CN103965057A - Method for preparing primary amine from nitrile - Google Patents
Method for preparing primary amine from nitrile Download PDFInfo
- Publication number
- CN103965057A CN103965057A CN201410171696.4A CN201410171696A CN103965057A CN 103965057 A CN103965057 A CN 103965057A CN 201410171696 A CN201410171696 A CN 201410171696A CN 103965057 A CN103965057 A CN 103965057A
- Authority
- CN
- China
- Prior art keywords
- primary amine
- nitrile
- prepared
- solvent
- reaction
- 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.)
- Granted
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a method for preparing primary amine from nitrile. According to the invention, under the catalysis of copper compound, nitrile and potassium borohydride undergo reduction reaction in a solvent; the primary amine is obtained through after-treatment after the reaction is finished. The method adopts the system of potassium borohydride/copper compound, so that the method is economical, safe, environment-friendly, low in pollution, and mild in reaction condition, and requires no high-temperature and high-pressure equipment; the yield of primary amine is higher than 80%; the reaction solvent is easy to purify and recycle; the cost is low; the catalyst of copper salt is easy to recycle and utilize; the method is environment-friendly, and can be applied to industrial production.
Description
Technical field
The invention belongs to organic synthesis field, be specifically related to a kind of method that nitrile is prepared primary amine.
Background technology
Primary amine is important chemical intermediate, is the important source material of the chemical such as synthetic medicine, agricultural chemicals, dyestuff.It is a kind of important method that nitrile reducing is prepared primary amine, and the reduction of nitrile at present adopts catalytic hydrogenation or lithium aluminium hydride reduction more, or metal catalytic sodium borohydride reduction.
Catalytic hydrogenation (is shown in (1) L.Shaik, S.R.K.Mohan, S.R.J.Reddy, TetrahedronLetters, 48 (1), 77-80; 2007; (2) Ostgard, Daniel, PCT Int.Appl, 2006050749,18May, 2006) adopt Pd/C or Raney Nis as catalyzer more, this method productive rate is higher, also can suppress the generation of by product (secondary amine that raw material and product form), but this method needs High Temperature High Pressure simultaneously, higher to equipment requirements in industrial production.In addition, the easy etching apparatus of ammonia solution using in reduction process.
Lithium aluminium hydride reduction method (is shown in (1) V.Gevorgyan and E.Lukevics, Chem.Commun, 1985,1234-1235) reaction is very fast, but use extremely unsettled lithium aluminum hydride, its easy spontaneous combustion, meets the i.e. explosive decomposition of water, aftertreatment is more dangerous, is not suitable for industrial production.Sodium borohydride reduction (is shown in (1) A.S.Bhanu Prasad, J.V.Bhaskar Kanth and M.Periasamy, Tetrahedron, 1992,48 (22), 4623-4628; ), document report catalysis of iodine sodium borohydride reduction nitrile is prepared primary amine, although productive rate is higher, iodine used is comparatively expensive, be difficult for reclaiming iodine, and the toxicity of iodine is stronger, is not suitable for industrial production.
In addition, also there are bibliographical information cobalt chloride or nickel chloride catalyst sodium borohydride to prepare primary amine and (see (1) Brown, Alan Daniel .PCT Int.Appl., 2005090287,29Sep, 2005; See (2) Khurana, Jitender M, Kukreja, Gagan; Synthetic Communications, 2002,32 (8), 1265-1269), this method comparative maturity, more expensive but shortcoming is used catalyst, recycling is trouble comparatively.
Summary of the invention
The object of the invention is to for the deficiencies in the prior art, a kind of method of preparing amine with POTASSIUM BOROHYDRIDE/copper compound reduction system nitrile is provided.The method productive rate compared with high, selectivity good, reductive agent used and catalyzer is cheap and easy to get, environmental pollution is little.
Nitrile is prepared a method for primary amine, and under the catalysis of copper compound, reduction reaction occurs in solvent for nitrile and POTASSIUM BOROHYDRIDE, after reacting completely, obtains primary amine through aftertreatment;
The structure of described nitrile is as shown in formula I:
The structure of described primary amine is as shown in formula II;
In formula I and (II), Ar is for replacing or unsubstituted aryl or heteroaryl, and the substituting group on described aryl or heteroaryl is selected from halogen, alkyl or alkoxyl group;
N is 0 or 1.
In the time that n is 0, CN is directly connected with aryl or heteroaryl, and raw material is aromatic nitriles; In the time that n is 1, raw material is the fatty nitrile with aromatic base.
Wherein, described aryl refers to not comprise heteroatomic aromatic nucleus, such as phenyl or naphthyl etc.; Described heteroaryl refers to heteroatomic aromatic nucleus such as comprising one or more N, O, S, such as furyl or pyridyl etc.
In the present invention, by adopting copper-potassium borohydride reduction system, the alkyl nitrile generation reduction reaction that can make various aromatic nitriles or contain aromatic nucleus, obtains primary amine with higher transformation efficiency, and has reduced the generation of by product primary amine; Potassium borohydride reduction used compared with sodium borohydride a little less than, stable in the air, no hygroscopicity, price is cheap compared with sodium borohydride, copper compound low price, safety and environmental protection used, is easy to reclaim.
As preferably, the substituting group on described aryl or heteroaryl is selected from chlorine, fluorine, C
1～C
5alkoxyl group or C
1～C
5alkyl; More preferably fluorine, chlorine, methyl or methoxyl group; Wherein, described substituting group can be one or more, can be identical or different between separately.
Described Ar is preferably the aryl that replaces or be replacement; As preferably, described aryl is phenyl, and now, the yield of reaction is high.
As further preferred, described nitrile is selected from the one in following compound:
P-chlorobenzyl cyanide, benzyl cyanide, cyanobenzene, 3,4-dichloro benzyl cyanide, 4-anisole formonitrile HCN, 2-chlorobenzonitrile, 3-fluorobenzonitrile or 4-p-methoxybenzeneacetonitrile.
Described copper compound comprises various cuprous oxide compound and the salt forming with cupric; As preferably, described copper compound is at least one in cupric oxide, Red copper oxide, cupric chloride, cuprous chloride, cupric bromide, cuprous bromide, cuprous iodide, cupric iodide, copper sulfate, acetylacetone copper.
Described solvent is polar solvent, and as preferably, described solvent is selected from C
1～C
4at least one in alkyl alcohol and water.
As preferably, described solvent is the mixed solvent of a kind of and water in methyl alcohol, ethanol, Virahol, the trimethyl carbinol, and wherein, the volume percent of water in mixed solvent is 15～25%.Experimental result shows, described reduction reaction is carried out in the mixed solvent of alcohol and water, can reduce to greatest extent the generation of by product secondary amine (product that raw material further reacts with product), improves the selectivity of reaction.
As further preferred, described copper compound is cupric chloride;
Described solvent is the mixed solvent of Virahol and water, and the volume ratio of Virahol and water is 3～4:1.Now, the yield of reaction is the highest, and side reaction is minimum, and can adapt to more reaction substrate.
Mol ratio 1.0～the 10.0:1 of described POTASSIUM BOROHYDRIDE and described nitrile, wherein, excessive POTASSIUM BOROHYDRIDE is conducive to the raising of productive rate, and as preferably, the mol ratio of described POTASSIUM BOROHYDRIDE and described nitrile is 3.0～5.0:1.
The mol ratio of described copper compound and described nitrile is 0.1～1.0:1, and as preferably, the mol ratio of described copper compound and described nitrile is 0.1～0.25:1, most preferably is 0.25.
Described reduction reaction can occur in wide temperature range, and temperature of reaction is-10 DEG C～100 DEG C; As preferably, the temperature of described reduction reaction is 50 DEG C～70 DEG C.
In reaction process, by the degree of carrying out of TLC or HPLC monitoring reaction, the reaction times is 0.5h-18h, substrate difference, and there is difference in the reaction times.
Preparation method's of the present invention specific operation process is exemplified below:
(1) in reaction flask, add 1mmol nitrile, 1-10.0mmol POTASSIUM BOROHYDRIDE, 0.1mmol-1.0mmol mantoquita, 0.5-5.0ml methyl alcohol or ethanol or Virahol or the trimethyl carbinol, 0-1.0ml water ,-15-75 DEG C is stirred 30-600min.
(2) remove reaction solvent, add ethyl acetate or ether or methylene dichloride to extract, organic phase, after washing, saturated common salt washing, is dried (anhydrous sodium sulphate or anhydrous magnesium sulfate).
(3) remove by filter siccative, remove the solvent of extraction, with aluminium sesquioxide chromatography (washing and dehydrating integrated machine is methylene dichloride and methyl alcohol), obtain primary amine.
Compared with the existing technology, beneficial effect of the present invention is embodied in:
(1) borane reducing agent potassium hydride KH is safe, economical; Catalyzer copper compound safety, economy, environmental protection.
(2) reaction conditions gentleness, does not need High Temperature High Pressure, does not need isolated air reaction.
(3) prepare primary amine reaction productive rate more than 80%, speed of response is fast, and reaction solvent, catalyzer easily reclaim, and cost is lower, pollutes little.
(4) in reaction, add water, can suppress the generation of by product secondary amine.
Embodiment
The preparation of embodiment 1 benzylamine
In reaction flask, add cyanobenzene (103mg, 1mmol), POTASSIUM BOROHYDRIDE (161mg, 3.0mmol), cupric chloride (25mg, 0.2mmol), methyl alcohol (1.0ml), 45 DEG C are stirred 1h.Remove reaction solvent, add ethyl acetate (3ml), organic phase, after washing, saturated common salt washing, is dried (anhydrous sodium sulphate).Remove by filter siccative, except desolventizing, with aluminium sesquioxide chromatography (eluting solvent is methylene dichloride and methyl alcohol), obtain weak yellow liquid benzylamine 66mg, productive rate 62%.(1H-NMR (400MHz, DMSO-d6) δ 2.64 (t, 2H), 2.80 (t, 2H), 7.18-7.29 (m, 5H); , and obtain by product dibenzylamine (secondary amine), productive rate 38% APCI-MS::foundm/z108.11.).(APCI-MS:foundm/z198.13)
The preparation of embodiment 2 benzylamines
In reaction flask, add cyanobenzene (103mg, 1mmol), POTASSIUM BOROHYDRIDE (161mg, 3.0mmol), cupric chloride (25mg, 0.2mmol), the trimethyl carbinol (0.8ml), water (0.2ml), 45 DEG C are stirred 1h.Remove reaction solvent, add ethyl acetate (3ml), organic phase, after washing, saturated common salt washing, is dried (anhydrous sodium sulphate).Remove by filter siccative, except desolventizing, with aluminium sesquioxide chromatography (eluting solvent is methylene dichloride and methyl alcohol), obtain weak yellow liquid benzylamine 94mg, productive rate 88%.(1H-NMR (400MHz, DMSO-d6) δ 2.64 (t, 2H), 2.80 (t, 2H), 7.18-7.29 (m, 5H); APCI-MS::found m/z108.11.), reaction obtains by product dibenzylamine, productive rate 5% (this productive rate is GC productive rate).
The preparation of embodiment 3 phenylethylamines
In reaction flask, add benzyl cyanide (120mg, 1mmol), POTASSIUM BOROHYDRIDE (216mg, 4.0mmol), cupric oxide (40mg, 0.3mmol), ethanol (1.2ml), water (0.3ml), 60 DEG C are stirred 12h.Remove reaction solvent, add ethyl acetate (3ml), organic phase, after washing, saturated common salt washing, is dried (anhydrous sodium sulphate).Remove by filter siccative, except desolventizing, with aluminium sesquioxide chromatography (eluting solvent is methylene dichloride and methyl alcohol), obtain weak yellow liquid phenylethylamine 97mg, productive rate 80%.(,
1H-NMR(400MHz,CDCl
3)δ2.64(t,2H,J＝6.4),2.80(t,2H,J＝6.4)，7.18-7.29(m,5H)；APCI-MS:found m/z122.12)
The preparation of embodiment 4 to chlorobenzene ethamine
In reaction flask, add p-chlorobenzyl cyanide (151mg, 1mmol), POTASSIUM BOROHYDRIDE (162mg, 3.0mmol), cupric chloride (26mg, 0.2mmol), Virahol (1.2ml), water (0.3ml), 50 DEG C are stirred 8h.Remove reaction solvent, add ethyl acetate (3ml), organic phase, after washing, saturated common salt washing, is dried (anhydrous sodium sulphate).Remove by filter siccative, except desolventizing, with aluminium sesquioxide chromatography (eluting solvent is methylene dichloride and methyl alcohol), obtain weak yellow liquid to chlorobenzene ethamine 141mg, productive rate 90%.(
1H-NMR(400MHz,DMSO-d6)δ2.68(s,2H),3.19(m,2H),7.24(d,2H),7.34(d,2H)；APCI-MS::found m/z156.00)
The preparation of embodiment 54-methoxybenzylamine
In reaction flask, add 4-anisole formonitrile HCN (135mg, 1mmol), POTASSIUM BOROHYDRIDE (161mg, 3.0mmol), cupric chloride (33mg, 0.25mmol), Virahol (1.2ml), water (0.3ml), 45 DEG C are stirred 8h.Remove reaction solvent, add methylene dichloride (3ml), organic phase, after washing, saturated common salt washing, is dried (anhydrous sodium sulphate).Remove by filter siccative, except desolventizing, with aluminium sesquioxide chromatography (eluting solvent is methylene dichloride and methyl alcohol), obtain weak yellow liquid 4-methoxybenzylamine 117mg, productive rate 85%.(
1H-NMR(400MHz,DMSO-d6)δ3.66(s,2H)3.72(s,3H),6.87(d,2H),7.21(d,2H)；APCI-MS:found m/z139.13)
Embodiment 63-chlorobenzene ethamine
In reaction flask, add 2-chlorobenzene acetonitrile (156mg, 1mmol), POTASSIUM BOROHYDRIDE (161mg, 3.0mmol), cupric chloride (26mg, 0.20mmol), Virahol (1.2ml), water (0.3ml), 60 DEG C are stirred 10h.Remove reaction solvent, add ethyl acetate (4ml), organic phase, after washing, saturated common salt washing, is dried (anhydrous sodium sulphate).Remove by filter siccative, except desolventizing, with aluminium sesquioxide chromatography (eluting solvent is methylene dichloride and methyl alcohol), obtain weak yellow liquid 3-chlorobenzene ethamine 125mg, productive rate 80%.(
1H-NMR(400MHz,DMSO-d6)δ1.77(s,2H),1.89(m,2H),2.75(m,2H)7.24(m,4H)；MS:found m/z156.02)
The preparation of embodiment 73-flunamine
In reaction flask, add 3-fluorobenzonitrile (121mg, 1mmol), POTASSIUM BOROHYDRIDE (161mg, 3.0mmol), cupric chloride (40mg, 0.3mmol), Virahol (1.0ml), water (0.2ml), 50 DEG C are stirred 12h.Remove reaction solvent, add ethyl acetate (3ml), organic phase, after washing, saturated common salt washing, is dried (anhydrous sodium sulphate).Remove by filter siccative, except desolventizing, with aluminium sesquioxide chromatography (eluting solvent is methylene dichloride and methyl alcohol), obtain weak yellow liquid 3-flunamine 102mg, productive rate 82%.(
1H-NMR(400MHz,DMSO-d6)δ1.56(s,2H),7.10-7.25(m,4H)；MS:found m/z126.02)
The preparation of embodiment 84-anisole ethamine
In reaction flask, add 4-p-methoxybenzeneacetonitrile (147mg, 1mmol), POTASSIUM BOROHYDRIDE (161mg, 3.0mmol), cupric chloride (26mg, 0.20mmol), Virahol (1.2ml), water (0.3ml), 45 DEG C are stirred 8h.Remove reaction solvent, add ethyl acetate (4ml), organic phase, after washing, saturated common salt washing, is dried (anhydrous sodium sulphate).Remove by filter siccative, except desolventizing, with aluminium sesquioxide chromatography (eluting solvent is methylene dichloride and methyl alcohol), obtain weak yellow liquid 4-anisole ethamine 128mg, productive rate 85%.(
1H-NMR(400MHz,DMSO-d6)δ2.66(m,2H),2.91(m,2H),3.72(s,3H),6.85(d,2H),7.12(d,2H)；MS:found m/z151.92.)。
Claims (10)
1. nitrile is prepared a method for primary amine, it is characterized in that, under the catalysis of copper compound, reduction reaction occurs in solvent for nitrile and POTASSIUM BOROHYDRIDE, after reacting completely, obtains primary amine through aftertreatment;
The structure of described nitrile is as shown in formula I:
The structure of described primary amine is as shown in formula II;
In formula I and (II), Ar is for replacing or unsubstituted aryl or heteroaryl, and the substituting group on described aryl or heteroaryl is selected from halogen, alkyl or alkoxyl group;
N is 0 or 1.
2. nitrile according to claim 1 is prepared the method for primary amine, it is characterized in that, the substituting group on described aryl or heteroaryl is selected from chlorine, fluorine, C
1～C
5alkoxyl group or C
1～C
5alkyl.
3. nitrile according to claim 1 and 2 is prepared the method for primary amine, it is characterized in that, described aryl is phenyl.
4. nitrile according to claim 1 is prepared the method for primary amine, it is characterized in that, described copper compound is at least one in cupric oxide, Red copper oxide, cupric chloride, cuprous chloride, cupric bromide, cuprous bromide, cuprous iodide, cupric iodide, copper sulfate, acetylacetone copper.
5. nitrile according to claim 1 is prepared the method for primary amine, it is characterized in that, described solvent is selected from C
1～C
4at least one in alkyl alcohol and water.
6. nitrile according to claim 5 is prepared the method for primary amine, it is characterized in that, described solvent is the mixed solvent of a kind of and water in methyl alcohol, ethanol, Virahol, the trimethyl carbinol, and wherein, the volume percent of water in mixed solvent is 15～25%.
7. nitrile according to claim 1 is prepared the method for primary amine, it is characterized in that, described copper compound is cupric chloride;
Described solvent is the mixed solvent of Virahol and water, and the volume ratio of Virahol and water is 3～4:1.
8. nitrile according to claim 1 is prepared the method for primary amine, it is characterized in that, the mol ratio of described POTASSIUM BOROHYDRIDE and described nitrile is 3.0～5.0:1.
9. nitrile according to claim 1 is prepared the method for primary amine, it is characterized in that, the mol ratio of described copper compound and described nitrile is 0.1～0.25:1.
10. nitrile according to claim 1 is prepared the method for primary amine, it is characterized in that, the temperature of described reduction reaction is 50 DEG C～70 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410171696.4A CN103965057B (en) | 2014-04-25 | 2014-04-25 | A kind of nitrile prepares the method for primary amine |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410171696.4A CN103965057B (en) | 2014-04-25 | 2014-04-25 | A kind of nitrile prepares the method for primary amine |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103965057A true CN103965057A (en) | 2014-08-06 |
| CN103965057B CN103965057B (en) | 2015-12-30 |
Family
ID=51235118
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410171696.4A Active CN103965057B (en) | 2014-04-25 | 2014-04-25 | A kind of nitrile prepares the method for primary amine |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103965057B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2659037C1 (en) * | 2017-02-28 | 2018-06-27 | Федеральное государственное унитарное предприятие "Государственный научно-исследовательский институт органической химии и технологии" (ФГУП "ГосНИИОХТ") | Method for producing beta-phenylethylamine |
| CN109651159A (en) * | 2019-01-21 | 2019-04-19 | 西南石油大学 | A kind of method that hydrogen migration selective reduction nitrile prepares primary amine |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1810765A (en) * | 2006-01-04 | 2006-08-02 | 四川大学 | Reduction of nitrile in nickel chloride/potassium borohydride reduction system to prepare amine |
| CN101011661A (en) * | 2006-12-20 | 2007-08-08 | 中国日用化学工业研究院 | Catalyst for preparing fatty primary amine by fatty nitrile hydrogenation and application thereof |
-
2014
- 2014-04-25 CN CN201410171696.4A patent/CN103965057B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1810765A (en) * | 2006-01-04 | 2006-08-02 | 四川大学 | Reduction of nitrile in nickel chloride/potassium borohydride reduction system to prepare amine |
| CN101011661A (en) * | 2006-12-20 | 2007-08-08 | 中国日用化学工业研究院 | Catalyst for preparing fatty primary amine by fatty nitrile hydrogenation and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| 于世钧 等: "LiAIH4和NaBH4的还原反应", 《辽宁师范大学学报（自然科学版）》, vol. 26, no. 1, 31 March 2003 (2003-03-31), pages 56 - 58 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2659037C1 (en) * | 2017-02-28 | 2018-06-27 | Федеральное государственное унитарное предприятие "Государственный научно-исследовательский институт органической химии и технологии" (ФГУП "ГосНИИОХТ") | Method for producing beta-phenylethylamine |
| CN109651159A (en) * | 2019-01-21 | 2019-04-19 | 西南石油大学 | A kind of method that hydrogen migration selective reduction nitrile prepares primary amine |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103965057B (en) | 2015-12-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Guo et al. | Iron-catalyzed cross-coupling of aryltrimethylammonium triflates and alkyl Grignard reagents | |
| Saha et al. | Selective hydrogenation of nitriles to secondary amines catalyzed by a pyridyl-functionalized and alkenyl-tethered NHC–Ru (II) complex | |
| CN100404497C (en) | Nitrile reducing process to prepare amine | |
| CN106905125A (en) | A kind of method that ketone α alkyl of cobalt catalysis is combined to ketones derivant | |
| Tang et al. | Synthesis of a water-soluble cationic chiral diamine ligand bearing a diguanidinium and application in asymmetric transfer hydrogenation | |
| CN103965057B (en) | A kind of nitrile prepares the method for primary amine | |
| CN108997440A (en) | The method that novel ferrocene bidentate ligand, ligand and mantoquita coordination prepare catalyst | |
| CN105566162B (en) | The preparation technology of rilpivirine intermediate | |
| CN105593220A (en) | Process for the production of furanic compounds comprising at least one amine function | |
| CN103755529B (en) | A kind of method preparing pyrogallol and Phloroglucinol monomethyl ether | |
| CN103214344B (en) | Method for converting alkyne into alcohol | |
| CN110950778A (en) | Process and catalyst system for preparing aromatic malononitrile | |
| CN103193660B (en) | Synthetic method of 4-alkoxy phenylamine compound | |
| CN1810765A (en) | Reduction of nitrile in nickel chloride/potassium borohydride reduction system to prepare amine | |
| WO2006030017A1 (en) | Synthesis of amine stereoisomers | |
| CN106431932A (en) | Synthesis method of N-2-ethylhexyl-N'-phenyl p-phenylenediamine | |
| CN106905166B (en) | A method of synthesis secondary amine | |
| CN107382741A (en) | It is catalyzed the method for the intermolecular hydroamination reaction of alkynes and amine | |
| CN102603545B (en) | Preparation method of 7-methoxy-1-naphthylethylamine | |
| CN103086894B (en) | Synthesis method of electroplating additive 3-methyl-3-aminobutyne | |
| CN104788324A (en) | Synthetic method of aminofluorene compounds | |
| CN104945376A (en) | synthesizing method for 3-aroyl indole compound | |
| CN106000451B (en) | A kind of Cyclamine catalyst and preparation method thereof | |
| CN103896793B (en) | Synthesis method of amide compounds | |
| CN109336934A (en) | Ferrocene bidentate ligand and its application in the asymmetric C-N cross-coupling reaction of copper catalysis |
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 | ||
| CP01 | Change in the name or title of a patent holder | ||
| CP01 | Change in the name or title of a patent holder |
Address after: 322118 Hengdian industrial district, Dongyang City, Jinhua, Zhejiang Co-patentee after: China Jiliang University Patentee after: Zhejiang Apeloa Medical Technology Co.,Ltd. Address before: 322118 Hengdian industrial district, Dongyang City, Jinhua, Zhejiang Co-patentee before: China Jiliang University Patentee before: Zhejiang Apeloa Medical Technology Co.,Ltd. |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20180926 Address after: 322118 Hengdian industrial district, Dongyang City, Jinhua, Zhejiang Co-patentee after: China Jiliang University Patentee after: ZHEJIANG APELOA JIAYUAN PHARMACEUTICAL Co.,Ltd. Address before: 322118 Hengdian industrial district, Dongyang City, Jinhua, Zhejiang Co-patentee before: CHINA JILIANG UNIVERSITY Patentee before: Zhejiang Apeloa Medical Technology Co.,Ltd. |