 catalyst Substances 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 14
- 238000004821 distillation Methods 0.000 claims description 12
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 9
- 229910017052 cobalt Inorganic materials 0.000 claims description 6
- 239000010941 cobalt Substances 0.000 claims description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 6
- ILZSSCVGGYJLOG-UHFFFAOYSA-N cobaltocene Chemical compound [Co+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 ILZSSCVGGYJLOG-UHFFFAOYSA-N 0.000 claims description 6
- NVJHHSJKESILSZ-UHFFFAOYSA-N [Co].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 Chemical compound [Co].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 NVJHHSJKESILSZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000008096 xylene Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 4
- 230000008016 vaporization Effects 0.000 claims description 4
- GWYPDXLJACEENP-UHFFFAOYSA-N 1,3-cycloheptadiene Chemical compound C1CC=CC=CC1 GWYPDXLJACEENP-UHFFFAOYSA-N 0.000 claims description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 238000007363 ring formation reaction Methods 0.000 abstract description 4
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 239000007858 starting material Substances 0.000 abstract description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 18
- 239000007787 solid Substances 0.000 description 6
- 238000001816 cooling Methods 0.000 description 5
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000007818 Grignard reagent Substances 0.000 description 2
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000004795 grignard reagents Chemical class 0.000 description 2
- NFWSQSCIDYBUOU-UHFFFAOYSA-N methylcyclopentadiene Chemical compound CC1=CC=CC1 NFWSQSCIDYBUOU-UHFFFAOYSA-N 0.000 description 2
- 150000003222 pyridines Chemical class 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- XVMSFILGAMDHEY-UHFFFAOYSA-N 6-(4-aminophenyl)sulfonylpyridin-3-amine Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=N1 XVMSFILGAMDHEY-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 238000006757 chemical reactions by type Methods 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/06—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
- C07D213/22—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom containing two or more pyridine rings directly linked together, e.g. bipyridyl
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/06—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
- C07D213/127—Preparation from compounds containing pyridine rings
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Pyridine Compounds (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a production process of 2,2' -bipyridine, belonging to the field of chemical synthesis. The process takes acetonitrile and acetylene as starting materials, generates 2-methylpyridine by bis (cyclopentadienyl) cobalt catalytic cyclization, then generates 2-cyanopyridine by tetraphenylporphyrin cobalt catalysis with ammonia gas, and finally generates 2,2' -bipyridine by bis (cyclopentadienyl) cobalt catalytic cyclization with acetylene. The production process is safe, low in cost, less in three wastes and suitable for industrial production.
Description
Technical Field
The invention relates to the field of chemical synthesis, in particular to a production process of 2,2' -bipyridine.
Background
2,2' -dipyridyl is an important organic synthesis intermediate and is also a metal chelating agent, and the dipyridyl is widely applied to the aspects of pesticides, medicines, dyes, spices and the like. Therefore, the method has important significance for the research of the industrial production process.
At present, the industrial production process of the 2,2' -bipyridine mainly comprises the following two processes:
(ii) pyridine in FeCl3Or the 2,2' -bipyridine is produced by self-coupling under the action of catalysts such as Raney Ni;
2-halogenated pyridine and Grignard reagent or zinc reagent thereof are coupled under the action of catalyst to produce 2,2' -bipyridine.
Method (i) if FeCl is used3A large amount of three wastes are generated; if Raney Ni is used, the fire is easy to catch fire, and the operation risk is high;
the 2-halogenated pyridine used in the second method is expensive, a large amount of metal is used in the process of preparing the Grignard reagent or the zinc reagent, the three wastes are more, and the cost is high.
Therefore, it is necessary to develop a safe, environment-friendly and low-cost 2,2' -bipyridine production process.
