CN106674020A - Method of preparing N-methylamine from amine, formic acid and silane - Google Patents
Method of preparing N-methylamine from amine, formic acid and silane Download PDFInfo
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- CN106674020A CN106674020A CN201611242928.6A CN201611242928A CN106674020A CN 106674020 A CN106674020 A CN 106674020A CN 201611242928 A CN201611242928 A CN 201611242928A CN 106674020 A CN106674020 A CN 106674020A
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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
- C07C209/44—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of carboxylic acids or esters thereof in presence of ammonia or amines, or by reduction of nitriles, carboxylic acid amides, imines or imino-ethers
- C07C209/46—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of carboxylic acids or esters thereof in presence of ammonia or amines, or by reduction of nitriles, carboxylic acid amides, imines or imino-ethers by reduction of carboxylic acids or esters thereof in presence of ammonia or amines
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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
- C07C209/44—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of carboxylic acids or esters thereof in presence of ammonia or amines, or by reduction of nitriles, carboxylic acid amides, imines or imino-ethers
- C07C209/52—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of carboxylic acids or esters thereof in presence of ammonia or amines, or by reduction of nitriles, carboxylic acid amides, imines or imino-ethers by reduction of imines or imino-ethers
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- 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
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
- C07D295/02—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements
- C07D295/027—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements containing only one hetero ring
- C07D295/03—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements containing only one hetero ring with the ring nitrogen atoms directly attached to acyclic carbon atoms
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Abstract
The invention relates to a method of preparing N-methylamine from amine, formic acid and silane. A simple copper salt is taken as a catalyst, formic acid and silane are separately taken as a methylation agent and a reducing agent, ether or methylbenzene is taken as a solvent, the dosage of the catalyst is 5mol%, the reaction temperature is 60-80 DEG C, the reaction time is 2-16h, and the highest separating yield reaches 98%. The method provided by the invention has the advantages that cheap metals are applied to the reaction system for the first time, and the catalyst is easily formed, free of ligand and cheap and easily available, and the experimental process is easy to implement; a renewable resource formic acid is used, so that use of a conventional toxic methylation agent or a lot of formaldehyde is avoided; the primer is wide in application range, and corresponding N-methylated products from primary amine, secondary amine, fatty amine, aromatic amine and imine.
Description
Technical field
The present invention relates to the synthetic method of N- methyl amines, particularly a kind of to prepare N- methyl amines by amine, formic acid and silane
Method.
Background technology
Due to the extensive application in pharmaceutical engineering, pesticide, dyestuff and Material Field, N- methyl amines in bulk chemical and
All occupy critical role in fine chemicals industry.As conventional antiallergic agent diphenhydramine, analgesic aminophenazone are all included
N- methyl structurals.The industrial process of N- methyl amines mainly using classical Eschweiler-Clarke reactions, that is, is adopted
Large excess of formaldehyde is used as raw material；And laboratory is then using highly active methylating reagent (such as dimethyl sulfate and iodomethane
Deng).These methods are because of autoreactivity property, the halogen for inevitably use toxic reagent, the raw material of air-sensitive, producing equivalent
Compound.Therefore, a kind of cheap, efficient, environmental friendliness, easily operated N- methylation methods are developed significant.
Nearly ten years, the green reproducible methylating reagent such as dimethyl carbonate, carbon dioxide, methanol is originated as methyl
Participate in N- methylation reactions and cause broad interest.Although but these methods above have selected from the use of raw material it is nontoxic
Raw material, but the problems such as due to itself chemical property, and noble metal catalyst has inevitably been used, higher reaction temperature
And pressure.For production cost, appointed condition and operating aspect all generate certain impact.Formic acid is wide as a kind of source
General Renewable resource, both can be obtained by the oxidation reaction of biomass；Also can be by the catalytic hydrogenation system of carbon dioxide
It is standby.Formic acid is not only nontoxic, bio-compatible, conveniently storage and transport.And in hydrogen storage material, food additive and prepare energy
The aspects such as product-derived, it all presents extremely excellent performance.Over the past two years, with formic acid as methylating reagent, with amine by also
Original prepares the method for N- methyl amines and has attracted increasing concern.
