CN107056631A - A kind of 2 alkenyl amino benzenes compounds preparation methods reacted based on Heck - Google Patents
A kind of 2 alkenyl amino benzenes compounds preparation methods reacted based on Heck Download PDFInfo
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- CN107056631A CN107056631A CN201710243009.9A CN201710243009A CN107056631A CN 107056631 A CN107056631 A CN 107056631A CN 201710243009 A CN201710243009 A CN 201710243009A CN 107056631 A CN107056631 A CN 107056631A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C227/04—Formation of amino groups in compounds containing carboxyl groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
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- 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
- C07D213/60—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 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
- C07D213/72—Nitrogen atoms
- C07D213/73—Unsubstituted amino or imino radicals
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Abstract
A kind of 2 alkenyl amino benzenes compounds preparation methods reacted based on Heck, it belongs to pharmaceutical-chemical intermediate and related chemistry technical field.This method uses adjacent halo aniline and acrylate as raw material, under palladium chtalyst effect, realizes the green of 2 alkenyl amino benzenes compounds, efficiently synthesizes.This method has that reaction condition is gentle, functional group compatibility is good, substrate spectrum is wide, advantages of environment protection.Because 2 alkenyl amino benzenes compounds are a kind of important organic synthesis intermediates, had a very wide range of applications in organic synthesis and pharmaceutical field, therefore, the present invention has larger application value and economic results in society.
Description
Technical field
The present invention relates to pharmaceutical-chemical intermediate and related chemistry technical field, be related to it is a kind of based on Heck reactions, with
Adjacent chloro aminobenzen, adjacent bromoaniline or adjacent iodo aniline and the 2- alkenyl amino benzenes compounds that acrylic ester compound is raw material
Preparation method.
Background technology
2- alkenyl amino benzenes compounds are the important synthesis of natural product of a class, medicine or functional molecular intermediate, are being had
Machine synthesis field has a very wide range of applications.2- alkenyl amino benzenes compounds, the table especially in terms of the synthesis such as medicine and agricultural chemicals
Reveal huge purposes, thus the synthesis of 2- alkenyl amino benzenes compounds is one of current study hotspot.Utilize palladium chtalyst
Heck reacts a kind of important synthesizing mean to form that C-C keys are synthesis 2- alkenyl aniline, and classical catalyst system and catalyzing is in palladium catalyst
Under existence condition, by part regulation and control realize its C-C coupling reaction [referring to:(a) Cherney,A.H.；Kadunce,N.T.；
Reisman,S.E.Chem.Rev.2015,115, 9587.(b)Dounay,A.B.；Overman,L.E.Chem.Rev.2003,
103,2945.(c) Kwok,T.J.；Virgilio,J.A.Org.Process Res.Dev.2005,9,694.(d)
Brovetto,M.；Gamenara,D.；Mendez,P.S.；Seoane,G.A.Chem.Rev. 2011,111,4346.].But
Such method has the following disadvantages：The use of part adds the cost of catalyst system and catalyzing；Post-reaction treatment is difficult；Easily cause and urge
Agent is poisoned；Severe reaction conditions etc..Although at present develop several other Heck catalytic reactions systems [referring to：(a)
Herrmann,W.A.；Brossmer,C.；Ofele.K.；Reisinger,C.-P.；Priermeier,T.； Beller,M.；
Fischer,H.Angew.Chem.Int.Ed.Engl.1995,34,1844.(b) Satyanarayana,G.；Helmchen,
G.Eur.J.Org.Chem.2014,2242.(c) Martinez,R.；Voica,F.；Genet,J.-P.；Darses,
S.Org.Lett.2007,9,3213. (d)Liu,C.；Tang,S.；Liu,D.；Yuan,J.；Zheng,L.；Meng,L.；
Lei,A. Angew.Chem.Int.Ed.2012,51,3638.(e)Nacci,V.C.A.；Monopoli,A.； Ieva,E.；
Cioffi,N.Org.Lett.2005,7,617.(f)Tian,J.；Moeller, K.D. Org.Lett.2005,7,5381.],
But these catalysis process are present that reaction condition is special, catalyst system and catalyzing is complicated, the shortcomings of easily cause catalyst poisoning.Thus open
Sending out a kind of, reaction condition is gentle, Atom economy is high, the synthesis side of the 2- alkenyl amino benzenes compounds of excellent catalytic effect, high income
Method is significant.
