CN102850281A - Synthesis method for 2,5-diphenylpyrazine - Google Patents
Synthesis method for 2,5-diphenylpyrazine Download PDFInfo
- Publication number
- CN102850281A CN102850281A CN2012103209787A CN201210320978A CN102850281A CN 102850281 A CN102850281 A CN 102850281A CN 2012103209787 A CN2012103209787 A CN 2012103209787A CN 201210320978 A CN201210320978 A CN 201210320978A CN 102850281 A CN102850281 A CN 102850281A
- Authority
- CN
- China
- Prior art keywords
- anhydrous
- chlorobenzene
- reaction
- diphenylpyrazine
- synthesis method
- 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
Abstract
The invention relates to a synthesis method for 2,5-diphenylpyrazine. The synthesis method comprises that: 3-(N-ethyl-N-phenyl)-propanenitrile and D-phenylglycinol are subjected to a reflux reaction for 60-70 hours in a chlorobenzene solvent in the presence of a catalyst anhydrous ZnCl2 under an anhydrous and anaerobic condition, wherein a use amount of ZnCl2 is 75-85 mol% of the amount of the raw materials; after the reaction is completed, the chlorobenzene is removed, and water is added to stir and dissolve; chloroform is adopted to extract; the extraction phase is subjected to drying and precipitation, and then is loaded on a silica gel chromatography column to separate; petroleum ether/dichloromethane ( a volume ratio of 7:3) is adopted to carry out elution, and the first component is collected; the eluant is removed to obtain the target product 2,5-diphenylpyrazine.
Description
One, technical field
The present invention relates to a kind of preparation method of organic fine chemical, exactly is a kind of 2, the synthetic method of 5-diphenyl pyrazine.
Two, background technology
The synthetic method of 2,5-diphenyl pyrazine has many bibliographical informations.As far back as 1975, J.Am.Chem.Soc. reported the synthetic method of this compound, 1993, synthesising communication again reported this material synthetic method (1, Alper, Howard; Wollowitz, Susan,
J.Am.Chem.Soc.1975,97,3541-3543.2、Joseph Daniel ; D. N. Dhar,
Synthetic Communications, 1993, 23, 2151-2157)。
The applicant has unexpectedly obtained another kind of compound 2, the 5-diphenyl pyrazine in the experiment of He oxazoline.
Three, summary of the invention
The present invention aims to provide compound 2, the 5-diphenyl pyrazine, and technical problem to be solved is that one-step synthesis obtains target product.
This synthetic method comprises synthesizes and separates, and described synthesizing is exactly that 3-(N-ethyl-N-phenyl)-propionitrile and D-benzene glycinol have the anhydrous ZnCl of catalyzer in chlorobenzene solvent
2When existing under the anhydrous and oxygen-free condition back flow reaction 60 ~ 70 hours, ZnCl
2Consumption be 75 ~ 85 mol % of material quantity.
Reaction is sloughed chlorobenzene after finishing, is added the water stirring and dissolving, uses chloroform extraction again, and upper silica gel column chromatography separates behind extraction phase drying, the precipitation, with sherwood oil/methylene dichloride (volume ratio 7:3) wash-out, collect the first component point, obtain target product 2, the 5-diphenyl pyrazine after sloughing eluent.
Building-up reactions is as follows:
One step of this synthetic method obtains target product, and technique is simple, and is easy to operate.
This reaction mechanism can be speculated as 3-(N-ethyl-N-phenyl)-propionitrile and decompose under the strong lewis acid zinc dichloride effect of 83.1%mol, the C-N bond rupture, generate small molecules group cyano group and cyanoethyl, then attack phenyl ring intermediate benzyne, generate adjacent cyano benzyl cyanide, the adjacent cyano benzyl cyanide of two molecules carries out condensation reaction, sloughs a part CH
2N
2, form 2,5-diphenyl pyrazine.
Four, description of drawings
Fig. 1 is the X-diffraction analysis figure of 2,5-diphenyl pyrazine.
Five, embodiment
In the 100mL two-mouth bottle, under the anhydrous and oxygen-free condition, add anhydrous ZnCl
20.6728g (4.947mmol), 40ml chlorobenzene, 3-(N-ethyl-N-phenyl)-propionitrile 1.0367g (5.95mmol), D-benzene glycinol 4.2 g, with the mixture 72h that at high temperature refluxes, stopped reaction, decompression is with desolventizing,, with the residuum water dissolution, and use CHCl
3(20mLx2) extraction, organic phase anhydrous sodium sulfate drying, rotation desolventizing, upper silica gel column chromatography column separating purification with sherwood oil/methylene dichloride (volume ratio 7:3) mixed solution wash-out, is collected the first component point, slough eluent and obtain target product 2, the 5-diphenyl pyrazine.Productive rate: 15%, ultimate analysis: Anal.Calc. for C
6H
16N
2O
4: C%:82.73; H:5.21; N:12.06; Found:C%:82.54; H%:5.04; N%:15.50; HRMS (EI): m/z (%): calcd for C
8H
12NO:232.1000; Found:232.1008;
The crystal structure determination of compound:
The monocrystalline of choosing suitable size at microscopically at room temperature carries out the experiment of X-ray single crystal diffraction, under the 293k temperature, on Oxford X-ray single crystal diffractometer, use through the MoKa of graphite monochromator monochromatization ray (λ=0.71073 A) and collect diffraction data with the w-Theta scan mode.The data obtained is carried out the Lp factor and experience absorption correction, and crystalline structure is solved by direct method, and diffraction data reduction and structure elucidation work use respectively SAINT-5.0 and SHELXS-97 program to finish.Crystal data is as follows:
Empirical formula C16 H12 N2
Formula weight 232.28
Temperature 293(2) K
Wavelength 0.71073 A
Crystal system, space group Monoclinic, P2(1)/c
Unit cell dimensions a = 13.422(3) A alpha = 90 deg.
b = 5.7453(12) A beta = 92.800(4) deg.
c = 7.6781(16) A gamma = 90 deg.
Volume 591.4(2) A^3
Z, Calculated density 2, 1.304 Mg/m^3
Absorption coefficient 0.078 mm^-1
F(000) 244
Crystal size 0.257 x 0.123 x 0.078 mm
Theta range for data collection 1.52 to 25.49 deg.
Limiting indices -15<=h<=16, -6<=k<=5, -9<=l<=9
Reflections collected / unique 3211 / 1097 [R(int) = 0.0235]
Completeness to theta = 25.49 100.0 %
Absorption correction Empirical
Max. and min. transmission 1.00000 and 0.56771
Refinement method Full-matrix least-squares on F^2
Data / restraints / parameters 1097 / 0 / 82
Goodness-of-fit on F^2 1.124
Final R indices [I>2sigma(I)] R1 = 0.0523, wR2 = 0.1304
R indices (all data) R1 = 0.0643, wR2 = 0.1381
Largest diff. peak and hole 0.194 and -0.175 e.A^-3;
Bond distance's data of crystal:
N(1)-C(8) 1.329(2)
N(1)-C(7) 1.337(2)
C(1)-C(2) 1.392(2)
C(1)-C(6) 1.393(2)
C(1)-C(7) 1.477(2)
C(2)-C(3) 1.375(2)
C(2)-H(2) 0.9300
C(3)-C(4) 1.378(3)
C(3)-H(3) 0.9300
C(4)-C(5) 1.371(3)
C(4)-H(4) 0.9300
C(5)-C(6) 1.378(2)
C(5)-H(5) 0.9300
C(6)-H(6) 0.9300
C(7)-C(8)#1 1.381(2)
C(8)-C(7)#1 1.381(2)
C(8)-H(8) 0.9300
The bond angle data of crystal:
C(8)-N(1)-C(7) 117.26(15)
C(2)-C(1)-C(6) 118.22(16)
C(2)-C(1)-C(7) 119.84(15)
C(6)-C(1)-C(7) 121.93(15)
C(3)-C(2)-C(1) 120.85(17)
C(3)-C(2)-H(2) 119.6
C(1)-C(2)-H(2) 119.6
C(2)-C(3)-C(4) 120.16(18)
C(2)-C(3)-H(3) 119.9
C(4)-C(3)-H(3) 119.9
C(5)-C(4)-C(3) 119.75(16)
C(5)-C(4)-H(4) 120.1
C(3)-C(4)-H(4) 120.1
C(4)-C(5)-C(6) 120.60(18)
C(4)-C(5)-H(5) 119.7
C(6)-C(5)-H(5) 119.7
C(5)-C(6)-C(1) 120.41(17)
C(5)-C(6)-H(6) 119.8
C(1)-C(6)-H(6) 119.8
N(1)-C(7)-C(8)#1 119.41(16)
N(1)-C(7)-C(1) 117.47(15)
C(8)#1-C(7)-C(1) 123.13(15)
N(1)-C(8)-C(7)#1 123.33(17)
N(1)-C(8)-H(8) 118.3
C(7)#1-C(8)-H(8) 118.3
Claims (2)
1. one kind 2, the synthetic method of 5-diphenyl pyrazine comprises and synthesizes and separate that it is characterized in that: described synthesizing is that 3-(N-ethyl-N-phenyl)-propionitrile and D-benzene glycinol have the anhydrous ZnCl of catalyzer in chlorobenzene solvent
2When existing under the anhydrous and oxygen-free condition back flow reaction 60 ~ 70 hours, ZnCl
2Consumption be 75 ~ 85 mol % of material quantity, reaction is sloughed chlorobenzene after finishing, is added the water stirring and dissolving, use again chloroform extraction, upper silica gel column chromatography separates behind extraction phase drying, the precipitation, with sherwood oil/methylene dichloride (volume ratio 7:3) wash-out, collect the first component point, obtain target product 2, the 5-diphenyl pyrazine after sloughing eluent.
2. by title complex claimed in claim 1 (I), it is characterized in that described title complex, under the 293k temperature, on Oxford X-ray single crystal diffractometer, with collecting diffraction data through the MoKa of graphite monochromator monochromatization ray (λ=0.71073 A) with the w-Theta scan mode, crystal belongs to rhombic system, spacer P2 (1)/c, unit cell parameters: a=14.90430 (10) A, alpha=90 deg; B=15.2204 (10) A, beta=90 deg; C=27.3737 (2) A, gamma=90 deg.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201210320978.7A CN102850281B (en) | 2012-04-29 | 2012-09-03 | Synthesis method for 2,5-diphenylpyrazine |
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN2012101306316A CN102643239A (en) | 2012-04-29 | 2012-04-29 | Synthetic method of 2,5-diphenyl pyrazine |
CN201210130631.6 | 2012-04-29 | ||
CN201210320978.7A CN102850281B (en) | 2012-04-29 | 2012-09-03 | Synthesis method for 2,5-diphenylpyrazine |
Publications (2)
Publication Number | Publication Date |
---|---|
CN102850281A true CN102850281A (en) | 2013-01-02 |
CN102850281B CN102850281B (en) | 2014-04-09 |
Family
ID=46656351
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN2012101306316A Pending CN102643239A (en) | 2012-04-29 | 2012-04-29 | Synthetic method of 2,5-diphenyl pyrazine |
CN201210320978.7A Active CN102850281B (en) | 2012-04-29 | 2012-09-03 | Synthesis method for 2,5-diphenylpyrazine |
Family Applications Before (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN2012101306316A Pending CN102643239A (en) | 2012-04-29 | 2012-04-29 | Synthetic method of 2,5-diphenyl pyrazine |
Country Status (1)
Country | Link |
---|---|
CN (2) | CN102643239A (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103450098A (en) * | 2013-09-13 | 2013-12-18 | 罗梅 | Method for synthesizing 2, 5-diphenyl pyrazine |
CN105906574A (en) * | 2016-04-29 | 2016-08-31 | 合肥祥晨化工有限公司 | Synthesizing method of 2,5-diphenyl pyrazine |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2012052996A2 (en) * | 2010-10-19 | 2012-04-26 | Yeda Research And Development Co. Ltd. | Novel ruthenium complexes and their uses in processes for formation and/or hydrogenation of esters, amides and derivatives thereof |
CN102718783A (en) * | 2012-07-12 | 2012-10-10 | 罗梅 | Chiral compound |
-
2012
- 2012-04-29 CN CN2012101306316A patent/CN102643239A/en active Pending
- 2012-09-03 CN CN201210320978.7A patent/CN102850281B/en active Active
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2012052996A2 (en) * | 2010-10-19 | 2012-04-26 | Yeda Research And Development Co. Ltd. | Novel ruthenium complexes and their uses in processes for formation and/or hydrogenation of esters, amides and derivatives thereof |
CN102718783A (en) * | 2012-07-12 | 2012-10-10 | 罗梅 | Chiral compound |
Non-Patent Citations (2)
Title |
---|
GNANAPRAKASAM BOOPATHY,ET,AL.: "Synthesis of Peptides and Pyrazines from β-Amino Alcohols through Extrusion of H2 Catalyzed by Ruthenium Pincer Complexes: Ligand-Controlled Selectivity", 《ANGEWANDTE CHEMIE》, vol. 50, no. 51, 26 October 2011 (2011-10-26), pages 12448 - 12452 * |
LUO, MEI,AT AL.: "A novel synthesis of 2,5-diphenylpyrazine", 《RESEARCH ON CHEMICAL INTERMEDIATES》, vol. 36, no. 5, 13 August 2010 (2010-08-13), pages 491 - 494 * |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103450098A (en) * | 2013-09-13 | 2013-12-18 | 罗梅 | Method for synthesizing 2, 5-diphenyl pyrazine |
CN105906574A (en) * | 2016-04-29 | 2016-08-31 | 合肥祥晨化工有限公司 | Synthesizing method of 2,5-diphenyl pyrazine |
CN105906574B (en) * | 2016-04-29 | 2018-08-03 | 合肥祥晨化工有限公司 | A kind of synthetic method of 2,5- diphenyl pyrazines |
Also Published As
Publication number | Publication date |
---|---|
CN102643239A (en) | 2012-08-22 |
CN102850281B (en) | 2014-04-09 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN101811919B (en) | Method for preparing amino acid schiff base metal complexes without solvent | |
Xia et al. | Synthesis, structure characterization and photocatalytic properties of two new uranyl naphthalene-dicarboxylate coordination polymer compounds | |
CN102887912B (en) | A kind of chiral zinc nitrogen complexes | |
MacNeill et al. | Synthesis, crystal structure and properties of novel isostructural two-dimensional lanthanide-based coordination polymers with 2, 3, 5, 6-tetrafluoro-1, 4-benzenedicarboxylic acid | |
CN102936259A (en) | Method for synthesizing cucurbit [6] uril, Q[6]-rear earth linear polymer and separating light rear earth from heavy rear earth | |
CN102516550B (en) | Seven-membered cucurbituril-rare earth metal linear tubular supramolecular polymer, preparation and application thereof | |
CN102850281B (en) | Synthesis method for 2,5-diphenylpyrazine | |
Capar et al. | β-octabromo-meso-tris (pentafluorophenyl) corrole: reductive demetalation-based synthesis of a heretofore inaccessible, perhalogenated free-base corrole | |
CN102702232A (en) | Method for preparation of fine cefamandole nafate | |
CN102827195B (en) | Rare-earth organic coordination polymer constructed by using m-phthalic acid and 2-pyridylformic acid as mixed ligand, and preparation method and application thereof | |
CN102807504B (en) | Method for synthesizing salicylamide | |
Fan et al. | Salen-type nickel (II), palladium (II) and copper (II) complexes having chiral and racemic camphoric diamine components | |
CN103319356A (en) | One-step green synthesis process of antimalarial raw material benflumetol | |
CN103483800B (en) | A kind of Zinc complex/polyurethanecomposite composite fluorescent material and preparation method | |
CN103275108A (en) | Preparation and synthesis method of chiral copper complex | |
CN103467386B (en) | Aryl pyrimidine ortho-position monocyano compounds and synthesis method thereof | |
CN102757350A (en) | Preparation method of erlotinib intermediate, i.e., 3-aminobenzeneacetylene | |
CN102827194A (en) | Rare-earth organic coordination polymer using 2,2'-dipyridine as auxiliary ligand and template, and preparation method and application thereof | |
CN101417983A (en) | Method for synthesizing 2,5-diphenyl pyrazine | |
CN102850383A (en) | Chiral zinc complex | |
CN103739556A (en) | Preparation method and detection method of 2,4-dibromopyrimidine | |
CN103450098A (en) | Method for synthesizing 2, 5-diphenyl pyrazine | |
CN103408423A (en) | Nature active product L-cichoric acid synthesis process | |
CN109608380B (en) | Synthetic method of prohnac intermediate 7- (p-bromobenzoyl) indol-2-one | |
CN102875386A (en) | Preparation and synthesis method for ammonium salt |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C14 | Grant of patent or utility model | ||
GR01 | Patent grant | ||
TR01 | Transfer of patent right |
Effective date of registration: 20191213 Address after: Room 207, main office building, No.118 Longxing Road, Haining Economic Development Zone, Haining City, Jiaxing City, Zhejiang Province Patentee after: Haining Economic Development Industrial Park Development and Construction Co., Ltd Address before: 151 box 230009, South District, HeFei University of Technology, Anhui, Hefei, Tunxi Road, Hefei, 193 Patentee before: Luo Mei |
|
TR01 | Transfer of patent right |