CN105294646A - Method for preparing nitrile by alcohol oxidation - Google Patents
Method for preparing nitrile by alcohol oxidation Download PDFInfo
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- CN105294646A CN105294646A CN201510594898.4A CN201510594898A CN105294646A CN 105294646 A CN105294646 A CN 105294646A CN 201510594898 A CN201510594898 A CN 201510594898A CN 105294646 A CN105294646 A CN 105294646A
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
- C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
- C07D333/26—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D333/38—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/24—Preparation of carboxylic acid nitriles by ammoxidation of hydrocarbons or substituted hydrocarbons
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C255/00—Carboxylic acid nitriles
- C07C255/01—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms
- C07C255/32—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms having cyano groups bound to acyclic carbon atoms of a carbon skeleton containing at least one six-membered aromatic ring
- C07C255/34—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms having cyano groups bound to acyclic carbon atoms of a carbon skeleton containing at least one six-membered aromatic ring with cyano groups linked to the six-membered aromatic ring, or to the condensed ring system containing that ring, by unsaturated carbon chains
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C255/00—Carboxylic acid nitriles
- C07C255/49—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
- C07C255/50—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton to carbon atoms of non-condensed six-membered aromatic rings
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C255/00—Carboxylic acid nitriles
- C07C255/49—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
- C07C255/54—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing cyano groups and etherified hydroxy groups bound to the carbon skeleton
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- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
- C07C319/20—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides by reactions not involving the formation of sulfide groups
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
- C07C323/50—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton
- C07C323/62—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/44—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D317/46—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 ortho- or peri-condensed with carbocyclic rings or ring systems condensed with one six-membered ring
- C07D317/48—Methylenedioxybenzenes or hydrogenated methylenedioxybenzenes, unsubstituted on the hetero ring
- C07D317/62—Methylenedioxybenzenes or hydrogenated methylenedioxybenzenes, unsubstituted on the hetero ring with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to atoms of the carbocyclic ring
- C07D317/68—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
Abstract
The invention provides a method for preparing nitrile by alcohol oxidation. The method comprises the following steps: mixing substrate alcohol which is shown as formula (I), a catalyst, a cocatalyst TEMPO, a ligand, an alkaline matter, 25 weight percent to 28 weight percent of ammonium hydroxide and a solvent; reacting for 2 to 24 hours with stirring in an oxygen atmosphere at 25 to 100 DEG C, and performing aftertreatment on reaction liquid to obtain a product nitrile which is shown in a formula (II). The method provided by the invention is environment friendly, wide in substrate application range, high in yield and mild in reaction conditions, has the preparation scale from grams to over hundreds of grams, and also has relatively high practical application value.
Description
(1) technical field
The present invention relates to a kind of method being prepared nitrile by alcohol oxidation, be specifically related to a kind of oxygen that adopts and make oxygenant, mantoquita or copper powder make catalyzer, 2,2,6,6-tetramethyl piperidine oxynitride (TEMPO) makes promotor, functionalized amino acid makes part, and ammoniacal liquor makes the novel method that nitrogenous source Direct Catalytic Oxidation alcohol generates nitrile.
(2) background technology
Nitrile compounds has in the production of medicine, agricultural chemicals, dyestuff and fine chemicals to be applied very widely.At present, most nitrile compounds reacts mainly through traditional Sandmeyer, prepared by the methods such as the nucleophilic substitution reaction of halide-containing and inorganic cyanide.But these methods also exist many defects, as employed stoichiometric toxic metal prussiate as cyanogen source; Severe reaction conditions; Produce the by products such as inorganic salt; Reaction of atomic is less economical.In recent years, adopt ammoniacal liquor to make nitrogenous source, the method that nitrile compounds prepared by direct oxidation alcohol under the effect of oxygenant receives to be paid close attention to widely.These methods efficiently avoid and use hypertoxic inorganic cyanide, improve atom utilization.At present, this kind of system adopts stoichiometric oxygenant usually, mainly pyridinium chloro-chromate (PCC), high iodine reagent, Manganse Dioxide (MnO
2), tertbutyl peroxide (TBHP), Potassium Persulphate (K
2s
2o
8) and DDQ (DDQ).But because the oxidisability of this kind of oxygenant is comparatively strong, inevitably causes the over oxidation of alcohol, thus cause reaction yield lower.
Compare with other oxygenants, oxygen is not only green gentle, cheap and easy to get, and its final reduction by product is water, both can not work the mischief to environment, and also can not cause secondary pollution to product, is a kind of clean, eco-friendly oxygenant.In recent years, adopt oxygen as oxygenant, make raw material with alcohol, the method preparing nitrile compounds through direct oxidation ammonification gets more and more people's extensive concerning.Such as: Mizuno seminar [Angew.Chem.Int.Ed.2009,48,6286 – 6288] adopts the ruthenium oxyhydroxide Ru (OH) of load
x/ Al
2o
3make catalyzer, at six normal atmosphere, 120 DEG C, under the tetrahydrofuran solution condition of 0.45mol/L ammoniacal liquor, achieve the conversion to aromatic nitriles of one-level aromatic alcohol and fragrant fusel, yield reaches as high as 96%.2013, Muldoon seminar [Chem.Commun., 2013,49,6030-6032] and Huang seminar [Org.Lett., 2013,8,1850-1853] report a kind of homogeneous catalytic oxidation system jointly participated in by TEMPO and dipyridyl respectively, this system adopts mantoquita to make catalyzer, air (oxygen) makes oxygenant, and one-level aromatic alcohol can be changed into nitrile, yield reaches as high as 95%.Above reported system is the reaction of mmole rank, only for methodological study, cannot carry out amplification and produce, not possess actual using value.
So research adopts oxygen to make oxygenant, and ammoniacal liquor makes nitrogenous source, by alcohol direct oxidation ammonification, the preparation process realizing nitrile compounds more than gram level to hectogram level still tool is of great significance.
(3) summary of the invention
The present invention aims to provide a kind of oxygen that adopts and makes oxygenant, mantoquita or copper powder make catalyzer, and TEMPO makes promotor, and functionalized amino acid makes part, ammoniacal liquor is made nitrogenous source Direct Catalytic Oxidation alcohol and is generated nitrile, and possesses the preparative scale novel method of more than gram level to hectogram level.
For achieving the above object, the present invention adopts following technical scheme:
Be oxidized the method preparing nitrile by alcohol, described method is:
By substrate alcohol, catalyzer, promotor TEMPO, part, alkaline matter, 25wt% ~ 28wt% ammoniacal liquor and solvent formula (I) Suo Shi, under oxygen (being generally normal pressure) atmosphere, in 25 ~ 100 DEG C of stirring reaction 2 ~ 24h, reaction solution obtains product nitrile shown in formula (II) through aftertreatment afterwards;
Shown in described formula (I), substrate alcohol is 1:0.01 ~ 0.3:0.01 ~ 0.3:0.01 ~ 0.5:0 ~ 1 with the ratio of the amount of substance that feeds intake of catalyzer, promotor TEMPO, part, alkaline matter; The volumetric usage of described ammoniacal liquor counts 1.0 ~ 6.6mL/g with the quality of described substrate alcohol;
Described catalyzer is mantoquita or copper powder, and described mantoquita is selected from one of following: cuprous iodide, cuprous bromide, cuprous chloride, cupric chloride, cupric bromide, copper trifluoromethanesulfcomposite, copper hydroxide, copper sulfate, cupric nitrate or neutralized verdigris;
Described part is selected from one of following: N-phenylglycine, N-phenyl α-amino-isovaleric acid, N-phenyl phenylalanine, N-phenylalanine, proline(Pro), glycine, Histidine, leucine, Isoleucine, Serine or aspartic acid;
Described alkaline matter is selected from one of following: sodium hydroxide, sodium methylate, sodium carbonate, sodium bicarbonate, sodium-acetate, salt of wormwood, cesium carbonate, potassium tert.-butoxide or potassiumphosphate;
Described solvent is selected from one of following: methyl alcohol, ethanol, DMF (DMF), methyl-sulphoxide (DMSO), water, acetonitrile, acetone, ethyl acetate, hexanaphthene, methylene dichloride or toluene;
In formula (I) or formula (II), R is hydrogen, methyl, methoxyl group, 3,4-methylene-dioxies, methylthio group, amino, allyloxy, phenylacetylene base, cyano group, fluorine, chlorine, bromine, iodine or nitro;
N=0 or 1;
M=0 or 1;
X is C, S, N or O.
It should be noted that, in preparation method of the present invention, can not add alkaline matter, the feed ratio of described alkaline matter counts 0 in this case.
The method being prepared nitrile by alcohol oxidation of the present invention, shown in preferred described formula (I), substrate alcohol is 1:0.01 ~ 0.1:0.01 ~ 0.1:0.01 ~ 0.3:0.1 ~ 0.25 with the ratio of the amount of substance that feeds intake of catalyzer, promotor TEMPO, part, alkaline matter; The volumetric usage of preferred described ammoniacal liquor counts 1.5 ~ 3.5mL/g with the quality of described substrate alcohol.
Preferred described mantoquita is cuprous iodide, copper trifluoromethanesulfcomposite or cupric chloride.
Preferred described part is N-phenylglycine, N-phenylalanine or N-phenyl phenylalanine, and its structural formula is as follows respectively:
Preferred described alkaline matter is sodium hydroxide, sodium carbonate or potassiumphosphate.
Preferred described solvent is methyl alcohol or ethanol; Further, the volumetric usage of described solvent is recommended to count 2.8 ~ 17.5mL/g with the quality of described substrate alcohol, preferably 4 ~ 10mL/g.
Preferable reaction temperature is 50 ~ 60 DEG C, and the reaction times is 12 ~ 24h.
Described reaction solution can carry out aftertreatment as follows: after reaction terminates, question response liquid is cooled to room temperature, removes solvent under reduced pressure, and residuum, through washing filtering, obtains product nitrile shown in formula (II) after filtration cakes torrefaction.
Further, concrete recommendation is of the present inventionly oxidized by alcohol the method preparing nitrile and is:
By substrate alcohol, catalyzer, promotor TEMPO, part, alkaline matter, 25wt% ~ 28wt% ammoniacal liquor and solvent formula (I) Suo Shi, under oxygen (being generally normal pressure) atmosphere, in 50 ~ 60 DEG C of stirring reaction 12 ~ 24h, question response liquid is cooled to room temperature afterwards, remove solvent under reduced pressure, residuum, through washing filtering, obtains product nitrile shown in formula (II) after drying;
Shown in described formula (I), substrate alcohol is 1:0.01 ~ 0.1:0.01 ~ 0.1:0.01 ~ 0.3:0.1 ~ 0.25 with the ratio of the amount of substance that feeds intake of catalyzer, promotor TEMPO, part, alkaline matter; The volumetric usage of described ammoniacal liquor counts 1.5 ~ 3.5mL/g with the quality of described substrate alcohol;
Described catalyzer is mantoquita or copper powder, and described mantoquita is cuprous iodide, copper trifluoromethanesulfcomposite or cupric chloride;
Described part is N-phenylglycine, N-phenylalanine or N-phenyl phenylalanine;
Described alkaline matter is sodium hydroxide, sodium carbonate or potassiumphosphate;
Described solvent is methyl alcohol or ethanol, and the volumetric usage of described solvent counts 4 ~ 10mL/g with the quality of described substrate alcohol.
Beneficial effect of the present invention is mainly reflected in:
(1) green clean oxygen is used to make oxygenant, whole reaction process environmental friendliness, pollution-free;
(2) wide application range of substrates, yield is high;
(3) reaction conditions is gentle, and adopt oxygen to make oxygenant, ammoniacal liquor makes nitrogenous source, and by alcohol direct oxidation ammonification, raw material is green gentle, cheap and easy to get, possesses gram level to the above preparative-scale of hectogram level, has higher actual application value.
(4) embodiment
Below in conjunction with specific embodiment, the present invention is described further, but protection scope of the present invention is not limited in this.
Embodiment 1
Phenylcarbinol (108.02g is added in the round-bottomed flask of 2L, 1000mmol, namely the R in structural formula (I) is H, X=C, n=1, m=0), cuprous iodide (9.50g, 50mmol), N-phenylglycine (7.51g, 50mmol), TEMPO (7.80g, 50mmol), sodium carbonate (10.60g, 100mmol), ammoniacal liquor (300mL, 25 ~ 28%), methyl alcohol 800mL, under condition of ice bath, with oxygen, the air in round-bottomed flask is substituted gas 3 times, then system stirs 12h under 50 DEG C of conditions, after reaction terminates, reaction solution is cooled to room temperature, dry after removing solvent under reduced pressure, obtain product cyanobenzene 95.79g, yield 93%.
