CN105418691A - Method for preparing bis-ferrocenyl pyridine derivative in supercritical carbon dioxide - Google Patents
Method for preparing bis-ferrocenyl pyridine derivative in supercritical carbon dioxide Download PDFInfo
- Publication number
- CN105418691A CN105418691A CN201510977197.9A CN201510977197A CN105418691A CN 105418691 A CN105418691 A CN 105418691A CN 201510977197 A CN201510977197 A CN 201510977197A CN 105418691 A CN105418691 A CN 105418691A
- Authority
- CN
- China
- Prior art keywords
- ferrocenyl
- preparation
- cobalt
- pyridine
- nitrile
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F17/00—Metallocenes
- C07F17/02—Metallocenes of metals of Groups 8, 9 or 10 of the Periodic System
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Pyridine Compounds (AREA)
Abstract
The invention relates to a novel method for synthesizing a bis-ferrocenyl pyridine derivative. According to the method, the bis-ferrocenyl pyridine derivative is synthesized from ferrocenyl ethyne and nitrile, which serve as raw materials, under the catalysis of carbonyl cobalt in supercritical carbon dioxide, which is adopted as a reaction medium, wherein the catalyst is dicarbonyl cyclopentadienyl cobalt [CpCo(CO)2] or ferrocenyl ethyne carbonyl cobalt cluster compound (a formula shown in the description). According to the method, the environment-friendly solvent, i.e., supercritical carbon dioxide is used, an organic solvent is not required to serve as an assistant, the operation is simple, the reaction time is short, the product is simple to separate, and the yield is relatively high.
Description
Technical field
The present invention relates to technical field of organic synthesis, particularly relate to a kind of method preparing di-ferrocene pyridine derivative in supercritical co.
Background technology
Ferrocenyl pyridine derivate has the constructional feature of pyridine and ferrocene concurrently, has a wide range of applications in catalysis, medicine and field of functional materials.In catalysis, ferrocenyl pyridine derivate can be used as the metal such as part and Pd formation heteropolynuclear coordination compound and prepares homogeneous catalyst; In field of medicaments, ferrocene and pyridine all have biological activity, they are incorporated in the structure of different compound, can produce and have bioactive compound; In field of functional materials, ferrocenyl pyridine derivate has unique texture and outstanding electricity, light, magnetic isoreactivity, after luxuriant ring and aromatic ring are connected, Pi-conjugated systems is expanded and extended, electronics can transmit between luxuriant ring and aromatic ring, can be applicable to prepare molecular switch, molecular motor, electrochemical ion probe and nonlinear optical material etc.The synthesis of ferrocenyl substituted pyridines often adopts the method for coupling, these class methods need the catalysis of Pd salt mostly, need a large amount of preliminary preparations, synthesis is realized by polystep reaction, length consuming time, cost is high, and is subject to the impact of existing substituted radical, is difficult to realize pyridine ring replaces while different functional groups specified location.Alkynes-nitrile [2+2+2] cycloaddition reaction of cobalt-carbonyl catalysis is typical atom economic reaction, can realize the synthesis of pyridine compounds and their like a cork, builds ferrocenyl pyridine derivate meet Green Chemistry principle with it.
Supercritical co has the superperformance that conventional organic solvents does not have: cheap, nontoxic, do not burn, easily separated, the feature such as reusable edible and environmental friendliness, and its density, viscosity, spread coefficient and solvating ability by change temperature, pressure regulates, and is desirable green chemical reaction solvent.Utilize supercritical co to carry out chemical reaction as reaction medium and relate to nearly all basic organic reaction, but about the research work rarely seen report of alkynes-nitrile cycloaddition aspect.
Summary of the invention
The object of this invention is to provide a kind of in supercritical CO 2 medium, utilize [2+2+2] cycloaddition reaction of the ferrocenyl acetylene of cobalt-carbonyl catalysis and nitrile to prepare the novel method of di-ferrocene pyridine derivative.The present invention has the advantages such as environmental friendliness, easy and simple to handle, with low cost, high yield.
