CN104447539A - Method for synthesizing binary and ternary aryl amide compounds - Google Patents
Method for synthesizing binary and ternary aryl amide compounds Download PDFInfo
- Publication number
- CN104447539A CN104447539A CN201410634539.2A CN201410634539A CN104447539A CN 104447539 A CN104447539 A CN 104447539A CN 201410634539 A CN201410634539 A CN 201410634539A CN 104447539 A CN104447539 A CN 104447539A
- Authority
- CN
- China
- Prior art keywords
- methyl
- ring
- acid
- quinoline
- grades
- 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.)
- Granted
Links
Classifications
-
- 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
- C07D215/16—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 hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D215/48—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Quinoline Compounds (AREA)
- Catalysts (AREA)
Abstract
The invention provides a synthetic method for forming binary and ternary aryl amide compounds by virtue of direct methyl functionalization. The method comprises the following steps: by taking a 2-methyl-N-heterocyclic aromatic hydrocarbon and an amine source as raw materials, taking metal copper as a catalyst, taking Brnsted acid as an additive, and taking molecular O2 (oxygen) as an oxidizing agent, activating sp3C-H of 2-methyl-N-heterocyclic aromatic hydrocarbon under an oxygen atmosphere to generate corresponding aldehyde, reacting aldehyde with different amine sources to generate the binary or ternary aryl amide compounds. The method has the characteristics that the metal copper with low price serves as the catalyst, the commercial 2-methyl-N-heterocyclic aromatic hydrocarbon serves as the substrate, the molecular O2 (oxygen) serves as an oxidizing agent, so that an oxidative amidation reaction is carried out. According to the method, the reaction conditions are mild, the operation is easy, the applicability is high and the industrial application prospects are good.
Description
[technical field]
The present invention relates to organic synthesis field, be specifically related to a kind of synthetic method being formed secondary, three grades of aromatic amides by the direct functionalization of methyl.
[background technology]
Amido linkage is one of modal functional group at pharmaceutical synthesis, fine chemistry industry and macromolecular material, and the fragrant medicine of result display more than 25% has amide functional group according to statistics.Therefore, the synthesis of aromatic amides is not only the emphasis that biology and pharmaceutical field are paid close attention to always, one of heat subject of organic synthesis and the research of other industrial circles especially.
For the synthesis of secondary or three grades of aromatic amides, the most traditional synthetic method is no more than the reaction by carboxylic acid or carboxylic acid derivative and amine, and the method not only exists the speed of the by product impact reaction of the not high defect of Atom economy but also generation equivalent.Because secondary or three grades of amide compounds have very high utility value, for many years the work building secondary or three grades of amide compounds was never stopped.In recent years, research worker updates from raw material and catalyzer, report about secondary or three grades of aromatic amides synthetic methods successively: (1) C.Ramalingan and Y.Park utilizes the traditional method Beckmann rearrangement reaction synthesizing secondary aromatic amides improved, although overcome traditional severe condition, such as avoid using a large amount of strong acid and very high temperature of reaction, but the HgCl needing toxicity larger
2make catalyzer; (2) people such as Y.J.Wu probes into the amidate action of aldehyde and amine, the undeniable advantage with high conversion, but due to the characteristic of aldehyde inherence, to preserve and use is enough to make people worried for a long time; (3) people such as B.Roberts and D.Liptrot finds that halogenated aryl hydrocarbon can be utilized to carry out aminocarboxylic glycosylation reaction obtains secondary aromatic amides, but the method not only needs transition metal to make catalyzer but also needs a large amount of alkali and the participation of part; (4) A.J.A.Watson and A.C.Maxwell utilizes alkohol and amine to carry out oxidation and generates secondary or three grades of aromatic amides, and but by product only has hydrogen generate need precious metal to make catalyzer (as: ruthenium) at present.These methods not only respective existing defects above, and they have a common weak point to be to depend on the conversion of functional functional group or the functional group of activation.As everyone knows, c h bond is the most ubiquitous chemical bond in the boundless universe.
