CN100404497C - Nitrile reducing process to prepare amine - Google Patents
Nitrile reducing process to prepare amine Download PDFInfo
- Publication number
- CN100404497C CN100404497C CNB2006100201063A CN200610020106A CN100404497C CN 100404497 C CN100404497 C CN 100404497C CN B2006100201063 A CNB2006100201063 A CN B2006100201063A CN 200610020106 A CN200610020106 A CN 200610020106A CN 100404497 C CN100404497 C CN 100404497C
- Authority
- CN
- China
- Prior art keywords
- nitrile
- add
- nickel
- raney
- amine
- 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.)
- Expired - Fee Related
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a method for preparing amine from reducing nitrile. The structural formula of the nitrile is disclosed in the drawing, wherein R is straight-chain alkyl, branched alkyl, substituted alkyl, etc.; R' is alkyl, halogen, hydroxyl, amido, carboxyl, etc. The present invention relates to a method for effectively reducing nitrile into corresponding primary amine by using borohydride as a reducing agent and raneys nickel as a catalyst. 2-(1-hydroxy cyclohexyl)-2-(4-methoxy phenyl) acetonitrile can be reduced into 1-(2-amino-1-(4-methoxy phenyl) ethyl) cyclohexanolas by regulating the activity of the system, and the 1-(2-amino-1-(4-methoxy phenyl) ethyl) cyclohexanolas is an intermediate for preparing venlafaxine hydrochloride as a phenylethylamine antidepressant drug. The use of the borohydride as the reducing agent is economic and safe. The reaction is carried out under moderate conditions and normal pressure without a high-pressure device nor protective gases, such as N2, etc. The yield of the primary amine is higher than 80 %. The present invention has the advantages of high speed rate, simple and convenient operation, easy solvent recovery and solvent purification, low cost and little pollution.
Description
Technical field
The present invention relates to the method that a kind of nitrile reducing prepares amine.
Background technology
As solvent, agricultural chemicals and medicine, nitrile reducing is a kind of method extremely important and commonly used for preparing amine to amine by widely.Yet nitrile is reduced into the stage that will experience imines in the process of amine, and this just forms coupled product (secondary amine) easily.So optionally nitrile reducing is that primary amine becomes a focus in recent years.Its method normally with lithium aluminum hydride or shortening (see (1) Walker.E.R.H.Chem.Soc.Rev.1976,5,23-50; (2) Klenke.B.Gilbert.I.H.J.Org.Chem.2001,66,2480-2483.) adopt the catalytic hydrogenation nitrile reducing, need High Temperature High Pressure usually.The main limitation of lithium aluminum hydride is to meet wet the decomposition and spontaneous combustion, easy initiation fire, and industrial production is dangerous big, and the price of lithium aluminum hydride, solvent load are big etc., and factor causes its use cost height.And the activity of sodium borohydride to be not enough to nitrile reducing be amine, need to add some auxiliary reagents usually and strengthen NaBH
4The active or primary amine of catching harsh one-tenth as human NiCl such as Jitender M.Khurana
2/ NaBH
4The aromatic nitrile of reduction system is that primary amine (is seen Khurana J.M.Kukreja G.Synthetic Communications 2002,32 (8), 1265-1269), but aliphatic nitrile do not had effect preferably.People such as Stephen Caddickt then use diacetyl oxide and (Boc)
2O catches the primary amine of formation, makes it (not see (1) StephenCaddick, Alexandra K.de K.Haynes, Duncan B.Judd and Meredith R.V.Williams Tetrahedron Letters 2000,41.3513-3516 with the imines coupling; (2) Stephen Caddick, Duncan B.Judd, Alexandra K.de K.Lewis; Melanie T.Reich and MeredithR.V.Williams Tetrahedron 2003; 59,5417-5423), also need to take off these blocking groups but will obtain primary amine.Raney's nickel is the classical catalyzer that is used for catalytic hydrogenation, but the hydrogen source that non-hydrogen also arranged in recent years as: the productive rate that usefulness Raney's nickel such as Shankare Gowda and formic acid hydrazine nitrile reducing obtain more than 70% (is seen Shankare Gowda and D.Channe Gowda Tetrahedron 2002,58,2211-2213), however the toxicity of hydrazine and medium productive rate are the defectives of this method.
Summary of the invention
The objective of the invention is to overcome the deficiencies in the prior art, provide a kind of with Raney's nickel/hydroborate system, the nitrile reducing that selectivity is better, productive rate is higher, cost is lower prepares the method for primary amine.
The structural formula of nitrile of the present invention is as follows:
Wherein: R is straight-chain alkyl, branched hydrocarbyl, substituted hydrocarbon radical etc.; R ' is alkyl, halogen, hydroxyl, amido, carboxyl etc.
Of the present invention is that the method for primary amine is as follows with Raney's nickel/hydroborate reduction system nitrile:
(1) in dry round-bottomed flask, adds 5-80mmol hydroborate (as lithium borohydride, sodium borohydride, POTASSIUM BOROHYDRIDE etc.), the careful Raney's nickel 1-80mmol that adds, add 0-80mL water again, 5-80mL ethanol or methyl alcohol and 10mmol nitrile ,-15～70 ℃ were stirred 45～120 minutes.
(2) elimination Raney's nickel, filtrate boils off ethanol or methyl alcohol with Rotary Evaporators, adds 5-100mL ethyl acetate or ether dissolution product, changes separating funnel over to, washes with water 3 to 4 times, and organic phase changes round-bottomed flask over to, adds anhydrous siccative (Na
2SO
4Or MgSO
4) dried overnight.
(3) elimination siccative boils off ethyl acetate or ether with Rotary Evaporators, and (developping agent is a methylene dichloride: methyl alcohol 20: 1), obtain primary amine, productive rate 80%～92% with the aluminium sesquioxide column chromatography.
The present invention has following beneficial effect with Raney's nickel/hydroborate reduction system nitrile:
(1) borane reducing agent hydride economy, safety;
(2) the reaction conditions gentleness is carried out under normal pressure, does not need high-tension apparatus, does not need N
2In protection gas;
(3) reaction primary amine productive rate is high more than 80%, and speed is fast, and solvent easily reclaims purifying, and cost is low, pollutes little.
Embodiment
Embodiment 1: present embodiment prepares phenylethylamine, and raw material is a benzyl cyanide:
In round-bottomed flask, add 5-80mmol KBH
4, put into a magnetic stirrer, add 0-80mL water, carefully add Raney's nickel 1-80mmol, add 5-80mL ethanol and 1.16mL (10mmol) benzyl cyanide again ,-15～70 ℃ of stirrings.Elimination Raney's nickel after 45 minutes, filtrate boils off ethanol with Rotary Evaporators, adds 50mL acetic acid ethyl dissolution product, changes the separating funnel of 125mL over to, washes with water 3 to 4 times, and organic phase changes the 100mL round-bottomed flask over to, adds anhydrous Na
2SO
4Dried overnight, the elimination siccative boils off ethyl acetate with Rotary Evaporators, and (developping agent is a methylene dichloride: methyl alcohol 20: 1), obtain the weak yellow liquid phenylethylamine, productive rate 92% with the aluminium sesquioxide column chromatography.
Embodiment 2: present embodiment prepares anisole ethamine, and raw material is a PARA METHOXY PHENYL ACETONITRILE
In round-bottomed flask, add 5-80mmol KBH
4, put into a magnetic stirrer, add 0-80mL water, carefully add Raney's nickel 1-80mmol, add 5-80mL ethanol and 1.36mL (10mmol) PARA METHOXY PHENYL ACETONITRILE again ,-15～70 ℃ of stirrings.Elimination Raney's nickel after 45 minutes, filtrate boils off ethanol with Rotary Evaporators, adds 50mL acetic acid ethyl dissolution product, changes the separating funnel of 125mL over to, washes with water 3 to 4 times, and organic phase changes the 100mL round-bottomed flask over to, adds anhydrous Na
2SO
4Dried overnight, the elimination siccative boils off ethyl acetate with Rotary Evaporators, and (developping agent is a methylene dichloride: methyl alcohol 20: 1), obtain colourless liquid to anisole ethamine, productive rate 86% with the aluminium sesquioxide column chromatography.
Embodiment 3: present embodiment prepares chlorobenzene ethamine, and raw material is a p-chlorobenzyl cyanide
In round-bottomed flask, add 5-80mmol KBH
4, put into a magnetic stirrer, add 0-80mL water, carefully add Raney's nickel 1-80mmol, add 5-80mL ethanol and 1.51g (10mmol) p-chlorobenzyl cyanide again ,-15～70 ℃ of stirrings.Elimination Raney's nickel after 45 minutes, filtrate boils off ethanol with Rotary Evaporators, adds 50mL acetic acid ethyl dissolution product, changes the separating funnel of 125mL over to, washes with water 3 to 4 times, and organic phase changes the 100mL round-bottomed flask over to, adds anhydrous Na
2SO
4Dried overnight, the elimination siccative boils off ethyl acetate with Rotary Evaporators, and (developping agent is a methylene dichloride: methyl alcohol 20: 1), obtain colourless liquid to anisole ethamine, productive rate 90% with the aluminium sesquioxide column chromatography.
Embodiment 4: present embodiment prepares n-amylamine, and raw material is positive valeronitrile
In round-bottomed flask, add 5-80mmol KBH
4, put into a magnetic stirrer, add 0-80mL water, carefully add Raney's nickel 1-80mmol, add the positive valeronitrile of 15mL methyl alcohol and 1.05mL (10mmol) again ,-15～70 ℃ of stirrings.Elimination Raney's nickel after 45 minutes, filtrate carefully boils off methyl alcohol with Rotary Evaporators, adds 50mL ether dissolution product, changes the separating funnel of 125mL over to, washes with water 3 to 4 times, and organic phase changes the 100mL round-bottomed flask over to, adds anhydrous Na
2SO
4Dried overnight, the elimination siccative boils off ether with Rotary Evaporators, and (developping agent is a methylene dichloride: methyl alcohol 20: 1), obtain the weak yellow liquid n-amylamine, productive rate 80% with the aluminium sesquioxide column chromatography.
Embodiment 5: the present embodiment preparation aligns amino dodecane, and raw material is positive lauronitrile
In round-bottomed flask, add 5-80mmol KBH
4, put into a magnetic stirrer, add 0-80mL water, carefully add Raney's nickel 1-80mmol, add the positive lauronitrile of 5-80mL ethanol and 2.21mL (10mmol) again ,-15～70 ℃ of stirrings.Elimination Raney's nickel after 45 minutes, filtrate boils off ethanol with Rotary Evaporators, adds 50mL acetic acid ethyl dissolution product, changes the separating funnel of 125mL over to, washes with water 3 to 4 times, and organic phase changes the 100mL round-bottomed flask over to, adds anhydrous Na
2SO
4Dried overnight, the elimination siccative boils off ethyl acetate with Rotary Evaporators, and (developping agent is a methylene dichloride: methyl alcohol 20: 1), obtain the positive amino dodecane of white solid, productive rate 82% with the aluminium sesquioxide column chromatography.
Embodiment 6: present embodiment prepares benzene methanamine, and raw material is a cyanobenzene
In round bottom Shao , add 5-80mmol KBH4, put into a magnetic stirrer, add 0-80mL water, carefully add Raney's nickel 1-80mmol, add 5-80mL ethanol and 1.02mL (10mmol) cyanobenzene again ,-15～70 ℃ of stirrings.Elimination Raney's nickel after 45 minutes, filtrate boils off ethanol with Rotary Evaporators, adds 50mL acetic acid ethyl dissolution product, changes the separating funnel of 125mL over to, washes with water 3 to 4 times, and organic phase changes the 100mL round-bottomed flask over to, adds anhydrous Na
2SO
4Dried overnight, the elimination siccative boils off ethyl acetate with Rotary Evaporators, and (developping agent is a methylene dichloride: methyl alcohol 20: 1), obtain the weak yellow liquid benzene methanamine, productive rate 82% with titanium dioxide two aluminium column chromatographies.
Embodiment 7: present embodiment prepares m-methyl-phenyl-methyl amine, raw material be between basic cyanobenzene
In round-bottomed flask, add 5-80mmol KBH
4, put into a magnetic stirrer, add 0-80mL water, carefully add Raney's nickel 1-80mmol, add methyl benzonitrile between 5-80mL ethanol and 1.21mL (10mmol) again ,-15～70 ℃ of stirrings.Elimination Raney's nickel after 45 minutes, filtrate boils off ethanol with Rotary Evaporators, adds 50mL acetic acid ethyl dissolution product, changes the separating funnel of 125mL over to, washes with water 3 to 4 times, and organic phase changes the 100mL round-bottomed flask over to, adds anhydrous Na
2SO
4Dried overnight, the elimination siccative boils off ethyl acetate with Rotary Evaporators, and (developping agent is a methylene dichloride: methyl alcohol 20: 1), obtain the weak yellow liquid m-methyl-phenyl-methyl amine, productive rate 80% with the aluminium sesquioxide column chromatography.
Embodiment 8: present embodiment prepares the O-ethoxyl methylamine, and raw material is the O-ethoxyl formonitrile HCN
In round-bottomed flask, add 5-80mmol KBH
4, put into a magnetic stirrer, add 0-80mL water, carefully add Raney's nickel 1-80mmol, add 5-80mL ethanol and 1.47g (10mmol) O-ethoxyl formonitrile HCN again ,-15～70 ℃ of stirrings.Elimination Raney's nickel after 45 minutes, filtrate boils off ethanol with Rotary Evaporators, adds 50mL acetic acid ethyl dissolution product, changes the separating funnel of 125mL over to, washes with water 3 to 4 times, and organic phase changes the 100mL round-bottomed flask over to, adds anhydrous Na
2SO
4Dried overnight, the elimination siccative boils off ethyl acetate with Rotary Evaporators, and (developping agent is a methylene dichloride: methyl alcohol 20: 1), obtain white solid O-ethoxyl methylamine, productive rate 81% with the aluminium sesquioxide column chromatography.
Embodiment 9: present embodiment prepares 1-(2-amino-1-(4-p-methoxy-phenyl) ethyl) hexalin, and raw material is 2-(1-hydroxy-cyclohexyl)-2-(4-p-methoxy-phenyl) acetonitrile
In round-bottomed flask, add 5-80mmol KBH
4, put into a magnetic stirrer, add 0-80mL water, carefully add Raney's nickel 1-80mmol, add 5-80mL ethanol and 2.45g (10mmol) 2-(1-hydroxy-cyclohexyl)-2-(4-p-methoxy-phenyl) acetonitrile again ,-15～70 ℃ of stirrings.Elimination Raney's nickel after 3 hours, filtrate boils off ethanol with Rotary Evaporators, adds 50mL acetic acid ethyl dissolution product, changes the separating funnel of 125mL over to, washes with water 3 to 4 times, and organic phase changes the 100mL round-bottomed flask over to, adds anhydrous Na
2SO
4Dried overnight, the elimination siccative boils off ethyl acetate with Rotary Evaporators, and (developping agent is a methylene dichloride: methyl alcohol 20: 1), obtain white solid 1-(2-amino-1-(4-methoxyphenyl) ethyl) hexalin, productive rate 85% with the aluminium sesquioxide column chromatography.
Claims (1)
1. a nitrile reducing prepares the method for amine, and the structural formula of described nitrile is as follows:
Wherein: R is that straight-chain alkyl, branched hydrocarbyl, substituted hydrocarbon radical: R ' is alkyl, halogen, hydroxyl, amido, carboxyl, it is characterized in that with the POTASSIUM BOROHYDRIDE being reductive agent, and Raney's nickel is a catalyzer, and nitrile reducing is that the method for primary amine is as follows:
(1) in dry round-bottomed flask, add the 5-80mmol POTASSIUM BOROHYDRIDE, carefully add Raney's nickel 1-80mmol, add 0-80mL water again, 5-80mL ethanol or methyl alcohol and 10mmol nitrile ,-15～70 ℃ were stirred 45～120 minutes;
(2) elimination Raney's nickel, filtrate boils off ethanol or methyl alcohol with Rotary Evaporators, adds 5-100mL ethyl acetate or ether dissolution product, changes separating funnel over to, washes with water 3 to 4 times, and organic phase changes round-bottomed flask over to, adds anhydrous siccative Na
2SO
4Or MgSO
4Dried overnight;
(3) elimination siccative boils off ethyl acetate or ether with Rotary Evaporators, obtains primary amine with the aluminium sesquioxide column chromatography, and developping agent is a methylene dichloride: methyl alcohol 20: 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100201063A CN100404497C (en) | 2006-01-04 | 2006-01-04 | Nitrile reducing process to prepare amine |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100201063A CN100404497C (en) | 2006-01-04 | 2006-01-04 | Nitrile reducing process to prepare amine |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1810766A CN1810766A (en) | 2006-08-02 |
| CN100404497C true CN100404497C (en) | 2008-07-23 |
Family
ID=36843907
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2006100201063A Expired - Fee Related CN100404497C (en) | 2006-01-04 | 2006-01-04 | Nitrile reducing process to prepare amine |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100404497C (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU2007343433A1 (en) * | 2007-01-09 | 2008-07-17 | Pharmathen S.A. | Improved process for the preparation of phenethylamine derivatives |
| CN101503365B (en) * | 2009-02-04 | 2012-11-07 | 成都樵枫科技发展有限公司 | Preparation of venlafaxine intermediate 1-[2-amino-1-(4-methoxy phenyl)ethyl] cyclohexanol |
| CN102093233A (en) * | 2009-12-09 | 2011-06-15 | 上海华理生物医药有限公司 | Method for preparing 1-[2-amino-1-(p-methoxy phenyl) ethyl] cyclohexanol hydrochloride |
| CN103880745B (en) * | 2014-02-26 | 2018-12-04 | 南通大学 | A kind of chemical synthesis process of the bromo- 1,2,3,4- tetrahydroisoquinoline -1- formic acid of 6- |
| CN104177268B (en) * | 2014-09-22 | 2015-10-28 | 山东华生化学股份有限公司 | A kind of preparation method of 1-[2-amino-1-(4-p-methoxy-phenyl) ethyl] hexalin |
| CN106831444A (en) * | 2016-12-08 | 2017-06-13 | 浙江优创材料科技股份有限公司 | A kind of valeronitrile hydro-reduction synthesizes the method for n-amylamine |
| CN106582656A (en) * | 2016-12-08 | 2017-04-26 | 浙江优创材料科技股份有限公司 | Synthesis method for nickel-base composite catalyst used for synthesizing n-amylamine from pentanenitrile |
| CN107216256B (en) * | 2017-05-19 | 2019-06-21 | 舞阳威森生物医药有限公司 | A kind of synthetic method of N, N- diisopropyl ethylenediamine |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1985000605A1 (en) * | 1983-07-27 | 1985-02-14 | American Hospital Supply Corporation | Process for selective nitrile reduction |
| JPS63255252A (en) * | 1987-04-14 | 1988-10-21 | Asahi Chem Ind Co Ltd | Method for reducing nitrile compound |
-
2006
- 2006-01-04 CN CNB2006100201063A patent/CN100404497C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1985000605A1 (en) * | 1983-07-27 | 1985-02-14 | American Hospital Supply Corporation | Process for selective nitrile reduction |
| JPS63255252A (en) * | 1987-04-14 | 1988-10-21 | Asahi Chem Ind Co Ltd | Method for reducing nitrile compound |
Non-Patent Citations (6)
| Title |
|---|
| Application of hydrazinium monoformate as new hydrogendonor with raney nickel: a facile reduction of nitro and nitrilemoieties. Shankare Gowda and D.Channe Gowda.Tetrahedron,No.第58期. 2002 |
| Application of hydrazinium monoformate as new hydrogendonor with raney nickel: a facile reduction of nitro and nitrilemoieties. Shankare Gowda and D.Channe Gowda.Tetrahedron,No.第58期. 2002 * |
| Rapid reduction of nitriles to prinary amines with nickelborideat ambient temperature. Jitender M. Khurana ,Gagan Kukreja.Synthetic Communications,No.第32期. 2002 |
| Rapid reduction of nitriles to prinary amines with nickelborideat ambient temperature. Jitender M. Khurana ,Gagan Kukreja.Synthetic Communications,No.第32期. 2002 * |
| 芳香胺的合成现状及展望. 何丽芳，郭忠诚.云南冶金，第34卷第3期. 2005 |
| 芳香胺的合成现状及展望. 何丽芳，郭忠诚.云南冶金，第34卷第3期. 2005 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1810766A (en) | 2006-08-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100404497C (en) | Nitrile reducing process to prepare amine | |
| CN102285891B (en) | Method for preparing arylamine by catalytic hydrogenation of aromatic nitro compound | |
| Jiang et al. | Environmentally friendly synthesis of secondary amines via one-pot reductive amination over a heterogeneous Co–N x catalyst | |
| JPH026440A (en) | Catalytic hydrogenation of aromatic amines and 4, 4'-methylenedianiline | |
| EP3877358B1 (en) | Process for producing substituted amino alcohols | |
| DE60307686T2 (en) | Hydrogenation of single-ring aromatic diamines | |
| CN101074199B (en) | Method of producing xylylenediamine | |
| CN1810765A (en) | Reduction of nitrile in nickel chloride/potassium borohydride reduction system to prepare amine | |
| CN104628577B (en) | The synthetic method of Bisolvon | |
| CA2419519A1 (en) | Process for producing diamines | |
| CN102199098B (en) | New synthesis method and application of (R)-N-benzyl-1-(4-methoxyphenyl)-2-propylamine | |
| CN103965057B (en) | A kind of nitrile prepares the method for primary amine | |
| Pandey et al. | Catalyst-and solvent-free efficient access to N-alkylated amines via reductive amination using HBpin | |
| US6114277A (en) | Process for preparing cyano group-containing aromatic methylamines | |
| WO1998043941A1 (en) | Production of 1,3-diaminopentane by hydrogenation of 3-aminopentanenitrile | |
| JPH0329781B2 (en) | ||
| CN110590563A (en) | Method for preparing benzylamine by continuously hydrogenating benzonitrile | |
| JPH0227334B2 (en) | ||
| KR100722981B1 (en) | Preparation of trans-4-methylcyclohexyl amine by catalytic hydrogenation | |
| CN104177268B (en) | A kind of preparation method of 1-[2-amino-1-(4-p-methoxy-phenyl) ethyl] hexalin | |
| CN101891572A (en) | Synthesis method for novel chiral asymmetric secondary amine belonging to N-substituted amino acid esters | |
| EP1640358A1 (en) | Synthesis of amine stereoisomers | |
| Chatterjee et al. | Selective Hydrogenation in Supercritical Carbon Dioxide Using Metal Supported Heterogeneous Catalyst | |
| CN118558321A (en) | Application of iron-copper oxide compound as catalyst in preparation of aniline or derivatives thereof by catalyzing reduction of nitrobenzene or derivatives thereof | |
| Su et al. | An Efficient Ceric Ammonium Nitrate‐Catalyzed Aromatic Amination of (Ferrocenyl)(phenyl) methanol |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| EE01 | Entry into force of recordation of patent licensing contract |
Assignee: AstaTech (Chengdu) Pharmaceutical Co., Ltd. Assignor: Sichuan University Contract record no.: 2011510000200 Denomination of invention: Nitrile reducing process to prepare amine Granted publication date: 20080723 License type: Exclusive License Open date: 20060802 Record date: 20110824 |
|
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20080723 Termination date: 20200104 |