CN103965057B - A kind of nitrile prepares the method for primary amine - Google Patents
A kind of nitrile prepares the method for primary amine Download PDFInfo
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- CN103965057B CN103965057B CN201410171696.4A CN201410171696A CN103965057B CN 103965057 B CN103965057 B CN 103965057B CN 201410171696 A CN201410171696 A CN 201410171696A CN 103965057 B CN103965057 B CN 103965057B
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Abstract
The invention discloses a kind of method that nitrile prepares primary amine, under the catalysis of copper compound, there is reduction reaction in nitrile and POTASSIUM BOROHYDRIDE in a solvent, after reacting completely, obtains described primary amine through aftertreatment; The method uses POTASSIUM BOROHYDRIDE/copper compound system, economic security, environmental pollution is little, and reaction conditions is gentle, does not need to use high-temperature high-pressure apparatus, prepare primary amine productive rate more than 80%, and the easy purifying of reaction solvent reclaims, and cost is low, and catalyzer mantoquita is easy to be recycled, environmental protection, can be used in industrial production.
Description
Technical field
The invention belongs to organic synthesis field, be specifically related to a kind of method that nitrile prepares primary amine.
Background technology
Primary amine is important chemical intermediate, is the important source material of the chemical such as synthesis medicine, agricultural chemicals, dyestuff.It is a kind of important method that nitrile reducing prepares primary amine, and the reduction of current nitrile adopts catalytic hydrogenation or lithium aluminium hydride reduction more, or metal catalytic sodium borohydride reduction.
Catalytic hydrogenation (see (1) L.Shaik, S.R.K.Mohan, S.R.J.Reddy, TetrahedronLetters, 48 (1), 77-80; 2007; (2) Ostgard, Daniel, PCTInt.Appl, 2006050749,18May, 2006) adopt Pd/C or Raney Ni as catalyzer more, this method productive rate is higher, also can suppress the generation of by product (secondary amine that raw material and product are formed), but this method needs High Temperature High Pressure simultaneously, higher to equipment requirements in industrial production.In addition, the easy etching apparatus of the ammonia solution used in reduction process.
Lithium aluminium hydride reduction method is (see (1) V.GevorgyanandE.Lukevics, Chem.Commun, 1985,1234-1235) reaction is very fast, but use the lithium aluminum hydride of extremely unstable, its easy spontaneous combustion, meet water and explosive decomposition, aftertreatment is more dangerous, is not suitable for industrial production.Sodium borohydride reduction (see (1) A.S.BhanuPrasad, J.V.BhaskarKanthandM.Periasamy, Tetrahedron, 1992,48 (22), 4623-4628; ), document report catalysis of iodine sodium borohydride reduction nitrile prepares primary amine, although productive rate is higher, iodine used costly, not easily reclaims iodine, and the toxicity of iodine is comparatively strong, is not suitable for industrial production.
In addition, also have bibliographical information cobalt chloride or nickel chloride catalyst sodium borohydride prepare primary amine (see (1) Brown, AlanDaniel .PCTInt.Appl., 2005090287,29Sep, 2005; See (2) Khurana, JitenderM, Kukreja, Gagan; SyntheticCommunications, 2002,32 (8), 1265-1269), this method comparative maturity, but shortcoming be used catalyst costly, recycling comparatively bothers.
Summary of the invention
The object of the invention is to for the deficiencies in the prior art, provide a kind of POTASSIUM BOROHYDRIDE/copper compound reduction system nitrile to prepare the method for amine.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 prepares a method for primary amine, and under the catalysis of copper compound, nitrile and POTASSIUM BOROHYDRIDE in a solvent reduction reaction occur, and after reacting completely, obtain 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 substituted 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.
When n is 0, CN is directly connected with aryl or heteroaryl, and raw material is aromatic nitriles; When 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 and comprises the heteroatomic aromatic nucleus such as one or more N, O, S, such as furyl or pyridyl etc.
In the present invention, by adopting copper-potassium borohydride reduction system, various aromatic nitriles or the alkyl nitrile generation reduction reaction containing aromatic nucleus can be made, obtain primary amine with higher transformation efficiency, and decrease the generation of byproduct primary amine; Potassium borohydride reduction used is weak compared with sodium borohydride, stable in the air, no hygroscopicity, and price comparatively sodium borohydride is cheap, 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 separately.
Described Ar is preferably the aryl replaced or for replacing; 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 cyanides, 4-methoxy benzonitrile, 2-chlorobenzonitrile, 3-fluorobenzonitrile or 4-p-methoxybenzeneacetonitrile.
Described copper compound comprises the oxide compound and salt that various cuprous and cupric formed; 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 the generation of by product secondary amine (product that raw material and product react further) to greatest extent, 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, that is reacted by TLC or HPLC monitoring carries out degree, and the reaction times is 0.5h-18h, and substrate is different, and there is difference in the reaction times.
The specific operation process of preparation method of the present invention 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 and extract, organic phase after washing, saturated common salt washing, dry (anhydrous sodium sulphate or anhydrous magnesium sulfate).
(3) excessively filter siccative, the solvent of removing extraction, with aluminium sesquioxide chromatography (washing and dehydrating integrated machine is methylene dichloride and methyl alcohol), obtains 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 is gentle, 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, pollute little.
(4) add water in reaction, the generation of by product secondary amine can be suppressed.
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.Removing reaction solvent, adds ethyl acetate (3ml), organic phase after washing, saturated common salt washing, dry (anhydrous sodium sulphate).Cross and 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 benzylamine
Cyanobenzene (103mg is added in reaction flask, 1mmol), POTASSIUM BOROHYDRIDE (161mg, 3.0mmol), cupric chloride (25mg, 0.2mmol), the trimethyl carbinol (0.8ml), water (0.2ml), 45 DEG C stir 1h.Removing reaction solvent, adds ethyl acetate (3ml), organic phase after washing, saturated common salt washing, dry (anhydrous sodium sulphate).Cross and 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::foundm/z108.11.), be obtained by reacting by product dibenzylamine, productive rate 5% (this productive rate is GC productive rate).
The preparation of embodiment 3 phenylethylamine
Benzyl cyanide (120mg is added in reaction flask, 1mmol), POTASSIUM BOROHYDRIDE (216mg, 4.0mmol), cupric oxide (40mg, 0.3mmol), ethanol (1.2ml), water (0.3ml), 60 DEG C stir 12h.Removing reaction solvent, adds ethyl acetate (3ml), organic phase after washing, saturated common salt washing, dry (anhydrous sodium sulphate).Cross and 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:foundm/z122.12)
The preparation of embodiment 4 pairs of chlorophenethylamine
P-chlorobenzyl cyanide (151mg is added in reaction flask, 1mmol), POTASSIUM BOROHYDRIDE (162mg, 3.0mmol), cupric chloride (26mg, 0.2mmol), Virahol (1.2ml), water (0.3ml), 50 DEG C stir 8h.Removing reaction solvent, adds ethyl acetate (3ml), organic phase after washing, saturated common salt washing, dry (anhydrous sodium sulphate).Cross and filter siccative, except desolventizing, with aluminium sesquioxide chromatography (eluting solvent is methylene dichloride and methyl alcohol), obtain weak yellow liquid to chlorophenethylamine 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::foundm/z156.00)
The preparation of embodiment 54-methoxybenzylamine
4-methoxy benzonitrile (135mg is added in reaction flask, 1mmol), POTASSIUM BOROHYDRIDE (161mg, 3.0mmol), cupric chloride (33mg, 0.25mmol), Virahol (1.2ml), water (0.3ml), 45 DEG C stir 8h.Removing reaction solvent, adds methylene dichloride (3ml), organic phase after washing, saturated common salt washing, dry (anhydrous sodium sulphate).Cross and 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:foundm/z139.13)
Embodiment 63-chlorophenethylamine
2-chlorobenzene acetonitrile (156mg is added in reaction flask, 1mmol), POTASSIUM BOROHYDRIDE (161mg, 3.0mmol), cupric chloride (26mg, 0.20mmol), Virahol (1.2ml), water (0.3ml), 60 DEG C stir 10h.Removing reaction solvent, adds ethyl acetate (4ml), organic phase after washing, saturated common salt washing, dry (anhydrous sodium sulphate).Cross and filter siccative, except desolventizing, with aluminium sesquioxide chromatography (eluting solvent is methylene dichloride and methyl alcohol), obtain weak yellow liquid 3-chlorophenethylamine 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:foundm/z156.02)
The preparation of embodiment 73-flunamine
3-fluorobenzonitrile (121mg is added in reaction flask, 1mmol), POTASSIUM BOROHYDRIDE (161mg, 3.0mmol), cupric chloride (40mg, 0.3mmol), Virahol (1.0ml), water (0.2ml), 50 DEG C stir 12h.Removing reaction solvent, adds ethyl acetate (3ml), organic phase after washing, saturated common salt washing, dry (anhydrous sodium sulphate).Cross and 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:foundm/z126.02)
The preparation of embodiment 84-methoxyphenethylamine
4-p-methoxybenzeneacetonitrile (147mg is added in reaction flask, 1mmol), POTASSIUM BOROHYDRIDE (161mg, 3.0mmol), cupric chloride (26mg, 0.20mmol), Virahol (1.2ml), water (0.3ml), 45 DEG C stir 8h.Removing reaction solvent, adds ethyl acetate (4ml), organic phase after washing, saturated common salt washing, dry (anhydrous sodium sulphate).Cross and filter siccative, except desolventizing, with aluminium sesquioxide chromatography (eluting solvent is methylene dichloride and methyl alcohol), obtain weak yellow liquid 4-methoxyphenethylamine 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:foundm/z151.92.)。
Claims (7)
1. nitrile prepares a method for primary amine, it is characterized in that, under the catalysis of copper compound, nitrile and POTASSIUM BOROHYDRIDE in a solvent reduction reaction occur, and after reacting completely, obtain 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 substituted 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;
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 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%.
2. nitrile according to claim 1 prepares 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 prepares the method for primary amine, it is characterized in that, described aryl is phenyl.
4. nitrile according to claim 1 prepares 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.
5. nitrile according to claim 1 prepares 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.
6. nitrile according to claim 1 prepares 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.
7. nitrile according to claim 1 prepares the method for primary amine, it is characterized in that, the temperature of described reduction reaction is 50 DEG C ~ 70 DEG C.
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| 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 |
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| 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 |
|---|
| LiAIH4和NaBH4的还原反应;于世钧 等;《辽宁师范大学学报（自然科学版）》;20030331;第26卷(第1期);第56-58页 * |
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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. |
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