CN104496835B - A kind of generation and synthesis method of chirality ammonium salt crystal - Google Patents
A kind of generation and synthesis method of chirality ammonium salt crystal Download PDFInfo
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- CN104496835B CN104496835B CN201410824652.7A CN201410824652A CN104496835B CN 104496835 B CN104496835 B CN 104496835B CN 201410824652 A CN201410824652 A CN 201410824652A CN 104496835 B CN104496835 B CN 104496835B
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- Prior art keywords
- gavaculine
- ammonium salt
- chirality
- benzene glycinol
- benzene
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- 239000013078 crystal Substances 0.000 title claims abstract description 13
- 150000003863 ammonium salts Chemical class 0.000 title description 4
- 238000001308 synthesis method Methods 0.000 title description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 22
- QMXOFBXZEKTJIK-UHFFFAOYSA-N Glycinol Natural products C1=C(O)C=C2OCC3(O)C4=CC=C(O)C=C4OC3C2=C1 QMXOFBXZEKTJIK-UHFFFAOYSA-N 0.000 claims abstract description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 12
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims abstract description 11
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 6
- -1 phenyl aldehyde Chemical class 0.000 claims abstract description 6
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims abstract description 5
- 238000010189 synthetic method Methods 0.000 claims abstract description 5
- 235000005074 zinc chloride Nutrition 0.000 claims abstract description 5
- 239000011592 zinc chloride Substances 0.000 claims abstract description 5
- 238000004440 column chromatography Methods 0.000 claims abstract description 4
- 238000000926 separation method Methods 0.000 claims abstract description 4
- 239000000126 substance Substances 0.000 claims abstract description 4
- 238000005406 washing Methods 0.000 claims abstract description 4
- 230000003197 catalytic effect Effects 0.000 claims abstract description 3
- 239000007810 chemical reaction solvent Substances 0.000 claims abstract description 3
- 238000001914 filtration Methods 0.000 claims abstract description 3
- 230000009466 transformation Effects 0.000 claims abstract description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 6
- 238000003786 synthesis reaction Methods 0.000 claims description 6
- 238000002447 crystallographic data Methods 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 230000005260 alpha ray Effects 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- 125000006850 spacer group Chemical group 0.000 claims description 2
- QNRATNLHPGXHMA-XZHTYLCXSA-N (r)-(6-ethoxyquinolin-4-yl)-[(2s,4s,5r)-5-ethyl-1-azabicyclo[2.2.2]octan-2-yl]methanol;hydrochloride Chemical compound Cl.C([C@H]([C@H](C1)CC)C2)CN1[C@@H]2[C@H](O)C1=CC=NC2=CC=C(OCC)C=C21 QNRATNLHPGXHMA-XZHTYLCXSA-N 0.000 claims 1
- 239000000706 filtrate Substances 0.000 claims 1
- 238000000034 method Methods 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 3
- HEVGGTGPGPKZHF-UHFFFAOYSA-N 1-(1,2-dimethyl-3-methylidenecyclopentyl)-4-methylbenzene Chemical compound CC1C(=C)CCC1(C)C1=CC=C(C)C=C1 HEVGGTGPGPKZHF-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- GSOLWAFGMNOBSY-UHFFFAOYSA-N cobalt Chemical compound [Co][Co][Co][Co][Co][Co][Co][Co] GSOLWAFGMNOBSY-UHFFFAOYSA-N 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 238000005564 crystal structure determination Methods 0.000 description 1
- 238000002050 diffraction method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000001404 mediated effect Effects 0.000 description 1
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A kind of chirality gavaculine-(L)-benzene glycinol ammonium salt, its chemical formula is as follows:?
Description
One, technical field
The present invention relates to a kind of generation and synthesis method of ammonium salt, is exactly the generation and synthesis method of a kind of chirality gavaculine-(L)-benzene glycinol amide salt.
Two, background technology
The synthetic method of ammonium salt has many bibliographical informations [1-6]:
1.Quaternaryammonium(hypo)ioditecatalysisforenantioselectiveoxidativecycloetherification,UyanikMuhammet;OkamotoHiroaki;YasuiTakeshi;IshiharaKazuaki,
Science.2010Jun11;328(5984):1365-6.
2.Researchprogressonchitosanquaternaryammoniumsalt,Li,Rong-chun,
HuaxueShiji
， 2011,33(10),895-898.
3.DiastereoselectiveAziridinationofChiralElectron-DeficientOlefinswith
N-Chloro-N-sodiocarbamatesCatalyzedbyChiralQuaternaryAmmoniumSalts,Murakami,Yuta;Takeda,Youhei;Minakata,Satoshi,
JournalofOrganicChemistry
, 2011,76(15),6277-6285.
4.Synthesisofchiralspirocyclo-quaternaryammoniumsaltsfromL-prolineandtheirapplicationasphase-transfercatalystsinasymmetricalkylation,Wang,Na;Lin,Song-Wen;Yang,Qing;Sun,Qi;Li,Run-Tao,
JournalofChinesePharmaceuticalSciences
, 2011,20(1),26-31.
5.Phosphorofluoridicacidammoniumsaltsandacids:Synthesis,NMRproperties,andapplicationasacidcatalysts,Murai,Toshiaki;Tonomura,Yusuke;Takenaka,Toru,
HeteroatomChemistry ,2011,22(3-4),417-425.
6.Cobalt-Mediated,EnantioselectiveSynthesisofC2andC1Dienes,Boyd,W.Christopher;Crimmin,MarkR.;Rosebrugh,LaurenE.;Schomaker,JenniferM.;Bergman,RobertG.;Toste,F.Dean
,JournaloftheAmericanChemicalSociety ,2010,132(46),16365-16367。
Summary of the invention
The present invention aims to provide chipal compounds gavaculine-(L)-benzene glycinol amide salt, and technical problem to be solved is that one-step synthesis obtains target product.
A kind of chirality gavaculine alleged by the present invention-(L)-benzene glycinol amide salt be by gavaculine and L-benzene glycinol prepare by the compound shown in following chemical formula:
（Ⅰ）
Chemical name: gavaculine-(L)-benzene glycinol amide salt, is called for short compound (I).
This synthetic method comprises synthesis and is separated, described synthesis mol ratio is that the gavaculine of 1:1.9 and L-benzene glycinol react, 50mL chlorobenzene does reaction solvent, catalyzer is made, return stirring 72 hours, heat filtering with 10mol% zinc chloride, filter is spin-dried for night, column chromatography for separation, by methylene chloride/methanol: 9/1 drip washing, obtains clear crystal.
The amino that this reaction mechanism can be speculated as carboxyl in gavaculine molecule and L-benzene glycinol forms amide salt rapidly under the effect of 10mol% zinc chloride in chlorobenzene solvent.
This synthetic method one step obtains target product, and technique is simple, easy to operate.
This compound shows good catalytic effect in the Henle reaction of phenyl aldehyde, and its transformation efficiency is up to 99%.
Three, accompanying drawing explanation
Fig. 1 is the X-diffraction analysis figure of gavaculine-(L)-benzene glycinol ammonium salt.
Four, embodiment
1. the preparation of gavaculine-(L)-benzene glycinol ammonium salt
Take Zinc Chloride Anhydrous 0.4067g (18.4mmol), gavaculine 3.1862g (23.23mmol) and L-benzene glycinol 6.0741g(44.27mmol) in 100mL round-bottomed flask, add 50mL chlorobenzene, return stirring is after 72 hours, stopped reaction, solvent is spin-dried for, carries out drip washing column chromatography for separation with methylene dichloride and anhydrous methanol 9:1, after several days, occur clear crystal.Productive rate: 85%, m.p.:146-148 ° C,
[a] 25 d =-256.41o (c, CH 3 oH), 1hNMR (300MHz, CDCl
3, 27 DEG C), δ (ppm)=7.28-7.42 (m; 6H), 7.19-7.20 (m, 1H); 7.00-7.08 (m, 2H), 6.61-6.64 (m; 3H), 4.10-4.12 (m, 1H); 3.55-3.60 (m; 2H), 3.16 (s, 1H);
13cNMR:171.4,148.9,140.3,137.4,128.9,128.8 (x2), 128.3 (x2), 127.9,117.7,116.8,115.7,65.9,57.3; IR:3385,3329,3059,2863,1496,1449,1386,1273,1199,1146,1056,1028,993,916,883,795,763,700,688,672,622,576,564; Ultimate analysis C
15h
18nO
3, actual value: C:65.46%, H, 6.43%, N, 10.15%; Theoretical value: C:65.68%, H, 6.61%, N, 10.21%;
The crystal structure determination of compound:
The monocrystalline choosing suitable size under the microscope at room temperature carries out the experiment of X-ray single crystal diffraction, at 293k temperature, on the X-ray single crystal diffraction instrument of Oxford, collect diffraction data with the MoK alpha-ray (λ=0.71073) through graphite monochromator monochromatization with ω-θ scan mode.Carry out the Lp factor and empirical absorption correction to the data obtained, crystalline structure is solved by direct method, and diffraction data reduction and structure elucidation work use SAINT-5.0 and SHELXS-97 program to complete respectively.Crystal data is as follows:
Empirical formula C15H18N2O3
Molecular weight 274.31
Temperature 293 (2) K
Wavelength 0.71073
Crystallographic system, spacer iris shape, P2 (1) 2 (1) 2 (1)
Unit cell parameters a=6.2412 (13) α=90 °.
b=12.161(3)?β=90°
c=18.983(4)?γ=90°
Volume 1440.8(5) ^3
Electric density 4,1.265Mg/m^3
Absorption correction parameter 0.089mm^-1
Number of electrons 584 in unit cell
Crystallographic dimension 0.165x0.101x0.076mm
The scope 1.989to25.996 at Theta angle
Index capture range-the 7<=h<=7 of HKL ,-8<=k<15 ,-21<=l<=23
Collection/independent diffraction data 8804/2831 [R (int)=0.0647]
The data integrity degree 100.0% of theta=30.5
The method Multi Slice Mode of absorption correction
The transmitance 1.00000and0.09689 of minimax
The Matrix least square method of the method F^2 that refine uses
Number/the number of parameters 2831/6/194 of data number/use restriction
The method 0.973 that refine uses
The consistence factor R 1=0.0620 of point diffraction, ω R2=0.1631
Identical factor R 1=0.1216, the ω R2=0.1961 of observable diffraction
Absolute configuration parameter-0.4(10)
Maximum summit on difference Fourier figure and peak valley 0.423and-0.233e. ^-3
bond distance's data of crystal:
N(1)-C(2)1.376(9)
N(1)-H(1A)0.8600
N(1)-H(1B)0.8600
N(2)-C(14)1.489(6)
N(2)-H(2A)0.97(6)
N(2)-H(2B)0.83(5)
N(2)-H(2C)1.03(6)
O(1)-C(7)1.253(6)
O(2)-C(7)1.259(6)
O(2)-H(3B)1.8866
O(3)-C(15)1.408(7)
O(3)-H(3B)0.8200
C(1)-C(6)1.359(8)
C(1)-C(2)1.375(9)
C(1)-H(1)0.9300
C(3)-C(2)1.342(9)
C(3)-C(4)1.347(9)
C(3)-H(3)0.9300
C(4)-C(5)1.377(8)
C(4)-H(4)0.9300
C(5)-C(6)1.386(7)
C(5)-H(5)0.9300
C(6)-C(7)1.494(8)
C(8)-C(9)1.371(9)
C(8)-C(13)1.403(8)
C(8)-H(8)0.9300
C(9)-C(10)1.368(10)
C(9)-H(9)0.9300
C(10)-C(11)1.372(9)
C(10)-H(10)0.9300
C(11)-C(12)1.384(8)
C(11)-H(11)0.9300
C(12)-C(13)1.372(7)
C(12)-H(12)0.9300
C(13)-C(14)1.497(7)
C(14)-C(15)1.494(7)
C(14)-H(14)0.9800
C(15)-H(15A)0.9700
C(15)-H(15B)0.9700
the bond angle data of crystal:
C(2)-N(1)-H(1A)120.0
C(2)-N(1)-H(1B)120.0
H(1A)-N(1)-H(1B)120.0
C(14)-N(2)-H(2A)111(3)
C(14)-N(2)-H(2B)110(3)
H(2A)-N(2)-H(2B)118(5)
C(14)-N(2)-H(2C)113(3)
H(2A)-N(2)-H(2C)100(4)
H(2B)-N(2)-H(2C)105(4)
C(7)-O(2)-H(3B)123.5
C(15)-O(3)-H(3B)109.5
C(6)-C(1)-C(2)121.9(6)
C(6)-C(1)-H(1)119.1
C(2)-C(1)-H(1)119.1
C(2)-C(3)-C(4)121.7(6)
C(2)-C(3)-H(3)119.2
C(4)-C(3)-H(3)119.2
C(3)-C(4)-C(5)119.9(6)
C(3)-C(4)-H(4)120.1
C(5)-C(4)-H(4)120.1
C(4)-C(5)-C(6)119.8(6)
C(4)-C(5)-H(5)120.1
C(6)-C(5)-H(5)120.1
C(1)-C(6)-C(5)118.1(5)
C(1)-C(6)-C(7)120.0(5)
C(5)-C(6)-C(7)121.9(6)
O(1)-C(7)-O(2)123.6(5)
O(1)-C(7)-C(6)118.9(5)
O(2)-C(7)-C(6)117.5(5)
C(9)-C(8)-C(13)121.0(6)
C(9)-C(8)-H(8)119.5
C(13)-C(8)-H(8)119.5
C(10)-C(9)-C(8)120.0(6)
C(10)-C(9)-H(9)120.0
C(8)-C(9)-H(9)120.0
C(9)-C(10)-C(11)119.7(6)
C(9)-C(10)-H(10)120.1
C(11)-C(10)-H(10)120.1
C(10)-C(11)-C(12)120.7(6)
C(10)-C(11)-H(11)119.7
C(12)-C(11)-H(11)119.7
C(13)-C(12)-C(11)120.3(6)
C(13)-C(12)-H(12)119.8
C(11)-C(12)-H(12)119.8
C(12)-C(13)-C(8)118.2(5)
C(12)-C(13)-C(14)122.3(5)
C(8)-C(13)-C(14)119.4(5)
N(2)-C(14)-C(15)108.9(4)
N(2)-C(14)-C(13)112.1(4)
C(15)-C(14)-C(13)114.1(4)
N(2)-C(14)-H(14)107.1
C(15)-C(14)-H(14)107.1
C(13)-C(14)-H(14)107.1
O(3)-C(15)-C(14)111.8(5)
O(3)-C(15)-H(15A)109.3
C(14)-C(15)-H(15A)109.3
O(3)-C(15)-H(15B)109.3
C(14)-C(15)-H(15B)109.3
H(15A)-C(15)-H(15B)107.9
C(3)-C(2)-C(1)118.7(7)
C(3)-C(2)-N(1)122.5(7)
C(1)-C(2)-N(1)118.8(7)
2. Henle reaction application
1.
(1E)-2-nitroethylene base benzene
Catalyst I (0.30mmol), phenyl aldehyde 0.10mL (0.986mmol) and Nitromethane 99Min. (0.50mL, 9.255mmol) at room temperature stir 40h, and productive rate is: 99%;
1hNMR (300MHz, CDCl
3), 8.00 (d, J=23Hz, 1H), 7.47 ~ 7.63 (m, 6H).
Claims (4)
1. a chirality gavaculine-L-benzene glycinol ammonium salt, its chemical formula is as follows:
2. chirality gavaculine-L-benzene glycinol ammonium salt according to claim 1, at 293k temperature, on the X-ray single crystal diffraction instrument of Oxford, with the MoK alpha-ray through graphite monochromator monochromatization
collect diffraction data with ω-θ scan mode, it is characterized in that crystal belongs to rhombic system, spacer P2 (1) 2 (1) 2 (1); Unit cell parameters:
α=90 °;
β=90 °;
γ=90 °.
3. the synthetic method of chirality gavaculine-L-benzene glycinol ammonium salt (I) according to claim 1, comprise synthesis and be separated, it is characterized in that: described synthesis mol ratio is that the gavaculine of 1:1.9 and L-benzene glycinol react, and 50mL chlorobenzene does reaction solvent, makees catalyzer with 10mol% zinc chloride, return stirring 72 hours, heat filtering, is spin-dried for filtrate, column chromatography for separation, by methylene chloride/methanol: 9/1 drip washing, obtains clear crystal.
4. the purposes of chirality gavaculine-L-benzene glycinol ammonium salt according to claim 1, its catalytic effect shown in the Henle reaction of phenyl aldehyde, its transformation efficiency is up to 99%.
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|---|---|---|---|---|
| CN102225915A (en) * | 2011-05-16 | 2011-10-26 | 罗梅 | Chiral oxazoline and synthesis method thereof |
| CN102627571A (en) * | 2012-04-11 | 2012-08-08 | 罗梅 | Preparation and synthesis method for chiral ammonium salt |
| CN103588821A (en) * | 2013-10-16 | 2014-02-19 | 合肥工业大学 | Chiral phenylglycinol nickel complex |
| CN103613507A (en) * | 2013-10-26 | 2014-03-05 | 合肥工业大学 | Chiral D-Phenylglycinol cobalt complex |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102225915A (en) * | 2011-05-16 | 2011-10-26 | 罗梅 | Chiral oxazoline and synthesis method thereof |
| CN102627571A (en) * | 2012-04-11 | 2012-08-08 | 罗梅 | Preparation and synthesis method for chiral ammonium salt |
| CN103588821A (en) * | 2013-10-16 | 2014-02-19 | 合肥工业大学 | Chiral phenylglycinol nickel complex |
| CN103613507A (en) * | 2013-10-26 | 2014-03-05 | 合肥工业大学 | Chiral D-Phenylglycinol cobalt complex |
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