CN104151171A - Method for preparing optically pure R-1-naphthylethylamine by splitting - Google Patents
Method for preparing optically pure R-1-naphthylethylamine by splitting Download PDFInfo
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- CN104151171A CN104151171A CN201410399401.9A CN201410399401A CN104151171A CN 104151171 A CN104151171 A CN 104151171A CN 201410399401 A CN201410399401 A CN 201410399401A CN 104151171 A CN104151171 A CN 104151171A
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- Prior art keywords
- naphthylethylamine
- naphthalene ethylamine
- naphthyl
- ethyl
- ethanamide
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- 238000000034 method Methods 0.000 title abstract description 13
- 239000003054 catalyst Substances 0.000 claims abstract description 10
- 238000002360 preparation method Methods 0.000 claims abstract description 10
- RUJHATQMIMUYKD-UHFFFAOYSA-N 2-naphthalen-1-ylethanamine Chemical compound C1=CC=C2C(CCN)=CC=CC2=C1 RUJHATQMIMUYKD-UHFFFAOYSA-N 0.000 claims abstract description 9
- 230000006340 racemization Effects 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 4
- 108010084311 Novozyme 435 Proteins 0.000 claims abstract description 4
- 239000001257 hydrogen Substances 0.000 claims abstract description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract 6
- 229910052759 nickel Inorganic materials 0.000 claims abstract 3
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 13
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 13
- 230000003287 optical effect Effects 0.000 claims description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 238000005194 fractionation Methods 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- 229960002510 mandelic acid Drugs 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 238000004440 column chromatography Methods 0.000 claims description 3
- 230000007062 hydrolysis Effects 0.000 claims description 3
- 238000006460 hydrolysis reaction Methods 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- 238000010992 reflux Methods 0.000 claims description 3
- 238000007789 sealing Methods 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 238000010792 warming Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000000638 solvent extraction Methods 0.000 claims description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims 1
- 239000003513 alkali Substances 0.000 claims 1
- 235000011114 ammonium hydroxide Nutrition 0.000 claims 1
- BDXKFBMUZNFKQH-SNVBAGLBSA-N (3R)-3-naphthalen-1-ylbutanamide Chemical compound C1(=CC=CC2=CC=CC=C12)[C@H](C)CC(=O)N BDXKFBMUZNFKQH-SNVBAGLBSA-N 0.000 abstract 1
- 125000002252 acyl group Chemical group 0.000 abstract 1
- 150000001408 amides Chemical class 0.000 abstract 1
- 238000004821 distillation Methods 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 230000001131 transforming effect Effects 0.000 abstract 1
- 239000000047 product Substances 0.000 description 6
- 108090000790 Enzymes Proteins 0.000 description 3
- 102000004190 Enzymes Human genes 0.000 description 3
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- -1 glyceryl alcohol derivative Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- AXSZGQWPAAHKDH-UHFFFAOYSA-N 2-hydroxy-2-naphthalen-1-ylacetic acid Chemical compound C1=CC=C2C(C(C(O)=O)O)=CC=CC2=C1 AXSZGQWPAAHKDH-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000011914 asymmetric synthesis Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000012084 conversion product Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- 239000012450 pharmaceutical intermediate Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000004540 process dynamic Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- Preparation Of Compounds By Using Micro-Organisms (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a method for preparing optically-pure R-1-naphthylethylamine by splitting. The method comprises the following steps: introducing hydrogen into a high-pressure kettle filled with 1-naphthylethylamine serving as a raw material, Novozym435 serving as a splitting catalyst and D-(-)-O-acetyl mandelic acid serving as an acyl donor and KT-02 (nickel type catalyst) serving as a racemization catalyst for reacting, and fully transforming the 1-naphthylethylamine to obtain (R)-(1-(1-naphthyl)ethyl)acetamide (ee value is 99 percent); and purifying amide, performing acidolysis to obtain a R-1-naphthylethylamine salt, and performing the operation of alkalization, distillation, drying, concentration and the like on the R-1-naphthylethylamine salt to obtain the R-1-naphthylethylamine, wherein the product yield and the ee value in the whole steps can be over 90 percent. The method has the characteristics of adoption of cheap and readily-available racemization catalyst, complete utilization of the raw material, high product yield and the like. The method has extremely high guidance and application values in the production and preparation of the R-1-naphthylethylamine.
Description
Technical field
The present invention relates to a kind of fractionation preparation method of optical homochiral amine, relate in particular to fractionation and the preparation method of optical purity R-1-naphthalene ethylamine.
Background technology
Optically pure Chiral Amine is a kind of very important pharmaceutical intermediate.Obtain at present optically pure Chiral Amine mainly by following several method: enzyme splits (Indian J. Chem. Sect. B 2005,44,1312-1316; J. Org. Chem. 1997,62,3488-3495); Chemistry splits: with chirality Alpha-hydroxy naphthylacetic acid (US6342636; Tetrahedron:asymmetry, 1998,9,2219-2212) or the chirality glyceryl alcohol derivative of protection split (Tetrahedron:asymmetry, 1996,7,1117-1122; Tetrahedron:asymmetry, 2002,13,2277-2282); By corresponding aldehyde, through asymmetric synthesis, obtain (WO2004/110976; J. Org. Chem. 1992,57,1237-1241).
In existing method, dissymmetric synthesis cost is high and often rare to the high product of optical purity; There is the low shortcoming of utilization ratio of raw material in chemical resolution method and enzyme process kinetic resolution, only has at most 50%; And in the enzyme process Dynamic Kinetic Resolution method of existing report, the racemization catalyst of using is the mixture of the precious metal such as some rutheniums, rhodium normally, these racemization catalyst costs are high, and while using these racemization catalyst in fractionation preparation process, although realize high conversion product, be difficult to obtain high optical purity.
Summary of the invention
The technical problem to be solved in the present invention is to find a kind of cheap racemization catalyst, realizes R-1-naphthalene ethylamine simultaneously and is splitting high yield and the high-optical-purity of preparing in planting.
In order to address the above problem, the invention provides a kind of fractionation preparation method of optical purity R-1-naphthalene ethylamine: 1) in autoclave, take toluene as solvent, the ratio of 1:1.0 ~ 2.0 adds raw material 1-naphthalene ethylamine and acry radical donor D-(-)-O-ethanoyl amygdalic acid in molar ratio, finally in the ratio of raw material 1-naphthalene ethylamine massfraction 1%-10%, add lipase novozym 435 and KT-02 again, autoclave sealing is carried out after nitrogen replacement, pass into hydrogen to pressure 0.1-1.0MPa and be warming up to 40-70 ℃ of reaction 18 hours, 1-naphthalene ethylamine can be converted into completely (R)-(N-(1-naphthyl) ethyl) ethanamide, and product ee value can reach 99%, after reaction finishes, solution is concentrated, column chromatography, obtain pure (R)-(N-(1-naphthyl) ethyl) ethanamide, 2) by step 1, make ((R)-(N-(1-naphthyl) ethyl) ethanamide is dissolved in the alcohol of 10 times of volume ratios and the mixing solutions of acid solution (v/v=1:1), then heating reflux reaction is 24 hours, and (R)-(N-(1-naphthyl) ethyl) ethanamide complete hydrolysis obtains R-1-naphthalene ethylamine salt, 3) step 2 gained R-1-naphthalene ethylamine salt is carried out to alkalinisation treatment, then by organic solvent extraction, dry, concentratedly can obtain optically pure R-1-naphthalene ethylamine, final whole step product yield can reach more than 90%, and product purity is 99%.
The racemization catalyst that the present invention uses in preparing optical purity R-1-naphthalene ethylamine process is the cheap feature being easy to get for KT-02 has, and the optical purity R-1-naphthalene ethylamine yield finally preparing is good, and optical purity is high.
specific implementation method
1) split preparation (R)-(N-(1-naphthyl) ethyl) ethanamide
In the autoclave of 1000mL, add 500mL toluene as solvent, add successively 85.5g1-naphthalene ethylamine, 106.7g D-(-)-O-ethanoyl amygdalic acid, 5g lipase novozym 435 and 7gKT-02, after adding, after sealing autoclave, with nitrogen, air in still is replaced, then in autoclave, pass into hydrogen to pressure 1.0MP, open to stir, and be warming up to 60 ℃ and react; After 20 hours, sampling detects, and 1-naphthalene ethylamine disappears and is converted into (R)-(N-(1-naphthyl) ethyl) ethanamide completely, and product ee value reaches 99%; After reaction finishes, solution is concentrated, the normal hexane that is then 10:1 by volume ratio and alcohol mixed solvent carry out column chromatography, obtain pure (R)-(N-(1-naphthyl) ethyl) ethanamide 101.6g, and yield is 95.4%.
2) acidolysis obtains R-1-naphthalene ethylamine salt
By (R) that make in upper step-(N-(1-naphthyl) ethyl) ethanamide 53g joins in the solution that the ethanol of 500ml and concentrated hydrochloric acid mix with volume ratio 1:1, then reflux, react after 24 hours, select plate and detect (R)-(N-(1-naphthyl) ethyl) ethanamide complete hydrolysis obtains R-1-naphthalene ethylamine salt.
3) alkalization obtains R-1-naphthalene ethylamine
The solution that step 2 gained is reacted completely adds the methylene dichloride of 500mL, then slowly drip sodium hydroxide solution, and stir, detect solution pH value to 13, stop dripping sodium hydroxide solution, separatory, upper water solution is used the dichloromethane extraction 3 times of 200mL again, by the dichloromethane solution that obtains of extraction several times with anhydrous sodium sulphate be dried, the concentrated R-1-naphthalene ethylamine 40.4g of obtaining, yield is that the ee value that 94.4%, HPLC detects the finished product is 99.4%.
Claims (4)
1. the fractionation preparation method of optical purity R-1-naphthalene ethylamine is characterized in that: 1) in autoclave, take toluene as solvent, the ratio of 1:1.0-2.0 adds raw material 1-naphthalene ethylamine and acry radical donor D-(-)-O-ethanoyl amygdalic acid in molar ratio, then in the ratio of raw material 1-naphthalene ethylamine massfraction 1%-10%, add lipase novozym 435 and KT-02(nickel type catalyzer), autoclave sealing is carried out after nitrogen replacement, pass into hydrogen to pressure 0.1-1.0MPa and be warming up to 40-70 ℃ of reaction 18 hours, 1-naphthalene ethylamine can be converted into completely (R)-(N-(1-naphthyl) ethyl) ethanamide, and product ee value reaches 99%, after reaction finishes, solution is concentrated, column chromatography, obtain pure (R)-(N-(1-naphthyl) ethyl) ethanamide, 2) (R) that make in step 1-(N-(1-naphthyl) ethyl) ethanamide is dissolved in the alcohol of 10 times of volume ratios and the mixing solutions of acid solution (v/v=1:1), then heating reflux reaction is 24 hours, and (R)-(N-(1-naphthyl) ethyl) ethanamide complete hydrolysis obtains R-1-naphthalene ethylamine salt, 3) step 2 gained R-1-naphthalene ethylamine salt is carried out to alkalinisation treatment, then by organic solvent extraction, dry, concentratedly can obtain optically pure R-1-naphthalene ethylamine, final whole step product yield can reach more than 93%, and product purity is 99%, according to described, its reaction equation is as follows:
2. according to claim 1, the preparation method of optical purity R-1-naphthalene ethylamine is characterized in that step 1) in acry radical donor be D-(-)-O-ethanoyl amygdalic acid, racemization catalyst is KT-02 nickel type catalyzer.
3. according to claim 1, the preparation method of optical purity R-1-naphthalene ethylamine is characterized in that step 2) in alcohol be methyl alcohol or ethanol; Acid is hydrochloric acid or sulfuric acid.
4. according to claim 1, the preparation method of optical purity R-1-naphthalene ethylamine is characterized in that step 3) in alkalinisation treatment alkali used be sodium hydroxide, potassium hydroxide or ammoniacal liquor; Extracting organic solvent used is toluene, methylene dichloride, 1,2-ethylene dichloride, ether etc.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410399401.9A CN104151171B (en) | 2014-08-14 | 2014-08-14 | The method of optical voidness R-1-naphthalene ethylamine is prepared in a kind of fractionation |
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| CN201410399401.9A CN104151171B (en) | 2014-08-14 | 2014-08-14 | The method of optical voidness R-1-naphthalene ethylamine is prepared in a kind of fractionation |
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| CN104151171B CN104151171B (en) | 2016-07-27 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105063162A (en) * | 2015-08-18 | 2015-11-18 | 陈永军 | Preparation of R-6-methoxy-1-aminoindane through resolution |
| CN105061218A (en) * | 2015-08-13 | 2015-11-18 | 陈永军 | Method for preparing (S)-1-aminoindane through dynamic kinetic resolution |
| CN105154513A (en) * | 2015-08-18 | 2015-12-16 | 陈永军 | Method for preparing R-5-methyl-1-aminoindan through resolution |
| CN111004236A (en) * | 2019-12-19 | 2020-04-14 | 卓和药业集团有限公司 | Dynamic kinetic resolution method of WXFL10203614 intermediate |
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| JPS59110656A (en) * | 1982-12-15 | 1984-06-26 | Hiroyuki Nohira | Optical resolution of 1-phenyl-2-(p-tolyl)ethylamine |
| US4983771A (en) * | 1989-09-18 | 1991-01-08 | Hexcel Corporation | Method for resolution of D,L-alpha-phenethylamine with D(-)mandelic acid |
| CN1835909A (en) * | 2003-06-13 | 2006-09-20 | 艾夫西亚药品有限公司 | Process for the preparation of aromatic amines |
| CN101514163A (en) * | 2009-04-02 | 2009-08-26 | 广州辉宏生物医药科技有限公司 | Optically pure Sibutramine and process for preparing salt derivative thereof |
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2014
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Patent Citations (4)
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| JPS59110656A (en) * | 1982-12-15 | 1984-06-26 | Hiroyuki Nohira | Optical resolution of 1-phenyl-2-(p-tolyl)ethylamine |
| US4983771A (en) * | 1989-09-18 | 1991-01-08 | Hexcel Corporation | Method for resolution of D,L-alpha-phenethylamine with D(-)mandelic acid |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105061218A (en) * | 2015-08-13 | 2015-11-18 | 陈永军 | Method for preparing (S)-1-aminoindane through dynamic kinetic resolution |
| CN105063162A (en) * | 2015-08-18 | 2015-11-18 | 陈永军 | Preparation of R-6-methoxy-1-aminoindane through resolution |
| CN105154513A (en) * | 2015-08-18 | 2015-12-16 | 陈永军 | Method for preparing R-5-methyl-1-aminoindan through resolution |
| CN111004236A (en) * | 2019-12-19 | 2020-04-14 | 卓和药业集团有限公司 | Dynamic kinetic resolution method of WXFL10203614 intermediate |
| CN111004236B (en) * | 2019-12-19 | 2022-04-05 | 卓和药业集团股份有限公司 | Dynamic kinetic resolution method of WXFL10203614 intermediate |
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| CN104151171B (en) | 2016-07-27 |
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