CN105837456A - Method for synthesizing chirality (R)-phenylglycinol hydrochloride - Google Patents

Method for synthesizing chirality (R)-phenylglycinol hydrochloride Download PDF

Info

Publication number
CN105837456A
CN105837456A CN201610271267.3A CN201610271267A CN105837456A CN 105837456 A CN105837456 A CN 105837456A CN 201610271267 A CN201610271267 A CN 201610271267A CN 105837456 A CN105837456 A CN 105837456A
Authority
CN
China
Prior art keywords
phenylglycinol
hydrochloride
phenylglycinol hydrochloride
rotates
solvent
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
Application number
CN201610271267.3A
Other languages
Chinese (zh)
Inventor
罗梅
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hefei Xiangchen Chemical Engineering Co Ltd
Original Assignee
Hefei Xiangchen Chemical Engineering Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Hefei Xiangchen Chemical Engineering Co Ltd filed Critical Hefei Xiangchen Chemical Engineering Co Ltd
Priority to CN201610271267.3A priority Critical patent/CN105837456A/en
Publication of CN105837456A publication Critical patent/CN105837456A/en
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
    • C07C213/02—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups
    • 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
    • C07B2200/07—Optical isomers

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention discloses a method for synthesizing (R)-phenylglycinol hydrochloride as shown in chemical formula (I) .The method comprises the steps that 2.0915 g of alpha-phenyl cinnamon nitrile, 5.2865 g of (R)-phenylglycinol and 2.7106 g of non-hydration zinc chloride react in chlorobenzene solution for 60 h, solvent is removed through rotation, residues are dissolved in water, extraction is conducted with CHCl3 (20mL*2), organic phase is dried with anhydrous sodium sulfate, solvent is removed through rotation, and a crude product is subjected to column chromatography with petroleum ether/dichloromethane (1:9) to obtain the white solid (R)-phenylglycinol hydrochloride.

Description

A kind of synthetic method of chirality (R)-phenylglycinol hydrochloride
One, technical field
The present invention relates to preparation and the synthetic method of a kind of quaternary ammonium salt, be exactly a kind of chirality (R)-phenylglycinol hydrochloride Synthetic method.
Two, background technology
The existing many document reports of the synthetic method of quaternary ammonium salt.As far back as 1956, Japanization association reported some quaternary ammonium salts Synthetic method, nineteen fifty-nine, American Chemical Society also reports the synthetic method of quaternary ammonium salt.
List of references:
1. Surrey, Alexander R.; Lesher, George Y.; Mayer, J. Richard; Webb, Wm. G. Journal of the American Chemical Society (1959),81 2894-7;
2. Davis, M. Journal of the Chemical Society (1956), 337-43。
Applicant, in the experiment of synthetic compound, does not obtains target product coordination compound, has but obtained another kind of Novel hand Property compound (R)-phenylglycinol hydrochloride.
Three, summary of the invention
It is desirable to provide chirality (R)-phenylglycinol hydrochloride, to be solved technical problem is that one-step synthesis obtains target Product.
One (R)-phenylglycinol hydrochloride alleged by the present invention is with anhydrous by α-phenylc nitrile, (R)-benzene glycinol Zinc chloride prepare by the compound shown in below formula:
(I).
Chemical name: (R)-phenylglycinol hydrochloride, is called for short compound (I).
This synthetic method includes synthesis and separates, and described synthesis is 2.0915g α-phenylc nitrile, (R)-benzene glycinol 5.2865g and without hydration zinc chloride 2.7106g react in chlorobenzene solution 60 hours, rotate removing solvent, by residue water Dissolve, and use CHCl3(20mLx2) extraction, organic facies anhydrous sodium sulfate is dried, and rotates and removes solvent, by thick product oil Ether/dichloromethane (1:9) column chromatography, obtains white solid (R)-phenylglycinol hydrochloride.
Its reaction mechanism can be speculated as (R)-benzene glycinol at α-phenylc nitrile and without, under hydration zinc chloride effect, forming one point Sub-hydrogen chloride, then (the R)-benzene glycinol with excess becomes salt, forms (R)-phenylglycinol 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)-phenylglycinol hydrochloride.
Five, detailed description of the invention
1. the preparation of chirality (R)-α-phenylethylamine hydrochlorate
In 100mL flask, under the conditions of anhydrous and oxygen-free, add anhydrous zinc chloride 2.7106g(19.9 mmol), (R)-benzene is sweet Ammonia alcohol 5.2865g, 2.0915g α-phenylc nitrile (10.2mmol) reacts 60 hours in chlorobenzene solution, rotates and removes solvent, By petroleum ether and dichloromethane 1:9 column chromatography for separation by volume, obtain target product (R)-phenylglycinol hydrochloride.Productivity: 95%, m.p:98-100 ° of C; [a]5 D=+11.58 º (c = 0.08, CH3OH), 1H NMR (500MHz, CDCl3) 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). 13C NMR (75 MHz, CDCl3) 130.1,123.0 (x2), 122.1,122.0 (x2), 57.4,50.5, elementary analysis result 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- (%): calcd for C8H12NO: 138.0919; found:138.0922. IR (KBr): 3424, 2253, 2127, 1656, 1051, 1027, 1005, 825, 764, 630；
Match crystal volume data is as follows:
Empirical formula C8 H12 Cl N O
Molecular weight 173.64
Temperature 290 (2) K
Wavelength 0.71073
Crystallographic system, space group rhombic system, P2 (1) 2 (1) 2 (1)
Cell parameter a=6.4408 (2) α=90 °.
b = 7.3044(6) Å β = 90 °.
c = 19.9208(13) Å γ = 90 °.
Volume 933.5 (6) ^3
Charge density 4,1.217Mg/m^3
Absorption correction parameter 0.355 mm^-1
Number of electrons 368 in unit cell
Crystal size 0.360 x 0.300 x 0.270 mm
Scope 2.046 to 25.996 at Theta angle
Index capture range-7≤h≤7 of HKL ,-8≤k≤5 ,-23≤l≤24
Collection/independent diffraction data 2276/1523 [R (int)=0.0319]
The data integrity degree 100.0% of theta=25.242 °
The method Multi Slice Mode of absorption correction
Transmitance 0.7456and 0.6626 of minimax
The Matrix least square method of method F^2 that refine uses
Number/number of parameters 1523/ 0/102 that data number/use limits
The method 0.991 that refine uses
The concordance factor R 1=0.0394 of point diffraction, ω R2=0.1076
The identical factor R 1=0.0439 of observable diffraction, ω R2=0.1110
Absolute configuration parameter 0.004(6)
Maximum summit on difference Fourier figure and peak valley 0.27and-0.24 e.A^-3
Crystal typical bond distance data:
Atom Atom Length/Å Atom Atom Length/Å
O1 C8 1.409(4) C1 C6 1.381(5)
C7 N1 1.498(4) C4 C5 1.382(5)
C7 C4 1.510(4) C4 C3 1.388(4)
C7 C8 1.517(5) C2 C3 1.389(5)
C1 C2 1.362(6) C5 C6 1.378(5)
Crystal typical bond angle data:
Atom Atom Atom Angle/ Atom Atom Atom Angle/
N1 C7 C4 110.7(3) C5 C4 C7 121.0(3)
N1 C7 C8 108.9(3) C3 C4 C7 120.4(3)
C4 C7 C8 112.1(3) C1 C2 C3 120.9(3)
C2 C1 C6 119.6(4) C4 C3 C2 119.9(3)
O1 C8 C7 112.5(3) C6 C5 C4 121.0(3)
C5 C4 C3 118.6(3) C5 C6 C1 120.0(4)

Claims (1)

1. having (the R)-phenylglycinol hydrochloride synthetic method shown in following chemical formula (I), including synthesis and separation, it is special Levy and be: described synthesis be 2.0915g α-phenylc nitrile, (R)-benzene glycinol 5.2865g and without hydration zinc chloride 2.7106g reacts 60 hours in chlorobenzene solution, rotates and removes solvent, by residue water dissolution, and uses CHCl3 20mLx2 Extraction, organic facies anhydrous sodium sulfate is dried, and rotates and removes solvent, by thick product petroleum ether/dichloromethane (1:9) post layer Analysis, obtains white solid (R)-phenylglycinol hydrochloride,
(I)。
CN201610271267.3A 2016-04-28 2016-04-28 Method for synthesizing chirality (R)-phenylglycinol hydrochloride Pending CN105837456A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201610271267.3A CN105837456A (en) 2016-04-28 2016-04-28 Method for synthesizing chirality (R)-phenylglycinol hydrochloride

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201610271267.3A CN105837456A (en) 2016-04-28 2016-04-28 Method for synthesizing chirality (R)-phenylglycinol hydrochloride

Publications (1)

Publication Number Publication Date
CN105837456A true CN105837456A (en) 2016-08-10

Family

ID=56589337

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201610271267.3A Pending CN105837456A (en) 2016-04-28 2016-04-28 Method for synthesizing chirality (R)-phenylglycinol hydrochloride

Country Status (1)

Country Link
CN (1) CN105837456A (en)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102863343A (en) * 2012-10-20 2013-01-09 罗梅 Preparation and synthesis method of chiral (R)-phenylglycinol hydrochloride
CN102952026A (en) * 2012-09-02 2013-03-06 罗梅 Preparation and synthetic method for chirality (S)-benzene ammonia alcohol hydrochloride
CN103204780A (en) * 2013-05-15 2013-07-17 罗梅 Synthetic method of chiral (S)-phenylglycinol hydrochloride
CN103539684A (en) * 2013-11-01 2014-01-29 罗梅 Synthetic method of chiral (R)-phenylglycinol hydrochloride
CN105130827A (en) * 2015-09-24 2015-12-09 合肥祥晨化工有限公司 Synthesis method of chiral -phenylglycinol hydrochloride

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102952026A (en) * 2012-09-02 2013-03-06 罗梅 Preparation and synthetic method for chirality (S)-benzene ammonia alcohol hydrochloride
CN102863343A (en) * 2012-10-20 2013-01-09 罗梅 Preparation and synthesis method of chiral (R)-phenylglycinol hydrochloride
CN103204780A (en) * 2013-05-15 2013-07-17 罗梅 Synthetic method of chiral (S)-phenylglycinol hydrochloride
CN103539684A (en) * 2013-11-01 2014-01-29 罗梅 Synthetic method of chiral (R)-phenylglycinol hydrochloride
CN105130827A (en) * 2015-09-24 2015-12-09 合肥祥晨化工有限公司 Synthesis method of chiral -phenylglycinol hydrochloride

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
张萍 等: "用NaBH_4-I2还原合成D-(-)-苯甘氨醇", 《化学试剂》 *

Similar Documents

Publication Publication Date Title
Moosavi-Zare et al. Solvent-free condensation of phenols with aldehydes and amides using 3-methyl-1-sulfonic acid imidazolium chloride
CN105728046A (en) Ruthenium metallic olefin metathesis catalyst and preparation and application methods thereof
Truong et al. Direct arylation of heterocycles through C–H bond cleavage using metal–organic-framework Cu 2 (OBA) 2 (BPY) as an efficient heterogeneous catalyst
CN107936263B (en) Coordination polymer with photoreaction activity and preparation method and application thereof
Yang et al. Platinum-catalyzed anti-stereocontrolled ring-opening of oxabicyclic alkenes with Grignard reagents
Zhou et al. Transition metal catalyzed asymmetric aryl carbon–heteroatom bond coupling reactions
CN109096174B (en) Synthesis method of N-alkyl-2, 5-unsubstituted [60] fullerene pyrrolidine derivative
US9447067B2 (en) Method of preparing intermediate of salmeterol
CN105837456A (en) Method for synthesizing chirality (R)-phenylglycinol hydrochloride
Wu et al. Catalyst-Free Synthesis of Spiropyrazolines from Chalcones and Cyclic Ketone N-Tosylhydrazones
Gu et al. A pair of novel Zn (II) enantiomeric coordination polymers based on a chiral multicarboxylate ligand: synthesis, crystal structures and molecular recognition properties
CN100393694C (en) Tetrabenzyl voglibose crystallizing and preparing process
Zhu et al. Organocatalytic enantioselective Michael addition of cyclic hemiacetals to nitroolefins: A facile access to chiral substituted 5-and 6-membered cyclic ethers
Vinson et al. Gold-catalyzed, SN1-type reaction of alcohols to afford ethers and Cbz-protected amines
CN103012447A (en) Chiral oxazoline zinc complex
CN105688983A (en) Preparation method and use of cyclic quinine quaternary ammonium salt compound
CN111349121A (en) Cobalt carbonyl complex and preparation method thereof
CN110790938A (en) Covalent organic framework film, preparation thereof and application thereof in identifying nitro explosives
Leemans et al. Novel synthesis of chiral unactivated 2-aryl-1-benzylaziridines
Nodes et al. Asymmetric Phase-Transfer-Catalyzed Synthesis of Five-Membered Cyclic γ-Amino Acid Precursors
Long et al. Iridium-catalyzed asymmetric ring-opening reactions of azabenzonorbornadiene with carboxylic acid nucleophiles
CN104086602B (en) A kind of carbonylic cobalt compound with tripodand and preparation method thereof
CN102786466B (en) Synthetic method of chiral Salan ligand
Sar et al. Expanding the chemical space of enol silyl ethers: catalytic dicarbofunctionalization enabled by iron catalysis
CN106478661A (en) Crystal formation E of benzoxazoles oxazines ketone compounds WA1-089 and preparation 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: 20160810

RJ01 Rejection of invention patent application after publication