Thus, direct by the functionalized method efficiently preparing secondary or three grades of aromatic amides of c h bond under developing a kind of mild conditions, being the most direct and optimal synthetic method, is also one of technical barrier of organic synthesis solution too impatient to wait.(reference: a) Y.Y.Lai, L.J.Huang, K.H.Lee, Z.Y.Xiao, K.F.Bastow, T.Yamoric, S.C.Kuo, Bioorg.Med.Chem.2005,13265; B) N.A.Owston, A.J.Parker, J.M.Williams, Org.Lett.2007,9,3599; C) Y.J.Wu, S.W.Wang, L.J.Zhang, G.S.Yang, X.C.Zhu, Z.H.Zhou, H.Zhu, S.H.Wu, Eur.J.Org.Chem.2010,326; D) B.Roberts, D.Liptrot, L.Alcaraz, T.Luker, M.J.Stocks, Org.Chem.2010,75,8410; E) A.J.A.Watson, A.C.Maxwell, J.M.J.Williams, Org.Lett, 2009,11,2667.)
The invention provides a kind of directly functionalized by methyl, metallic copper catalysis, mild condition, simple to operate, raw material are easy to get and high suitability prepares the synthetic method of secondary or three grades of aromatic amides.
[summary of the invention]
The object of the invention is development a kind of directly functionalized by methyl, with metallic copper make catalyzer, additive is done in bronsted acid, 2-methyl-N-heterocyclic aromatic compounds cheap and easy to get and ammonium source are raw material, select oxygen to make oxygenant, high suitability prepares the method for secondary or three grades of aromatic amides.
Goal of the invention of the present invention is realized by following technological method:
The secondary of one as shown in structural formula (I) or the synthetic method of three grades of aromatic amides,
Comprise following operation steps:
Metallic copper catalyzer, bronsted acid, amine source, 2-methyl-N-heterocyclic aromatic compounds will be housed
reaction vessel vacuumize, fill oxygen, then add organic solvent sealing; Be heated to 100 ~ 150 DEG C of reaction 8 ~ 24h, be cooled to room temperature after reaction terminates, with saturated sodium bicarbonate washing, then use chloroform extraction, dry, underpressure distillation is concentrated except desolventizing, and thick product, through pillar layer separation, obtains target product.
Wherein said N-heterocycle is pyridine ring, thiazole ring, pyrazine ring, benzothiazole ring, quinoxaline ring, quinoline ring or phenanthroline ring;
Described R
1for amino, trimethyl-acetyl, methyl, fluorine, chlorine, bromine, nitro, methyl-formiate or methoxyl group;
When structural formula (I) is secondary aromatic amides, corresponding R
2for hydrogen, R
3for phenyl, 2-p-methoxy-phenyl, 2-chloro-phenyl-, 4-aminomethyl phenyl, 4-chloro-phenyl-, 4-nitrophenyl, sec.-propyl or normal-butyl;
When structural formula (I) is three grades of aromatic amides, corresponding R
2=R
3, R
2~ R
3for piperidine ring, morpholine ring or Pyrrolidine ring.
Further, the mol ratio in described metallic copper catalyzer, bronsted acid, 2-methyl-N-heterocyclic aromatic compounds and amine source is [0.05 ~ 0.2]: [0.5 ~ 1.0]: 1:[1.0 ~ 2.0].
Described organic solvent is selected from one or more of Isosorbide-5-Nitrae-dioxane, DMF, chlorobenzene, methyl-phenoxide, toluene or tetrahydrofuran (THF).
Further, described metallic copper catalyzer is selected from Cu, CuBr, CuCl, CuI, Cu (OAc)
2, CuBr, CuBr
2, CuI
2, CuO or Cu (OTf)
2one or more.
Further, described bronsted acid is selected from one or more of acetic acid, phenylformic acid, toluylic acid, Phenylsulfonic acid or diphenylphosphoric acid.
Further, described amine source is selected from aniline, p-Nitroaniline, p-Chlorobenzoic acid amide, open-chain crown ether, Ortho-Chloro aniline, ORTHO ANISIDINE, Isopropylamine, n-Butyl Amine 99, piperidines, morpholine or Pyrrolidine.
