CN109180497A - A kind of preparation method of N- alkylate - Google Patents

A kind of preparation method of N- alkylate Download PDF

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Publication number
CN109180497A
CN109180497A CN201811027523.XA CN201811027523A CN109180497A CN 109180497 A CN109180497 A CN 109180497A CN 201811027523 A CN201811027523 A CN 201811027523A CN 109180497 A CN109180497 A CN 109180497A
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alkylate
reaction
preparation
mofs
aromatic alcohol
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CN109180497B (en
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桑欣欣
王大伟
王利魁
石刚
倪才华
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Jiangnan University
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Jiangnan University
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/04—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups
    • C07C209/14—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of hydroxy groups or of etherified or esterified hydroxy groups
    • C07C209/18—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of hydroxy groups or of etherified or esterified hydroxy groups with formation of amino groups bound to carbon atoms of six-membered aromatic rings or from amines having nitrogen atoms bound to carbon atoms of six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
    • C07C213/08—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions not involving the formation of amino groups, hydroxy groups or etherified or esterified hydroxy groups

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention discloses a kind of preparation methods of N- alkylate, are reacted with Ni-MOFs material catalysis aromatic alcohol with anil and generate N- alkylate.Method of the invention does not need solvent, shows high activity and selectivity during the reaction, and the catalyst is stablized in catalyst system and convenient for recycling and recycling, and after being repeated 5 times reaction, catalytic activity is without being substantially reduced.

Description

A kind of preparation method of N- alkylate
Technical field
The present invention relates to a kind of preparation methods of N- alkylate, are specifically catalyzed and synthesized using Ni-MOFs material N- alkylate, belongs to catalytic field.
Background technique
Itrogenous organic substance is indispensable one of the compound of life process, is the important component of life entity, such as Amino acid and nucleotide.Meanwhile organonitrogen compound also occupies an important position in pharmaceutical chemistry and organic chemistry.Numerous In nitrogenous compound, aminated compounds and its derivative are mainly also to be important a part, are widely used in pesticide, doctor In all kinds of industrial and agricultural productions such as medicine, dyestuff, high molecular material, food additives.From the angle of Atom economy and environmental protection For, the N- alkylation reaction method tool of alkohol and amine has an enormous advantage.
The N- alkylation reaction method of early stage alcohol and amine often requires very high reaction temperature and pressure, and yield It is not very high.With the development of Organometallic Chemistry and alcohol method for oxidation, gradually it is applied to using transition metal-catalyzed method The dehydration N- alkylation reaction of alcohol and amine, and obtain more preferably reaction effect.Not only may be used using transition-metal catalyst To substantially reduce the temperature of reaction, simplify experimental implementation, it can also effectively accelerate reaction rate and improve the selectivity of product. But the transition metal for being catalyzed such reaction at present is mostly noble metal, such catalyst preparation process is complicated, higher cost, and more For homogeneous catalysis system, the organic solvent used is easy pollution environment, also will increase the cost of reaction to the processing of waste liquid.Such as It has been reported that use the complex of Rh for homogeneous catalyst, using toluene as solvent, the yield of target product is up to 86% (D1:MuratNevin Gürbüz,David Sémeril,and Eur.J.Inorg.Chem.2018,1236-1243).Therefore, it is necessary to the N- alkyl of a kind of environmentally protective, yield and high conversion rate Change the preparation method of product to replace existing method.
Summary of the invention
To achieve the above object, the present invention provides a kind of preparation method of N- alkylate, and this method is with Ni-MOFs Catalyst, aromatic alcohol and anil are raw material, and reaction obtains N- alkylate, and reaction equation is as follows:
Wherein R1 and R2 is hydrogen, C1-C3Alkyl, the C being optionally substituted by halogen1-C3Alkyl, halogen, C1-C3Alkoxy, phenyl etc.； R1 and R2 is hydrogen, methyl, ethyl, n-propyl, normal-butyl, trifluoromethyl, F, Cl, Br.
Specifically, reaction step is as follows:
(1) 2:1-1:1 is added in reaction vessel aromatic alcohol in molar ratio with anil, addition Ni-MOFs, then plus Enter alkali, is reacted 5-24 hours under 80-150 DEG C of heating condition.
(2) gained reaction solution in step (1) is filtered, with silica gel column purification, petroleum ether eluted product, leacheate is eluted, To get N- alkylate after removing solvent.It is filtered after reaction technology, recycles catalyst.
The alkali is alkali commonly used in the art, preferably cesium carbonate, potassium carbonate, potassium hydroxide.The dosage of alkali is aromatic alcohol 1-1.5 times of dosage molar ratio.The leacheate is leacheate commonly used in the art, and preferred mass is than the acetic acid second for 1:10 The mixture of ester and petroleum ether.
In step (1), the reaction temperature is 80-150 DEG C, 100-120 DEG C of preferable temperature.
In step (1), the reaction time is 5-24 hours, preferably 10-15 hours.
The Ni-MOFs is that ligand is terephthalic acid (TPA), trimesic acid, 2- amino terephthalic acid (TPA), 2,5- dihydroxy The crystalline, porous framework material that base terephthalic acid (TPA) and nickel salts are formed, can be obtained by known references or commercially available mode ?.
In step (1), the dosage of the Ni-MOFs is the 1%-5% of aromatic alcohol quality.
The method that the present invention prepares N- alkylate has very high yield and conversion ratio, and reacting is solvent-free Under the conditions of carry out, reduce using and discharging for organic solvent compared with prior art.Meanwhile Ni-MOFs material catalytic alcohol Amine N- alkylated reaction has high cyclical stability, catalyst activity still with higher after applying 5 times, even if not supplementing machine Tool loss, which can continue to be catalyzed such, reacts and has the same effect.
Specific embodiment
The present invention is further explained in the light of specific embodiments, but embodiment is not constituted to limit of the invention System.All raw materials in embodiment can pass through commercially available acquisition.
Embodiment 1:
Benzyl alcohol and each 2mmol of aniline, Ni-BDC (H are added in 50ml Schlenk pipe2BDC=terephthalic acid (TPA)) 15mg, potassium hydroxide 2mmol, reaction solution react 10 hours in 120 DEG C, after mixed liquor centrifuge separation, centrifugate 200-300 mesh Silica gel post separation (ethyl acetate/petroleum ether that eluent is 1:10), after removing solvent, obtains product structure formula are as follows:
Centrifugation gained catalyst is with ethanol washing 3-5 times, after dry, repeat the catalysis and reacts 5 times, products collection efficiency does not occur Significant change illustrates that the catalyst has good cyclical stability.
Embodiment 2:
By the Ni-BTC (H of the catalyst in embodiment 13BTC=trimesic acid) 15mg substitution, remaining condition is constant.
Embodiment 3:
By the catalyst Ni-BDC-NH in embodiment 12(H2BDC-NH2=2- amino terephthalic acid (TPA)) 15mg substitution, Remaining condition is constant.
Embodiment 4:
With 4- methylbenzyl alcohol and aniline reaction, remaining obtains product structure formula with embodiment 1 are as follows:
Embodiment 5:
With 4- fluorinated benzyl alcohol and aniline reaction, remaining obtains product structure formula with embodiment 1 are as follows:
Embodiment 6:
With 2- fluorinated benzyl alcohol and aniline reaction, catalyst is the catalyst that recycles in embodiment 1, remaining with embodiment 1, Obtain product structure formula are as follows:
Embodiment 7:
With 2- bromo benzyl alcohol and aniline reaction, remaining obtains product structure formula with embodiment 6 are as follows:
Embodiment 8:
With 4- trifluoromethyl benzyl alcohol and aniline reaction, remaining obtains product structure formula with embodiment 6 are as follows:
Embodiment 9:
It is reacted with benzyl alcohol with 4- aminoanisole, remaining obtains product structure formula with embodiment 6 are as follows:
Embodiment 10:
It is reacted with benzyl alcohol with 4- Fluoroaniline, remaining obtains product structure formula with embodiment 6 are as follows:
Comparative example 1:
Catalyst in embodiment 1 commercialization NiO 15mg is substituted, remaining condition is constant.
Comparative example 2:
Catalyst in embodiment 1 commercialization Ni 15mg is substituted, remaining condition is constant.
The yield of product and conversion ratio see the table below in each embodiment, comparative example and prior art D1.
Yield % Conversion ratio % Waste liquid
Embodiment 1 92 100 Nothing
Embodiment 2 85 100 Nothing
Embodiment 3 95 100 Nothing
Embodiment 4 88 100 Nothing
Embodiment 5 82 100 Nothing
Embodiment 6 80 100 Nothing
Embodiment 7 90 100 Nothing
Embodiment 8 87 100 Nothing
Embodiment 9 81 100 Nothing
Embodiment 10 85 100 Nothing
Comparative example 1 50 90 Nothing
Comparative example 2 60 90 Nothing
D1 86 -- Toluene

Claims (7)

1. a kind of preparation method of N- alkylate, it is characterised in that: comprise the following steps that: this method is with Ni-MOFs For catalyst, aromatic alcohol and anil are raw material, and reaction obtains N- alkylate, and reaction equation is as follows:
Wherein R1 and R2 is hydrogen, C1-C3Alkyl, the C being optionally substituted by halogen1-C3Alkyl, halogen, C1-C3Alkoxy, phenyl.
2. the preparation method of N- alkylate according to claim 1, it is characterised in that: R1 and R2 be hydrogen, Methyl, ethyl, n-propyl, normal-butyl, trifluoromethyl, F, Cl, Br.
3. the preparation method of N- alkylate according to claim 1, it is characterised in that: its reaction step is as follows:
(1) 2:1-1:1 is added in reaction vessel aromatic alcohol in molar ratio with anil, and Ni-MOFs is added, adds Alkali reacts 5-24 hours under 80-150 DEG C of heating condition；
(2) gained reaction solution in step (1) is filtered, with silica gel column purification, petroleum ether eluted product, leacheate elution is removed To get N- alkylate after solvent.
4. the preparation method of N- alkylate according to claim 3, it is characterised in that: the alkali be cesium carbonate, One of potassium carbonate or potassium hydroxide, dosage are 1-1.5 times of aromatic alcohol dosage molar ratio；The leacheate is quality Than the mixture of ethyl acetate and petroleum ether for 1:10.
5. the preparation method of N- alkylate according to claim 3, it is characterised in that: the reaction temperature is temperature 100-120 DEG C of degree；Reaction time is 10-15 hours.
6. the preparation method of N- alkylate according to claim 1, it is characterised in that: the Ni-MOFs is to match Body is that terephthalic acid (TPA), trimesic acid, 2- amino terephthalic acid (TPA), 2,5-Dihydroxyterephthalic acid and nickel salts are formed Crystalline, porous framework material.
7. the preparation method of N- alkylate according to claim 1, it is characterised in that: the use of the Ni-MOFs Amount is the 1%-5% of aromatic alcohol quality.
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Publication number Priority date Publication date Assignee Title
CN111450893A (en) * 2020-04-30 2020-07-28 重庆工商大学 Preparation of palladium-loaded quasi-MOF photocatalyst with special morphology and one-pot multi-step hydrogenation N-alkylation reaction
CN112479894A (en) * 2020-12-02 2021-03-12 江南大学 Method for realizing N-alkylation by using alcohols as carbon source under photocatalysis

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111450893A (en) * 2020-04-30 2020-07-28 重庆工商大学 Preparation of palladium-loaded quasi-MOF photocatalyst with special morphology and one-pot multi-step hydrogenation N-alkylation reaction
CN112479894A (en) * 2020-12-02 2021-03-12 江南大学 Method for realizing N-alkylation by using alcohols as carbon source under photocatalysis
CN112479894B (en) * 2020-12-02 2021-10-29 江南大学 Method for realizing N-alkylation by using alcohols as carbon source under photocatalysis

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