CN103408463B - 2-[(4-cyano-benzyl)amino]ethyl acetate hydrochloride preparation method - Google Patents
2-[(4-cyano-benzyl)amino]ethyl acetate hydrochloride preparation method Download PDFInfo
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- CN103408463B CN103408463B CN201310352651.2A CN201310352651A CN103408463B CN 103408463 B CN103408463 B CN 103408463B CN 201310352651 A CN201310352651 A CN 201310352651A CN 103408463 B CN103408463 B CN 103408463B
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- ethyl acetate
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- amino
- benzyl
- cyano
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- QJPZTOKLGODALX-UHFFFAOYSA-N Cl.C(C)(=O)OCCNCC1=CC=C(C=C1)C#N Chemical compound Cl.C(C)(=O)OCCNCC1=CC=C(C=C1)C#N QJPZTOKLGODALX-UHFFFAOYSA-N 0.000 title abstract 3
- 238000002360 preparation method Methods 0.000 title description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Natural products CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 11
- WZWIQYMTQZCSKI-UHFFFAOYSA-N 4-cyanobenzaldehyde Chemical compound O=CC1=CC=C(C#N)C=C1 WZWIQYMTQZCSKI-UHFFFAOYSA-N 0.000 claims abstract 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 15
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 230000002829 reductive effect Effects 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- MVEAAGBEUOMFRX-UHFFFAOYSA-N ethyl acetate;hydrochloride Chemical class Cl.CCOC(C)=O MVEAAGBEUOMFRX-UHFFFAOYSA-N 0.000 claims description 8
- VOXANKRFRUBRGI-UHFFFAOYSA-N ethylamino acetate hydrochloride Chemical compound Cl.CCNOC(C)=O VOXANKRFRUBRGI-UHFFFAOYSA-N 0.000 claims description 7
- BEOOHQFXGBMRKU-UHFFFAOYSA-N sodium cyanoborohydride Chemical compound [Na+].[B-]C#N BEOOHQFXGBMRKU-UHFFFAOYSA-N 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 3
- 235000002597 Solanum melongena Nutrition 0.000 claims description 3
- 244000061458 Solanum melongena Species 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 239000000706 filtrate Substances 0.000 claims description 3
- 239000012074 organic phase Substances 0.000 claims description 3
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 2
- -1 4-cyanobenzyl ethyl Chemical group 0.000 claims 2
- 239000005457 ice water Substances 0.000 claims 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims 1
- 239000000243 solution Substances 0.000 claims 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 abstract description 7
- 239000002994 raw material Substances 0.000 abstract description 6
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 abstract description 4
- 229910000041 hydrogen chloride Inorganic materials 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 230000035484 reaction time Effects 0.000 abstract description 3
- 238000006268 reductive amination reaction Methods 0.000 abstract description 2
- BETKWADSTYCNPH-UHFFFAOYSA-N 2-[(4-cyanophenyl)methylamino]ethyl acetate Chemical compound C(C)(=O)OCCNCC1=CC=C(C=C1)C#N BETKWADSTYCNPH-UHFFFAOYSA-N 0.000 abstract 1
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 abstract 1
- 238000013375 chromatographic separation Methods 0.000 abstract 1
- 150000003839 salts Chemical class 0.000 abstract 1
- 239000003513 alkali Substances 0.000 description 6
- 125000006505 p-cyanobenzyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1C#N)C([H])([H])* 0.000 description 6
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 238000001035 drying Methods 0.000 description 4
- 238000001953 recrystallisation Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- QVTPWONEVZJCCS-UHFFFAOYSA-N 2-formylbenzonitrile Chemical compound O=CC1=CC=CC=C1C#N QVTPWONEVZJCCS-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- 102400000064 Neuropeptide Y Human genes 0.000 description 3
- 238000004440 column chromatography Methods 0.000 description 3
- 229940125904 compound 1 Drugs 0.000 description 3
- 229960004756 ethanol Drugs 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 101710151321 Melanostatin Proteins 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000007810 chemical reaction solvent Substances 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 230000006837 decompression Effects 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- URPYMXQQVHTUDU-OFGSCBOVSA-N nucleopeptide y Chemical compound C([C@@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CC(N)=O)C(=O)N[C@@H](CC(C)C)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)O)C(=O)N[C@@H](CCCNC(N)=N)C(=O)N[C@@H](CCC(N)=O)C(=O)N[C@@H](CCCNC(N)=N)C(=O)N[C@@H](CC=1C=CC(O)=CC=1)C(N)=O)NC(=O)[C@H](CC=1NC=NC=1)NC(=O)[C@H](CCCNC(N)=N)NC(=O)[C@H](CC(C)C)NC(=O)[C@H](C)NC(=O)[C@H](CO)NC(=O)[C@H](CC=1C=CC(O)=CC=1)NC(=O)[C@H](CC=1C=CC(O)=CC=1)NC(=O)[C@H](CCCNC(N)=N)NC(=O)[C@H](C)NC(=O)[C@H](CC(C)C)NC(=O)[C@H](CC(O)=O)NC(=O)[C@H](CCC(O)=O)NC(=O)[C@H](C)NC(=O)[C@H]1N(CCC1)C(=O)[C@H](C)NC(=O)[C@H](CC(O)=O)NC(=O)[C@H](CCC(O)=O)NC(=O)CNC(=O)[C@H]1N(CCC1)C(=O)[C@H](CC(N)=O)NC(=O)[C@H](CC(O)=O)NC(=O)[C@H]1N(CCC1)C(=O)[C@H](CCCCN)NC(=O)[C@H](CO)NC(=O)[C@H]1N(CCC1)C(=O)[C@@H](N)CC=1C=CC(O)=CC=1)C1=CC=C(O)C=C1 URPYMXQQVHTUDU-OFGSCBOVSA-N 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- SFLSHLFXELFNJZ-QMMMGPOBSA-N (-)-norepinephrine Chemical compound NC[C@H](O)C1=CC=C(O)C(O)=C1 SFLSHLFXELFNJZ-QMMMGPOBSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- 229960000549 4-dimethylaminophenol Drugs 0.000 description 1
- 0 C*CNC(NCCCC(C(N(CC(OC*)=O)Cc1ccc(CNC(N)=O)cc1)=O)NC(C(c1ccccc1)c1ccccc1)=O)=N Chemical compound C*CNC(NCCCC(C(N(CC(OC*)=O)Cc1ccc(CNC(N)=O)cc1)=O)NC(C(c1ccccc1)c1ccccc1)=O)=N 0.000 description 1
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 1
- 239000004348 Glyceryl diacetate Substances 0.000 description 1
- 101800003845 Neuropeptide Y Proteins 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 206010047139 Vasoconstriction Diseases 0.000 description 1
- 125000000539 amino acid group Chemical group 0.000 description 1
- 239000005557 antagonist Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 229960001701 chloroform Drugs 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229960000935 dehydrated alcohol Drugs 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- JUOXYWXXPHUSAI-UHFFFAOYSA-N ethylamino acetate Chemical compound CCNOC(C)=O JUOXYWXXPHUSAI-UHFFFAOYSA-N 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 235000019443 glyceryl diacetate Nutrition 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002660 neuropeptide Y receptor antagonist Substances 0.000 description 1
- 229960002748 norepinephrine Drugs 0.000 description 1
- SFLSHLFXELFNJZ-UHFFFAOYSA-N norepinephrine Natural products NCC(O)C1=CC=C(O)C(O)=C1 SFLSHLFXELFNJZ-UHFFFAOYSA-N 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 108090000765 processed proteins & peptides Proteins 0.000 description 1
- 238000004393 prognosis Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 239000012321 sodium triacetoxyborohydride Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000025033 vasoconstriction Effects 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to the field of medical intermediate, and specifically relates to a method for preparing 2-[(4-cyano-benzyl)amino]ethyl acetate hydrochloride. The method is characterized in that: p-cyanobenzaldehyde and amino ethyl acetate hydrochloride are adopted as raw materials; reductive amination is carried out, such that 2-[(4-cyano-benzyl)amino]ethyl acetate is obtained; and the product is subjected to salt formation with hydrogen chloride, such that the 2-[(4-cyano-benzyl)amino]ethyl acetate hydrochloride is prepared. The method provided by the invention has the advantages of short reaction time, high yield, no need of column chromatographic separation, high product quality, and the like.
Description
Technical field
The invention belongs to medicine intermediate field, be specifically related to the method that one prepares 2-[(4-cyanobenzyls) is amino] ethyl acetate hydrochloride.
Background technology
Neuropeptide tyrosine (neuropeptide Y, NPY) be a peptide species, containing 36 amino-acid residues, be distributed widely in each system mammiferous, discharge together with norepinephrine, be a kind of important substance regulating vasoconstriction diastole, occur in the disease of some Major Systems of human body, develop and play an important role in prognosis.Patent WO9719911 discloses a kind of selective N PY antagonist (R)-2-(2-(2,2-phenylbenzene kharophen)-5-guanidine radicals-N-(4-(urea methyl) benzyl) valeryl amido) ethyl acetate diacetin, its structure is as follows:
2-[(4-cyanobenzyls) is amino] ethyl acetate (1) prepares the important intermediate of above-mentioned NPY antagonist.Patent WO9719911 disclose 1 preparation method as follows:
This method will be dissolved in a large amount of methyl alcohol to cyanobenzaldehyde (2), ethyl aminoacetate hydrochloride (3) and sodium cyanoborohydride, after stirring at room temperature reacts 26 hours, carry out column chromatography for separation using petrol ether/ethyl acetate as eluent and obtain oily matter 1, yield 54%.The long reaction time of the method, the solvent load of column chromatography purification is large, does not meet the requirement of Green Chemistry, is difficult to suitability for industrialized production.Meanwhile, because the fusing point of 1 is lower, be at room temperature oily matter, be unfavorable for transport and preserve.
Summary of the invention
The object of the invention is to find that a kind of efficiency is high, yield good, the preparation method of eco-friendly 2-[(4-cyanobenzyls) is amino] ethyl acetate hydrochloride (4).
The present invention dissociates into ethyl aminoacetate by adding alkali in reaction system by 3, is conducive to, with 2, reductive amination process occurs.The compound 1 generated, without separation, directly and hydrogenchloride salify, then obtains the hydrochloride of pure compound 4(compound 1 by recrystallization).Compared with literature method, method of the present invention has that the reaction times is short, yield is high, do not need column chromatography for separation, high quality.In addition, compound 1 is converted into HCl, solid, is convenient to preserve.
Preparation method of the present invention comprises:
Reaction process comprises: be dissolved in solvent by raw material 2 and 3, add alkali, stirring reaction 1-2 hour, then add reductive agent, continues to be stirred to react completely, and is poured in frozen water by reaction mixture, then through extraction, dry, concentrating under reduced pressure obtains oily matter crude product 1; This oily matter crude product is dissolved in solvent, under stirring, passes into HCl gas, by the solid filtering of precipitation, drying, to obtain final product.
Wherein alkali is preferably from triethylamine, pyridine or DMAP.
Reductive agent is preferably from sodium borohydride, POTASSIUM BOROHYDRIDE, sodium cyanoborohydride or sodium triacetoxy borohydride.
Raw material 2: raw material 3: alkali: the mol ratio of reductive agent is preferably 1:1 ~ 1.5:1 ~ 1.5:0.5 ~ 2.More preferably 1:1.1:1.1:0.8 ~ 1.
The mixed solvent of one or any two kind of reaction solvent preferably in anhydrous methanol, dehydrated alcohol, anhydrous isopropyl alcohol of the first step reaction.
The optimum condition of the first step reaction is: alkali is triethylamine; Solvent is anhydrous methanol; Reductive agent is sodium cyanoborohydride; Raw material 2: raw material 3: alkali: the mol ratio of reductive agent is 1:1.1:1.1:0.8 ~ 1.
The mixed solvent of one or any two kind of reaction solvent preferably in methylene dichloride, ethyl acetate, acetone, trichloromethane of second step reaction.
After preparing 4, also preferred ethanol or recrystallisation from isopropanol further.More preferably ethanol.
Preparation method of the present invention whole process compared with patent WO9719911 only needs a recrystallization can obtain the stable sterling being beneficial to transport preservation of proterties, and reaction required time significantly shortens, and total recovery 61.2% ~ 73.6%(patent WO9719911 is 54%).In addition, the present invention compared with prior art " three wastes " discharge significantly reduces, and more meets the requirement of Green Chemistry.
Embodiment
Embodiment 1
The synthesis of 2-[(4-cyanobenzyls) is amino] ethyl acetate hydrochloride (4)
Add successively in 500mL eggplant bottle cyanobenzaldehyde (20.0g, 0.153mol), ethyl aminoacetate hydrochloride (23.4g, 0.167mol), 150mL anhydrous methanol, adds 23.4mL triethylamine after being stirred to dissolve, continue to stir 1h, sodium cyanoborohydride (9.6g, 0.153mol) is added at ice bath cooling maintenance 0 ~ 5 DEG C; Insulated and stirred 1h, by reaction solution impouring 200mL frozen water, with dichloromethane extraction three times (200mL × 3), merge organic phase, saturated common salt washes three times, and anhydrous sodium sulfate drying spends the night, and filter, filtrate decompression is spin-dried for obtain yellow-green colour oily matter.Add 180mL acetic acid ethyl dissolution, the ethyl acetate solution of saturated HCl is dripped to pH1 ~ 2 under ice bath, continue to stir 0.5h, filter to obtain white solid 31.7g, after oven dry, add 140ml ethanol and be heated to backflow, stand at low temperature, separates out solid, leaches solid drying and obtain 23.8g, yield 61.2%, m.p.204 ~ 206 DEG C.
1H-NMR(300MHz DMSO)δ(ppm):1.23(3H,t,J=7.1Hz,-CH
2CH
3),3.95(2H,s,-NHCH
2COO-),4.19(2H,q,J=7.1Hz,-COOCH
2 CH
3),4.26(2H,s,PhCH
2NH-),7.78(2H,d,J=8.1Hz,ArH),7.93(2H,d,J=8.2Hz,ArH).
Embodiment 2
The synthesis of 2-[(4-cyanobenzyls) is amino] ethyl acetate hydrochloride (4)
Add successively in 500mL eggplant bottle cyanobenzaldehyde (20.0g, 0.153mol), ethyl aminoacetate hydrochloride (23.4g, 0.167mol) with 150mL anhydrous methanol, 23.4mL triethylamine is added after stirring and dissolving, continue to stir 1h, under ice bath cooling, add sodium cyanoborohydride (8.0g, 0.127mol); After reaction 0.5h, drip saturated sodium bicarbonate and decompose remaining sodium cyanoborohydride, reclaim under reduced pressure major part methyl alcohol, add frozen water 100mL, use 200mL, 100mL, 100mL dichloromethane extraction successively three times, merge organic phase, saturated common salt washes three times, anhydrous sodium sulfate drying spends the night, and filter, filtrate decompression is spin-dried for obtain yellow-green colour oily matter.Add 150mL acetic acid ethyl dissolution, the ethyl acetate solution dripping saturated HCl under ice bath, to pH1 ~ 2, filters to obtain white solid 36.7g, obtains 28.6g with dehydrated alcohol recrystallization, yield 73.6%, m.p.204 ~ 206 DEG C.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310352651.2A CN103408463B (en) | 2013-08-14 | 2013-08-14 | 2-[(4-cyano-benzyl)amino]ethyl acetate hydrochloride preparation method |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310352651.2A CN103408463B (en) | 2013-08-14 | 2013-08-14 | 2-[(4-cyano-benzyl)amino]ethyl acetate hydrochloride preparation method |
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| Publication Number | Publication Date |
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| CN103408463A CN103408463A (en) | 2013-11-27 |
| CN103408463B true CN103408463B (en) | 2015-05-27 |
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| CN201310352651.2A Expired - Fee Related CN103408463B (en) | 2013-08-14 | 2013-08-14 | 2-[(4-cyano-benzyl)amino]ethyl acetate hydrochloride preparation method |
Country Status (1)
| Country | Link |
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| CN (1) | CN103408463B (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0885186B1 (en) * | 1995-11-30 | 2003-03-26 | Dr. Karl Thomae GmbH | Amino acid derivatives, pharmaceutical compositions containing these compounds and processes for preparing them |
-
2013
- 2013-08-14 CN CN201310352651.2A patent/CN103408463B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0885186B1 (en) * | 1995-11-30 | 2003-03-26 | Dr. Karl Thomae GmbH | Amino acid derivatives, pharmaceutical compositions containing these compounds and processes for preparing them |
Non-Patent Citations (1)
| Title |
|---|
| Diastereoselective lithium salt-assisted 1,3-dipolar cycloaddition of azomethine ylides to the fullerene C60;Vitaliy A. Ioutsi et al.;《Tetrahedron》;20100219;第66卷(第16期);3037–3041 * |
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| CN103408463A (en) | 2013-11-27 |
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