The content of the invention
The invention provides a kind of new Heck catalytic reaction systems, for preparing 2- alkenyl amino benzenes compounds, the party
Method is raw material using adjacent halo aniline and acrylic ester compound, realizes homogeneous and heterogeneous palladium catalyzed adjacent halo aniline
Reacted with the Heck of acrylic ester compound, synthesize 2- alkenyl amino benzenes compounds.This method have catalyst system and catalyzing it is simple,
The advantages of mild condition, Atom economy are good, environment-friendly, easy realization is industrialized.The present invention have larger application value and
Economic results in society.
The technical solution adopted by the present invention is：A kind of 2- alkenyl amino benzenes compounds preparation methods reacted based on Heck,
Using 2- halos aniline and acrylic ester compound as raw material, by palladium chtalyst Heck coupling reactions, a series of 2- alkenyls are synthesized
Amino benzenes compounds, this method comprises the following steps：
Synthetic route is as follows：
Wherein：R=hydrogen, C1-6Straight or branched alkyl, halogen, nitro or cyano group, X=Cl, Br or I, R1It is hydrogen, first
Base, ethyl or phenyl ring, R2It is methyl or ethyl；
(1) adjacent halo aniline, palladium salt catalyst, acrylic ester compound, alkali and organic solvent are added sequentially to instead
Answer in device, 25~120 DEG C are reacted 12~36h hours；The mol ratio of the adjacent halo aniline and acrylic ester compound is 1:1
~1:5, the mol ratio of adjacent halo aniline and alkali is 1:0.5~1:5, the mol ratio of adjacent halo aniline and palladium salt catalyst is 1:
0.02~1:0.3；
(2) after reaction terminates, removal of solvent under reduced pressure carries out silica gel post separation with eluant, eluent, obtains 2- alkenyl phenyl amines
Compound.
Adjacent halo amino benzenes compounds include the adjacent chlorobenzene containing alkyl, containing halogen, containing nitro, containing cyano group
Amine, adjacent bromoaniline or adjacent iodo aniline；Acrylic ester compound includes the ethyl acrylate containing alkyl or contains aromatic ring
Acrylic ester compound；X on phenyl ring is chlorine, bromine or iodine group；R on phenyl ring be hydrogen, alkyl chain, phenyl ring, chlorine, bromine,
Nitro, cyano group or alkoxy grp；R on acrylic ester compound1It is hydrogen, methyl, ethyl or phenyl ring；Esters of acrylic acid chemical combination
R on thing2It is methyl or ethyl；The mol ratio of adjacent halo aniline and acrylic ester compound is 1:1~1:5.
Range of reaction temperature is 25~120 DEG C, preferably 60~100 DEG C.
Reaction time range is 12~36h, preferably 18~24h.
Alkali used is organic amine or basic salt, selected from potassium carbonate, calcium carbonate, sodium carbonate, cesium carbonate, sodium acid carbonate, phosphorus
Sour potassium, potassium dihydrogen phosphate, dipotassium hydrogen phosphate, sodium phosphate, potassium hydroxide, sodium hydroxide, calcium hydroxide, ammoniacal liquor, triethylamine, three fourths
Amine, N, N- diisopropyl ethyl amines, pyridine；
Palladium salt catalyst is selected from palladium bichloride, acid chloride, palladium charcoal, acetopyruvic acid palladium, palladium dydroxide, palladium trifluoroacetate, nitre
Sour palladium, palladium sulfate.It is preferred that palladium bichloride, acid chloride and palladium charcoal.
The amount of organic solvent is 1~200mL, and it is sub- that the organic solvent is selected from benzene, toluene, Isosorbide-5-Nitrae-dioxane, dimethyl
Sulfone, ethanol, methanol, the tert-butyl alcohol, isopropanol, dichloromethane, chloroform, n-butyl ether, carbon tetrachloride, dimethyl adipate, second
Acetoacetic ester, petroleum ether, methyl tertiary butyl ether(MTBE), tetrahydrofuran, acetone, N,N-dimethylformamide, acetonitrile, hexamethylene, n-hexane
In one or more.
The mol ratio of adjacent halo aniline and palladium salt catalyst is 1:0.02~1:0.3.
The mol ratio of adjacent halo aniline and alkali is 1:0.5~1:5.
The mol ratio of adjacent halo aniline and acrylic ester compound is 1:1~1:5
Beneficial effect：The 2- alkenyl aniline synthesis methods of the present invention, with reaction condition is gentle, functional group compatibility is good,
Wide application range of substrates, advantages of environment protection, be specially：
(1) part is not used in this method, the cost of catalyst system and catalyzing is reduced；Post-reaction treatment is simple；Avoid part
The problems such as using caused catalyst poisoning, severe reaction conditions.
(2) this method is the Heck reactions carried out for the adjacent halo amino benzenes compounds of substrate, in the prior art because of amino
The presence of substituted radical, easily causes palladium catalyst to be poisoned, and is difficult to be catalyzed with palladium bichloride etc., causes reaction system to answer
It is miscellaneous, severe reaction conditions.It is non-in the generation of reaction system situ because of the use of the reproducibility reagent such as triethylamine in the application
The palladium black of phase, or directly use heterogeneous palladium charcoal as catalyst, it is to avoid the poisoning of catalyst, can use gentle, simple bar
Part, realizes the Heck reactions of adjacent halo amino benzenes compounds.
(3) excellent catalytic effect, high income, according to the data grasped, in the Heck reactions reported at present, has no palladium
It is catalyzed the relevant report of the Heck reactions of amino-contained compound.Exemplified by using palladium charcoal as catalyst, the yield in the application is
More than 79%, it is as shown in the table.
To sum up, this method is reaction condition is gentle, Atom economy is high, the 2- alkenyl aniline of excellent catalytic effect, high income
The synthetic method of class compound.Because 2- alkenyl aniline is a kind of important organic synthesis intermediate, have non-in pharmaceutical field
Often it is widely applied, therefore, the present invention has larger application value and economic results in society.
Embodiment
The preparation method of 2- alkenyls aniline of the present invention, with raw material is cheap and easy to get, catalyst reusable edible, anti-
Answer mild condition, the advantages of environment-friendly, Atom economy is high, show good application prospect.
With reference to specific embodiment, the present invention is expanded on further.These embodiments be merely to illustrate the present invention and without
In limitation the scope of the present invention.The simple replacement or improvement that technical staff in the art is done to the present invention belong to this hair
Within bright protected technical scheme.
Embodiment 1：Ethyl 3- (2-aminophenyl) acrylate (3a) synthesis
Accurately weigh o-bromoaniline (86.0mg, 0.5mmol), ethyl acrylate (100.1mg, 1.0mmol), acid chloride
(2.2mg, 0.01mmol) and potassium carbonate (138.2mg, 1.0 mmol), and be added sequentially in 50mL Schlenk bottles, add
Ethyl acetate (6.0 mL), is placed in 60 DEG C of oil baths and reacts 24h.After reaction terminates, removal of solvent under reduced pressure uses petroleum ether/second
Acetoacetic ester is as eluant, eluent, and silica gel post separation, 3- (2- aminophenyls)-ethyl acrylate yield is 99%.1H NMR
(400MHz,CDCl3):δ 1.33 (t, J=7.2Hz, 3H), 4.26 (q, J=7.2Hz, 2H), 6.35 (d, J=15.8Hz,
1H),6.70-6.79(m, 2H),7.15-7.19(m,1H),7.37-7.39(m,1H),7.80-7.85(m,1H)；13C NMR
(100MHz,CDCl3):δ14.3,29.7,60.4,116.8,118.2,119.0,120.0, 128.1,140.0,145.3,
167.5.