The reported reaction that N- methyl (alkyl) amine is prepared by amine, formic acid (carboxylic acid), silane at present, according to reduction examination
The difference of agent can be divided into following a few classes：Silane, borine, hydrogen, formic acid are used as reducing agent.Report master with borine as reducing agent
The 1970s and 1980s in last century is concentrated on, the functional group compatibility of such reduction system is poor, therefore substrate type is not wide, joined
See：(a)Gribble,G.W.；Heald,P.W.Synthesis1975,650-652.(b)Marchini,P.；Liso,G.；
Reho,A.；Liberatore,F.；Moracci,F.M.J.Org.Chem.1975,40,3453-3456.(c)Trapani,G.；
Reho,A.；Latrofa,A.Synthesis1983,10,1013-1014.Hydrogen needs certain reaction pressure as reducing agent
Power, the requirement of the pressure performance of safety, equipment to experimental implementation is higher, and equipment cost is high, referring to：I.Sorribes,
J.R.Cabrero-Antonino,C.Vicent,K.Junge and M.Beller,J.Am.Chem.Soc.,2015,137,
13580-13587；Formic acid provides the report one at present only of reducing agent as hydrogen storage material, and the selectivity of product compared with
Difference, referring to：S.Savourey,G.Lefevre,J.-C.Berthet and T.Cantat,Chem.Commun.,2014,50,
14033-14036。
Used as a kind of high-efficiency reducing agent, silane species is various, easy to operate, from being widely used in amine, first over 2014
Sour (carboxylic acid) and silane prepare the reaction of N- methyl (alkyl) amine.Beller seminars are using Pt/dppp catalyst system and catalyzings in benzene silicon
Realize first with amine, formic acid and silane to prepare N- methyl amines under the reduction of alkane, referring to：I.Sorribes,K.Junge
and M.Beller,Chem.Eur.J.,2014,20,7878-7883.Subsequently they are using similar Pt/dppe catalyst system and catalyzings
The reaction that amine, high carboxylic acid and silane prepare N- alkylamines is realized, referring to：I.Sorribes,K.Junge and
M.Beller,J.Am.Chem.Soc.,2014,136,14314-14319.Subsequently, metal Ru, rhodium, iridium catalyst system and catalyzing are also suitable
In the reaction, referring to：M.Minakawa,M.Okubo and M.Kawatsura,Tetrahedron Lett.,2016,57,
4187-4190；T.V.Q.Nguyen,W.-J.Yoo and S.Kobayashi,Adv.Synth.Catal.,2016,358,
452-458；K.G.Andrews,D.M.Summers,L.J.Donnelly and R.M.Denton,Chem.Commun.,
2016,52,1855-1858.Zhu Lei seminars use heterogeneous Pt/C catalyst system and catalyzings, realize amine or imines, formic acid and silane
N- alkylamines are prepared, catalyst is capable of achieving to reclaim 3 times, but catalytic effect has declined, referring to：L.Zhu,L.-S.Wang,
B.Li,W.Li and B.Fu,Catal.Sci.Technol.,2016,6,6172-6176.Fu Yao seminars first will be nonmetallic
The phenyl-pentafluoride borine of catalyst three is applied to the reaction, can smoothly realize that amine, high carboxylic acid and silane prepare N- alkylamines, and this is also
The report of unique non-metallic catalyst so far, referring to：(a)M.-C.Fu,R.Shang,W.-M.Cheng and Y.Fu,
Angew.Chem.Int.Ed.,2015,54,9042-9046；(b)Q.Zhang,M.C.Fu,H.Z.Yu and Y.Fu,
J.Org.Chem.,2016,81,6235-6243。
Being by above formic acid (carboxylic acid) can be with the report for preparing N- methyl (alkyl) amine of carbon source, silane as reducing agent
Find out, existing metal catalyst system has all used noble metal catalyst (platinum, ruthenium, rhodium, iridium) and relatively expensive part；
From the point of view of experimental implementation process, strict anhydrous and oxygen-free environment is also needed mostly, i.e. operating condition is relatively harsh.These are to industry
Production is all unfavorable.Therefore, develop it is a kind of it is cheap, that water oxygen is compatible, being applicable to industrial catalyst system and catalyzing can be with
Production cost is substantially reduced, simplifies experimental implementation, improve preparation efficiency.
Additionally, Chinese patent (CN103073372B) also discloses that the method for synthesizing N- (first) alkylamine by (first) alcohol, urge
Agent is the ionic liquid of sulfonic acid funtionalized, and product yield is 31-95%.
The content of the invention
The purpose of the present invention is that the noble metal used in the method for N- methyl amines is prepared for existing amine, formic acid and silane
A kind of the problems such as catalyst system and catalyzing, relative complex experimental implementation process, there is provided catalyst system and catalyzing of cheap metal.The method using it is cloudy from
Mantoquita containing close element silicon (oxygen, fluorine) in son is catalyst, realizes formic acid and amine reduction under temperate condition and prepares N- methyl
The purpose of amine.Using reproducible raw material, catalyst is cheap and easy to get, experimental implementation is simple, high catalytic efficiency, the substrate scope of application
Extensively.The present invention relates to reaction equation is as follows：
The technical solution used in the present invention is：A kind of method that N- methyl amines are prepared by amine, formic acid and silane, preparation process
It is as follows：
Step one is added to catalyst, solvent, amine, silane and formic acid in reaction vessel, lifts temperature and is reacted；
After step 2 reaction terminates, reaction system is cooled to into room temperature, pillar layer separation is separated and obtains N- methyl amines.
Preferably, catalyst is copper salt catalyst.
Preferably, copper salt catalyst is Cu (OAc)2、Cu(NO3)2·2.5H2O、CuSO4.5H2O、Cu(acac)2、Cu
(OTf)2、CuF2In one kind.
Wherein, it is 40~120 DEG C, preferably 60~80 DEG C that temperature is lifted in step one.
Wherein, the response time is 2~16h in step one.
Preferably, amine is the one kind in primary amine, secondary amine, fatty amine, aromatic amine, imines.
Wherein, when amine is Primary Fatty amine, aromatic amine, the response time is preferably 12-16h in step one, when amine is two
When in level fatty amine, aromatic amine, imines, the response time is preferably 6-8h in step one.
Preferably, catalyst adding proportion is 1~5%.Preferably, the mol ratio of amine, formic acid and silane is 1:1.1~
2.5:2~6.
Wherein, when amine is Primary Fatty amine, aromatic amine, the mol ratio of amine, formic acid and silane is 1：1.5~2.5：3~
6., the one kind in amine is secondary aliphatic amine, aromatic amine, imines, the mol ratio of amine, formic acid and silane is 1：1.1~:1.5:2
~3
Preferably, solvent is the one kind in n-butyl ether, toluene, ether, tetrahydrofuran, DMF, acetonitrile.
Preferably, reaction vessel is round-bottomed flask in step one, and reaction vessel can also be the non-enclosed appearance of other types
Device, because the present invention program under the conditions of harsh anhydrous and oxygen-free without the need for carrying out, in reaction environment and the use model of consersion unit
Place more relaxed.
The present invention has the advantages and positive effects that：
Originated as the methyl for preparing N- methyl amines using formic acid in 1 raw material, formic acid can be by the oxidation reaction of biomass
Obtain, be a kind of Renewable resource of wide material sources, and convenient storage transport, have a clear superiority in terms of commercial production；
2 present invention are applied to amine, formic acid and silane and prepare N- methyl using cheap metal catalyst-copper salt catalyst first
Amine, without the need for part, while keeping in high yield reaction cost can be substantially reduced, and can be applied to commercial production catalyst system and catalyzing
Need；
3 this method can prepare N- methyl amines under conditions of more gently, and reaction temperature is relatively low, is swift in response,
Preparation process is simple, and preparing reaction can be carried out in air atmosphere, and experimental implementation process is safer, it is not necessary to use high withstand voltage
Equipment, greatly reduces equipment cost and maintenance cost in production；
4 wide application range of substrates, it is adaptable to which primary amine, secondary amine, fatty amine, aromatic amine, imines, separation yield is up to
98%.
Specific embodiment
The present invention relates to a kind of method that N- methyl amines are prepared by amine, formic acid and silane, in order to adapt to industrialized needs,
By many experiments and screening, a kind of cheap, water oxygen compatibility, mild condition, easy to operate and preparation method in high yield are researched and developed.
Formic acid both can be obtained as a kind of Renewable resource of wide material sources by the oxidation reaction of biomass；Also can be by titanium dioxide
Prepared by the catalytic hydrogenation of carbon, its wide material sources, stores convenient transportation, can be widely used in commercial production, therefore of the invention
Scheme uses formic acid to participate in reaction as methyl source and prepares N- methyl amines.
Reaction is as follows：
Concrete preparation process is as follows：
Step one is added to catalyst, solvent, amine, silane and formic acid in reaction vessel, mixes post-heating and is warming up to 40
~120 DEG C, react 2-16h；
Step 2 reaction terminates to stop heating, and reaction system is cooled to into room temperature, and in reaction system ethyl acetate is added
5mL and 3mol/L hydrochloric acid 3mL, are stirred at room temperature 3h.After organic faciess are dried, N- methyl amine products are obtained by pillar layer separation,
Calculate separation yield.
Wherein, solvent in reaction system select n-butyl ether, toluene, ether, tetrahydrofuran, DMF,
Any one in acetonitrile；Amine is from any one in primary amine, secondary amine, fatty amine, aromatic amine, imines；By screening,
Silane is PhSiH3。
Wherein template reaction, preparing DMA yield by methylphenylamine can be carried out point by gas chromatogram
Analysis, adds ethyl acetate 5mL and 3mol/L hydrochloric acid 3mL specially in the reaction system after cooling, and 3h is stirred at room temperature, and adds interior
The mark trimethoxy-benzene of thing 1,3,5-, takes organic faciess circulation of qi promoting analysis of hplc, calculated yield.
The present invention program, than the catalytic efficiency of right multiple catalysts, have selected respectively the catalysis of ferrum system in selecting catalyst
Agent, cobalt series catalyst, nickel catalyst, zinc system catalyst and Cu-series catalyst this several cheap metal catalyst, by comparing
Product yield is judging its catalytic effect in the reaction of N- methyl amines is prepared for each catalyst, and specific experiment step is as follows：
1) by 5mol% catalyst, 1mL solvents, 0.5mmol (0.0536g) methylphenylamine, 1.5mmol (0.1623g)
Phenylsilane and 0.75mmol (0.0345g) formic acid, in being added to round-bottomed flask, controlling reaction temperature is 80 DEG C, the response time
12h；
2) reaction is cooled to reaction system after room temperature after terminating, and adds 5mL ethyl acetate and 3mol/L hydrochloric acid 3mL, room
The lower stirring 3h of temperature；
3) trimethoxy-benzene of internal standard substance 1,3,5- is added in reaction system, taking a small amount of organic faciess carries out gas chromatogram point
Analysis, calculated yield.
Impact of the catalyst type of table 1 to N- methyl amine synthetic reactions
Table 1 is impact of all kinds of catalyst to N- methyl amine synthetic reactions, by data as can be seen that Fe-series catalyst,
Cobalt series catalyst, nickel catalyst, zinc system catalyst and part Cu-series catalyst do not have catalysis under this experiment condition and make
With containing the copper salt catalyst of close element silicon (such as oxygen, fluorine), the Cu (OAc) such as in screening test only in anion2、Cu
(NO3)2.2.5H2O、CuSO4.5H2O、Cu(acac)2、Cu(OTf)2And CuF2To N- methyl amines synthetic reaction under this experiment condition
With catalytic effect, wherein Cu (OAc)2、Cu(OTf)2And CuF2Catalytic effect is splendid, yield up to 99%.
Impact of the catalyst amount of embodiment 1 to N- methyl amine synthetic reactions
A kind of method for preparing N- methyl amines by amine, formic acid and silane, catalyst selects catalytic effect preferably Cu
(OAc)2, the yield of the catalyst n-methyl product of addition different proportion is compared, comprise the following steps that：
1) by 1-5mol% catalyst Cu (OAc)2, 1mL n-butyl ethers, 0.5mmol (0.0536g) methylphenylamine,
1.5mmol (0.1623g) phenylsilanes and 0.75mmol (0.0345g) formic acid, in being added to round-bottomed flask, controlling reaction temperature is
80 DEG C, response time 12h；
2) reaction is cooled to reaction system after room temperature after terminating, and 5mL ethyl acetate and 3mol/ are added in reaction system
L hydrochloric acid 3mL, under room temperature 3h is stirred；
3) trimethoxy-benzene of internal standard substance 1,3,5- is added in reaction system, taking a small amount of organic faciess carries out gas chromatogram point
Analysis, calculated yield.
Impact of the catalyst amount of table 2 to N- methyl amine synthetic reactions
By the data in table 2, it can be seen that can obtain N- methyl amines using the catalyst of 1-5% consumptions, wherein,
5% catalyst amount is the consumption the most suitable of the N- methyl amine synthetic reactions.
Impact of the silane species of embodiment 2 to N- methyl amine synthetic reactions
A kind of method for preparing N- methyl amines by amine, formic acid and silane, silane is used as the reducing agent in reaction system, as
A kind of high-efficiency reducing agent, silane species is various, easy to operate.PMHS, Et have now been selected respectively3SiH、(EtO)2MeSiH、
(EtO)3SiH、Ph2SiH2And PhSiH3(phenylsilane) participates in reaction, comprises the following steps that：
1) by 5mol% catalyst Cu (OTf)2, 1mL n-butyl ethers, 0.5mmol (0.0536g) methylphenylamine, 1.5mmol
Silane and 0.75mmol (0.0345g) formic acid, in being added to round-bottomed flask, controlling reaction temperature is 80 DEG C, response time 12h；
2) reaction system is cooled to room temperature by reaction after terminating, and 5mL ethyl acetate and 3mol/L are added in reaction system
3h is stirred under hydrochloric acid 3mL, room temperature；
3) trimethoxy-benzene of internal standard substance 1,3,5- is added in reaction system, taking a small amount of organic faciess carries out gas chromatogram point
Analysis, calculated yield.
Impact of the silane species of table 3 to N- methyl amine synthetic reactions
By the data of table 3, it can be seen that using PhSiH3This silane can obtain higher receipts in the inventive method system
The N- methyl amines of rate, wherein PhSiH3For phenylsilane.
Impact of the solvent species of embodiment 3 to N- methyl amine synthetic reactions
A kind of method that N- methyl amines are prepared by amine, formic acid and silane, respectively than right n-butyl ether, toluene, ether, Isosorbide-5-Nitrae-
Dioxane, tetrahydrofuran, DMF and acetonitrile participate in reacting as solvent, comprise the following steps that：
1) by 5mol% catalyst CuF2, 1mL solvents, 0.5mmol (0.0536g) methylphenylamine, 1.5mmol
(0.1623g) phenylsilane and 0.75mmol (0.0345g) formic acid, in being added to round-bottomed flask, controlling reaction temperature is 80 DEG C, instead
12h between seasonable；
2) reaction system is cooled to room temperature by reaction after terminating, and 5mL ethyl acetate and 3mol/L are added in reaction system
3h is stirred under hydrochloric acid 3mL, room temperature；
3) trimethoxy-benzene of internal standard substance 1,3,5- is added in reaction system, taking a small amount of organic faciess carries out gas chromatogram point
Analysis, calculated yield.
Impact of the solvent species of table 4 to N- methyl amine synthetic reactions
Drawn by data in table 4, above-mentioned all kinds of solvents are applied to the present invention program, and wherein toluene and ether solvent are to this
N- methyl amine synthetic reactions have preferable effect.
Impact of the species of the amine of embodiment 4 to N- methyl amine synthetic reactions
A kind of method for preparing N- methyl amines by amine, formic acid and silane, chooses respectively different types of secondary aliphatic amine, virtue
Fragrant amine, imines participate in synthetic reaction as raw material, comprise the following steps that：
1) by 5mol% catalyst Cu (OAc)2, 1mL toluene, 0.5mmol amine, 1.5mmol (0.1623g) phenylsilanes and
0.75mmol (0.0345g) formic acid, in being added to round-bottomed flask, controlling reaction temperature is 80 DEG C, response time 8h；
2) reaction terminate stop heating, reaction system is cooled to into room temperature, in reaction system add ethyl acetate 5mL and
3mol/L hydrochloric acid 3mL, are stirred at room temperature 3h.After organic faciess are dried, N- methyl amine products are obtained by pillar layer separation, calculate and divide
From yield.
Impact of the species of the amine of table 5 to N- methyl amine synthetic reactions
Can be seen that according to data analysiss in table 5, the N- methyl amines synthetic method is for secondary aliphatic amine, aromatic amine, imines
It is respectively provided with the preferable suitability and functional group compatibility.
Impact of the species of the amine of embodiment 5 to N- methyl amine synthetic reactions
A kind of method for preparing N- methyl amines by amine, formic acid and silane, chooses respectively different types of primary amine as original
Material participates in synthetic reaction, comprises the following steps that：
1) by 5mol% catalyst Cu (OAc)2, 1mL toluene, 0.2mmol primary amines, 1.0mmol phenylsilanes and 0.5mmol
Formic acid, in being added to round-bottomed flask, controlling reaction temperature is 80 DEG C, response time 16h；
2) reaction terminate stop heating, reaction system is cooled to into room temperature, in reaction system add ethyl acetate 5mL and
3mol/L hydrochloric acid 3mL, are stirred at room temperature 3h.After organic faciess are dried, N- methyl amine products are obtained by pillar layer separation, calculate and divide
From yield.
Impact of the species of the amine of table 6 to N- methyl amine synthetic reactions
Can be seen that according to data analysiss in table 6, by adjusting reagent dosage and response time, the N- methyl amine synthetic methods
It is equally applicable to Primary Fatty amine and aromatic amine；The experiment content of integrated embodiment 5 and embodiment 6 is, it can be seen that present invention side
The reaction scheme that method is related to can be applied to the amine of most classifications, can be widely used in commercial production, meet various industry
The needs of production.
Impact of the reaction temperature of embodiment 6 to N- methyl amine synthetic reactions
A kind of method that N- methyl amines are prepared by amine, formic acid and silane, reaction temperature choose respectively 40 DEG C, 60 DEG C, 70 DEG C,
75 DEG C, 80 DEG C and 120 DEG C, comprise the following steps that：
1) by 5mol% catalyst Cu (OTf)2, 1mL toluene, 0.5mmol (0.0536g) methylphenylamine, 1.5mmol
(0.1623g) phenylsilane and 0.75mmol (0.0345g) formic acid, in being added to round-bottomed flask, controlling reaction temperature, the response time
12h；
2) reaction system is cooled to room temperature by reaction after terminating, and 5mL ethyl acetate and 3mol/L are added in reaction system
3h is stirred under hydrochloric acid 3mL, room temperature；
3) trimethoxy-benzene of internal standard substance 1,3,5- is added in reaction system, taking a small amount of organic faciess carries out gas chromatogram point
Analysis, calculated yield.
Impact of the reaction temperature of table 7 to N- methyl amine synthetic reactions
The N- methyl amines synthetic method equal energy in 40-120 DEG C of temperature range is can be seen that according to data analysiss in table 7
N- methyl amine products are accessed, the of a relatively high N- methyl amine products of yield are especially obtained in that in 60-80 DEG C of temperature range,
Such reaction temperature is comparatively gentle, and reaction can not only be reduced during industrialization large-scale production is applied to will
Ask, improve the safety of reaction, additionally it is possible to reaction cost is reduced in terms of the energy.
Catalytic efficiency of the different catalysts in N- methyl amine synthetic reactions under the cryogenic conditions of embodiment 7
A kind of method for preparing N- methyl amines by amine, formic acid and silane, chooses Cu (OAc)2、Cu(OTf)2And CuF2As
Catalyst participates in reaction in the reaction condition that reaction temperature is 60 DEG C, and compares its catalytic efficiency by N- methyl amine yields,
Comprise the following steps that：
1) by 5mol% catalyst, 1mL n-butyl ethers, 0.5mmol (0.0536g) methylphenylamine, 1.5mmol
(0.1623g) phenylsilane and 0.75mmol (0.0345g) formic acid, in being added to round-bottomed flask, controlling reaction temperature, the response time
12h；
2) reaction is cooled to reaction system after room temperature after terminating, and 5mL ethyl acetate and 3mol/ are added in reaction system
L hydrochloric acid 3mL, under room temperature 3h is stirred；
3) trimethoxy-benzene of internal standard substance 1,3,5- is added in reaction system, taking a small amount of organic faciess carries out gas chromatogram point
Analysis, calculated yield.
Catalytic efficiency of the catalyst to N- methyl amine synthetic reactions under 8 60 DEG C of reaction temperatures of table
Even if can be seen that the copper catalyst under relatively low reaction temperature by the data of table 8 can still keep higher urging
Change efficiency.
Impact of the response time of embodiment 8 to N- methyl amine synthetic reactions
A kind of method for preparing N- methyl amines by amine, formic acid and silane, reacts respectively 2h, 4h, 6h, 8h, 12h and 16h, tool
Body step is as follows：
1) by 5mol% catalyst CuF2, 1mL n-butyl ethers, 0.5mmol (0.0536g) methylphenylamine, 1.5mmol
(0.1623g) phenylsilane and 0.75mmol (0.0345g) formic acid, in being added to round-bottomed flask, controlling reaction temperature, the response time
12h；
2) reaction system is cooled to room temperature by reaction after terminating, and 5mL ethyl acetate and 3mol/L are added in reaction system
3h is stirred under hydrochloric acid 3mL, room temperature；
3) trimethoxy-benzene of internal standard substance 1,3,5- is added in reaction system, taking a small amount of organic faciess carries out gas chromatogram point
Analysis, calculated yield.
Impact of the response time of table 9 to N- methyl amine synthetic reactions
Data analysiss can be seen that for secondary amine as raw material by above experimental result, the N- methyl amine synthetic methods
Preferred reaction time be 6-8h, this synthetic method only needs to the short period under lower temperature conditions and is just obtained in that 99%
Yield.
Impact of each material mol ratio to N- methyl amine synthetic reactions in the reaction system of embodiment 9
A kind of method for preparing N- methyl amines by amine, formic acid and silane, the mol ratio of the amine, formic acid and silane of addition is 1：
1.1-1.5：2-3, wherein amine are secondary amine, are comprised the following steps that：
1) by 5mol% catalyst Cu (OTf)2, 1mL n-butyl ethers, 0.5mmol (0.0536g) methylphenylamine phenylsilanes and
The concrete consumption of formic acid is shown in Table 10, in being added to round-bottomed flask, controlling reaction temperature, and response time 8h；
2) reaction system is cooled to room temperature by reaction after terminating, and 5mL ethyl acetate and 3mol/L are added in reaction system
3h is stirred under hydrochloric acid 3mL, room temperature；
3) trimethoxy-benzene of internal standard substance 1,3,5- is added in reaction system, taking a small amount of organic faciess carries out gas chromatogram point
Analysis, calculated yield.
The impact of the formic acid of table 10 and silane dosage to N- methyl amine synthetic reactions
Data analysiss can be seen that when with secondary amine as raw material by above experimental result, the use of mol ratio be 1.1-1.5：
The formic acid and silane of 2-3 are obtained in that synthetic product in high yield.
Impact of each material mol ratio to N- methyl amine synthetic reactions in the reaction system of embodiment 10
It is a kind of that the method for N- methyl amines is prepared by amine, formic acid and silane, wherein the mol ratio of the amine for adding, formic acid and silane
For 1：1.5~2.5：3~6, wherein amine is primary amine, is comprised the following steps that：
1) by 5mol% catalyst Cu (OTf)2, 1mL n-butyl ethers, 0.2mmol (0.0186g) aniline, silane and formic acid adds
Enter in reaction vessel, the concrete consumption of wherein phenylsilane and formic acid is shown in Table 11, controlling reaction temperature, response time 16h；
2) reaction system is cooled to room temperature by reaction after terminating, and 5mL ethyl acetate and 3mol/L are added in reaction system
3h is stirred under hydrochloric acid 3mL, room temperature；
3) trimethoxy-benzene of internal standard substance 1,3,5- is added in reaction system, taking a small amount of organic faciess carries out gas chromatogram point
Analysis, calculated yield.
The impact of the formic acid of table 11 and silane dosage to N- methyl amine synthetic reactions
Data analysiss can be seen that when with primary amine as raw material by above experimental result, the N- methyl amine synthetic methods
The formic acid of middle addition and the mol ratio of silane are 1.5~2.5：Higher N- methyl amine yields are obtained in that when 3~6.
Several embodiments of the present invention have been described in detail above, but the content is only the preferable enforcement of the present invention
Example, it is impossible to be considered as the practical range for limiting the present invention.All impartial changes made according to the present patent application scope and improvement
Deng, all should still belong to the present invention patent covering scope within.
Claims (10)
1. a kind of method that N- methyl amines are prepared by amine, formic acid and silane, it is characterised in that：Preparation process is as follows：
Step one is added to catalyst, solvent, amine, silane and formic acid in reaction vessel, lifts temperature and is reacted；
After step 2 reaction terminates, reaction system is cooled to into room temperature, pillar layer separation is separated and obtains N- methyl amines.
2. a kind of method that N- methyl amines are prepared by amine, formic acid and silane according to claim 1, it is characterised in that：Institute
Catalyst is stated for copper salt catalyst.
3. a kind of method that N- methyl amines are prepared by amine, formic acid and silane according to claim 2, it is characterised in that：Institute
Copper salt catalyst is stated for Cu (OAc)2、Cu(NO3)2.2.5H2O、CuSO4.5H2O、Cu(acac)2、Cu(OTf)2、CuF2In one
Kind.
4. according to arbitrary a kind of described method for preparing N- methyl amines by amine, formic acid and silane, its feature in claim 1-3
It is：The amine is the one kind in primary amine, secondary amine, fatty amine, aromatic amine, imines.
5. according to arbitrary a kind of described method for preparing N- methyl amines by amine, formic acid and silane, its feature in claim 1-3
It is：It is 40~120 DEG C, preferably 60~80 DEG C that temperature is lifted in the step one.
6. according to arbitrary a kind of described method for preparing N- methyl amines by amine, formic acid and silane, its feature in claim 1-3
It is：The response time is 2~16h in the step one.
7. according to arbitrary a kind of described method for preparing N- methyl amines by amine, formic acid and silane, its feature in claim 1-3
It is：Catalyst adding proportion is 1~5%.
8. according to arbitrary a kind of described method for preparing N- methyl amines by amine, formic acid and silane, its feature in claim 1-3
It is：The mol ratio of amine, formic acid and silane is 1：1.1~2.5：2~6.
9. according to arbitrary a kind of described method for preparing N- methyl amines by amine, formic acid and silane, its feature in claim 1-3
It is：The solvent is in n-butyl ether, toluene, ether, tetrahydrofuran, 1,4- dioxane, N,N-dimethylformamide, acetonitrile
One kind.
10. a kind of method that N- methyl amines are prepared by amine, formic acid and silane according to claim 1, it is characterised in that：Step
Reaction vessel described in rapid one is round-bottomed flask.
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