1HNMR(500MHz,Chloroform-d)δ7.61–7.53(m,3H),7.43(t,J＝7.8Hz,2H)。
13CNMR(126MHz,Chloroform-d)δ132.5,131.8,128.9,118.5,112.1。
Embodiment 2
Reactant used is to methylbenzyl alcohol (122.03g, 1000mmol, namely the R in structural formula (I) is 4-methyl, n=1, m=0, X=C), cuprous iodide (9.50g, 50mmol), N-phenylglycine (7.51g, 50mmol), TEMPO (7.80g, 50mmol), sodium hydroxide (4.00g, 100mmol), ammoniacal liquor (300mL, 25 ~ 28%), ethanol 800mL, under condition of ice bath, with oxygen, the air in round-bottomed flask is substituted gas 3 times, then system stirs 24h under 25 DEG C of conditions, after reaction terminates, reaction solution is cooled to room temperature, revolve and steam except desolventizing, residuum washing filtering, product 107.64g is obtained after drying, yield 92%.
1HNMR(500MHz,Chloroform-d)δ7.54(d,J＝8.2Hz,2H),7.28(d,J＝8.0Hz,2H),2.43(s,3H)。
13CNMR(126MHz,Chloroform-d)δ143.6,131.9,129.8,119.1,109.3,21.8。
Embodiment 3
Reactant used is O-methoxy phenylcarbinol (138.02g, 1000mmol, namely the R in structural formula (I) is 2-methoxyl group, n=1, m=0, X=C), experimental technique and step are with embodiment 2, difference is: cuprous iodide (9.50g, 50mmol), N-phenylalanine (8.26g, 50mmol), TEMPO (7.80g, 50mmol), sodium hydroxide (4.00g, 100mmol), ammoniacal liquor (300mL, 25 ~ 28%), methyl alcohol 800mL, 24h is stirred under 60 DEG C of conditions, finally obtain product 119.71g, yield 90%.
1HNMR(500MHz,Chloroform-d)δ7.57–7.51(m,2H),7.04–6.95(m,2H),3.93(s,3H)。
13CNMR(126MHz,Chloroform-d)δ161.2,134.3,133.7,120.7,116.4,111.3,101.8,55.9。
Embodiment 4
Reactant used is 3, 4, 5-trimethoxybenzyl alcohol (23.76g, 120mmol, namely the R in structural formula (I) is 3, 4, 5-trimethoxy, X=C, n=1, m=0), experimental technique and step are with embodiment 2, difference is: cuprous iodide (1.83g, 9.60mmol), N-phenylglycine (9.12g, 60mmol), TEMPO (1.50g, 9.60mmol), sodium hydroxide (0.50g, 12mmol), ammoniacal liquor (36mL, 25 ~ 28%), methyl alcohol 96mL, 2h is stirred under 100 DEG C of conditions, finally obtain product 21.53g, yield 93%.
1HNMR(500MHz,Chloroform-d)δ6.88(s,2H),3.91(s,3H),3.89(s,6H)。
13CNMR(126MHz,Chloroform-d)δ153.6,142.4,118.9,109.5,106.7,61.1,56.4。
Embodiment 5
Reactant used is to allyloxy phenylcarbinol (24.60g, 150mmol, namely the R in structural formula (I) is 4-allyloxy, X=C, n=1, m=0), experimental technique and step are with embodiment 2, difference is: cupric chloride (1.28g, 7.5mmol), N-phenylglycine (1.13g, 7.5mmol), TEMPO (1.17g, 7.5mmol), sodium hydroxide (0.61g, 15mmol), ammoniacal liquor (45mL, 25 ~ 28%), methyl alcohol 120mL, 24h is stirred under 50 DEG C of conditions, finally obtain product 21.46g, yield 90%.
1HNMR(500MHz,Chloroform-d)δ7.59(d,J＝8.9Hz,2H),6.98(d,J＝8.9Hz,2H),6.05(ddd,J＝22.5,10.5,5.3Hz,1H),5.43(d,J＝17.3Hz,1H),5.35(d,J＝10.5Hz,1H),4.60(d,J＝5.3Hz,2H)。
13CNMR(126MHz,Chloroform-d)δ161.9,133.9,132.1,119.1,118.4,115.5,104.2,69.0。
Embodiment 6
Reactant used be to phenylacetylene base phenylcarbinol (41.60g, 200mmol, the R namely in structural formula (I) is 4-phenylacetylene base, X=C, n=1, m=0), experimental technique and step are with embodiment 2, difference is: cuprous iodide (3.81g, 20mmol), N-phenylglycine (3.03g, 20mmol), TEMPO (3.13g, 20mmol), potassiumphosphate (8.49g, 40mmol), ammoniacal liquor (60mL, 25 ~ 28%), methyl alcohol 160mL, stirs 24h under 50 DEG C of conditions, finally obtain product 18.07g, yield 89%.
1HNMR(500MHz,Chloroform-d)δ7.68–7.61(m,4H),7.58–7.53(m,3H),7.40(dd,J＝5.1,1.9Hz,2H)。
13CNMR(126MHz,Chloroform-d)δ133.4,132.7,132.1,131.8,129.1,128.5,128.3,128.0,122.2,118.5,118.0,111.5,111.3,93.8,87.7。
Embodiment 7
Reactant used be to methylthio phenyl methyl alcohol (23.10g, 150mmol, the R namely in structural formula (I) is 4-methylthio group, X=C, n=1, m=0), experimental technique and step are with embodiment 2, difference is: cuprous iodide (2.85g, 15mmol), N-phenylglycine (2.27g, 15mmol), TEMPO (2.34g, 15mmol), sodium hydroxide (1.22g, 30mmol), ammoniacal liquor (45mL, 25 ~ 28%), methyl alcohol 120mL, stirs 24h under 50 DEG C of conditions, finally obtain product 20.56g, yield 92%.
1HNMR(500MHz,Chloroform-d)δ7.54(d,J＝8.6Hz,2H),7.28(d,J＝8.5Hz,2H),2.52(s,3H)。
13CNMR(126MHz,Chloroform-d)δ146.1,132.2,125.7,118.9,107.9,14.8。
Embodiment 8
Reactant used is p nitrobenzyl alcohol (30.60g, 200mmol, namely the R in structural formula (I) is 4-nitro, X=C, n=1, m=0), experimental technique and step are with embodiment 2, and difference is: cuprous iodide (11.41g, 60mmol), N-phenylglycine (9.00g, 60mmol), TEMPO (1.56g, 10mmol), ammoniacal liquor (60mL, 25 ~ 28%), methyl alcohol 160mL, stirs 24h under 50 DEG C of conditions, finally obtain product 28.15g, yield 92%.
1HNMR(500MHz,Chloroform-d)δ8.38(d,J＝8.9Hz,2H),7.90(d,J＝8.9Hz,2H)。
13CNMR(126MHz,Chloroform-d)δ150.1,133.5,124.3,118.4,116.7。
Embodiment 9
Reactant used be to chlorobenzene methanol (28.40g, 200mmol, the R namely in structural formula (I) is 4-chlorine, X=C, n=1, m=0), experimental technique and step are with embodiment 2, difference is: cuprous iodide (1.90g, 10mmol), N-phenyl phenylalanine (2.41g, 10mmol), TEMPO (1.56g, 10mmol), sodium hydroxide (0.80g, 20mmol), ammoniacal liquor (60mL, 25 ~ 28%), ethanol 160mL, stirs 24h under 80 DEG C of conditions, finally obtain product 24.66g, yield 90%.
1HNMR(500MHz,Chloroform-d)δ7.62(d,J＝8.7Hz,2H),7.49(d,J＝8.7Hz,2H)。
13CNMR(126MHz,Chloroform-d)δ139.6,133.4,129.7,117.9,110.9。
Embodiment 10
Reactant used be to bromobenzene methyl alcohol (37.00g, 200mmol, the R namely in structural formula (I) is 4-bromine, X=C, n=1, m=0), experimental technique and step are with embodiment 2, difference is: copper trifluoromethanesulfcomposite (3.62g, 10mmol), N-phenylglycine (1.50g, 10mmol), TEMPO (1.56g, 10mmol), sodium hydroxide (2.00g, 50mmol), ammoniacal liquor (60mL, 25 ~ 28%), methyl alcohol 160mL, stirs 24h under 50 DEG C of conditions, finally obtain product 34.78g, yield 94%.
1HNMR(500MHz,Chloroform-d)δ7.65(d,J＝8.6Hz,2H),7.54(d,J＝8.6Hz,2H)。
13CNMR(126MHz,Chloroform-d)δ133.4,132.7,128.0,117.9,111.4。
Embodiment 11
Reactant used be adjacent bromobenzene methyl alcohol (37.00g, 200mmol, the R namely in structural formula (I) is 2-bromine, X=C, n=1, m=0), experimental technique and step are with embodiment 2, difference is: cuprous iodide (1.90g, 10mmol), N-phenylglycine (1.50g, 10mmol), TEMPO (1.56g, 10mmol), sodium hydroxide (8.00g, 200mmol), ammoniacal liquor (60mL, 25 ~ 28%), methyl alcohol 160mL, stirs 18h under 100 DEG C of conditions, finally obtain product 32.93g, yield 90%.
1HNMR(500MHz,Chloroform-d)δ7.69(ddd,J＝14.0,7.8,1.5Hz,2H),7.46(dtd,J＝19.4,7.6,1.5Hz,2H)。
13CNMR(126MHz,Chloroform-d)δ134.3,133.8,133.2,127.6,125.34,117.1,115.9。
Embodiment 12
Reactant used be styryl carbinol (134.00g, 1000mmol, the R namely in structural formula (I) is H, X=C, n=1, m=1), experimental technique and step are with embodiment 1, difference is: cuprous iodide (9.50g, 50mmol), N-phenylglycine (7.51g, 50mmol), TEMPO (7.80g, 50mmol), sodium hydroxide (4.00g, 50mmol), ammoniacal liquor (300mL, 25 ~ 28%), methyl alcohol 800mL, stirs 24h under 50 DEG C of conditions, finally obtain product 118.68g, yield 92%.
1HNMR(500MHz,Chloroform-d)δ7.53–7.36(m,6H),5.90(d,J＝16.7Hz,1H)。
13CNMR(126MHz,Chloroform-d)δ150.6,133.6,131.2,129.1,127.3,118.1,96.4。
Embodiment 13
Reactant used be 2-thiophen(e)alcohol (57.12g, 500mmol, the R namely in structural formula (I) is H, X=S, n=0, m=0), experimental technique and step are with embodiment 1, difference is: cuprous iodide (4.76g, 25mmol), N-phenylglycine (3.79g, 25mmol), TEMPO (3.91g, 25mmol), sodium hydroxide (2.03g, 50mmol), ammoniacal liquor (60mL, 25 ~ 28%), methyl alcohol 160mL, stirs 24h under 50 DEG C of conditions, finally obtain product 49.05g, yield 90%.
1HNMR(500MHz,Chloroform-d)δ7.60(d,J＝4.4Hz,2H),7.11(t,J＝4.4Hz,1H)。
13CNMR(126MHz,Chloroform-d)δ137.2,132.5,127.5,114.0,109.5。
Embodiment 14
Reactant used is 3, sub-3,5-dimethoxybenzoic alcohol (the 45.65g of 4-, 1000mmol, namely the R in structural formula (I) is 3, the sub-dimethoxy of 4-, X=C, n=1, m=0), experimental technique and step are with embodiment 2, difference is: cuprous iodide (1.90g, 10mmol), N-phenylglycine (1.50g, 10mmol), TEMPO (1.56g, 10mmol), sodium hydroxide (7.2g, 180mmol), ammoniacal liquor (300mL, 25 ~ 28%), methyl alcohol 800mL, 24h is stirred under 50 DEG C of conditions, finally obtain product 136.85g, yield 93%.
1HNMR(500MHz,Chloroform-d)δ7.23(dd,J＝8.1,1.4Hz,1H),7.06(d,J＝1.4Hz,1H),6.88(d,J＝8.1Hz,1H),6.09(s,2H)。
13CNMR(126MHz,Chloroform-d)δ151.6,148.1,128.2,118.8,111.5,109.2,105.2。
Shown by the above embodiments, oxygen is utilized to make oxygenant under normal pressure provided by the present invention, mantoquita or copper powder make catalyzer, functionalized amino acid makes part, and TEMPO makes promotor, and ammoniacal liquor makes nitrogenous source, under certain temperature and alkaline condition, realize the method that alcohol oxidation generates nitrile, there is the features such as wide application range of substrates is general, speed of response fast, operation is easy to control, low, safe, the whole process of cost is environmentally friendly, pollution-free.
Claims (10)
1. be oxidized the method preparing nitrile by alcohol, it is characterized in that, described method is:
By substrate alcohol, catalyzer, promotor TEMPO, part, alkaline matter, 25wt% ~ 28wt% ammoniacal liquor and solvent formula (I) Suo Shi, under oxygen atmosphere, in 25 ~ 100 DEG C of stirring reaction 2 ~ 24h, reaction solution obtains product nitrile shown in formula (II) through aftertreatment afterwards;
Shown in described formula (I), substrate alcohol is 1:0.01 ~ 0.3:0.01 ~ 0.3:0.01 ~ 0.5:0 ~ 1 with the ratio of the amount of substance that feeds intake of catalyzer, promotor TEMPO, part, alkaline matter; The volumetric usage of described ammoniacal liquor counts 1.0 ~ 6.6mL/g with the quality of described substrate alcohol;
Described catalyzer is mantoquita or copper powder, and described mantoquita is selected from one of following: cuprous iodide, cuprous bromide, cuprous chloride, cupric chloride, cupric bromide, copper trifluoromethanesulfcomposite, copper hydroxide, copper sulfate, cupric nitrate or neutralized verdigris;
Described part is selected from one of following: N-phenylglycine, N-phenyl α-amino-isovaleric acid, N-phenyl phenylalanine, N-phenylalanine, proline(Pro), glycine, Histidine, leucine, Isoleucine, Serine or aspartic acid;
Described alkaline matter is selected from one of following: sodium hydroxide, sodium methylate, sodium carbonate, sodium bicarbonate, sodium-acetate, salt of wormwood, cesium carbonate, potassium tert.-butoxide or potassiumphosphate;
Described solvent is selected from one of following: methyl alcohol, ethanol, DMF (DMF), methyl-sulphoxide (DMSO), water, acetonitrile, acetone, ethyl acetate, hexanaphthene, methylene dichloride or toluene;
In formula (I) or formula (II), R is hydrogen, methyl, methoxyl group, 3,4-methylene-dioxies, methylthio group, amino, allyloxy, phenylacetylene base, cyano group, fluorine, chlorine, bromine, iodine or nitro;
N=0 or 1;
M=0 or 1;
X is C, S, N or O.
2. be oxidized by alcohol the method preparing nitrile as claimed in claim 1, it is characterized in that, shown in described formula (I), substrate alcohol is 1:0.01 ~ 0.1:0.01 ~ 0.1:0.01 ~ 0.3:0.1 ~ 0.25 with the ratio of the amount of substance that feeds intake of catalyzer, promotor TEMPO, part, alkaline matter.
3. be oxidized by alcohol the method preparing nitrile as claimed in claim 1, it is characterized in that, the volumetric usage of described ammoniacal liquor counts 1.5 ~ 3.5mL/g with the quality of described substrate alcohol.
4. be oxidized by alcohol the method preparing nitrile as claimed in claim 1, it is characterized in that, described mantoquita is cuprous iodide, copper trifluoromethanesulfcomposite or cupric chloride.
5. be oxidized by alcohol the method preparing nitrile as claimed in claim 1, it is characterized in that, described part is N-phenylglycine, N-phenylalanine or N-phenyl phenylalanine.
6. be oxidized by alcohol the method preparing nitrile as claimed in claim 1, it is characterized in that, described alkaline matter is sodium hydroxide, sodium carbonate or potassiumphosphate.
7. be oxidized by alcohol the method preparing nitrile as claimed in claim 1, it is characterized in that, described solvent is methyl alcohol or ethanol.
8. the method being prepared nitrile by alcohol oxidation as described in one of claim 1 ~ 7, it is characterized in that, the volumetric usage of described solvent counts 2.8 ~ 17.5mL/g with the quality of described substrate alcohol.
9. be oxidized by alcohol the method preparing nitrile as claimed in claim 1, it is characterized in that, temperature of reaction is 50 ~ 60 DEG C, and the reaction times is 12 ~ 24h.
10. be oxidized by alcohol the method preparing nitrile as claimed in claim 1, it is characterized in that, described method is:
By substrate alcohol, catalyzer, promotor TEMPO, part, alkaline matter, 25wt% ~ 28wt% ammoniacal liquor and solvent formula (I) Suo Shi, under oxygen atmosphere, in 50 ~ 60 DEG C of stirring reaction 12 ~ 24h, question response liquid is cooled to room temperature afterwards, remove solvent under reduced pressure, residuum, through washing filtering, obtains product nitrile shown in formula (II) after filtration cakes torrefaction;
Shown in described formula (I), substrate alcohol is 1:0.01 ~ 0.1:0.01 ~ 0.1:0.01 ~ 0.3:0.1 ~ 0.25 with the ratio of the amount of substance that feeds intake of catalyzer, promotor TEMPO, part, alkaline matter; The volumetric usage of described ammoniacal liquor counts 1.5 ~ 3.5mL/g with the quality of described substrate alcohol;
Described catalyzer is mantoquita or copper powder, and described mantoquita is cuprous iodide, copper trifluoromethanesulfcomposite or cupric chloride;
Described part is N-phenylglycine, N-phenylalanine or N-phenyl phenylalanine;
Described alkaline matter is sodium hydroxide, sodium carbonate or potassiumphosphate;
Described solvent is methyl alcohol or ethanol, and the volumetric usage of described solvent counts 4 ~ 10mL/g with the quality of described substrate alcohol.
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Cited By (5)
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| CN106866326A (en) * | 2017-03-07 | 2017-06-20 | 浙江工业大学 | A kind of method that primary alconol prepares nitrile |
| CN106905097A (en) * | 2017-03-07 | 2017-06-30 | 浙江工业大学 | It is a kind of to aoxidize the method that primary alconol prepares aldehyde |
| CN109092372A (en) * | 2018-09-30 | 2018-12-28 | 湖北大学 | A kind of catalyst and method of elective oxidation of primary alcohols |
| CN109956887A (en) * | 2017-12-14 | 2019-07-02 | 中国科学院大连化学物理研究所 | A method of catalysis 1,4 cyclohexane dimethanol ammoxidation cracking preparation 1,4- hexamethylene dimethoxy nitrile |
| CN110975936A (en) * | 2019-11-11 | 2020-04-10 | 桂林理工大学 | Copper-based catalytic system for efficiently catalyzing and oxidizing alcohol at room temperature without solvent and method thereof |
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| CN106866326A (en) * | 2017-03-07 | 2017-06-20 | 浙江工业大学 | A kind of method that primary alconol prepares nitrile |
| CN106905097A (en) * | 2017-03-07 | 2017-06-30 | 浙江工业大学 | It is a kind of to aoxidize the method that primary alconol prepares aldehyde |
| CN109956887A (en) * | 2017-12-14 | 2019-07-02 | 中国科学院大连化学物理研究所 | A method of catalysis 1,4 cyclohexane dimethanol ammoxidation cracking preparation 1,4- hexamethylene dimethoxy nitrile |
| CN109956887B (en) * | 2017-12-14 | 2021-06-01 | 中国科学院大连化学物理研究所 | Method for preparing 1, 4-cyclohexanedicarbonitrile by catalyzing ammoxidation and cracking of 1, 4-cyclohexanedimethanol |
| CN109092372A (en) * | 2018-09-30 | 2018-12-28 | 湖北大学 | A kind of catalyst and method of elective oxidation of primary alcohols |
| CN110975936A (en) * | 2019-11-11 | 2020-04-10 | 桂林理工大学 | Copper-based catalytic system for efficiently catalyzing and oxidizing alcohol at room temperature without solvent and method thereof |
| CN110975936B (en) * | 2019-11-11 | 2023-01-03 | 桂林理工大学 | Copper-based catalytic system for efficiently catalyzing and oxidizing alcohol at room temperature without solvent and method thereof |
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