Embodiment 2：Ethyl 3- (2-amino-5-methylphenyl) acrylate (3b) synthesis
It is accurate weigh 4- methyl 2- bromanilines (93.0mg, 0.5mmol), ethyl acrylate (100.1 mg, 1.0mmol),
Palladium charcoal (18.6mg) and sodium carbonate (212.0mg, 2.0mmol), and be added sequentially in 50mL Schlenk bottles, add acetone
(6.0mL), is placed in 100 DEG C of oil baths and reacts 14h.After reaction terminates, removal of solvent under reduced pressure is made using petrol ether/ethyl acetate
For eluant, eluent, silica gel post separation, 3- (5- methyl-2-aminos phenyl)-ethyl acrylate yield is 82%.1H NMR(400MHz,
CDCl3):δ 1.33 (t, J=7.1Hz, 3H), 2.24 (s, 3H), 4.25 (q, J=7.1Hz, 2H), 6.35 (d, J=15.8Hz,
1H), 6.64 (d, J=8.1 Hz, 1H), 6.98-7.00 (m, 1H), 7.20 (s, 1H), 7.82 (d, J=15.8Hz, 1H)；13C
NMR(100MHz,CDCl3):δ14.3,20.4,60.4,117.1,117.9,120.1,128.2, 140.1,142.8,167.3.
Embodiment 3：Ethyl 3- (2-amino-5- (trifluoromethyl) phenyl) acrylate (3c) conjunction
Into
It is accurate weigh 4- trifluoromethyl 2- chloroanilines (97.8mg, 0.5mmol), ethyl acrylate (150.0mg,
1.5mmol), palladium charcoal (9.8mg) and triethylamine (50.5mg, 0.5mmol), and be added sequentially in 50mL Schlenk bottles, plus
Enter acetone (20.0mL), be placed in 80 DEG C of oil baths and react 30h.After reaction terminates, removal of solvent under reduced pressure uses petroleum ether/acetic acid
Ethyl ester is as eluant, eluent, and silica gel post separation, 3- (5- trifluoromethyl -2- aminophenyls)-ethyl acrylate yield is 80%.1H
NMR(400MHz,CDCl3):δ 1.34 (t, J=7.1Hz, 3H), 4.27 (q, J=7.1Hz, 2H), 6.40 (d, J=15.8Hz,
1H), 6.74 (d, J=8.5Hz, 1H), 7.38 (dd, J=8.6Hz, 15.7Hz, 1H), 7.61 (s, 1H), 7.76 (d, J=
8.6Hz, 1H)；13C NMR(100MHz,CDCl3):δ14.3,29.7,60.7,116.2,119.2,120.0, 120.6,
120.9,125.3,125.4,127.8,138.5,147.8,166.8.
Embodiment 4：Ethyl 3- (2-amino-5-chlorophenyl) acrylate (3d) synthesis
Accurately weigh the chloro- 2- Iodoanilines (126.8mg, 0.5mmol) of 4-, ethyl acrylate (50.1 mg, 0.5mmol), palladium
Charcoal (6.4mg) and potassium hydroxide (140.3mg, 2.5mmol), and be added sequentially in 50mL Schlenk bottles, add toluene
(2.0mL), is placed in 120 DEG C of oil baths and reacts 18h.After reaction terminates, removal of solvent under reduced pressure is made using petrol ether/ethyl acetate
For eluant, eluent, silica gel post separation, 3- (the chloro- 2- aminophenyls of 5-)-ethyl acrylate yield is 90%.1H NMR(400MHz,
CDCl3):δ 1.33 (t, J=7.2Hz, 3H), 4.26 (q, J=7.2Hz, 2H), 6.34 (d, J=15.8Hz, 1H), 6.66 (d,
J=8.6Hz, 1H), 7.12 (dd, J=2.4Hz, 15.8Hz, 1H), 7.35 (d, 2.4Hz, 1H), 7.72 (d, 15.8Hz, 1H)
；13C NMR(100MHz,CDCl3):δ14.3,29.7,60.6,118.0,119.4,121.2, 123.8,127.3,130.9,
138.5,143.7,166.9.
Embodiment 5：Ethyl 3- (2-amino-5-bromophenyl) acrylate (3e) synthesis
It is accurate weigh the bromo- 2- Iodoanilines (149.0mg, 0.5mmol) of 4-, ethyl acrylate (100.1mg, 1.0mmol),
Palladium nitrate (3.5mg, 0.015mmol) and pyridine (158.2mg, 2.0mmol), and be added sequentially in 50mL Schlenk bottles,
Tetrahydrofuran (15.0mL) is added, is placed in 70 DEG C of oil baths and reacts 20h.After reaction terminates, removal of solvent under reduced pressure uses petroleum ether
/ ethyl acetate is as eluant, eluent, and silica gel post separation, 3- (the bromo- 2- aminophenyls of 5-)-ethyl acrylate yield is 78%.1H
NMR(400MHz,CDCl3):δ1.33(t,J=7.2Hz, 3H), 4.26 (q,J=7.2Hz, 2H), 6.33 (d,J=15.8Hz,
1H),6.59(d,J=8.5Hz, 1H), 7.24 (d,J=8.6Hz, 1H), 7.476-7.482 (m, 1H), 7.68-7.82 (m,
1H)；13C NMR(100MHz,CDCl3):δ14.3,29.7,60.6,110.6,118.2,119.4,121.7, 130.2,
133.7,138.4,144.3,166.9.
Embodiment 6：Ethyl 3- (2-amino-5-fluorophenyl) acrylate (3f) synthesis
Accurately weigh the fluoro- 2- bromanilines (95.0mg, 0.5mmol) of 4-, ethyl acrylate (250.2mg, 2.5mmol), hydrogen
Palladium oxide (1.4mg, 0.01mmol) and potassium phosphate (212.3mg, 1.0 mmol), and it is added sequentially to 50mL Schlenk bottles
In, hexamethylene (25.0mL) is added, is placed in 60 DEG C of oil baths and reacts 26h.After reaction terminates, removal of solvent under reduced pressure uses oil
Ether/ethyl acetate is as eluant, eluent, and silica gel post separation, 3- (the fluoro- 2- aminophenyls of 5-)-ethyl acrylate yield is 94%.1H
NMR(400MHz,CDCl3):δ 1.33 (t, J=7.1Hz, 3H), 4.26 (q, J=7.1Hz, 2H), 6.33 (d, J=15.8Hz,
1H), 6.66-6.70 (m, 1H), 6.88-6.93 (m, 1H), 7.07-7.10 (m, 1H), 7.77 (d, J=15.8 Hz, 1H)；13C
NMR(100 MHz,CDCl3):δ14.3,29.7,60.6,113.2,113.5,118.1,118.2, 118.3,119.4,
138.75,138.78,141.2,155.2,157.5,166.9。
Claims (5)
1. a kind of 2- alkenyl amino benzenes compounds preparation methods reacted based on Heck, with 2- halos aniline and esters of acrylic acid
Compound is raw material, by palladium chtalyst Heck coupling reactions, synthesizes a series of 2- alkenyls amino benzenes compounds, it is characterised in that should
Method comprises the following steps：
Synthetic route is as follows：
Wherein：R=hydrogen, C1-6Straight or branched alkyl, halogen, nitro or cyano group, X=Cl, Br or I, R1Be hydrogen, methyl, ethyl or
Phenyl ring, R2It is methyl or ethyl；
（1）Adjacent halo aniline, palladium salt catalyst, acrylic ester compound, alkali and organic solvent are added sequentially to reactor
In, 25 ~ 120 oC react 12 ~ 36 h hours；The mol ratio of the adjacent halo aniline and acrylic ester compound is 1:1~1:
5, the mol ratio of adjacent halo aniline and alkali is 1:0.5~1:5, the mol ratio of adjacent halo aniline and palladium salt catalyst is 1:0.02~1:
0.3；
（2）After reaction terminates, removal of solvent under reduced pressure carries out silica gel post separation with eluant, eluent, obtains 2- alkenyl amino benzenes compounds.
2. a kind of 2- alkenyl amino benzenes compounds preparation methods reacted based on Heck according to claim 1, its feature
It is：The palladium salt catalyst is selected from palladium bichloride, acid chloride, palladium charcoal, acetopyruvic acid palladium, palladium dydroxide, palladium trifluoroacetate, nitre
Sour palladium or palladium sulfate.
3. a kind of 2- alkenyl amino benzenes compounds preparation methods reacted based on Heck according to claim 1, its feature
It is：The alkali is selected from potassium carbonate, calcium carbonate, sodium carbonate, cesium carbonate, sodium acid carbonate, potassium phosphate, potassium dihydrogen phosphate, phosphoric acid hydrogen
Dipotassium, sodium phosphate, potassium hydroxide, sodium hydroxide, calcium hydroxide, ammoniacal liquor, triethylamine, tri-n-butylamine,N,N- diisopropyl ethyl amine,
Pyridine.
4. a kind of 2- alkenyl amino benzenes compounds preparation methods reacted based on Heck according to claim 1, its feature
It is：The organic solvent be selected from benzene, toluene, 1,4- dioxane, dimethyl sulfoxide (DMSO), ethanol, methanol, the tert-butyl alcohol, isopropanol,
Dichloromethane, chloroform, n-butyl ether, carbon tetrachloride, dimethyl adipate, ethyl acetate, petroleum ether, methyl tertiary butyl ether(MTBE),
Tetrahydrofuran, acetone,N,NOne or more in-dimethylformamide, acetonitrile, hexamethylene, n-hexane.
5. a kind of 2- alkenyl amino benzenes compounds preparation methods reacted based on Heck according to claim 1, its feature
It is：The amount of described organic solvent is 1 ~ 200 mL.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007084135A2 (en) * | 2005-01-28 | 2007-07-26 | Merck & Co., Inc. | Inhibitors of checkpoint kinases |
| CN101678330A (en) * | 2007-05-14 | 2010-03-24 | 诺迪克化学探索公司 | Process for the production of palladium supported catalysts for catalyzing heck, suzuki-miyaura sonogashira coupling and buchwald-hartwig reactions |
| WO2014201206A1 (en) * | 2013-06-12 | 2014-12-18 | Amgen Inc. | Bicyclic sulfonamide compounds as sodium channel inhibitors |
| US20160264518A1 (en) * | 2015-03-13 | 2016-09-15 | Forma Therapeutics, Inc. | Alpha-cinnamide compounds and compositions as hdac8 inhibitors |
-
2017
- 2017-04-14 CN CN201710243009.9A patent/CN107056631A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007084135A2 (en) * | 2005-01-28 | 2007-07-26 | Merck & Co., Inc. | Inhibitors of checkpoint kinases |
| CN101678330A (en) * | 2007-05-14 | 2010-03-24 | 诺迪克化学探索公司 | Process for the production of palladium supported catalysts for catalyzing heck, suzuki-miyaura sonogashira coupling and buchwald-hartwig reactions |
| WO2014201206A1 (en) * | 2013-06-12 | 2014-12-18 | Amgen Inc. | Bicyclic sulfonamide compounds as sodium channel inhibitors |
| US20160264518A1 (en) * | 2015-03-13 | 2016-09-15 | Forma Therapeutics, Inc. | Alpha-cinnamide compounds and compositions as hdac8 inhibitors |
Non-Patent Citations (3)
| Title |
|---|
| JON VALGEIRSSON等: "Bioisosteric Modifications of 2-Arylureidobenzoic Acids: Selective Noncompetitive Antagonists for the Homomeric Kainate Receptor Subtype GluR5", 《J. MED. CHEM.》 * |
| P. JAKE SLAVISH等: "Design and synthesis of a novel tyrosine kinase inhibitor template", 《BIOORGANIC & MEDICINAL CHEMISTRY》 * |
| WENYAN HAO等: "A Highly Efficient Copper(I)-Catalyzed Cascade Reaction of o-Alkenylphenyl Isothiocyanates with Isocyanides Leading to 5H-Benzo[d]imidazo[5,1-b]-[1,3]thiazines", 《EUR. J. ORG. CHEM.》 * |
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