Disclosure of Invention
The invention aims to provide a safe, environment-friendly and low-cost 2,2' -bipyridyl production process. The process takes acetonitrile and acetylene as starting materials, generates 2-methylpyridine by bis (cyclopentadienyl) cobalt catalytic cyclization, then generates 2-cyanopyridine by tetraphenylporphyrin cobalt catalysis with ammonia gas, and finally generates 2,2' -bipyridine by bis (cyclopentadienyl) cobalt catalytic cyclization with acetylene, and the process route is as follows:
the specific process steps of the process route of the invention are as follows:
the first step is as follows: adding acetonitrile and bis (cyclopentadienyl) cobalt into a high-pressure reaction kettle, vacuumizing, introducing deoxygenated acetylene gas, heating to 130-;
the second step is that: vaporizing 2-methylpyridine, mixing the vaporized 2-methylpyridine with ammonia gas and air, feeding the mixture into a fixed bed reactor filled with a cobalt catalyst, heating the mixture to the temperature of 300 ℃ and 320 ℃, maintaining the total pressure at 8-15 kg, and after the reaction is finished, carrying out reduced pressure distillation to obtain 2-cyanopyridine;
the third step: adding 2-cyanopyridine and bis (cyclopentadienyl) cobalt into xylene in a high-pressure reaction kettle, vacuumizing, introducing deoxygenated acetylene gas, heating to 150 ℃ and 180 ℃, maintaining the total pressure at 8-18 kg, and after the reaction is finished, carrying out reduced pressure distillation to obtain 2,2' -bipyridine, and recycling the xylene.
Further, in the above technical solution, in the first step and the third step, other cobaltocene catalysts can be used, and the structural general formula is as follows:
Preferably, in the actual catalytic reaction process, it is best to have cyclopentadienyl rings different from each other up and down, one of the cyclopentadienyl rings is a simple five-membered ring (n ═ 1, R ═ H), and the other cyclopentadienyl ring is a polysubstituted seven-ring (n ═ 1, R ═ Me).
Further, in the above technical scheme, in the first step, the mass ratio of acetonitrile to bis (cyclopentadienyl) cobalt is 350-200: 1.
Further, in the above technical solution, in the second step, the cobalt porphyrin catalyst is cobalt tetraphenylporphyrin. The addition of equivalent NaBAr4 is beneficial to improving the catalytic activity and reducing the reaction time.
Further, in the above technical solution, in the second step, the mass ratio of the 2-methylpyridine to the cobalt catalyst is 850-: 1.
further, in the above technical scheme, in the third step, the mass ratio of 2-cyanopyridine to bis (cyclopentadienyl) cobalt is 250-150: 1.
Advantageous effects of the invention
1. The invention does not need a large amount of metal, only needs a small amount of catalyst, and has less three wastes;
2. the invention adopts the metallic cobalt catalyst to complete the whole operation, and selects different ligands to adjust the activity of the catalyst according to the reaction characteristics of each step, thereby realizing different reaction types.
Detailed Description
Example 1
The embodiment comprises the following steps:
step one, adding 100kg of acetonitrile and 0.4kg of bis (cyclopentadienyl) cobalt into a high-pressure reaction kettle, vacuumizing, introducing deoxygenated acetylene gas, heating to 150 ℃, maintaining the total pressure at 12 kg, reacting for 22h, and carrying out reduced pressure distillation to obtain 211kg of 2-methylpyridine, a colorless transparent liquid and the yield of 93%; HNMR (400MHz, CDCl3) 8.51(m,1H),7.57-7.60(m,1H),7.05-7.08(m,1H),7.15-7.17(m,1H),2.58(s,3H).
Secondly, 211kg of 2-methylpyridine is vaporized and mixed with ammonia gas and air, the mixture enters a fixed bed reactor filled with 0.3kg of cobalt tetraphenylporphyrin, the temperature is raised to 320 ℃, the total pressure is maintained at 9kg, the reaction is carried out for 20 hours, 213.5kg of 2-cyanopyridine is obtained by reduced pressure distillation, the mixture is cooled and solidified into light yellow solid, and the yield is 90.5%; HNMR (400MHz, CDCl3) 8.73-8.75(m,1H),7.85-7.89(m,1H),7.71-7.74(m,1H),7.54-7.57(m,1H).
Step three, adding 213.5kg of 2-cyanopyridine and 0.97kg of bis (cyclopentadienyl) cobalt into 500L of dimethylbenzene in a high-pressure reaction kettle, vacuumizing, introducing deoxygenated acetylene gas, heating to 170 ℃, maintaining the total pressure at 8kg, reacting for 26 hours, carrying out reduced pressure distillation to obtain 303kg of 2,2' -bipyridine, cooling to obtain a white solid, and melting point: 69-70 ℃, m/z 156.1, GC: 99.4%, yield 94.6%. H NMR (400MHz in CDCl3) 7.28-7.32(m,2H),7.80-7.84(m,2H),8.40(d,2H),8.68(d,2H).
Example 2
The embodiment comprises the following steps:
step one, adding 100kg of acetonitrile and 0.5kg of (cyclopentadienyl cycloheptadiene) cobalt into a high-pressure reaction kettle, vacuumizing, introducing deoxygenated acetylene gas, heating to 150 ℃, maintaining the total pressure at 10 kg, reacting for 22h, and carrying out reduced pressure distillation to obtain 207.8kg of 2-methylpyridine, colorless transparent liquid and the yield of 91.6%; HNMR (400MHz, CDCl3) 8.51(m,1H),7.57-7.60(m,1H),7.05-7.08(m,1H),7.15-7.17(m,1H),2.58(s,3H).
Secondly, vaporizing 207.8kg of 2-methylpyridine, mixing the vaporized 2-methylpyridine with ammonia gas and air, feeding the mixture into a fixed bed reactor filled with 0.26kg of cobalt tetraphenylporphyrin, heating the mixture to 320 ℃, maintaining the total pressure at 13 kg, reacting for 18h, carrying out reduced pressure distillation to obtain 215.3kg of 2-cyanopyridine, cooling and solidifying the 2-cyanopyridine into light yellow solid with the yield of 92.7 percent; HNMR (400MHz, CDCl3) 8.73-8.75(m,1H),7.85-7.89(m,1H),7.71-7.74(m,1H),7.54-7.57(m,1H).
Step three, adding 215.3kg of 2-cyanopyridine and 1.2kg of (cyclopentadienyl cycloheptadiene) cobalt into 500L of dimethylbenzene in a high-pressure reaction kettle, vacuumizing, introducing deoxygenated acetylene gas, heating to 170 ℃, maintaining the total pressure at 15 kg, reacting for 16h, carrying out reduced pressure distillation to obtain 314.6kg of 2,2' -bipyridine, cooling to obtain a white solid, and melting point: 69-70 ℃, m/z 156.1, GC: 99.7 percent, the yield is 97.4 percent, and the dimethylbenzene is recycled and reused. H NMR (400MHz in CDCl3) 7.28-7.32(m,2H),7.80-7.84(m,2H),8.40(d,2H),8.68(d,2H).
Example 3
The embodiment comprises the following steps:
step one, adding 100kg of acetonitrile and 0.36kg of (full methyl cyclopentadiene/cycloheptadiene) cobalt into a high-pressure reaction kettle, vacuumizing, introducing deoxygenated acetylene gas, heating to 150 ℃, maintaining the total pressure at 13 kg, reacting for 22h, and carrying out reduced pressure distillation to obtain 213.9kg of 2-methylpyridine, colorless transparent liquid and the yield of 94.3%; HNMR (400MHz, CDCl3) 8.51(m,1H),7.57-7.60(m,1H),7.05-7.08(m,1H),7.15-7.17(m,1H),2.58(s,3H).
Secondly, vaporizing 213.9kg of 2-methylpyridine, mixing the vaporized 2-methylpyridine with ammonia gas and air, feeding the mixture into a fixed bed reactor filled with 0.31kg of cobalt tetraphenylporphyrin and equivalent NaBAr4(Ar is 3, 5-bis (trifluoromethyl) phenyl), heating to 300 ℃, maintaining the total pressure at 12 kg, reacting for 2h, carrying out reduced pressure distillation to obtain 228.8kg of 2-cyanopyridine, cooling and solidifying the 2-cyanopyridine into light yellow solid with the yield of 95.7%; HNMR (400MHz, CDCl3) 8.73-8.75(m,1H),7.85-7.89(m,1H),7.71-7.74(m,1H),7.54-7.57(m,1H).
Step three, in a high-pressure reaction kettle, adding 228.8kg of 2-cyanopyridine and 0.95kg of (fully methylcyclopentadiene/cycloheptadiene) cobalt into 500L of xylene recovered in example 2, vacuumizing, introducing deoxygenated acetylene gas, heating to 170 ℃, maintaining the total pressure at 12 kg, reacting for 16h, distilling under reduced pressure to obtain 324kg of 2,2' -bipyridine, cooling to obtain a white solid, and melting point: 69-70 ℃, m/z 156.1, GC: 99.9% and 94.4% yield. H NMR (400MHz in CDCl3) 7.28-7.32(m,2H),7.80-7.84(m,2H),8.40(d,2H),8.68(d,2H).
The above description is only for the preferred embodiment of the present invention, and is not intended to limit the present invention in any way. Any simple modification, change and equivalent changes of the above embodiments according to the technical essence of the invention are still within the protection scope of the technical solution of the invention.
Claims (6)
1. The production process of the 2,2' -bipyridine is obtained by three steps of reactions and is characterized in that the reaction route is as follows:
the method comprises the following steps:
the first step is as follows: adding acetonitrile and cobaltocene catalyst into a high-pressure reaction kettle, vacuumizing, introducing deoxygenated acetylene gas, heating to 130-;
the second step is that: vaporizing 2-methylpyridine, mixing the vaporized 2-methylpyridine with ammonia gas and air, feeding the mixture into a fixed bed reactor filled with a cobalt porphyrin catalyst, heating the mixture to the temperature of 300 ℃ and 320 ℃, maintaining the total pressure at 8-15 kg, and after the reaction is finished, carrying out reduced pressure distillation to obtain 2-cyanopyridine; in the step, the cobalt porphyrin catalyst is cobalt tetraphenylporphyrin;
the third step: adding 2-cyanopyridine and cobaltocene catalyst into xylene in a high-pressure reaction kettle, vacuumizing, introducing deoxygenated acetylene gas, heating to 160-180 ℃, maintaining the total pressure at 8-18 kg, performing reduced pressure distillation after the reaction is finished to obtain 2,2' -bipyridine, and recovering the xylene for reuse.
2. The process according to claim 1 for the production of 2,2' -bipyridine, wherein: in the first step and the third step, the cobaltocene catalyst is bis (cyclopentadienyl) cobalt, (cyclopentadienyl cycloheptadiene) cobalt or (fully methyl cyclopentadienyl/cycloheptadiene) cobalt.
3. The process according to claim 1 for the production of 2,2' -bipyridine, wherein: in the second step, an equivalent amount of NaBAr is added into the cobalt porphyrin catalyst4Wherein Ar ═ 3, 5-bistrifluoromethylphenyl.
4. The process according to claim 1 for the production of 2,2' -bipyridine, wherein: in the first step, the mass ratio of the acetonitrile to the cobaltocene catalyst is 350-200: 1.
5. The process according to claim 1 for the production of 2,2' -bipyridine, wherein: in the second step, the mass ratio of the 2-methylpyridine to the cobalt porphyrin catalyst is 850-: 1.
6. the process according to claim 1 for the production of 2,2' -bipyridine, wherein: in the third step, the mass ratio of the 2-cyanopyridine to the cobaltocene catalyst is 250-150: 1.
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| Title |
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| An example of structure-activity relationship in homogeneous catalysis: organocobalt compounds in the synthesis of pyridines;H.Bonnenmann，等;《NEW JOURNAL OF CHEMISTRY》;19871231;第11卷(第7期);549-559 * |
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