The technical scheme that the present invention specifically adopts is as follows:
The method of synthesis di-ferrocene pyridine derivative provided by the present invention, comprise the nitrile that represents with ferrocenyl acetylene and formula IV for raw material, in supercritical CO 2 medium, catalyze and synthesize the di-ferrocene pyridine derivative that formula I and formula II represents by cobalt-carbonyl, reaction formula of the present invention is as follows:
The present invention prepares the method for di-ferrocene pyridine derivative, and step is as follows:
(1) raw material ferrocenyl acetylene, nitrile are dropped in reactor by a certain percentage, add cobalt-carbonyl as catalyzer simultaneously, pass into CO
2gas, drains air in still, pumps into liquid CO by after reactor preheating
2;
(2) reacting by heating still, opens and stirs, temperature in the kettle is raised, and Keep agitation is until reaction terminates;
(3) reaction terminate after, after reactor is cooled to room temperature, slowly release carbonic acid gas, pressure release to normal pressure, with the abundant washing reaction still of methylene dichloride;
(4) the concentrated rear separating-purifying of gained washings obtains product;
Wherein, the R in formula IV is the alkyl of C1-C12, the thiazolinyl of C1-C12, the alkoxyl group of C1-C12, the cycloalkyl of C3-C12, the aryl of C6-C18 or ferrocenyl;
Wherein, the nitrile described in step (1) comprises cyanobenzene and acetonitrile;
Wherein, the ferrocenyl acetylene described in step (1) and the mol ratio of nitrile are 1: 6 ~ 1: 10;
Wherein, the cobalt carbonyl catalyst described in step (1) is dicarbapentaborane cyclopentadienyl cobalt [CpCo (CO)
2] or ferrocenyl acetylene cobalt-carbonyl duster compound [Co
2(CO)
6(μ
2-η
2-FcC ≡ CH)], be preferably dicarbapentaborane cyclopentadienyl cobalt [CpCo (CO)
2];
Wherein, the molecular fraction of the catalyzer described in step (1) is 3 ~ 20%, is preferably 15%;
Wherein, the pressure pumping into carbonic acid gas described in step (1) is 5 ~ 12MPa, is preferably 8 ~ 10MPa;
Wherein, the preheating temperature described in step (1) is 50 DEG C, and warm up time is 20min;
Wherein, the temperature of reaction described in step (2) is 60 ~ 120 DEG C, is preferably 90 DEG C ~ 110 DEG C;
Wherein, the reaction times described in step (2) is 6 ~ 12 hours;
Wherein, step (3) and (4) described solvent comprise at least one in sherwood oil, methylene dichloride, ethyl acetate, normal hexane, are analytical pure, before use without the need to process.
Wherein, the concentration method described in step (4) is distillation under vacuum, as concentrated with rotavapor under vacuum.The purge process told refers to column chromatography technology, Preparative TLC chromatographic technique and recrystallization separating and purifying technology.
The invention provides the novel method preparing di-ferrocene pyridine derivative of a kind of environmental friendliness, easy and simple to handle, with low cost, high yield.
Embodiment
Below in conjunction with embodiment, the present invention will be further described, but be not limited thereto.
Embodiment 1 synthesizes 2-phenyl-4,6-bis-ferrocenyl pyridine and 2-phenyl-3,6-bis-ferrocenyl pyridine
Be equipped with in teflon-lined reactor to 50mL and add ferrocenyl acetylene (100mg, 0.48mmol, 1equiv.), cyanobenzene (300 μ L, 3.0mmol, 6equiv.), CpCo (CO)
2[10 μ L, 0.07mmol, Co (15mol.%)], and put into suitable magneton.Use CO
2replace 2 times air, carry out preheating 20 minutes in the middle of the oil bath of reactor being inserted 50 DEG C, pump into carbonic acid gas to 10MPa.Open stirring, reactor is warming up to 110 DEG C, react 10 hours.After reaction terminates, reactor is cooled to room temperature.By slow for carbonic acid gas pressure release to normal pressure.Use washed with dichloromethane reactor, complete reaction mixture is collected in 100ml round-bottomed flask.Underpressure distillation is removed unnecessary methylene chloride and is obtained crude product.Crude product sherwood oil and ethyl acetate (V/V=20: 1) make eluent, carry out column chromatography for separation (200-300 order silica gel), obtain the mixture of 2-phenyl-4,6-bis-ferrocenyl pyridine and 2-phenyl-3,6-bis-ferrocenyl pyridine.Mixture makees eluent with sherwood oil and ethyl acetate (V/V=200: 1) again, be prepared TLC separation, obtain orange crystal 2-phenyl-4, the 6-bis-ferrocenyl pyridine 69mg that purity is greater than 99%, isolated yield is 55%, and fusing point is 171-172 DEG C; Orange crystal 2-phenyl-3, the 6-bis-ferrocenyl pyridine 30mg that purity is greater than 99%, isolated yield is 24%, and fusing point is 180-182 DEG C.
(1) Structural Identification of 2-phenyl-4,6-bis-ferrocenyl pyridine:
Ir data IR (KBr) v/cm
-1: 3131 (v
cH, Cp), 1598,1549 (v
c=C, Ph), 1401 (v
c=C, Cp), 1107,1003 (δ
cH, Cp), 820 (γ
cH, Cp).
Nuclear magnetic resonance data:
1hNMR (500MHz, CDCl
3, TMS): δ 8.16 (s, 1H, pyridyl), 8.15 (s, 1H, pyridyl), 7.59-7.40 (m, 5H, Ph), 5.07-4.08 (m, 18H, Fc);
13cNMR (125MHz, CDCl
3, TMS): δ 158.70,156.35,148.72,115.35,114.35 (pyridyl), 139.88,128.74,128.59,126.93 (Ph), 84.51,82.03,69.96,69.74,69.65,67.58,66.92 (Fc).
Mass-spectrometric data: ESIMScalcdforC
31h
25fe
2n523.07, found524.10 (M+1).
Elemental analysis data: Anal.Cal.forC
31h
25fe
2n:C, 71.16; H, 4.82; N, 2.68; Found:C, 71.33; H, 4.78; N, 2.67%.
Analytical results shows, the target product structure of acquisition is correct.
(2) Structural Identification of 2-phenyl-3,6-bis-ferrocenyl pyridine:
Ir data IR (KBr) v/cm
-1: 3123 (v
cH, Cp), 1582,1544 (v
c=C, Ph), 1402 (v
c=C, Cp), 1106,1002 (δ
cH, Cp), 821 (γ
cH, Cp).
Nuclear magnetic resonance data:
1hNMR (500MHz, CDCl
3, TMS): δ 8.02 (d, J=8.5Hz, 1H, pyridyl), 7.38 (d, J=8.0Hz, 1H, pyridyl), 7.43-7.40 (m, 2H, Ph), 7.31-7.29 (m, 3H, Ph), 4.98-4.05 (m, 18H, Fc);
13cNMR (125MHz, CDCl
3, TMS): δ 156.16,156.03,138.78,129.37,117.90 (pyridyl), 141.01,129.95,127.57,127.53 (Ph), 85.47,84.32,70.02,69.72,69.60,69.53,68.12,67.52 (Fc).
Mass-spectrometric data: ESIMScalcdforC
31h
25fe
2n523.07, found524.10 (M+1).
Elemental analysis data: Anal.Calc.forC
31h
25fe
2n:C, 71.16; H, 4.82; N, 2.68.Found:C, 70.85; H, 5.05; N2.57%..
Analytical results shows, the target product structure of acquisition is correct.
Embodiment 2-in-1 one-tenth 2-phenyl-4,6-bis-ferrocenyl pyridine and 2-phenyl-3,6-bis-ferrocenyl pyridine
Be equipped with in teflon-lined reactor to 50mL and add ferrocenyl acetylene (100mg, 0.48mmol, 1equiv.), cyanobenzene (300 μ L, 3.0mmol, 6equiv.), CpCo (CO)
2[10 μ L, 0.07mmol, Co (15mol.%)], and put into suitable magneton.Use CO
2replace 2 times air, carry out preheating 20 minutes in the middle of the oil bath of reactor being inserted 50 DEG C, pump into carbonic acid gas to 8MPa.Open stirring, reactor is warming up to 110 DEG C, react 10 hours.
Last handling process is identical with embodiment 1, and obtain orange crystal 2-phenyl-4,6-bis-ferrocenyl pyridine and 2-phenyl-3,6-bis-ferrocenyl pyridine that purity is greater than 99%, isolated yield is respectively 42% and 18%.
Analytical results shows, the target product structure of acquisition is correct.
Embodiment 3 synthesizes 2-methyl-4,6-bis-ferrocenyl pyridine and 2-methyl-3,6-bis-ferrocenyl pyridine
Be equipped with in teflon-lined reactor to 50mL and add ferrocenyl acetylene (100mg, 0.48mmol, 1equiv.), acetonitrile (250 μ L, 4.8mmol, 10equiv.), CpCo (CO)
2[10 μ L, 0.07mmol, Co (15mol.%)], and put into suitable magneton.Use CO
2replace 2 times air, carry out preheating 20 minutes in the middle of the oil bath of reactor being inserted 50 DEG C, pump into carbonic acid gas to 10MPa.Open stirring, reactor is warming up to 110 DEG C, react 10 hours.By slow for carbonic acid gas pressure release to normal pressure.Use washed with dichloromethane reactor, complete reaction mixture is collected in 100ml round-bottomed flask.Underpressure distillation is removed unnecessary methylene chloride and is obtained crude product.Crude product sherwood oil and ethyl acetate (V/V=20: 1) make eluent, carry out column chromatography for separation (200-300 order silica gel), obtain the orange crystal 2-methyl-4 that purity is greater than 99%, 6-bis-ferrocenyl pyridine 49mg, isolated yield is 44%, and fusing point is 191-192 DEG C; Orange crystal 2-methyl-3, the 6-bis-ferrocenyl pyridine 18mg that purity is greater than 99%, isolated yield is 16%, and fusing point is 182-183 DEG C.
(1) Structural Identification of 2-methyl-4,6-bis-ferrocenyl pyridine:
Ir data IR (KBr) v/cm
-1: 3083 (v
cH, Cp), 1599,1549 (v
c=C, pyridyl), 1407 (v
c=C, Cp), 1105,999 (δ
cH, Cp), 818 (γ
cH, Cp).
Nuclear magnetic resonance data:
1hNMR (500MHz, CDCl
3, TMS): δ 7.31 (s, 1H, pyridyl), 6.99 (s, 1H, pyridyl), 4.94-4.07 (m, 18H, Fc), 2.56 (s, 3H, CH
3);
13cNMR (125MHz, CDCl
3, TMS): δ 158.27,157.59,148.01,117.18,114.37 (pyridyl), 84.59,81.88,69.90,69.84,69.59,67.47,66.80 (Fc), 24.75 (CH
3).
Mass-spectrometric data: ESIMScalcdforC
26h
23fe
2n461.05, found462.05 (M+1).
Elemental analysis data: Anal.Calc.forC
26h
23fe
2n:C, 67.72; H, 5.03; N, 3.04.Found:C, 67.54, H, 5.14, N, 2.88%.
Analytical results shows, the target product structure of acquisition is correct.
(2) Structural Identification of 2-methyl-3,6-bis-ferrocenyl pyridine:
Ir data IR (KBr) v/cm
-1: 3112 (v
cH, Cp), 1583,1560 (v
c=C, pyridyl), 1401 (v
c=C, Cp), 1104,1000 (δ
cH, Cp), 820 (γ
cH, Cp).
Nuclear magnetic resonance data:
1hNMR (500MHz, CD
3oD, TMS): δ 8.04 (d, J=7.0Hz, 1H, pyridyl), 7.49 (d, J=8.0Hz, 1H, pyridyl), 4.99 (s, 2H, Fc), 4.60-4.09 (m, 16H, Fc), 2.61 (s, 3H, CH
3);
13cNMR (125MHz, CDCl
3, TMS): δ 155.79,154.78,137.32,129.81,117.47 (pyridyl), 85.57,84.55,69.56,69.47,68.36,67.31 (Fc), 24.48 (CH
3).
Mass-spectrometric data: ESIMScalcdforC
26h
23fe
2n461.05, found462.05 (M+1).
Elemental analysis data: Anal.Calc.forC
26h
23fe
2n:C, 67.72; H, 5.03; N, 3.04.Found:C, 67.45; H, 4.88; N, 2.97%.
Analytical results shows, the target product structure of acquisition is correct.
Embodiment 4 synthesizes 2-methyl-4,6-bis-ferrocenyl pyridine and 2-methyl-3,6-bis-ferrocenyl pyridine
Be equipped with in teflon-lined reactor to 50mL and add ferrocenyl acetylene (100mg, 0.48mmol, 1equiv.), acetonitrile (250 μ L, 4.8mmol, 10equiv.), CpCo (CO)
2[10 μ L, 0.07mmol, Co (15mol.%)], and put into suitable magneton.Use CO
2replace 2 times air, carry out preheating 20 minutes in the middle of the oil bath of reactor being inserted 50 DEG C, pump into carbonic acid gas to 10MPa.Open stirring, reactor is warming up to 90 DEG C, react 10 hours.
Last handling process is identical with embodiment 3, and obtain orange crystal 2-methyl-4,6-bis-ferrocenyl pyridine and 2-methyl-3,6-bis-ferrocenyl pyridine that purity is greater than 99%, isolated yield is respectively 16% and 5%.
Analytical results shows, the target product structure of acquisition is correct.
Content disclosed according to the present invention, those skilled in the art can apply the present invention to greatest extent.Therefore, appeal preferred specific embodiment and only illustrate, but not limit the scope of the invention by any way.
Claims (9)
1. synthesize the method for di-ferrocene pyridine derivative, it is characterized in that: comprise the nitrile that represents with ferrocenyl acetylene and formula IV for raw material, in supercritical CO 2 medium, catalyze and synthesize by cobalt-carbonyl the di-ferrocene pyridine derivative that formula I and II represents:
Raw material ferrocenyl acetylene, nitrile are dropped in reactor by a certain percentage, adds cobalt-carbonyl as catalyzer simultaneously; Pass into CO
2gas, drains air in still, pumps into liquid CO by after reactor preheating
2; Reacting by heating still, opens and stirs, temperature in the kettle is raised, and Keep agitation is until reaction terminates; After reaction terminates, after reactor is cooled to room temperature, slowly release carbonic acid gas, pressure release is to normal pressure; With the abundant washing reaction still of methylene dichloride, after gained washings is concentrated, separating-purifying obtains product.
2. the preparation method according to claims 1, is characterized in that, the R in described formula IV is the alkyl of C1-C12, the thiazolinyl of C1-C12, the alkoxyl group of C1-C12, the cycloalkyl of C3-C12, the aryl of C6-C18 or ferrocenyl.
3. the preparation method according to claims 1 or 2, is characterized in that, described nitrile is cyanobenzene and acetonitrile.
4. the preparation method according to claims 1, is characterized in that, described ferrocenyl acetylene and the mol ratio of nitrile are 1: 6 ~ 1: 10.
5. the preparation method according to claims 1, is characterized in that, described cobalt carbonyl catalyst is dicarbapentaborane cyclopentadienyl cobalt [CpCo (CO)
2] or ferrocenyl acetylene cobalt-carbonyl duster compound [Co
2(CO)
6(μ
2-η
2-FcC ≡ CH)], be preferably dicarbapentaborane cyclopentadienyl cobalt [CpCo (CO)
2].
6. the preparation method according to claims 1, is characterized in that, the molecular fraction of described catalyzer is 3 ~ 20%, is preferably 15%.
7. the preparation method according to claims 1, is characterized in that, the described pressure pumping into carbonic acid gas is 5 ~ 12MPa, is preferably 8 ~ 10MPa.
8. the preparation method according to claims 1, is characterized in that, described temperature of reaction is 60 ~ 120 DEG C, is preferably 90 DEG C ~ 110 DEG C.
9. the preparation method according to claims 1, is characterized in that, described concentration process adopts distillation under vacuum, and purification process adopts column chromatography technology, thin-layer chromatography or recrystallization.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510977197.9A CN105418691A (en) | 2015-12-24 | 2015-12-24 | Method for preparing bis-ferrocenyl pyridine derivative in supercritical carbon dioxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510977197.9A CN105418691A (en) | 2015-12-24 | 2015-12-24 | Method for preparing bis-ferrocenyl pyridine derivative in supercritical carbon dioxide |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105418691A true CN105418691A (en) | 2016-03-23 |
Family
ID=55497284
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510977197.9A Pending CN105418691A (en) | 2015-12-24 | 2015-12-24 | Method for preparing bis-ferrocenyl pyridine derivative in supercritical carbon dioxide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105418691A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108690095A (en) * | 2018-06-18 | 2018-10-23 | 东莞市联洲知识产权运营管理有限公司 | A kind of synthetic method of the ferrocenecarboxylic acid based on supercritical carbon dioxide liquid |
| CN113831259A (en) * | 2021-11-05 | 2021-12-24 | 内蒙古工业大学 | Synthetic method of aromatic azo compound |
-
2015
- 2015-12-24 CN CN201510977197.9A patent/CN105418691A/en active Pending
Non-Patent Citations (6)
| Title |
|---|
| FRANCISCO MONTILLA: "CpCo(CO)2-catalysed cyclotrimerisation of alkynes in supercritical carbon dioxide", 《JOURNAL OF ORGANOMETALLIC CHEMISTRY》 * |
| YA-QI WANG等: "Synthesis, structure and electrochemistry of new diferrocenyl pyridine derivatives", 《POLYHEDRON》 * |
| 王亚琦: "多二茂铁基吡啶和苯衍生物的合成及电化学性质研究", 《内蒙古工业大学博士学位论文》 * |
| 王亚琦等: "环加成反应合成双二茂铁基吡啶", 《第十七届全国金属有机化学学术讨论会论文集》 * |
| 王亚琦等: "羰基钴催化炔腈环加成反应产物的高效液相色谱分析", 《第十八届全国金属有机化学学术讨论会论文集》 * |
| 王春翔等: "过渡金属催化［2+2+2］环加成反应合成吡啶衍生物", 《化学进展》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108690095A (en) * | 2018-06-18 | 2018-10-23 | 东莞市联洲知识产权运营管理有限公司 | A kind of synthetic method of the ferrocenecarboxylic acid based on supercritical carbon dioxide liquid |
| CN113831259A (en) * | 2021-11-05 | 2021-12-24 | 内蒙古工业大学 | Synthetic method of aromatic azo compound |
| CN113831259B (en) * | 2021-11-05 | 2023-07-25 | 内蒙古工业大学 | Synthesis method of aromatic azo compound |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Schmalz et al. | On the enantioselective deprotonation/silylation of prochiral mono-and 1, 2-dimethoxybenzene-Cr (CO) 3 derivatives | |
| CN110183378B (en) | Nicotinamide derivative and catalytic synthesis method thereof | |
| CN108558692B (en) | Preparation method of amide compound | |
| CN108912044B (en) | Method for synthesizing polysubstituted pyridine by using copper-catalyzed alkenyl azide | |
| CN105418691A (en) | Method for preparing bis-ferrocenyl pyridine derivative in supercritical carbon dioxide | |
| CN107629051B (en) | Method for synthesizing evodiamine by carbonylation reaction three-step method | |
| CN109627163A (en) | The directly Olefination method in phenol compound ortho position and Olefination phenol compound | |
| CN111592507A (en) | Novel green and simple method for preparing polysubstituted furan | |
| CN109422680B (en) | Synthesis method of N-acetylquinoline-2-amide and derivatives thereof | |
| CN112920033A (en) | Preparation method of o-alkynyl phenylcyclobutanone and preparation method of naphthalenone | |
| CN105272987A (en) | Preparation method of 3-cyano-N-confused porphyrin compound | |
| CN107915687B (en) | High-efficiency preparation method of polysubstituted phenazine derivative and oxide thereof | |
| KR101769204B1 (en) | New method for preparation of chiral chromanol derivatives | |
| CN115353487A (en) | Method for synthesizing N- (2-pyridyl) amide compound under air bubbling condition | |
| CN105693778B (en) | The method of N- methoxymethylamide guiding synthesis ferrocene and Pyridione derivatives | |
| CN109824501B (en) | Aryl iodine compound containing carboxydifluoro methylene at ortho position and preparation method thereof | |
| CN109748809B (en) | Method for synthesizing 2-substituted amino-1, 4-naphthoquinone derivative | |
| CN108929251B (en) | Method for direct trifluoromethylation of C (sp3) -H | |
| CN105622493B (en) | Method for synthesizing fully-substituted pyridine compound through cascade reaction of enaminone and aldehyde | |
| CN105601639B (en) | A kind of 6- tertbutyloxycarbonyls octahydro -2H- pyrans [3,2-c] and the synthetic method of pyridine -8- carboxylic acids | |
| CN108440400B (en) | Synthetic method of fluorine-containing alkyl pyridone derivative | |
| CN110002976B (en) | Method for synthesizing beta-trifluoromethyl-beta-hydroxy-1, 2-diphenyl acetone by copper-catalyzed alkenyl azide | |
| CN108456146B (en) | Method for preparing aromatic ether by applying drug functional group to C-H methoxylation | |
| CN109331868B (en) | Phenylglycine bifunctional catalyst, and preparation method and application thereof | |
| CN104496885B (en) | A kind of preparation method of the Nitroisatoic of 4 amino of N methyl 5 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20160323 |