CN104860803A - Biphenyl compound and preparation method and application thereof - Google Patents
Biphenyl compound and preparation method and application thereof Download PDFInfo
- Publication number
- CN104860803A CN104860803A CN201510226928.6A CN201510226928A CN104860803A CN 104860803 A CN104860803 A CN 104860803A CN 201510226928 A CN201510226928 A CN 201510226928A CN 104860803 A CN104860803 A CN 104860803A
- Authority
- CN
- China
- Prior art keywords
- biphenyl
- ketone compound
- preparation
- phenyl
- compound according
- 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
- RPZIAPJLZGRNDA-UHFFFAOYSA-N CC1(c2cccc(OC)c2)C(C(CCc2ccccc2)=O)=CC=CC1 Chemical compound CC1(c2cccc(OC)c2)C(C(CCc2ccccc2)=O)=CC=CC1 RPZIAPJLZGRNDA-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
- C07C49/76—Ketones containing a keto group bound to a six-membered aromatic ring
- C07C49/782—Ketones containing a keto group bound to a six-membered aromatic ring polycyclic
- C07C49/784—Ketones containing a keto group bound to a six-membered aromatic ring polycyclic with all keto groups bound to a non-condensed ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
- C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
- C07C49/76—Ketones containing a keto group bound to a six-membered aromatic ring
- C07C49/80—Ketones containing a keto group bound to a six-membered aromatic ring containing halogen
- C07C49/813—Ketones containing a keto group bound to a six-membered aromatic ring containing halogen polycyclic
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
- C07C49/76—Ketones containing a keto group bound to a six-membered aromatic ring
- C07C49/84—Ketones containing a keto group bound to a six-membered aromatic ring containing ether groups, groups, groups, or groups
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to the technical field of organic synthesis and discloses a biphenyl compound and a preparation method and an application thereof. The biphenyl compound has a structure stated by any one of the following formulas (1) to (7): (img file= 'DDA0000711989940000011. TIF' wi= '1764' he= '1496'/). Phenolic ketone and bromoaromatics are used for preparing the biphenyl compound through the Barbier-Grignard reaction, the reagents that are used are not needed to be subjected to non-aqueous processing, the reaction can be performed in the air, the rigorous condition of isolation of oxygen from water, which is required by the traditional Grignard reaction strictly, is broken; a series of new biphenyl compounds is obtained through synthesis, the reaction yield is high and can reach 92%; the biphenyl compound can be used as intermediates of intermediate drug synthesis and organic synthesis.
Description
Technical field
The invention belongs to technical field of organic synthesis, particularly biphenyl ketone compound and its preparation method and application.
Background technology
Biphenyl ketone compound is important organic synthesis and the intermediate of pharmaceutical synthesis, in organic synthesis and pharmaceutical synthesis, occupy consequence.First and the Grignard reagent reaction generation phenates with naphthols, biphenyl compound is generated again with phenates and Grignard reagent reaction, this is the novel method (Angew.Chem.Int.Ed.2010,49,4566-4570) of the synthesis biphenyl compound be in the news for 2010.Although this is a kind of completely new approach synthesizing biphenyl class, it is many to there is Grignard reagent consumption in it, and the loaded down with trivial details drawback with strictly controlling anhydrous and oxygen-free condition of operation, is difficult to be promoted in the synthesis of reality generates.
Summary of the invention
In order to overcome the shortcoming of above-mentioned prior art with not enough, primary and foremost purpose of the present invention is to provide a kind of biphenyl ketone compound.
Another object of the present invention is the preparation method providing a kind of above-mentioned biphenyl ketone compound.The method adopts bar Bill-grignard reaction directly to obtain a series of new biphenyl ketone compound with phenolic ketone and the synthesis of bromo aromatic hydrocarbon.And reaction conditions is simple, can carry out under air, water existence condition, solve the condition restriction that conventional form reaction requires the empty G&W of strict separation.
Still a further object of the present invention is to provide above-mentioned biphenyl ketone compound as the application of the intermediate of intermediate pharmaceutical synthesis and organic synthesis.
Object of the present invention is realized by following proposal:
A kind of biphenyl ketone compound, has as shown in the formula the structure described in any one of (1) ~ (7):
The above-mentioned chemical name with the biphenyl ketone compound of formula (1) ~ (7) described structure is respectively:
Formula (1): 1-(2-phenyl) phenyl-3-phenyl-1-acetone (1-Biphenyl-2-yl-3-phenyl-propan-1-one);
Formula (2): 1-(2-p-methylphenyl) phenyl-3-phenyl-1-acetone (1-(4'-Methyl-biphenyl-2-yl)-3-phenyl-propan-1-one);
Formula (3): 1-(2-o-methoxyphenyl) phenyl-3-phenyl-1-acetone (1-(2'-Methoxy-biphenyl-2-yl)-3-phenyl-propan-1-one);
Formula (4): 1-(between 2-fluorophenyl) phenyl-3-phenyl-1-acetone (1-(3'-Fluoro-biphenyl-2-yl)-3-phenyl-propan-1-one);
Formula (5): 1-(2-rubigan) phenyl-3-phenyl-1-acetone (1-(4'-Chloro-biphenyl-2-yl)-3-phenyl-propan-1-one);
Formula (6): 1-(2-m-methoxyphenyl) phenyl-3-phenyl-1-acetone (1-(3'-Methoxy-biphenyl-2-yl)-3-phenyl-propan-1-one);
Formula (7): 4-m-methoxyphenyl benzophenone ((3'-Methoxy-biphenyl-4-yl)-phenyl-methanone).
Present invention also offers a kind of preparation method of above-mentioned biphenyl ketone compound, the method utilizes phenolic ketone and bromo aromatic hydrocarbon to prepare biphenyl ketone compound by bar Bill-grignard reaction.
Described phenolic ketone can be o-hydroxy-phenyl Propiophenone
or 4-dihydroxy benaophenonel
Described bromo aromatic hydrocarbon can be bromobenzene, to methyl bromobenzene, O-methoxy bromobenzene, m-bromofluorobenzene, para chlorobromobenzene or meta-methoxy bromobenzene.
Also be added with magnesium in above-mentioned reaction, its consumption preferably with bromo aromatic hydrocarbon mole amount identical.Add magnesium in reaction process of the present invention and can react production form reagent with bromo aromatic hydrocarbon, then react with phenolic ketone, obtain target product.
The amount of phenolic ketone used and bromo aromatic hydrocarbon can be reacted by arbitrary proportion, and preferred molar ratio is 1:3.
Above-mentioned reaction is carried out, as CuBr under the catalysis of any three kinds of metal halides
2, BiCl
3, AgBr hybrid catalyst system, preferably, with phenolic ketone mole amount can be for norm metal catalyst components consumption: CuBr
215%, BiCl
35%, AgBr 10%.
React 8 ~ 16h at described reaction conditions can be 65 ~ 110 DEG C, at being preferably 96 DEG C, react 12h.
Product after above-mentioned reaction terminates can wash by ethyl acetate, extract, and uses TCL separating-purifying, thus obtains the product after purifying.The productive rate of aforesaid method is high, can reach 92%.
Above-mentioned reaction is preferably carried out in tetrahydrofuran solvent system or tetrahydrofuran (THF)/toluene solvant system.
The new biphenyl ketone compound of the invention described above can generate tertiary alcohol with Grignard reagent addition, also generation secondary alcohol can be reduced, or there is the biphenyl ketone etc. of substitution reaction generation with other group, therefore can be used as the intermediate of intermediate pharmaceutical synthesis and organic synthesis.
Mechanism of the present invention is:
The present invention adopts phenolic ketone and bromo aromatic hydrocarbon to prepare biphenyl ketone compound by bar Bill-grignard reaction, agents useful for same is without the need to Non-aqueous processing, and reaction can be carried out in atmosphere, the severe condition that isolating oxygen G&W is strict with in conventional form reaction are broken, synthesis obtains a series of new biphenyl ketone compound, and reaction yield is high, can 92% be reached.The a series of new biphenyl ketone compound prepared can be used as the intermediate of middle pharmaceutical synthesis and organic synthesis.
Accompanying drawing explanation
Fig. 1 is the hydrogen nuclear magnetic resonance spectrogram of formula (1) biphenyl ketone compound.
Fig. 2 is the mass spectrum of formula (1) biphenyl ketone compound.
Fig. 3 is the high resolution mass spectrum figure of formula (1) biphenyl ketone compound.
Fig. 4 is the carbon-13 nmr spectra figure of formula (1) biphenyl ketone compound.
Fig. 5 is the hydrogen nuclear magnetic resonance spectrogram of formula (2) biphenyl ketone compound.
Fig. 6 is the hydrogen nuclear magnetic resonance spectrogram of formula (3) biphenyl ketone compound.
Fig. 7 is the hydrogen nuclear magnetic resonance spectrogram of formula (4) biphenyl ketone compound.
Fig. 8 is the hydrogen nuclear magnetic resonance spectrogram of formula (5) biphenyl ketone compound.
Fig. 9 is the hydrogen nuclear magnetic resonance spectrogram of formula (6) biphenyl ketone compound.
Figure 10 is the hydrogen nuclear magnetic resonance spectrogram of formula (7) biphenyl ketone compound.
Embodiment
Below in conjunction with embodiment and accompanying drawing, the present invention is described in further detail, but embodiments of the present invention are not limited thereto.
Embodiment 1
By toluene, tetrahydrofuran (THF), magnesium chips mixing, the Catalysts Cu Br that to add with the amount of phenolic ketone (mole amount) be benchmark
2(15%)+BiCl
3(5%)+AgBr (10%), then add o-hydroxy-phenyl Propiophenone/4-dihydroxy benaophenonel and bromo aromatic hydrocarbon, react 8 ~ 16h under 65 ~ 110 DEG C of constant temperature return stirrings, under being more preferably 96 DEG C of constant temperature return stirrings, react 12h.Magnesium chips used mole amount identical with bromo aromatic hydrocarbon, the amount of phenolic aldehyde used and bromo aromatic hydrocarbon can be added by arbitrary proportion, and the ratio of the amount of preferred mole is 1:3.
When having reacted rear standing cool to room temperature, stir cancellation with saturated ammonium chloride solution, suction filtration, washs filter residue by ethyl acetate, and filtrate is extracted with ethyl acetate (3 × 10mL).Merge organic layer, by organic over anhydrous dried over mgso, filter, rotary evaporation obtains crude product, with the crude product that TCL separating-purifying obtains, the productive rate of biphenyl ketone compound is 72 ~ 92%, prepares different biphenyl ketone compound agents useful for same and productive rate is shown in Table 1.The new biphenyl ketone compound of the invention described above can generate tertiary alcohol with Grignard reagent addition, also generation secondary alcohol can be reduced, or there is the biphenyl ketone etc. of substitution reaction generation with other group, therefore can be used as the intermediate of intermediate pharmaceutical synthesis and organic synthesis.
Table 1 reaction reagent, product and productive rate
Embodiment 2
Carry out structural analysis to the biphenyl ketone compound that embodiment 1 prepares, data are as follows, and proton nmr spectra, carbon-13 nmr spectra, mass spectrum, high resolution mass spectrum the results are shown in Figure 1 ~ 10.
(1)1-Biphenyl-2-yl-3-phenyl-propan-1-one
1H NMR(300MHz,CDCl
3):δ7.36-7.28(m,9H),7.23(d,J＝1.6Hz,1H),7.16(dd,J＝7.5,1.7Hz,1H),7.09-7.01(m,2H),6.60(t,J＝7.5Hz,1H),5.14(d,J＝48.7Hz,1H),3.79-3.33(m,3H).
13C NMR(75MHz,CDCl
3):δ153.23,140.16,136.39,133.83,132.34,131.74,131.04,130.91,130.01,129.61,128.81,128.76,128.00,126.77,126.43,126.00,125.71,125.43,123.30,122.11,120.92,118.87,40.83,36.34；IR(KBr):3029,2924,1758,1664,1602,1483,1449,1242,1115,755,699；GC-MS:286.HR-ESI-MS:m/z calcd for 287.1430[M+H]
+C
21H
18O；found at 287.1433.
(2)1-(4'-Methyl-biphenyl-2-yl)-3-phenyl-propan-1-one
1H NMR(300MHz,CDCl
3)δ7.70(d,J＝8.1Hz,2H),7.54(t,J＝7.3Hz,2H),7.37–7.27(m,5H),7.17(t,J＝8.2Hz,3H),3.52(s,2H),2.45(s,3H),1.72–1.20(m,2H)；
13C NMR(75MHz,CDCl
3)δ194.68,169.84,148.66,144.26,135.03,133.06,132.10,132.04,130.38,130.21,129.68,129.59,129.33,129.23,128.71,127.38,125.96,123.25,40.89,21.95；IR(KBr):3030,2855,1762,1661,1603,1483,1451,1294,1240,1117,934,752；GC-MS:300.HR-ESI-MS:m/z calcd for301.1587[M+H]
+C
22H
20O；found at 301.1588.
(3)1-(2'-Methoxy-biphenyl-2-yl)-3-phenyl-propan-1-one
1H NMR(300MHz,CDCl
3):δ7.36–7.29(m,4H),7.22(ddd,J＝7.4,4.2,2.1Hz,4H),7.11–7.05(m,1H),7.04–6.96(m,2H),6.92–6.84(m,2H),6.45(d,J＝78.5Hz,1H),6.13(td,J＝7.4,2.5Hz,1H),3.86–3.77(m,3H),3.37(dd,J＝9.9,7.5Hz,2H),1.46(d,J＝99.2Hz,2H)；
13C NMR(75MHz,CDCl
3):δ153.42,140.26,135.00,134.64,130.31,130.06,129.44,128.98,128.77,128.64,128.51,128.39,126.07,121.41,121.06,120.16,119.83,115.64,110.93,110.83,55.64,55.54,35.74,35.56；IR(KBr):3030,2924,1727,1626,1601,1487,1457,1245,1024,935,754；GC-MS:316.HR-ESI-MS:m/z calcd for 317.1536[M+H]
+C
22H
20O
2；found at 317.1539.
(4)1-(3'-Fluoro-biphenyl-2-yl)-3-phenyl-propan-1-one
1H NMR(300MHz,CDCl
3):δ7.54(ddd,J＝3.6,2.9,1.3Hz,1H),7.40–7.31(m,4H),7.25–7.18(m,3H),7.15–6.97(m,5H),3.62–3.34(m,2H),1.87–1.65(m,2H)；
13C NMR(75MHz,CDCl
3):δ152.99,142.34,139.67,135.32,132.51,130.71,130.04,129.93,129.70,128.71,128.49,128.24,126.37,124.71,122.23,122.19,120.93,115.73,114.73,114.45,113.60,113.31,36.20；IR(KBr):3028,2923,1660,1607,1582,1486,1448,1236,1032,867,754；GC-MS:304.HR-ESI-MS:m/z calcd for 305.1336[M+H]
+C
21H
17FO；found at 305.1345.
(5)1-(4'-Chloro-biphenyl-2-yl)-3-phenyl-propan-1-one
1H NMR(300MHz,CDCl
3):δ7.34–7.31(m,2H),7.24–7.20(m,3H),7.16(dd,J＝7.5,1.6Hz,1H),7.09–7.00(m,2H),6.96–6.81(m,4H),6.60(t,J＝7.5Hz,1H),3.79(s,2H),3.44(d,J＝7.5Hz,2H)；
13C NMR(75MHz,CDCl
3):δ159.81,153.08,141.52,139.97,136.15,131.68,130.72,129.58,129.48,128.72,128.65,128.51,128.29,126.27,125.22,120.75,119.21,115.64,112.98,112.61,55.25,36.17；IR(KBr):3022,2926,1661,1580,1481,1439,1233,1031,866,752；GC-MS:320.
(6)1-(3'-Methoxy-biphenyl-2-yl)-3-phenyl-propan-1-one
1H NMR(300MHz,CDCl
3):δ7.37–7.30(m,5H),7.26–7.21(m,3H),7.05(ddd,J＝7.3,5.0,0.9Hz,2H),6.95–6.83(m,3H),3.91–3.83(m,2H),3.81–3.68(m,3H),3.57–3.39(m,2H)；
13C NMR(75MHz,CDCl
3):δ159.81,159.68,153.11,136.20,131.64,129.58,128.52,127.06,120.76,115.67,113.97,113.37,112.99,112.63,111.01,110.50,55.45,55.25,36.18；IR(KBr):3030,2933,1721,1620,1609,1481,1452,1242,1020,930,751；GC-MS:316.
(7)(3'-Methoxy-biphenyl-4-yl)-phenyl-methanone
1H NMR(300MHz,CDCl
3):δ7.52–7.02(m,9H),6.91–6.76(m,3H),6.50(d,J＝10.0Hz,1H),3.83–3.75(m,3H)；
13C NMR(75MHz,CDCl
3):δ159.44,155.48,148.96,140.05,132.36,130.49,129.59,128.62,128.47,128.01,127.36,124.94,120.69,117.83,115.85,114.96,114.03,112.53,81.90,55.61,55.38；IR(KBr):3025,2933,2836,1595,1509,1486,1442,1247,1173,1041,876,806,701；GC-MS:288.HR-ESI-MS:m/z calcd for 289.1223[M+H]
+C
20H
16O
2；found at289.1229.
Above-described embodiment is the present invention's preferably embodiment; but embodiments of the present invention are not restricted to the described embodiments; change, the modification done under other any does not deviate from spirit of the present invention and principle, substitute, combine, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (8)
1. a biphenyl ketone compound, is characterized in that having the structure as shown in the formula described in any one of (1) ~ (7):
2. a preparation method for biphenyl ketone compound according to claim 1, is characterized in that the method utilizes phenolic ketone and bromo aromatic hydrocarbon to prepare biphenyl ketone compound by bar Bill-grignard reaction.
3. the preparation method of biphenyl ketone compound according to claim 2, is characterized in that: described phenolic ketone is o-hydroxy-phenyl Propiophenone or 4-dihydroxy benaophenonel.
4. the preparation method of biphenyl ketone compound according to claim 2, is characterized in that: described bromo aromatic hydrocarbon is bromobenzene, to methyl bromobenzene, O-methoxy bromobenzene, m-bromofluorobenzene, para chlorobromobenzene or meta-methoxy bromobenzene.
5. the preparation method of biphenyl ketone compound according to claim 2, is characterized in that: the mol ratio of phenolic ketone used and bromo aromatic hydrocarbon is 1:3.
6. the preparation method of biphenyl ketone compound according to claim 2, is characterized in that: described reaction conditions for reacting 8 ~ 16h at 65 ~ 110 DEG C.
7. the preparation method of biphenyl ketone compound according to claim 2, is characterized in that: described reaction conditions for react 12h at 96 DEG C.
8. biphenyl ketone compound according to claim 1 is as the application of the intermediate of middle pharmaceutical synthesis and organic synthesis.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510226928.6A CN104860803B (en) | 2015-05-06 | 2015-05-06 | Biphenyl ketonic compound and its preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510226928.6A CN104860803B (en) | 2015-05-06 | 2015-05-06 | Biphenyl ketonic compound and its preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104860803A true CN104860803A (en) | 2015-08-26 |
| CN104860803B CN104860803B (en) | 2016-11-30 |
Family
ID=53907044
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510226928.6A Expired - Fee Related CN104860803B (en) | 2015-05-06 | 2015-05-06 | Biphenyl ketonic compound and its preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104860803B (en) |
-
2015
- 2015-05-06 CN CN201510226928.6A patent/CN104860803B/en not_active Expired - Fee Related
Non-Patent Citations (3)
| Title |
|---|
| CHAO.JUN LI ET AL.: "AQUEOUS BARBIER-GRIGNARD TYPE REACTION:SCOPE, MECHANISM, AND SYNTHETIC APPLICATIONS", 《TETRAHEDRON》 * |
| JING ZENG ET AL.: "Selective Co/Ti Cooperatively Catalyzed Biaryl Couplings of Aryl Halides with Aryl Metal Reagents", 《ORGANIC LETTERS》 * |
| MUSHENG XU ET AL.: "Photogeneration and Chemistry of Biphenyl Quinone Methides from Hydroxybiphenyl Methanols", 《PHOTOCHEMISTRY AND PHOTOBIOLOGY》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104860803B (en) | 2016-11-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Jensen et al. | Preparation and reactions of functionalized arylmagnesium reagents | |
| CN103087105B (en) | Chiral phosphine ligand and comprise the metal catalyst of this part and their application | |
| CN108503601A (en) | The synthetic method of 1- alkyl -5- arylthio -1,2,3- triazole compounds | |
| Yang et al. | Cu (I)/Ag (I)-mediated decarboxylative trifluoromethylation of arylpropiolic acids with Me3SiCF3 at room temperature | |
| CN104910036B (en) | A kind of containing continuous quaternary carbon center cyclopropane alpha-amino acid derivatives and synthetic method | |
| Shimizu et al. | Water‐soluble calixarenes as new inverse phase‐transfer catalysts. Their scope in aqueous biphasic alkylations and mechanistic implications | |
| CN108503552B (en) | Preparation method of trifluoromethyl aromatic amine | |
| CN106008402A (en) | Epsilon-trifluoromethyl substituted amide preparing method | |
| CN112457276B (en) | Method for synthesizing butylphthalide | |
| CN105949118A (en) | Preparation method of 2-aryl quinoline derivatives | |
| CN110272366B (en) | Method for synthesizing diaryl selenide | |
| CN109809967B (en) | Method for synthesizing chiral alcohol | |
| CN109456237B (en) | Method for synthesizing alkynyl sulfone | |
| CN108467408B (en) | Diaryl phosphorus compound with hydroxyphenyl functional group and preparation method thereof | |
| CN104860803A (en) | Biphenyl compound and preparation method and application thereof | |
| CN113548965B (en) | Preparation method of 1,4 eneyne compound | |
| Raju et al. | Palladium-Catalyzed Regio-and Stereoselective Hydrosulfonation of Propiolate Esters | |
| CN107029759B (en) | Ruthenium trichloride reacts the application prepared in imines with alcohol compound in catalysis nitrobenzene compounds | |
| Fu et al. | Cu (acac) 2-Catalyzed Synthesis of Functionalized Bis (arylmethyl) zinc Reagents and Their Olefination Reaction with Aromatic Aldehydes | |
| CN106167473B (en) | 1,4,2- dioxy nitrogen azole compounds and its synthetic method | |
| CN113511966B (en) | Synthesis method of trifluoromethyl substituted dihydrophenanthrene compound | |
| CN108383754A (en) | The preparation method and application of a kind of aryl oxime compound | |
| KR101132870B1 (en) | Concise synthesis of Licochalcone A through water-accelerated [3,3]-sigmatropic rearrangement reaction | |
| CN111484420B (en) | Method for synthesizing triarylmethane derivative and triarylmethane derivative obtained by same | |
| CN109384641B (en) | Synthesis method of 1, 2-vicinal diol compound |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| EXSB | Decision made by sipo to initiate substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20161130 Termination date: 20190506 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |