CN105130827A - Synthesis method of chiral -phenylglycinol hydrochloride - Google Patents
Synthesis method of chiral -phenylglycinol hydrochloride Download PDFInfo
- Publication number
- CN105130827A CN105130827A CN201510614296.0A CN201510614296A CN105130827A CN 105130827 A CN105130827 A CN 105130827A CN 201510614296 A CN201510614296 A CN 201510614296A CN 105130827 A CN105130827 A CN 105130827A
- Authority
- CN
- China
- Prior art keywords
- hydrochloride
- benzene glycinol
- phenylglycinol
- synthesis method
- target product
- 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.)
- Pending
Links
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 title claims description 14
- 238000001308 synthesis method Methods 0.000 title abstract description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims abstract description 9
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- GNEPOXWQWFSSOU-UHFFFAOYSA-N dichloro-methyl-phenylsilane Chemical compound C[Si](Cl)(Cl)C1=CC=CC=C1 GNEPOXWQWFSSOU-UHFFFAOYSA-N 0.000 claims abstract description 6
- GFHNAMRJFCEERV-UHFFFAOYSA-L cobalt chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Co+2] GFHNAMRJFCEERV-UHFFFAOYSA-L 0.000 claims abstract description 5
- 239000000126 substance Substances 0.000 claims abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000012047 saturated solution Substances 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims abstract description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 18
- 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 description 18
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 18
- 238000010189 synthetic method Methods 0.000 claims description 8
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- 238000003786 synthesis reaction Methods 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 4
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 3
- KSXJJXIDBVLDBZ-QRPNPIFTSA-N (2R)-2-amino-2-phenylethanol hydrochloride Chemical compound Cl.N[C@H](C1=CC=CC=C1)CO KSXJJXIDBVLDBZ-QRPNPIFTSA-N 0.000 abstract 2
- IJXJGQCXFSSHNL-QMMMGPOBSA-N (R)-(-)-2-Phenylglycinol Chemical compound OC[C@H](N)C1=CC=CC=C1 IJXJGQCXFSSHNL-QMMMGPOBSA-N 0.000 abstract 1
- 239000002904 solvent Substances 0.000 abstract 1
- 238000000034 method Methods 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 4
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 4
- 239000013078 crystal Substances 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- YEHGSOZIZRABBU-OGFXRTJISA-N (1r)-1-phenylethanamine;hydrochloride Chemical compound Cl.C[C@@H](N)C1=CC=CC=C1 YEHGSOZIZRABBU-OGFXRTJISA-N 0.000 description 1
- 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 description 1
- 238000002447 crystallographic data Methods 0.000 description 1
- 238000002050 diffraction method Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A synthesis method of (R) -phenylglycinol hydrochloride shown in the following chemical formula (I) comprises the steps of reacting 5mL of methyl phenyl dichlorosilane, (R) -phenylglycinol 8.9005g and cobalt chloride hexahydrate 7.3955g in chlorobenzene solution for 60 hours, removing a solvent by rotation, preparing a saturated solution by using dichloromethane and absolute ethyl alcohol, and obtaining a target product (R) -phenylglycinol hydrochloride after natural volatilization for several days?
Description
One, technical field
The present invention relates to a kind of generation and synthesis method of quaternary ammonium salt, is exactly the synthetic method of a kind of chirality (R)-benzene glycinol hydrochloride.
Two, background technology
The synthetic method of quaternary ammonium salt has many bibliographical informations.As far back as 1956, Japanization association reported the synthetic method of some quaternary ammonium salts, and nineteen fifty-nine, American Chemical Society also reports the synthetic method of quaternary ammonium salt.
Reference:
1.Surrey,AlexanderR.;Lesher,GeorgeY.;Mayer,J.Richard;Webb,Wm.G.JournaloftheAmericanChemicalSociety(1959),812894-7;
2
.Davis,M.JournaloftheChemicalSociety(1956),337-43。
Applicant, in the experiment of synthetic compound, does not obtain target product title complex, but obtains another kind of chipal compounds (R)-benzene glycinol hydrochloride.
Three, summary of the invention
The present invention aims to provide chirality (R)-benzene glycinol hydrochloride, and technical problem to be solved is that one-step synthesis obtains target product.
One (R) alleged by the present invention-benzene glycinol hydrochloride be by dichloromethyl phenylsilane, (R)-benzene glycinol and cobalt chloride hexahydrate prepare by the compound shown in following chemical formula:
（Ⅰ）
Chemical name: (R)-benzene glycinol hydrochloride, is called for short compound (I).
This synthetic method comprises synthesis and is separated, described synthesis is 5mL dichloromethyl phenylsilane, (R)-benzene glycinol 8.9005g and cobalt chloride hexahydrate 7.3955g reacts 60 hours in chlorobenzene solution, rotate except desolventizing, with methylene dichloride and dehydrated alcohol preparation saturated solution, naturally volatilize after a couple of days, obtain target product (R)-benzene glycinol hydrochloride.
Its reaction mechanism can be speculated as (R)-benzene glycinol under dichloromethyl phenylsilane and cobalt chloride hexahydrate effect, forms a part hydrogenchloride, then with excessive (R)-benzene glycinol salify, forms (R)-benzene glycinol hydrochloride.
This synthetic method one step obtains target product, and technique is simple, easy to operate.
Four, accompanying drawing explanation
Fig. 1 is the X-diffraction analysis figure of (R)-benzene glycinol hydrochloride.
Five, embodiment
1. the preparation of chirality (R)-α-phenylethylamine hydrochloride
In 100mL flask, under anhydrous and oxygen-free condition, add CoCL2 6H2O 7.3955g, 2.5927g(21.78mmol), (R)-benzene glycinol 8.9005g, dichloromethyl phenylsilane 5mL, chlorobenzene 40mL, reflux mixture 60h, stopped reaction, rotates except desolventizing, with methylene dichloride and dehydrated alcohol preparation saturated solution, naturally volatilize after a couple of days, obtain target product (R)-benzene glycinol hydrochloride.; Productive rate: 92%, m.p:98-100 ° C; [a]
5 d=+11.58o (c=0.08, CH
3oH),
1hNMR (500MHz, CDCl
3) 8.45(s, br, 1H), 7.30 – 7.49 (m, 5H), 5.74 – 5.82 (m, 1H), 4.14 (d, J=4.5Hz, 1H), 2.40 (s, br, 1H).
13cNMR (75MHz, CDCl
3) 130.1,123.0 (x2), 122.1,122.0 (x2), 57.4,50.5, results of elemental analyses is as follows: theoretical value: C, and 55.34%; H, 6.97%; N, 8.07%; Measured value: C, 55.28%; H, 6.78%; N, 7.82%.; HRMS (EI): m/z – Cl
-(%): calcdforC
8h
12nO:138.0919; Found:138.0925.IR (KBr): 3424,2253,2127,1656,1051,1027,1005,825,764,630;
Match crystal volume data is as follows:
Empirical formula C8H12ClNO
Molecular weight 173.64
Temperature 293 (2) K
Wavelength 0.71073
Crystallographic system, spacer rhombic system, P2 (1) 2 (1) 2 (1)
Unit cell parameters a=6.423 (2) α=90 °.
b=7.299(2)?β=90°.
c=19.910(8)?γ=90°.
Volume 933.5 (6) ^3
Electric density 4,1.236Mg/m^3
Absorption correction parameter 0.355mm^-1
Number of electrons 368 in unit cell
Crystallographic dimension 0.160x0.110x0.050mm
The scope 2.046to25.996 at Theta angle
Index capture range-the 7<=h<=7 of HKL ,-8<=k<=9 ,-15<=l<=24
Collection/independent diffraction data 5583/1828 [R (int)=0.0446]
The data integrity degree 100.0% of theta=25.242 °
The method Multi Slice Mode of absorption correction
The transmitance 0.7456and0.6626 of minimax
The Matrix least square method of the method F^2 that refine uses
Number/the number of parameters 1828/0/105 of data number/use restriction
The method 1.171 that refine uses
The consistence factor R 1=0.0548 of point diffraction, ω R2=0.1125
Identical factor R 1=0.0635, the ω R2=0.1161 of observable diffraction
Absolute configuration parameter 0.00(6)
Maximum summit on difference Fourier figure and peak valley 0.416and-0.176e.A^-3
the typical bond distance's data of crystal:
N(1)-C(2)1.491(5)
N(1)-H(1A)0.8900
N(1)-H(1B)0.8900
N(1)-H(1C)0.8900
O(1)-C(1)1.407(5)
O(1)-H(1)0.75(5)
C(1)-C(2)1.515(5)
C(1)-H(1D)0.9700
C(1)-H(1E)0.9700
C(2)-C(3)1.509(5)
C(2)-H(2)0.9800
C(3)-C(4)1.382(5)
C(3)-C(8)1.382(5)
C(4)-C(5)1.381(6)
C(4)-H(4)0.9300
C(5)-C(6)1.366(6)
C(5)-H(5)0.9300
C(6)-C(7)1.365(6)
C(6)-H(6)0.9300
C(7)-C(8)1.380(6)
C(7)-H(7)0.9300
C(8)-H(8)0.9300
the typical bond angle data of crystal:
C(2)-N(1)-H(1A)109.5
C(2)-N(1)-H(1B)109.5
H(1A)-N(1)-H(1B)109.5
C(2)-N(1)-H(1C)109.5
H(1A)-N(1)-H(1C)109.5
H(1B)-N(1)-H(1C)109.5
C(1)-O(1)-H(1)106(4)
O(1)-C(1)-C(2)112.6(3)
O(1)-C(1)-H(1D)109.1
C(2)-C(1)-H(1D)109.1
O(1)-C(1)-H(1E)109.1
C(2)-C(1)-H(1E)109.1
H(1D)-C(1)-H(1E)107.8
N(1)-C(2)-C(3)111.3(3)
N(1)-C(2)-C(1)108.8(3)
C(3)-C(2)-C(1)112.1(3)
N(1)-C(2)-H(2)108.2
C(3)-C(2)-H(2)108.2
C(1)-C(2)-H(2)108.2
C(4)-C(3)-C(8)118.5(4)
C(4)-C(3)-C(2)120.9(3)
C(8)-C(3)-C(2)120.5(3)
C(5)-C(4)-C(3)120.0(4)
C(5)-C(4)-H(4)120.0
C(3)-C(4)-H(4)120.0
C(6)-C(5)-C(4)120.9(4)
C(6)-C(5)-H(5)119.5
C(4)-C(5)-H(5)119.5
C(7)-C(6)-C(5)119.6(4)
C(7)-C(6)-H(6)120.2
C(5)-C(6)-H(6)120.2
C(6)-C(7)-C(8)120.2(4)
C(6)-C(7)-H(7)119.9
C(8)-C(7)-H(7)119.9
C(7)-C(8)-C(3)120.8(4)
C(7)-C(8)-H(8)119.6
C(3)-C(8)-H(8)119.6
Claims (1)
1. one kind has (the R)-benzene glycinol hydrochloride synthetic method shown in following chemical formula (I), comprise synthesis and be separated, it is characterized in that: described synthesis is 5mL dichloromethyl phenylsilane, (R)-benzene glycinol 8.9005g and cobalt chloride hexahydrate 7.3955g reacts 60 hours in chlorobenzene solution, rotate except desolventizing, with methylene dichloride and dehydrated alcohol preparation saturated solution, naturally volatilize after a couple of days, obtain target product (R)-benzene glycinol hydrochloride
(I)
。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510614296.0A CN105130827A (en) | 2015-09-24 | 2015-09-24 | Synthesis method of chiral -phenylglycinol hydrochloride |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510614296.0A CN105130827A (en) | 2015-09-24 | 2015-09-24 | Synthesis method of chiral -phenylglycinol hydrochloride |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105130827A true CN105130827A (en) | 2015-12-09 |
Family
ID=54716464
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510614296.0A Pending CN105130827A (en) | 2015-09-24 | 2015-09-24 | Synthesis method of chiral -phenylglycinol hydrochloride |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105130827A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105837456A (en) * | 2016-04-28 | 2016-08-10 | 合肥祥晨化工有限公司 | Method for synthesizing chirality (R)-phenylglycinol hydrochloride |
| CN106242985A (en) * | 2016-07-28 | 2016-12-21 | 合肥祥晨化工有限公司 | Synthesis method and application of chiral L-valine hydrochloride crystal |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101973891A (en) * | 2010-11-04 | 2011-02-16 | 罗梅 | Preparation of chiral (S)-alpha-phenylethylamine hydrochloride and synthesis method thereof |
| CN103539684A (en) * | 2013-11-01 | 2014-01-29 | 罗梅 | Synthetic method of chiral (R)-phenylglycinol hydrochloride |
-
2015
- 2015-09-24 CN CN201510614296.0A patent/CN105130827A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101973891A (en) * | 2010-11-04 | 2011-02-16 | 罗梅 | Preparation of chiral (S)-alpha-phenylethylamine hydrochloride and synthesis method thereof |
| CN103539684A (en) * | 2013-11-01 | 2014-01-29 | 罗梅 | Synthetic method of chiral (R)-phenylglycinol hydrochloride |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105837456A (en) * | 2016-04-28 | 2016-08-10 | 合肥祥晨化工有限公司 | Method for synthesizing chirality (R)-phenylglycinol hydrochloride |
| CN106242985A (en) * | 2016-07-28 | 2016-12-21 | 合肥祥晨化工有限公司 | Synthesis method and application of chiral L-valine hydrochloride crystal |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105130827A (en) | Synthesis method of chiral -phenylglycinol hydrochloride | |
| CN102718783B (en) | Chiral compound | |
| CN102731539A (en) | Preparation and synthesizing method of chiral compound | |
| CN102952026B (en) | Preparation and synthetic method for chirality (S)-benzene ammonia alcohol hydrochloride | |
| CN102807577A (en) | Chiral compound | |
| CN103342710B (en) | Chiral zinc complex | |
| CN103588821A (en) | Chiral phenylglycinol nickel complex | |
| JP2016535033A5 (en) | ||
| CN102936204A (en) | Chiral compound | |
| CN102863343B (en) | Preparation and synthesis method of chiral (R)-phenylglycinol hydrochloride | |
| CN103539684A (en) | Synthetic method of chiral (R)-phenylglycinol hydrochloride | |
| CN103570768B (en) | A kind of cobalt nitrogen complex | |
| CN103483285A (en) | Synthesis method of chiral bisoxazoline copper complex crystal | |
| CN105198768A (en) | Synthesis method for 2-aminobutanamide | |
| CN103570562A (en) | Chiral Ni complex | |
| CN103613559A (en) | Synthesis method of chiral oxazoline nickel complex | |
| CN102977127A (en) | Chiral compound | |
| CN103804429B (en) | A kind of chirality leucinol cobalt complex | |
| CN103204780A (en) | Synthetic method of chiral (S)-phenylglycinol hydrochloride | |
| CN105541642A (en) | Synthesis method of chiral (S)-leucinol hydrochloride | |
| CN103709047A (en) | Chiral (R)-phenylethylamine hydrochloride copper chloride complex | |
| CN101973889B (en) | Method for preparing and synthesizing chiral (R)-alpha-phenethylamine hydrochloride | |
| CN103819355A (en) | Synthetic method of chiral acetyl phenylethylamine | |
| CN102924288B (en) | Method for preparing and synthesizing ammonium salt | |
| CN103570765B (en) | Chiral oxazoline manganese complex crystal and synthetic method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20151209 |
|
| RJ01 | Rejection of invention patent application after publication |