Further, described 2-methyl-N-heterocyclic aromatic compounds (II) is selected from 2-picoline, 2-methylthiazol, 2-methylpyrazine, 2-methylbenzothiazole, 2-methyl-quinoxaline, 2-toluquinoline, 2-methyl-4-quinolylamine, 2-methyl-4-pivalyl amido quinoline, 2, 6-dimethyl quinoline, 2-methyl-6-fluorine quinoline, 2-methyl-6-chloroquinoline, 2-methyl-6-bromoquinoline, 2-methyl-6-nitroquinoline, 2-methyl-6-methyl-formiate quinoline, 2-methyl-6-methoxy quinoline, 2-methyl-8-methoxy quinoline or 2, 9-dimethyl-1, 10-phenanthroline.
The invention provides a kind of directly functionalized by methyl, metallic copper catalysis, mild condition, simple to operate, raw material are easy to get and high suitability prepares the synthetic method of secondary or three grades of aromatic amides, have good prospects for commercial application.
[Brief Description Of Drawings]
Fig. 1 is the synthesis path figure of secondary provided by the invention or three grades of aromatic amides compounds.
[embodiment]
Be described further synthetic method of the present invention below in conjunction with synthesis example of the present invention, it should be noted that, embodiment does not form the restriction to application claims protection domain:
synthesis example 1
The synthesis of N-phenylquinoline-2-methane amide
In reaction vessel, add the cuprous iodide of 10mol%, vacuumize, backfill oxygen, then adds 0.2mmol acetic acid, 0.2mmol2-toluquinoline, 0.4mmol aniline and 1mL methyl-phenoxide, sealing; React 24h. question response liquid at being heated to 100 DEG C and be cooled to room temperature, with saturated sodium bicarbonate solution washing, then with chloroform extraction, dry, underpressure distillation is concentrated except desolventizing, and namely thick product obtains target product through pillar layer separation, and productive rate is 69%.Through nuclear-magnetism inspection without other impurities left.
1H NMR(400MHz,CDCl
3)δ10.24(s,1H),8.35-8.42(m,2H),8.19(d,J＝8.4Hz,1H),7.79-7.92(m,4H),7.65(dd,J
1＝J
2＝8.0Hz,1H),7.42(dd,J
1＝J
2＝8.0Hz,2H),7.17(t,J＝7.6Hz,1H)；
13C NMR(100MHz,CDCl3)δ162.18,149.68,146.31,137.87,137.80,130.33,129.68,129.44,129.12,128.17,127.83,124.36,119.79,118.77.
synthesis example 2
The synthesis of N-(4-methylphenyl) quinoline-2-formamide
In reaction vessel, add 0.4mmol 4-monomethylaniline, the cuprous bromide of 0.2mmol diphenylphosphoric acid and 10mol% and 10mol% copper powder, vacuumize, backfill oxygen, then 0.2mmol 2-toluquinoline and 0.5mL Isosorbide-5-Nitrae-dioxane and 0.5mL methyl-phenoxide is added, sealing; React 8h. question response liquid at being heated to 130 DEG C and be cooled to room temperature, with saturated sodium bicarbonate solution washing, then with chloroform extraction, dry, underpressure distillation is concentrated except desolventizing, and namely thick product obtains target product through pillar layer separation, and productive rate is 60%.Through nuclear-magnetism inspection without other impurities left.
1H NMR(400MHz,CDCl
3)δ10.18(s,1H),8.35-8.41(m,2H),8.18(d,J＝8.4Hz,1H),7.91(d,J＝8.0Hz,1H),7.80(dd,J
1＝J
2＝8.0Hz,1H),7.74(d,J＝8.4Hz,2H),7.65(dd,J
1＝J
2＝8.0Hz,1H),7.22(d,J＝8.4Hz,2H),2.36(s,3H)；
13C NMR(100MHz,CDCl
3)δ162.04,149.83,146.33,137.83,135.29,133.98,130.30,129.68,129.63,129.41,128.10,127.83,119.77,119.68,118.78,20.97.
synthesis example 3
The synthesis of N-(2-methoxyl group-phenyl) quinoline-2-formamide
In reaction vessel, add the cuprous chloride of 0.1mmol phenylformic acid and 20mol%, vacuumize, backfill oxygen, then adds 0.2mmol 2-toluquinoline, 0.2mmol 2-anisidine and 1mL chlorobenzene, sealing; React 24h. question response liquid at being heated to 100 DEG C and be cooled to room temperature, with saturated sodium bicarbonate solution washing, then with chloroform extraction, dry, underpressure distillation is concentrated except desolventizing, and namely thick product obtains target product through pillar layer separation, and productive rate is 34%.Through nuclear-magnetism inspection without other impurities left.
1H NMR(400MHz,CDCl
3)δ10.82(s,1H),8.65(dd,J
1＝1.6Hz,J
2＝8.0Hz,1H),8.34-8.41(m,2H),8.21(d,J＝8.4Hz,1H),7.90(d,J＝8.4Hz,1H),7.79(dd,J
1＝J
2＝8.0Hz,1H),7.64(dd,J
1＝J
2＝7.6Hz,1H),7.03-7.13(m,2H),6.96-6.98(dd,J
1＝1.2Hz,J
2＝8.0Hz,1H),4.02(s,3H)；
13C NMR(100MHz,CDCl
3)δ162.19,150.19,148.92,146.43,137.68,130.12,130.01,129.36,128.04,127.76,127.65,124.02,121.14,119.80,118.80,110.20
synthesis example 4
The synthesis of N-(the chloro-phenyl of 2-) quinoline-2-formamide
In reaction vessel, add the neutralized verdigris of 0.2mmol Phenylsulfonic acid and 10mol%, vacuumize, backfill oxygen, then adds the chloro-aniline of 0.4mmol 2-, 0.2mmol 2-toluquinoline and 1mL toluene, sealing; React 12h. question response liquid at being heated to 140 DEG C and be cooled to room temperature, with saturated sodium bicarbonate solution washing, then with chloroform extraction, dry, underpressure distillation is concentrated except desolventizing, and namely thick product obtains target product through pillar layer separation, and productive rate is 67%.Through nuclear-magnetism inspection without other impurities left.
1H NMR(400MHz,CDCl
3)δ10.98(s,1H),8.70(d,J＝8.4Hz,1H),8.38(b,2H),8.21(d,J＝8.4Hz,1H),7.91(d,J＝8.0Hz,1H),7.81(dd,J
1＝J
2＝8.0Hz,1H),7.66(dd,J
1＝J
2＝7.6Hz,1H),7.46(d,J＝8.0Hz,1H),7.36(dd,J
1＝J
2＝8.0Hz,1H),7.09(ddd,J
1＝1.2Hz,J
2＝7.6Hz,J
2＝7.6Hz,1H)；
13C NMR(100MHz,CDCl
3)δ162.35,149.47,146.35,137.89,134.84,130.35,130.08,129.51,129.27,128.33,127.79,127.73,124.62,123.58,121.02,118.65.
synthesis example 5
The synthesis of N-(the chloro-phenyl of 4-) quinoline-2-formamide
In reaction vessel, add the chloro-aniline of 0.4mmol 4-, the cupric bromide of 0.1mmol toluylic acid and 0.1mmol diphenylphosphoric acid and 10mol% and 10mol% cupric iodide, vacuumize, backfill oxygen, then 0.2mmol 2-toluquinoline is added and 1mLN, N-dimethyl formyl is pressed, sealing; React 19h. question response liquid at being heated to 130 DEG C and be cooled to room temperature, with the washing of ammonia saturated sodium bicarbonate solution, then with chloroform extraction, dry, underpressure distillation is concentrated except desolventizing, and namely thick product obtains target product through pillar layer separation, and productive rate is 66%.Through nuclear-magnetism inspection without other impurities left.
1H NMR(400MHz,CDCl
3)δ10.25(s,1H),8.38(b,2H),8.18(d,J＝8.4Hz,1H),7.92(d,J＝7.6Hz,1H),7.80-7.84(m,3H),7.67(dd,J
1＝J
2＝8.0Hz,1H),7.38(d,J＝8.8Hz,2H)；
13C NMR(100MHz,CDCl
3)δ162.21,149.37,146.30,137.99,136.41,130.45,129.65,129.51,129.30,129.15,128.30,127.87,120.98,118.72.
.
synthesis example 6
The synthesis of N-(4-nitro-phenyl) quinoline-2-formamide
In reaction vessel, add 0.4mmol 4-nitro-analine, the cuprous iodide of 0.2mmol diphenylphosphoric acid and 20mol%, vacuumizes, and backfill oxygen, then adds 0.2mmol 2-toluquinoline and 1mL methyl-phenoxide, sealing; React 24h. question response liquid at being heated to 150 DEG C and be cooled to room temperature, with saturated sodium bicarbonate solution washing, then with chloroform extraction, dry, underpressure distillation is concentrated except desolventizing, and namely thick product obtains target product through pillar layer separation, and productive rate is 39%.Through nuclear-magnetism inspection without other impurities left.
1H NMR(400MHz,CDCl
3)δ10.59(s,1H),8.38-8.43(m,2H),8.31(d,J＝9.2Hz,2H),8.21(d,J＝8.4Hz,1H),8.04(d,J＝9.2Hz,2H),7.95(d,J＝8.4Hz,1H),7.85(dd,J
1＝J
2＝8.0Hz,1H),7.70(dd,J
1＝J
2＝8.0Hz,1H)；
13C NMR(100MHz,CDCl
3)δ162.60,148.65,146.26,143.65,143.53,138.28,130.72,129.71,129.65,128.68,127.94,125.25,119.25,118.71.
.
synthesis example 7
The synthesis of N-sec.-propyl-quinoline-2-formamide
In reaction vessel, add cuprous iodide and the 5mol% cupric oxide of 0.2mmol diphenylphosphoric acid and 10mol%, vacuumize, backfill oxygen, then adds 0.4mmol Isopropylamine, 0.2mmol 2-toluquinoline and 1mL chlorobenzene and 1mL tetrahydrofuran (THF), sealing; React 15h. question response liquid at being heated to 100 DEG C and be cooled to room temperature, with saturated sodium bicarbonate solution washing, then with chloroform extraction, dry, underpressure distillation is concentrated except desolventizing, and namely thick product obtains target product through pillar layer separation, and productive rate is 29%.Through nuclear-magnetism inspection without other impurities left.
1H NMR(400MHz,CDCl
3)δ8.29-8.33(m,2H),8.11-8.13(m,2H),7.88(d,J＝8.4Hz,1H),7.74-7.79(m,1H),7.59-7.63(m,1H),4.30-4.39(m,1H),1.35(d,J＝6.4Hz)；
13C NMR(100MHz,CDCl
3)δ163.58,150.06,146.48,137.44,130.02,129.65,129.28,127.79,127.77,118.86,41.56,22.85.
synthesis example 8
The synthesis of N-cyclohexyl-quinoline-2-formamide
In reaction vessel, add 0.2mmol phenylformic acid and 15mol% trifluoracetic acid copper, vacuumize, backfill oxygen, then adds 0.4mmol piperidines, 0.2mmol 2-toluquinoline and 1mL methyl-phenoxide, sealing; React 12h. question response liquid at being heated to 130 DEG C and be cooled to room temperature, with saturated sodium bicarbonate solution washing, then with chloroform extraction, dry, underpressure distillation is concentrated except desolventizing, and namely thick product obtains target product through pillar layer separation, and productive rate is 41%.Through nuclear-magnetism inspection without other impurities left.
1H NMR(400MHz,CDCl3)δ8.25(d,J＝8.4Hz,1H),8.11(d,J＝8.4Hz,1H),7.85(d,J＝8.0Hz,1H),7.74-7.78(m,1H),7.66(d,J＝8.0Hz,1H),7.58-7.62(m,1H),3.81(t,J＝5.2Hz,2H),3.52(t,J＝5.2Hz,2H),1.73(b,6H)；
13C NMR(100MHz,CDCl
3)δ167.60,154.42,146.79,137.12,130.00,129.74,127.94,127.65,127.38,120.41,48.35,43.36,26.52,25.60,24.60。
Claims (7)
1. there is the secondary of following structural formula (I) or a synthetic method for three grades of aromatic amides,
Comprise following reactions steps:
By be equipped with metallic copper catalyzer, bronsted acid, amine source, 2-methyl-N-heterocyclic aromatic compounds reaction vessel vacuumize, fill oxygen, then add organic solvent sealing; Be heated to 100 ~ 150 DEG C of reaction 8 ~ 24h, be cooled to room temperature after reaction terminates, with saturated sodium bicarbonate washing, then use chloroform extraction, dry, underpressure distillation is concentrated except desolventizing, and thick product, through pillar layer separation, obtains target product;
Described N-heterocycle is selected from pyridine ring, thiazole ring, pyrazine ring, benzothiazole ring, quinoxaline ring, quinoline ring or phenanthroline ring;
Described R
1be selected from amino, trimethyl-acetyl, methyl, fluorine, chlorine, bromine, nitro, methyl-formiate or methoxyl group;
Work as R
2when being hydrogen, R
3phenyl, 2-p-methoxy-phenyl, 2-chloro-phenyl-, 4-aminomethyl phenyl, 4-chloro-phenyl-, 4-nitrophenyl or sec.-propyl or normal-butyl;
Work as R
2=R
3, R
2~ R
3for piperidine ring, morpholine ring or Pyrrolidine ring.
2. the synthetic method of secondary according to claim 1 or three grades of aromatic amides, it is characterized in that, the mol ratio in described metallic copper catalyzer, bronsted acid, 2-methyl-N-heterocyclic aromatic compounds and amine source is [0.05 ~ 0.2]: [0.5 ~ 1.0]: 1:[1.0 ~ 2.0].
3. the synthetic method of secondary according to claim 1 or three grades of aromatic amides, it is characterized in that, described organic solvent is selected from one or more of Isosorbide-5-Nitrae-dioxane, DMF, chlorobenzene, methyl-phenoxide, toluene or tetrahydrofuran (THF).
4. the synthetic method of secondary according to claim 1 or three grades of aromatic amides, is characterized in that, described metallic copper catalyzer is selected from Cu, CuBr, CuCl, CuI, Cu (OAc)
2, CuBr, CuBr
2, CuI
2, CuO or Cu (OTf)
2one or more.
5. the synthetic method of secondary according to claim 1 or three grades of aromatic amides, is characterized in that, described bronsted acid is selected from one or more of acetic acid, phenylformic acid, toluylic acid, Phenylsulfonic acid or diphenylphosphoric acid.
6. the synthetic method of secondary according to claim 1 or three grades of aromatic amides, it is characterized in that, described amine source is selected from aniline, p-Nitroaniline, p-Chlorobenzoic acid amide, open-chain crown ether, Ortho-Chloro aniline, ORTHO ANISIDINE, Isopropylamine, n-Butyl Amine 99, piperidines, morpholine or Pyrrolidine.
7. 2-methyl-N-heterocyclic aromatic compounds according to claim 1 is selected from 2-picoline, 2-methylthiazol, 2-methylpyrazine, 2-methylbenzothiazole, 2-methyl-quinoxaline, 2-toluquinoline, 2-methyl-4-quinolylamine, 2-methyl-4-pivalyl amido quinoline, 2,6-dimethyl quinoline, 2-methyl-6-fluorine quinoline, 2-methyl-6-chloroquinoline, 2-methyl-6-bromoquinoline, 2-methyl-6-nitroquinoline, 2-methyl-6-methyl-formiate quinoline, 2-methyl-6-methoxy quinoline, 2-methyl-8-methoxy quinoline or 2,9-dimethyl-1,10-phenanthroline.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410634539.2A CN104447539B (en) | 2014-11-12 | 2014-11-12 | A kind of two grades, the synthetic method of three-level aromatic amides |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410634539.2A CN104447539B (en) | 2014-11-12 | 2014-11-12 | A kind of two grades, the synthetic method of three-level aromatic amides |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104447539A true CN104447539A (en) | 2015-03-25 |
| CN104447539B CN104447539B (en) | 2017-09-15 |
Family
ID=52894370
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410634539.2A Active CN104447539B (en) | 2014-11-12 | 2014-11-12 | A kind of two grades, the synthetic method of three-level aromatic amides |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104447539B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106565517A (en) * | 2016-10-18 | 2017-04-19 | 湖南大学 | Method for preparing amide from aryl methane derivative and nitrile |
| CN108329261A (en) * | 2018-04-18 | 2018-07-27 | 哈尔滨工业大学（威海） | A kind of environment-friendly preparation method thereof without transition metal-catalyzed amides compound |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013052394A1 (en) * | 2011-10-05 | 2013-04-11 | Merck Sharp & Dohme Corp. | 2-pyridyl carboxamide-containing spleen tyrosine kinase (syk) inhibitors |
-
2014
- 2014-11-12 CN CN201410634539.2A patent/CN104447539B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013052394A1 (en) * | 2011-10-05 | 2013-04-11 | Merck Sharp & Dohme Corp. | 2-pyridyl carboxamide-containing spleen tyrosine kinase (syk) inhibitors |
Non-Patent Citations (4)
| Title |
|---|
| IAN R. GEORGE，等: "Synthesis of lodopyridone", 《TETRAHEDRON》, vol. 69, 16 July 2013 (2013-07-16) * |
| MICHELE GALLETTA,等: "2,9-Dicarbonyl-1,10-phenanthroline derivatives with an unprecedented Am(III)/Eu(III) selectivity under highly acidic conditions", 《DALTON TRANS.》, vol. 42, 11 September 2013 (2013-09-11) * |
| YE WANG,等: "Manganese Oxide Promoted Liquid-Phase Aerobic Oxidative Amidation of Methylarenes to Monoamides Using Ammonia Surrogates", 《ANGEW. CHEM. INT. ED.》, vol. 51, 31 December 2012 (2012-12-31) * |
| 府莹: "《STN检索报告》", 7 January 2016, article "201410634539.2" * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106565517A (en) * | 2016-10-18 | 2017-04-19 | 湖南大学 | Method for preparing amide from aryl methane derivative and nitrile |
| CN108329261A (en) * | 2018-04-18 | 2018-07-27 | 哈尔滨工业大学（威海） | A kind of environment-friendly preparation method thereof without transition metal-catalyzed amides compound |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104447539B (en) | 2017-09-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1984890A (en) | Method for producing 1, 2-dihydropyridine-2-one compound | |
| CN109134362A (en) | A kind of method that the nonmetal catalyzed active carboxylic acid's ester decarboxylation of photoinduction introduces azacyclo- | |
| CN103467388B (en) | Method for synthesizing aryl or heteroaryl substituted quinazoline compound | |
| Zhao et al. | SO2F2-Promoted Dehydration of Aldoximes: A Rapid and Simple Access to Nitriles | |
| CN104447686B (en) | Polysubstituted 2-pyrroles's pyridine derivate and preparation method thereof | |
| KR101067069B1 (en) | Process for preparing phenanthridine derivatives using trifluoroacetic acid | |
| CN104447539A (en) | Method for synthesizing binary and ternary aryl amide compounds | |
| CN103664769A (en) | Synthesis method of dipyridyl derivative or analogue | |
| CN104945383A (en) | Preparation method for topiroxostat | |
| CN106349161B (en) | Preparation method of 4- (2',2',2' -trifluoro) ethyl quinoline series | |
| CN103450111B (en) | Green synthesis method of benzothiazole heterocyclic compound | |
| CN109422700A (en) | A kind of synthetic method of N- acetyl group quinoxaline -2- amide and its derivative | |
| CN104447540A (en) | Synthetic method of primary aryl amide compounds | |
| CN103934028B (en) | The Mn catalyst of pyridine-2-formic acid derivates and synthetic method thereof and application | |
| CN105294776B (en) | A kind of preparation method of the symmetrical dimer of nitrogen heterocyclic ring aromatic compound | |
| CN108864164A (en) | A kind of synthetic method of the 2- alkynyl Benzazole compounds of level-one amine guiding | |
| CN104557725B (en) | A kind of method of the diaryl benzimidazole of one pot process 1,2 and its derivative | |
| CN112300085A (en) | Alkenyl method of methyl heterocyclic compound | |
| CN104974077A (en) | Synthetic method of 2-chloromethylpyridinehydrochloride | |
| CN111533689A (en) | 2, 2' -biquinoline compound and one-pot preparation method thereof | |
| CN104496881A (en) | Preparation method for synthesizing indoline from amide compounds by catalysis of copper salt | |
| CN104016913B (en) | A kind of method preparing amide compound | |
| CN107573215A (en) | A kind of synthetic method of diarylcarbinols class compound | |
| CN109320433B (en) | Preparation method of 4-trifluoromethyl benzonitrile | |
| CN104710350A (en) | Synthesis method of sodium trichloro pyridinol |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |