CN108147996A - A kind of synthetic method of aryl methylene double pyrazole ester monopotassium salt - Google Patents
A kind of synthetic method of aryl methylene double pyrazole ester monopotassium salt Download PDFInfo
- Publication number
- CN108147996A CN108147996A CN201810030425.5A CN201810030425A CN108147996A CN 108147996 A CN108147996 A CN 108147996A CN 201810030425 A CN201810030425 A CN 201810030425A CN 108147996 A CN108147996 A CN 108147996A
- Authority
- CN
- China
- Prior art keywords
- reaction
- monopotassium salt
- aryl methylene
- synthetic method
- double pyrazole
- 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
- C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
- C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
- C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/13—Crystalline forms, e.g. polymorphs
Abstract
A kind of synthetic method of aryl methylene double pyrazole ester monopotassium salt, is related to chemosynthesis technical field.In a solvent, it by phenylhydrazine, aromatic aldehyde, potassium resource and dimethyl butyn or diethyl butyn hybrid reaction, cools down, filter after reaction, obtain solid phase, through recrystallization after being washed with ethyl alcohol, obtain aryl methylene double pyrazole ester monopotassium salt.The shortcomings such as the product separation that the present invention solves heterogeneous reaction is difficult, the problem of overcoming organic micromolecule catalyst pollution products, and the intermediate for also avoiding multistep reaction isolates and purifies trouble, and yield is low.
Description
Technical field
The present invention relates to chemosynthesis technical fields.
Background technology
Aryl methylene double pyrazole derivative has important bioactivity, has been widely used as antitumor and anticancer agent, for treating brain
The diseases such as ischemic and myocardial ischemia.It is also commonly used for antipyretic-antalgic, antidepression, antimycotic, anti-inflammatory agents and mycobacterium tuberculosis suppression
Preparation.In addition, aryl methylene double pyrazole derivative has been used as pesticide and dyestuff, metal ion-chelant reagent.
The important physiological activity and potential medical value having due to aryl methylene double pyrazole derivative synthesize them
The research of method has been a concern.
A series of synthetic methods are had reported, by being catalyzed the aromatic aldehyde of a molecule and 3- methyl-1s-phenyl -5- of two molecules
Pyrazolone is condensed, often using xanthic acid [Kuarm, B.S.; Rajitha, B. Synth. Commun. 2012,
42,2382-2387.], phosphomolybdic acid [Phatangare, K.R.; Padalkar, V.S.; Gupta, V.D.; Patil,
V.S.; Umape, P.G.;Sekar, N. Synth. Commun. 2012,42,1349-1358.], silica gel load sulphur
Acid [Niknam, K.;Mirzaee, S. Synth. Commun. 2011,41,2403-2413.], dodecyl sulphate
Sodium [Wang, W.; Wang, S.X.; Qin, X.Y.; Li, J.T. Synth. Commun. 2005, 35, 1263–
1269.] etc. catalyst.
And in recent years, research uses aromatic aldehyde, phenylhydrazine and the fragrant methylene of ethyl acetoacetate one pot reaction direct polycondensation synthesis
Base double pyrazole derivative, such as 2012, the reports such as Niknam use the silica gel load N- Propylpiperazines catalyzed by amino sulfonic acid multicomponent
React [Tayebi S.; Niknam K. Iran. J. Catal. 2012, 2, 69 –74.].2014, Zhou and
Zhang reports using propionic acid 2- hydroxyl second ammoniums be catalyzed the multi-component reaction synthesize aryl methylene double pyrazole derivative [Zhou,
Z. & Zhang, Y. Green Chem. Lett. and Rev., 2014, 7, 18-23.].2017, Lalitha etc.
Report uses the glycerin catalytic multi-component reaction [Ramesh1, R.; Nagasundaram1, N.;
Meignanasundar1, D.; Vadivel, P.; Lalitha, A. Res Chem Intermed 2017, 43,
1767–1782.]。
Literature method promotes reaction using heterogeneous catalyst at present, and there are product separation difficulties, and what product was difficult to purify asks
Topic, and use organic micromolecule catalyst often pollution products, it is impossible to meet the requirement of drug.And it is closed using multistep
Into long there is also route, total recovery is low, the shortcomings of using the pyrazolone raw material for being not easy to obtain.And aryl methylene double pyrazole ester list potassium
Salt is there are no the method that document report can be prepared directly, although can be theoretically prepared as the method described in above-mentioned document
Aryl methylene double pyrazole ester and potassium resource compound synthesis, but since different potassium resource compounds can form more sylvite and different positions
The polymorphic types potassium salt compound such as sylvite put, it is clear that it is impossible to meet pharmaceutical purity requirements.
Invention content
The present invention seeks to be directed to more than one pot reaction there are the defects of and propose without additional catalyst or promotion
Agent succinctly can efficiently obtain the synthetic method of corresponding aryl methylene double pyrazole ester monopotassium salt.
The technical scheme is that:In a solvent, by phenylhydrazine, aromatic aldehyde, potassium resource and dimethyl butyn or acetylenedicarboxylic acid
Diethylester hybrid reaction cools down, filters, obtains solid phase after reaction, and through recrystallization after being washed with ethyl alcohol, it is double to obtain aryl methylene
Pyrazoles ester monopotassium salt.
The present invention without using any additional catalyst or accelerating agent, directly using phenylhydrazine, aromatic aldehyde, potassium carbonate as potassium resource and
Dimethyl butyn or diethyl butyn one pot reaction synthesising target compound, potassium carbonate both as potassium resource, were also made
Promote to react for alkaline reagent, simplify post processor.The product separation that the present invention solves heterogeneous reaction is difficult, has overcome
The problem of machine micromolecule catalyst pollution products, the intermediate for also avoiding multistep reaction isolate and purify trouble, and the low grade of yield lacks
Point.
Further, the throwing of phenylhydrazine of the present invention, aromatic aldehyde, potassium resource and dimethyl butyn or diethyl butyn
It is 2: 1: 2~4: 2 to expect molar ratio.
The present invention is without using any additional catalyst or accelerating agent, and potassium resource therein is the same as anti-into alkaline reagent promotion is also served as
Should, therefore, can more it be reacted fully for 2~4: 1 using potassium resource and the molar ratio of aromatic aldehyde.
Currently preferred potassium resource is K2CO3.Highly basic potassium hydroxide and weak base saleratus are all unfavorable for reaction progress,
And mild alkaline reagent potassium carbonate can not only effectively provide potassium resource, and can effectively promote the conversion of the reaction.
Currently preferred solvent is ethyl alcohol.Polar protic etoh solvent is conducive to the conversion of the reaction.
The reaction temperature is 25~80 DEG C.Experimental research find that reaction temperature change can influence to convert, as a result, it has been found that
Raising temperature is conducive to the conversion of this reaction, and the reaction time is made to shorten to 5 hours.
Description of the drawings
Fig. 1 is benzylidene -4,4'- two (3- hydroxyl -1- Phenylpyrazole -5- methyl formates) potassium that the present invention synthesizes
The molecular structure of (4a).
Specific embodiment
First, the synthetic method of aryl methylene bispyrazolone monopotassium salt:
2.0 mmol dimethyl butyns or diethyl butyn, 552 mg are added in 25ml round-bottomed flasks(4.0
mmol)Potassium carbonate, 216 mg(2.0 mmol)For phenylhydrazine in 3 mL alcohol solvents, 30 min of stirring at normal temperature adds 1.0
Oil bath is warming up to reflux after mmol aromatic aldehydes(80℃), continue to stir, thin plate chromatography TLC(Solvent is 1 by volume ratio:3 acetic acid
Ethyl ester and petroleum ether mixing composition)Tracing detection, 5h reactions are terminated, are cooled to room temperature, filtered, washed twice using ethyl alcohol, with 95%
Ethyl alcohol, which simply recrystallizes, obtains pure product, and corresponding compound is shown in Table 1.
Reaction equation is as follows:
The composite result of 1 aryl methylene bispyrazolone monopotassium salt of table:
The molecular structural formula of above each product and characterization experimental data:
1st, benzylidene -4,4'- two (3- hydroxyl -1- Phenylpyrazole -5- methyl formates) potassium (4a):
Experimental data:White solid;1H NMR (DMSO-d 6, 400 MHz ) δ (ppm): 7.92 (d, J =
7.6 Hz, 4H), 7.40 (dd, J= 7.6, 8.0 Hz, 4H), 7.29 (d, J = 7.6 Hz, 2H), 7.21
(dd, J= 7.2, 7.6 Hz, 2H), 7.17 (dd, J= 7.2, 7.6 Hz, 2H), 7.05 (dd, J= 7.2,
7.2 Hz, 1H), 6.72 (s, 1H), 3.80 (s, 6H); 13C NMR (DMSO-d 6, 100 MHz) δ (ppm):
164.2, 158.4, 146.0, 140.1, 139.6, 128.9, 127.9, 127.9, 125.6, 125.2, 121.2,
105.3, 51.4, 32.1; IR (KBr, cm-1): v 3418, 3032, 2948, 1657, 1589, 1478, 1018,
938, 750, 701。
The monocrystalline characterization of compound 4a:
(1)The molecular structure of benzylidene -4,4'- two (3- hydroxyl -1- Phenylpyrazole -5- methyl formates) potassium (4a) is shown in
Fig. 1.
(2)The single crystal data of benzylidene -4,4'- two (3- hydroxyl -1- Phenylpyrazole -5- methyl formates) potassium (4a):
Following table is the crystal parameter of compound 4a:
By Fig. 1 and upper table, have one on the constructed aryl methylene double pyrazole derivative of the analytic demonstration of compound 4a monocrystalline
A pyrazoles potassium alcoholate structural unit.
2nd, to methoxybenzylidene -4,4'- two (3- hydroxyl -1- Phenylpyrazole -5- methyl formates) potassium (4b):
Experimental data:White solid;1H NMR (DMSO-d 6, 400 MHz ) δ (ppm): 7.92 (d, J = 8.0
Hz, 4H), 7.40 (dd, J= 7.6, 8.0 Hz, 4H), 7.22-7.19 (m, 4H), 6.74 (d, J= 8.8
Hz, 2H), 6.65 (s, 1H), 3.80 (s, 6H), 3.67 (s, 3H); 13C NMR (DMSO-d 6, 100 MHz)
δ (ppm): 164.2, 158.3, 157.2, 140.2, 139.6, 138.1, 128.9, 128.7, 125.5,
121.1, 113.3, 105.6, 55.3, 51.4, 51.3; IR (KBr, cm-1): v 3423, 3037, 2948,
1663, 1593, 1486, 1018, 938, 832, 766。
3rd, benzylidene -4,4'- two (3- hydroxyl -1- Phenylpyrazole -5- Ethyl formates) potassium (4c):
Experimental data:White solid;1H NMR (DMSO-d 6, 400 MHz ) δ (ppm): 7.91 (d, J = 8.0
Hz, 4H), 7.40 (dd, J= 7.6, 7.6 Hz, 4H), 7.32 (d, J = 8.0 Hz, 2H), 7.21 (dd, J
= 7.2, 8.0 Hz, 2H), 7.17 (dd, J= 8.0, 7.6 Hz, 2H), 7.04 (dd, J= 7.2, 7.6 Hz,
1H), 6.70 (s, 1H), 4.27 (q, J = 7.2 Hz, 2H), 1.30 (t, J = 7.2 Hz, 3H); 13C NMR
(DMSO-d 6, 100 MHz) δ (ppm): 163.8, 158.3, 146.2, 140.1, 139.9, 128.9, 127.9,
127.8, 125.5, 125.1, 121.2, 105.1, 60.0, 32.3, 14.6; IR (KBr, cm-1): v 3433,
3033, 2949, 1659, 1585, 1472, 1015, 938, 748, 701。
4th, to chlorobenzene methylene -4,4'- two (3- hydroxyl -1- Phenylpyrazole -5- methyl formates) potassium (4d):
Experimental data:White solid;1H NMR (DMSO-d 6, 400 MHz ) δ (ppm): 7.93 (d, J = 8.0
Hz, 4H), 7.41 (dd, J= 8.0, 7.6 Hz, 4H), 7.30 (d, J = 8.4 Hz, 2H), 7.24 (dd, J
= 7.2 Hz, 2H), 7.20 (dd, J= 6.4, 7.2 Hz, 2H), 6.73 (s, 1H), 3.81 (s, 6H); 13C
NMR (DMSO-d 6, 100 MHz) δ (ppm): 164.1, 158.4, 144.9, 140.1, 139.5, 129.9,
129.7, 128.9, 127.9, 125.6, 121.2, 104.9, 51.4, 31.8; IR (KBr, cm-1): v 3422,
3031, 2947, 1666, 1593, 1487, 1013, 939, 832, 767。
5th, m-chloro benzylidene -4,4'- two (3- hydroxyl -1- Phenylpyrazole -5- methyl formates) potassium (4e):
Experimental data:White solid;1H NMR (DMSO-d 6, 400 MHz ) δ (ppm): 7.94 (d, J = 8.4
Hz, 4H), 7.42 (dd, J= 7.6, 8.0 Hz, 4H), 7.31 (s, 1H), 7.28-7.21 (m, 4H), 7.15
(d, J= 7.6 Hz, 1H), 6.77 (s, 1H), 3.83 (s, 6H); 13C NMR (DMSO-d 6, 100 MHz) δ
(ppm): 164.1, 158.4, 148.7, 140.0, 139.5, 132.7, 129.9, 129.0, 127.5, 126.7,
125.7, 125.3, 121.3, 104.7, 51.5, 32.1; IR (KBr, cm-1): v 3417, 3032, 2949,
1667, 1599, 1482, 1018, 934, 793, 765。
6th, bromophenyl methylene -4,4'- two (3- hydroxyl -1- Phenylpyrazole -5- methyl formates) potassium (4f):
Experimental data:White solid;1H NMR (DMSO-d 6, 400 MHz ) δ (ppm): 7.93 (d, J = 7.6
Hz, 4H), 7.40 (dd, J= 7.6, 8.0 Hz, 4H), 7.78 (d, J = 7.2 Hz, 1H), 7.45-7.38
(m, 5H), 7.27-7.19 (m, 3H), 7.03 (dd, J= 7.6, 7.2 Hz, 1H), 6.61 (s, 1H), 3.80
(s, 6H); 13C NMR (DMSO-d 6, 100 MHz) δ (ppm): 164.1, 158.8, 143.7, 140.3,
140.1, 132.7, 131.2, 128.9, 127.6, 127.0, 125.5, 123.8, 121.1, 103.8, 51.5,
33.7,; IR (KBr, cm-1): v 3423, 3028, 2947, 1662, 1594, 1486, 1017, 934, 768,
748。
7th, methyl benzylidene -4,4'- two (3- hydroxyl -1- Phenylpyrazole -5- methyl formates) potassium (4g):
Experimental data:White solid;1H NMR (DMSO-d 6, 400 MHz ) δ (ppm): 7.93 (d, J = 8.0
Hz, 4H), 7.40 (dd, J= 8.0, 7.6 Hz, 4H), 7.21 (dd, J= 7.2, 7.2 Hz, 2H), 7.12-
7.04 (m, 3H), 6.87 (d, J= 6.8 Hz, 1H), 6.68 (s, 1H), 3.80 (s, 6H) , 2.20 (s,
3H); 13C NMR (DMSO-d 6, 100 MHz) δ (ppm): 164.2, 158.4, 146.0, 140.2, 139.7,
136.5, 128.9, 128.5, 127.8, 125.9, 125.5, 125.1, 121.2, 105.4, 51.4, 32.1,
21.8; IR (KBr, cm-1): v 3414, 3031, 2950, 1668, 1599, 1484, 1019, 933, 792,
765。
8th, to fluorobenzylidene -4,4'- two (3- hydroxyl -1- Phenylpyrazole -5- Ethyl formates) potassium (4h):
Experimental data:White solid;1H NMR (DMSO-d 6, 400 MHz ) δ (ppm): 7.93 (d, J = 7.6
Hz, 4H), 7.42 (dd, J= 7.2, 7.6 Hz, 4H), 7.36 (dd, J= 6.4, 7.6 Hz, 2H), 7.22
(dd, J= 6.8, 7.6 Hz, 2H), 7.01 (dd, J= 8.4, 8.4 Hz, 2H), 7.05 (dd, J= 7.2,
7.2 Hz, 1H), 6.72 (s, 1H), 4.29 (q, J = 6.8 Hz, 4H), 1.32 (t, J = 6.8 Hz,
6H); 13C NMR (DMSO-d 6, 100 MHz) δ (ppm): 163.8, 159.3, 158.3, 142.3 (d, J =
3.0 Hz), 140.1, 139.8, 129.5, 129.5, 128.9, 125.6, 121.3, 114.4 (d, J = 10.7
Hz), 105.1, 60.0, 31.7, 14.6; IR (KBr, cm-1): v 3425, 3031, 2949, 1667, 1598,
1488, 1012, 940, 831, 767。
9th, to bromobenzene methylene -4,4'- two (3- hydroxyl -1- Phenylpyrazole -5- Ethyl formates) potassium (4i):
Experimental data:White solid;1H NMR (DMSO-d 6, 400 MHz ) δ (ppm): 7.85 (d, J = 8.0
Hz, 4H), 7.45-7.39 (m, 6H), 7.28-7.22 (m, 4H), 6.72 (s, 1H), 4.30 (q, J = 6.8
Hz, 4H), 1.31 (t, J = 6.8 Hz, 6H); 13C NMR (DMSO-d 6, 100 MHz) δ (ppm): 163.7,
158.3, 145.6, 140.1, 139.8, 130.7, 130.2, 128.9, 125.6, 121.3, 118.3, 104.7,
60.0, 31.9, 14.6; IR (KBr, cm-1): v 3433, 3032, 2943, 1666, 1599, 1487, 1013,
940, 831, 769。
2nd, the synthetic reaction condition Optimum Experiment of aryl methylene bispyrazolone monopotassium salt:
With 284mg(2.0 mmol)Dimethyl butyn, 216 mg(2.0 mmol)Phenylhydrazine, 106 mg(1.0 mmol)Benzene first
Aldehyde uses the potassium resource of different molar equivalents as model reaction, research(K2CO3、KHCO3Or KOH), different solvents(THF、
CH2Cl2, MeCN or EtOH)With influence of the differential responses temperature to reaction.
Reaction equation is as follows:
Reaction condition optimization the results are shown in Table 2.
The composite result contrast table of 2 aryl methylene bispyrazolone monopotassium salt of table
By table 2 the result shows that:
Different potassium resource reagents reaction is influenced it is bigger, highly basic potassium hydroxide and weak base saleratus be all unfavorable for this react into
Row, and mild alkaline reagent potassium carbonate can not only effectively provide potassium resource, and can effectively promote turning for the reaction
Change(Serial number 1-3 examples in contrast table 2).
In common solvent tetrahydrofuran, dichloromethane, acetonitrile and the ethyl alcohol studied, polar protic etoh solvent has
Conducive to the conversion of the reaction(Serial number 1,4-6 examples in contrast table 2).
The use of ethyl alcohol is solvent, changes influence of the dosage investigation of potassium carbonate to reaction, the results showed that the carbon of two times of equivalents
Sour potassium provides best result(Serial number 1,6-10 examples in contrast table 2).And when reaction temperature change, as a result, it has been found that raising temperature has
Conducive to the conversion of this reaction, the reaction time also shortens to 5 hours.
Claims (5)
1. a kind of synthetic method of aryl methylene double pyrazole ester monopotassium salt, it is characterised in that in a solvent, by phenylhydrazine, aromatic aldehyde, potassium
Source and dimethyl butyn or diethyl butyn hybrid reaction cool down, filter, solid phase obtained, with second after reaction
Through recrystallization after alcohol washing, aryl methylene double pyrazole ester monopotassium salt is obtained.
2. the synthetic method of aryl methylene double pyrazole ester monopotassium salt according to claim 1, it is characterised in that the phenylhydrazine, virtue
The molar ratio of aldehyde, potassium resource and dimethyl butyn or diethyl butyn is 2: 1: 2~4: 2.
3. the synthetic method of aryl methylene double pyrazole ester monopotassium salt according to claim 2, it is characterised in that the potassium resource is
K2CO3。
4. the synthetic method of aryl methylene double pyrazole ester monopotassium salt according to claim 2, it is characterised in that the solvent is
Ethyl alcohol.
5. the synthetic method of aryl methylene double pyrazole ester monopotassium salt according to claim 2, it is characterised in that the reaction temperature
Spend is 25~80 DEG C.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201810030425.5A CN108147996B (en) | 2018-01-12 | 2018-01-12 | Synthetic method of arylmethylene bispyrazole ester monopotassium salt |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201810030425.5A CN108147996B (en) | 2018-01-12 | 2018-01-12 | Synthetic method of arylmethylene bispyrazole ester monopotassium salt |
Publications (2)
Publication Number | Publication Date |
---|---|
CN108147996A true CN108147996A (en) | 2018-06-12 |
CN108147996B CN108147996B (en) | 2021-09-24 |
Family
ID=62461455
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201810030425.5A Active CN108147996B (en) | 2018-01-12 | 2018-01-12 | Synthetic method of arylmethylene bispyrazole ester monopotassium salt |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN108147996B (en) |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2008121861A2 (en) * | 2007-03-28 | 2008-10-09 | Xenon Pharmaceuticals Inc. | Pyrazole and pyrrole compounds useful in treating iron disorders |
WO2014159214A1 (en) * | 2013-03-14 | 2014-10-02 | Chdi Foundation, Inc. | Histone deacetylase inhibitors and compositions and methods of use thereof |
-
2018
- 2018-01-12 CN CN201810030425.5A patent/CN108147996B/en active Active
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2008121861A2 (en) * | 2007-03-28 | 2008-10-09 | Xenon Pharmaceuticals Inc. | Pyrazole and pyrrole compounds useful in treating iron disorders |
WO2014159214A1 (en) * | 2013-03-14 | 2014-10-02 | Chdi Foundation, Inc. | Histone deacetylase inhibitors and compositions and methods of use thereof |
Non-Patent Citations (3)
Title |
---|
CHENG YANG, ET AL.,: ""A Green and Efficient One-Pot Pseudo-Five-Component Reaction for Synthesis of Bis(pyrazol-5-ol) Derivatives via Tandem Cyclocondensation-Knoevenagel–Michael Reaction"", 《CHEMISTRYSELECT》 * |
VICTOR HADI,ET AL.,: ""Development of the next generation of HIV-1 integrase inhibitors: Pyrazolone as a novel inhibitor scaffold"", 《BIOORGANIC & MEDICINAL CHEMISTRY LETTERS》 * |
X.-C. TU ET AL.: ""Multicomponent domino reactions of acetylenedicarboxylates: divergent synthesis of multi-functionalized pyrazolones and C-tethered bispyrazol-5-ols"", 《TETRAHEDRON LETTERS》 * |
Also Published As
Publication number | Publication date |
---|---|
CN108147996B (en) | 2021-09-24 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Luo et al. | Chemoenzymatic Synthesis and Application of Bicyclo [2.2. 2] octadiene Ligands: Increased Efficiency in Rhodium-Catalyzed Asymmetric Conjugate Additions by Electronic Tuning We acknowledge Dr. John Whittall for initial inspiration, Dr. Neil Berry for preliminary modeling and the EPSRC for a Dorothy Hodgkin Postgraduate Award to YL | |
CN110467555B (en) | Axial chiral aryl indole compound and synthesis method thereof | |
Pradhan et al. | Fe (DS) 3, an efficient Lewis acid-surfactant-combined catalyst (LASC) for the one pot synthesis of chromeno [4, 3-b] chromene derivatives by assembling the basic building blocks | |
CN110452150A (en) | A kind of axial chirality indoles-naphthalene compounds and preparation method thereof | |
CN111777637B (en) | Axial chiral oxindole-derived styrene phosphine oxide catalyst and preparation method and application thereof | |
CN108659041B (en) | Phosphine ligand compound based on tetramethyl spiroindane skeleton, intermediate thereof, preparation method and application | |
CN109734600B (en) | Synthesis method of chiral beta-hydroxy acid ester compound | |
CN101107228B (en) | Process for producing (Z)-1-phenyl-1-(N,N-diethylaminocarbonyl)-2-phthalimidomethylcyclopropane | |
Wu et al. | Chiral Brønsted acid-catalyzed alkylation of C3-substituted indoles with o-hydroxybenzyl alcohols: highly enantioselective synthesis of diarylindol-2-ylmethanes and evaluation on their cytotoxicity | |
CN108794426B (en) | Heterocyclic dithiocarbamate compound and preparation method thereof | |
CN105712922B (en) | The synthetic method of pyrrolin class and azoles | |
CN110003274A (en) | Phosphonylation dihydro-isoquinoline ketone compounds and preparation method thereof | |
CN106146334A (en) | 2,3-diaryl-2-propargyl amide groups-3-arylamino methyl propionate derivant and its preparation method and application | |
CN108467376A (en) | A kind of synthetic method of dibenzofuran derivative | |
CN105820174A (en) | Polysubstituted thienoindole derivative and preparation method thereof | |
CN108147996A (en) | A kind of synthetic method of aryl methylene double pyrazole ester monopotassium salt | |
CN113651788B (en) | 3-aminoalkylchromone compound and preparation method thereof | |
CN103087033B (en) | Synthesis method of poly-substituted oxacycloheptatriene-3(2H) ketone compounds | |
CN112321514B (en) | Chiral barbituric acid compound and preparation method thereof | |
CN109988083A (en) | The preparation method of high-optical-purity escitalopram oxalate intermediate S configuration glycol | |
Saidalimu et al. | Activation of Trifluoromethylthio Moiety by Appending Iodonium Ylide under Copper Catalysis for Electrophilic Trifluoromethylation Reaction | |
CN106083690A (en) | A kind of preparation method of polysubstituted 3 methylene indolones | |
CN102766095B (en) | Preparation method of electron-deficient group-containing multi-substituted pyrazole derivative | |
CN107176957A (en) | Chiral pyrazol quinoline ketone spiral shell [ethylene thiourea] spiral shell producing oxindoles compound and its derivative | |
CN109456155A (en) | A method of tetralin ketone derivatives quickly being prepared based on substitution cyclobutanol oxidation open loop/cyclization |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |