CN104496828A - N,N-dialkylaniline self-assembly synthesis method for 4, 4'-diamino diphenyl methane derivative - Google Patents
N,N-dialkylaniline self-assembly synthesis method for 4, 4'-diamino diphenyl methane derivative Download PDFInfo
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Abstract
The invention discloses an N,N-dialkylaniline self-assembly synthesis method for 4, 4'-diamino diphenyl methane derivative and belongs to the organic chemical synthesis technology field. The method is as follows: taking the N,N-dialkylaniline as the raw material, taking the ferric trichloride hexahydrate or anhydrous ferric chloride as the oxidizing agent, taking the alkali as the additive, in the solvent, further oxidizing, concentrating, purifying for preparing the 4, 4'-diamino diphenyl methane derivative. The method has certain universality, the reaction condition is moderate, the requirement to the production device is low, the technology is simple and the raw material can be easily obtained and the reaction time is short; the 4, 4'-diamino diphenyl methane derivative prepared by the method are high in yield and quality; the method can be widely used for the industrial production for the 4, 4'-diamino diphenyl methane derivative; the product prepared by the method can be widely used for producing the curing agent, chain extender, antioxygen, active agent, adhesive and the vulcanizing agent, and the product can be used as the detection agent for tungsten and the application prospect is good.
Description
Technical field
The invention belongs to organic chemical synthesis technical field, be specifically related to a kind of N, N-dialkyl aniline self assembly 4, the method for 4 '-diaminodiphenylmethane derivative.
Background technology
4,4 '-diaminodiphenylmethane derivative is the important organic synthesis intermediate of a class, mainly for the production of the oxidation inhibitor etc. of the solidifying agent of polyisocyanates compounds, epoxy resin, the chainextender of polyurethane elastomer and rubber.Meanwhile, 4,4 '-diaminodiphenylmethane derivative is also important fine chemical product, can be used as the detection reagent of tungsten.
Existing 4, the synthetic method of 4 '-diaminodiphenylmethane and derivative thereof is numerous, realizes usually through N, N-dialkyl aniline and formaldehyde condensation, diphenylmethane diamine and dimethyl carbonate.As " a kind of heterogeneous synthesis 4; method of 4 '-tetramethyl-diaminodiphenylmethane " patent that number of patent application is 200810054844.9, disclosed in be under a nitrogen atmosphere with diphenylmethane diamine and methylcarbonate for raw material, zeolite molecular sieve is catalyzer, and control temperature is at 160 ~ 220 DEG C, and under high pressure, reaction prepares 4 in 4 ~ 8 hours, 4 '-(N, N, N ', N '-tetramethyl-) diaminodiphenylmethane.Mainly there is following deficiency in the method:
(1) diphenylmethane diamine and methylcarbonate is adopted to be Material synthesis 4 in aforesaid method, 4 '-(N, N, N ', N '-tetramethyl-) diaminodiphenylmethane, use 4 of the method synthesis, 4 '-diaminodiphenylmethane derivant structure is abundant not, is of limited application.
(2) aforesaid method needs temperature of reaction controlled at 160 ~ 220 DEG C under a nitrogen atmosphere and under high pressure react, and reaction conditions is harsher, requires higher, substantially increase industrial production cost to conversion unit.
(3) in aforesaid method, reaction need continue 4 ~ 8 hours, and the production cycle is longer, thus adds the time cost of production.
Summary of the invention
The object of the invention is for existing 4, the weak point of 4 '-diaminodiphenylmethane derivative synthesizing process, provide a kind of 4, the synthetic method of 4 '-diaminodiphenylmethane derivative.Present method has certain universality, for the productive rate that alkyl various on nitrogen-atoms replaces and on phenyl ring, the aniline of halogen substiuted can obtain; Present method reaction conditions is gentle, requires low to production unit, and technique is simple, and preparation feedback production safety, easily operates, and raw material is easy to get, and the reaction times is short, and efficiency is higher, purifies simple, is conducive to suitability for industrialized production.
The technical scheme realizing the object of the invention is: a kind of N, the self assembly 4 of N-dialkyl aniline, the method of 4 '-diaminodiphenylmethane derivative, with the N of formula (I), N-dialkyl aniline for raw material, Iron(III) chloride hexahydrate or FERRIC CHLORIDE ANHYDROUS are oxygenant, alkali is additive, in a solvent, 4 of formula (II) is prepared, 4 '-diaminodiphenylmethane derivative through oxidation step, simple process that is concentrated, that purify.Its concrete grammar step is as follows:
(1) oxidizing reaction is carried out
With various N, N-dialkyl aniline is raw material, Iron(III) chloride hexahydrate or FERRIC CHLORIDE ANHYDROUS are oxygenant, alkali is additive, in a solvent, according to N, N-dialkyl aniline mmole: Iron(III) chloride hexahydrate or FERRIC CHLORIDE ANHYDROUS mmole: alkali mmole: the ratio of solvent milliliter is 0.4: (0.4 ~ 1.2): (0.2 ~ 0.6): the ratio of 2, first add N in the reactor, N-dialkyl aniline and solvent, under stirring, add alkali again, finally add Iron(III) chloride hexahydrate or FERRIC CHLORIDE ANHYDROUS, after reinforced complete, oil bath temperature rises to 85 ~ 120 DEG C of open circuits, Keep agitation carries out oxidizing reaction 2.5 ~ 4.5 hours, just prepare 4, the reaction solution of 4 '-diaminodiphenylmethane derivative.
Described alkali is salt of wormwood, N, one in N-diisopropylethylamine, sodium hydroxide, phenanthroline, triethylamine, solvent is the one in methylene dichloride, trichloromethane, methyl alcohol, water, ethyl acetate, toluene, triethylamine, methyl-sulphoxide, DMF.
(2) carry out that product is concentrated, purifying
After (1) step completes, to the reaction solution of 4,4 '-diaminodiphenylmethane derivative that (1) step is prepared, add excessive ammonia, stir 5 minutes.With dichloromethane extraction, TLC detects until without product in extraction liquid, merge organic phase, organic phase anhydrous magnesium sulfate drying, filters, by rotary evaporation concentrated filtrate, collect concentrated solution, concentrated solution, through purification by silica gel column chromatography, carries out wash-out with elutriant, concentrates, drains to obtain product to the effluent liquid of silica gel column chromatography through rotary evaporation.
Described elutriant is ethyl acetate: the ratio of sherwood oil is 1: the mixed solution of (70 ~ 100).
R in formula (I), (II)
1for methyl, R
2can be hydrogen or alkyl, R
3for halogen.
After the present invention adopts technique scheme, mainly contain following effect:
(1) N, N-dialkyl aniline is easily obtained by corresponding aniline, and raw material sources are extensive, and be easy to obtain various 4,4 '-diaminodiphenylmethane derivative, can meet the demand to 4,4 '-diaminodiphenylmethane specific diversity.
(2) N, N-dialkyl aniline self assembly 4,4 '-diaminodiphenylmethane, provides methylene radical without the need to additionally adding formaldehyde material etc.
(3) oxygenant Iron(III) chloride hexahydrate or FERRIC CHLORIDE ANHYDROUS are cheaply easy to get, and production cost is low, easy to utilize.
(4) reaction conditions is gentle, and synthetic operation is easy, without the need to anhydrous and oxygen-free and condition of high voltage, with low cost.
(5) reaction times is short, and feed stock conversion is higher, is convenient to suitability for industrialized production.
The inventive method can be widely used in 4, the suitability for industrialized production of 4 '-diaminodiphenylmethane derivative.The product adopting the inventive method to prepare can be widely used as solidifying agent, chainextender, oxidation inhibitor, promoting agent, sizing agent, vulcanizing agent etc., and also can be used as the detection reagent of tungsten, market application foreground is good.
Embodiment
Below in conjunction with embodiment, further illustrate the present invention.
Embodiment 1
A kind of N, N-dialkyl aniline self assembly 4, the method for 4 '-diaminodiphenylmethane derivative, its concrete steps are as follows:
(1) with N, accelerine is raw material, Iron(III) chloride hexahydrate is oxygenant, triethylamine is additive, in toluene solvant, according to N, accelerine mmole: Iron(III) chloride hexahydrate mmole: triethylamine mmole: the ratio of toluene milliliter is the ratio of 0.4: 1.0: 0.4: 2, first add N in the reactor, accelerine (48.5mg, 0.4mmol) with toluene (2mL), under stirring, add triethylamine (55.4 μ L again, 0.4mmol), finally add Iron(III) chloride hexahydrate (270.3mg, 1.0mmol), after reinforced complete, oil bath temperature rises to 85 DEG C, Keep agitation carries out oxidizing reaction 3.5 hours, just prepare 4, 4 '-(N, N, N ', N '-tetramethyl-) reaction solution of diaminodiphenylmethane.
After (2) (1) steps complete, to (1) step is prepared 4, 4 '-(N, N, N ', N '-tetramethyl-) reaction solution of diaminodiphenylmethane, add excessive ammonia, stir 5 minutes with dichloromethane extraction, TLC detects until without product in extraction liquid, merge organic phase, organic phase anhydrous magnesium sulfate drying, filter, by rotary evaporation concentrated filtrate, collect concentrated solution, concentrated solution is through purification by silica gel column chromatography, wash-out is carried out with elutriant, the effluent liquid of silica gel column chromatography is concentrated through rotary evaporation, drain to obtain faint yellow solid 4, 4 '-(N, N, N ', N '-tetramethyl-) diaminodiphenylmethane (29.8mg, yield 88%).
Described elutriant is ethyl acetate: the ratio of sherwood oil is 1: the mixed solution of (70 ~ 100).
Embodiment 2
A kind of N, N-dialkyl aniline self assembly 4, the method for 4 '-diaminodiphenylmethane derivative, its concrete steps with embodiment 1, wherein:
In step (1), with N, accelerine is raw material, Iron(III) chloride hexahydrate is oxygenant, triethylamine is additive, in toluene solvant, according to N, accelerine mmole: Iron(III) chloride hexahydrate mmole: triethylamine mmole: the ratio of toluene milliliter is the ratio of 0.4: 1.0: 0.4: 2, first add N in the reactor, accelerine (48.5mg, 0.4mmol) with toluene (2mL), under stirring, add triethylamine (55.4 μ L again, 0.4mmol), finally add Iron(III) chloride hexahydrate (270.3mg, 1.0mmol), after reinforced complete, oil bath temperature rises to 100 DEG C, Keep agitation carries out oxidizing reaction 3.5 hours, just prepare 4, 4 '-(N, N, N ', N '-tetramethyl-) reaction solution of diaminodiphenylmethane.
In step (2), elutriant is ethyl acetate: the ratio of sherwood oil is 1: the mixed solution of (70 ~ 100), obtains faint yellow solid 4,4 '-(N, N, N ', N '-tetramethyl-) diaminodiphenylmethane (29.4mg, yield 87%).
Embodiment 3
A kind of N, N-dialkyl aniline self assembly 4, the method for 4 '-diaminodiphenylmethane derivative, its concrete steps with embodiment 1, wherein:
In step (1), with N, N trimethylaniline is raw material, Iron(III) chloride hexahydrate is oxygenant, triethylamine is additive, in toluene solvant, according to N, accelerine mmole: Iron(III) chloride hexahydrate mmole: triethylamine mmole: the ratio of toluene milliliter is the ratio of 0.4: 1.0: 0.4: 2, first add N in the reactor, accelerine (48.5mg, 0.4mmol) with toluene (2mL), under stirring, add triethylamine (55.4 μ L again, 0.4mmol), finally add Iron(III) chloride hexahydrate (270.3mg, 1.0mmol), after reinforced complete, oil bath temperature rises to 120 DEG C, Keep agitation carries out oxidizing reaction 3.5 hours, just prepare 4, 4 '-(N, N, N ', N '-tetramethyl-) reaction solution of diaminodiphenylmethane.
In step (2), elutriant is ethyl acetate: the ratio of sherwood oil is 1: the mixed solution of (70 ~ 100), obtains faint yellow solid 4,4 '-(N, N, N ', N '-tetramethyl-) diaminodiphenylmethane (17.6mg, yield 52%).
Embodiment 4
A kind of N, N-dialkyl aniline self assembly 4, the method for 4 '-diaminodiphenylmethane derivative, its concrete steps with embodiment 1, wherein:
In step (1), with N, accelerine is raw material, Iron(III) chloride hexahydrate is oxygenant, N, N-diisopropylethylamine is additive, in toluene solvant, according to N, accelerine mmole: Iron(III) chloride hexahydrate mmole: N, N-diisopropylethylamine mmole: the ratio of toluene milliliter is the ratio of 0.4: 1.0: 0.4: 2, first add N in the reactor, accelerine (48.5mg, 0.4mmol) with toluene (2mL), under stirring, add N again, N-diisopropylethylamine (69.7 μ L, 0.4mmol), finally add Iron(III) chloride hexahydrate (270.3mg, 1.0mmol), after reinforced complete, oil bath temperature rises to 85 DEG C, Keep agitation carries out oxidizing reaction 3.5 hours, just prepare 4, 4 '-(N, N, N ', N '-tetramethyl-) reaction solution of diaminodiphenylmethane.
In step (2), elutriant is ethyl acetate: the ratio of sherwood oil is 1: the mixed solution of (70 ~ 100), obtains faint yellow solid 4,4 '-(N, N, N ', N '-tetramethyl-) diaminodiphenylmethane (25.7mg, yield 76%).
Embodiment 5
A kind of N, N-dialkyl aniline self assembly 4, the method for 4 '-diaminodiphenylmethane derivative, its concrete steps with embodiment 1, wherein:
In step (1), with N, accelerine is raw material, Iron(III) chloride hexahydrate is oxygenant, triethylamine is additive, in toluene solvant, according to N, accelerine mmole: Iron(III) chloride hexahydrate mmole: triethylamine mmole: the ratio of toluene milliliter is the ratio of 0.4: 1.0: 0.4: 2, first add N in the reactor, accelerine (48.5mg, 0.4mmol) with toluene (2mL), under stirring, add triethylamine (55.4 μ L again, 0.4mmol), finally add Iron(III) chloride hexahydrate (270.3mg, 1.0mmol), after reinforced complete, oil bath temperature rises to 85 DEG C, Keep agitation carries out oxidizing reaction 4.5 hours, just prepare 4, 4 '-(N, N, N ', N '-tetramethyl-) reaction solution of diaminodiphenylmethane.
In step (2), elutriant is ethyl acetate: the ratio of sherwood oil is 1: the mixed solution of (70 ~ 100), obtains faint yellow solid 4,4 '-(N, N, N ', N '-tetramethyl-) diaminodiphenylmethane (26.1mg, yield 77%).
Embodiment 6
A kind of N, N-dialkyl aniline self assembly 4, the method for 4 '-diaminodiphenylmethane derivative, its concrete steps with embodiment 1, wherein:
In step (1), with N, accelerine is raw material, Iron(III) chloride hexahydrate is oxygenant, triethylamine is additive, in toluene solvant, according to N, accelerine mmole: Iron(III) chloride hexahydrate mmole: triethylamine mmole: the ratio of toluene milliliter is the ratio of 0.4: 1.2: 0.4: 2, first add N in the reactor, accelerine (48.5mg, 0.4mmol) with toluene (2mL), under stirring, add triethylamine (55.4 μ L again, 0.4mmol), finally add Iron(III) chloride hexahydrate (324.4mg, 1.2mmol), after reinforced complete, oil bath temperature rises to 85 DEG C, Keep agitation carries out oxidizing reaction 3.5 hours, just prepare 4, 4 '-(N, N, N ', N '-tetramethyl-) reaction solution of diaminodiphenylmethane.
In step (2), elutriant is ethyl acetate: the ratio of sherwood oil is 1: the mixed solution of (70 ~ 100), obtains faint yellow solid 4,4 '-(N, N, N ', N '-tetramethyl-) diaminodiphenylmethane (25.7mg, yield 76%).
Embodiment 7
A kind of N, N-dialkyl aniline self assembly 4, the method for 4 '-diaminodiphenylmethane derivative, its concrete steps with embodiment 1, wherein:
In step (1), take methylphenylamine as raw material, Iron(III) chloride hexahydrate is oxygenant, triethylamine is additive, in toluene solvant, according to methylphenylamine mmole: Iron(III) chloride hexahydrate mmole: triethylamine mmole: the ratio of toluene milliliter is the ratio of 0.4: 1.0: 0.4: 2, first add methylphenylamine (42.9mg in the reactor, 0.4mmol) with toluene (2mL), under stirring, add triethylamine (55.4 μ L again, 0.4mmol), finally add Iron(III) chloride hexahydrate (270.3mg, 1.0mmol), after reinforced complete, oil bath temperature rises to 85 DEG C, Keep agitation carries out oxidizing reaction 3.5 hours, just prepare 4, 4 '-(N, N '-dimethyl) reaction solution of diaminodiphenylmethane.
In step (2), elutriant is ethyl acetate: the ratio of sherwood oil is 1: the mixed solution of (70 ~ 100), obtains faint yellow solid 4,4 '-(N, N '-dimethyl) diaminodiphenylmethane (15.1mg, yield 50%).
Embodiment 8
A kind of N, N-dialkyl aniline self assembly 4, the method for 4 '-diaminodiphenylmethane derivative, its concrete steps with embodiment 1, wherein:
In step (1), with N-ethyl-N-methylaniline for raw material, Iron(III) chloride hexahydrate is oxygenant, triethylamine is additive, in toluene solvant, according to N-ethyl-N-methylaniline mmole: Iron(III) chloride hexahydrate mmole: triethylamine mmole: the ratio of toluene milliliter is the ratio of 0.4: 1.0: 0.4: 2, first add N-ethyl-N-methylaniline (54.1mg in the reactor, 0.4mmol) with toluene (2mL), under stirring, add triethylamine (55.4 μ L again, 0.4mmol), finally add Iron(III) chloride hexahydrate (270.3mg, 1.0mmol), after reinforced complete, oil bath temperature rises to 85 DEG C, Keep agitation carries out oxidizing reaction 3.5 hours, just prepare 4, 4 '-(N, N '-diethyl-N, N '-dimethyl) reaction solution of diaminodiphenylmethane.
In step (2), elutriant is ethyl acetate: the ratio of sherwood oil is 1: the mixed solution of (70 ~ 100), obtains faint yellow solid 4,4 '-(N, N '-diethyl-N, N '-dimethyl) diaminodiphenylmethane (11.7mg, yield 31%).
Embodiment 9
A kind of N, N-dialkyl aniline self assembly 4, the method for 4 '-diaminodiphenylmethane derivative, its concrete steps with embodiment 1, wherein:
In step (1), with the chloro-N of 3-, accelerine is raw material, Iron(III) chloride hexahydrate is oxygenant, triethylamine is additive, in toluene solvant, according to the chloro-N of 3-, accelerine mmole: Iron(III) chloride hexahydrate mmole: triethylamine mmole: the ratio of toluene milliliter is the ratio of 0.4: 1.0: 0.4: 2, first add the chloro-N of 3-in the reactor, accelerine (62.2mg, 0.4mmol) with toluene (2mL), under stirring, add triethylamine (55.4 μ L again, 0.4mmol), finally add Iron(III) chloride hexahydrate (270.3mg, 1.0mmol), after reinforced complete, oil bath temperature rises to 85 DEG C, Keep agitation carries out oxidizing reaction 3.5 hours, just prepare 3, 3 '-two chloro-4, 4 '-(N, N, N ', N '-tetramethyl-) reaction solution of diaminodiphenylmethane.
In step (2), elutriant is ethyl acetate: the ratio of sherwood oil is 1: the mixed solution of (70 ~ 100), obtain faint yellow solid 3,3 '-two chloro-4,4 '-(N, N, N ', N '-tetramethyl-) diaminodiphenylmethane (18.1mg, yield 42%).
Embodiment 10
A kind of N, N-dialkyl aniline self assembly 4, the method for 4 '-diaminodiphenylmethane derivative, its concrete steps with embodiment 1, wherein:
In step (1), with the bromo-N of 3-, accelerine is raw material, Iron(III) chloride hexahydrate is oxygenant, triethylamine is additive, in toluene solvant, according to the bromo-N of 3-, accelerine mmole: Iron(III) chloride hexahydrate mmole: triethylamine mmole: the ratio of toluene milliliter is the ratio of 0.4: 1.0: 0.4: 2, first add the bromo-N of 3-in the reactor, accelerine (80.0mg, 0.4mmol) with toluene (2mL), under stirring, add triethylamine (55.4 μ L again, 0.4mmol), finally add Iron(III) chloride hexahydrate (270.3mg, 1.0mmol), after reinforced complete, oil bath temperature rises to 85 DEG C, Keep agitation carries out oxidizing reaction 3.5 hours, just prepare 3, 3 '-two bromo-4, 4 '-(N, N, N ', N '-tetramethyl-) reaction solution of diaminodiphenylmethane.
In step (2), elutriant is ethyl acetate: the ratio of sherwood oil is 1: the mixed solution of (70 ~ 100), obtain faint yellow solid 3,3 '-two bromo-4,4 '-(N, N, N ', N '-tetramethyl-) diaminodiphenylmethane (16.5mg, yield 30%).
Embodiment 11
A kind of N, N-dialkyl aniline self assembly 4, the method for 4 '-diaminodiphenylmethane derivative, its concrete steps with embodiment 1, wherein:
In step (1), with the iodo-N of 3-, accelerine is raw material, Iron(III) chloride hexahydrate is oxygenant, triethylamine is additive, in toluene solvant, according to the iodo-N of 3-, accelerine mmole: Iron(III) chloride hexahydrate mmole: triethylamine mmole: the ratio of toluene milliliter is the ratio of 0.4: 1.0: 0.4: 2, first add the iodo-N of 3-in the reactor, accelerine (98.8mg, 0.4mmol) with toluene (2mL), under stirring, add triethylamine (55.4 μ L again, 0.4mmol), finally add Iron(III) chloride hexahydrate (270.3mg, 1.0mmol), after reinforced complete, oil bath temperature rises to 85 DEG C, Keep agitation carries out oxidizing reaction 3.5 hours, just prepare 3, 3 '-two iodo-4, 4 '-(N, N, N ', N '-tetramethyl-) reaction solution of diaminodiphenylmethane.
In step (2), elutriant is ethyl acetate: the ratio of sherwood oil is 1: the mixed solution of (70 ~ 100), obtain faint yellow solid 3,3 '-two iodo-4,4 '-(N, N, N ', N '-tetramethyl-) diaminodiphenylmethane (23.6mg, yield 35%).
Embodiment 12-28
A kind of N, N-dialkyl aniline self assembly 4, the concrete steps of the method for 4 '-diaminodiphenylmethane derivative, with embodiment 1, different piece is wherein as shown in the table.
Table 1
Claims (4)
1. a N, N-dialkyl aniline self assembly 4, the method for 4 '-diaminodiphenylmethane derivative, is characterized in that concrete method steps is as follows:
(1) oxidizing reaction is carried out
With various N, N-dialkyl aniline is raw material, Iron(III) chloride hexahydrate or FERRIC CHLORIDE ANHYDROUS are oxygenant, alkali is additive, in a solvent, according to N, N-dialkyl aniline mmole: Iron(III) chloride hexahydrate or FERRIC CHLORIDE ANHYDROUS mmole: alkali mmole: the ratio of solvent milliliter is 0.4: (0.4 ~ 1.2): (0.2 ~ 0.6): the ratio of 2, first add N in the reactor, N-dialkyl aniline and solvent, under stirring, add alkali again, finally add Iron(III) chloride hexahydrate or FERRIC CHLORIDE ANHYDROUS, after reinforced complete, oil bath temperature rises to 85 ~ 120 DEG C of open circuits, Keep agitation carries out oxidizing reaction 2.5 ~ 4.5 hours, just prepare 4, the reaction solution of 4 '-diaminodiphenylmethane derivative,
Described alkali is salt of wormwood, N, one in N-diisopropylethylamine, sodium hydroxide, phenanthroline, triethylamine, solvent is the one in methylene dichloride, trichloromethane, methyl alcohol, water, ethyl acetate, toluene, triethylamine, methyl-sulphoxide, DMF;
(2) carry out that product is concentrated, purifying
After (1) step completes, to the reaction solution of 4,4 '-diaminodiphenylmethane derivative that (1) step is prepared, add excessive ammonia, stir 5 minutes.With dichloromethane extraction, TLC detects until without product in extraction liquid, merge organic phase, organic phase anhydrous magnesium sulfate drying, filters, by rotary evaporation concentrated filtrate, collect concentrated solution, concentrated solution, through purification by silica gel column chromatography, carries out wash-out with elutriant, concentrates, drains to obtain product to the effluent liquid of silica gel column chromatography through rotary evaporation;
Described elutriant is ethyl acetate: the ratio of sherwood oil is 1: the mixed solution of (70 ~ 100).
2. according to a kind of N according to claim 1, N-dialkyl aniline self assembly 4,4 '-diaminodiphenylmethane derivative, it is characterized in that: in step (1), raw material is N, accelerine, oxygenant is Iron(III) chloride hexahydrate, additive is triethylamine, in toluene solvant, according to DMA mmole: Iron(III) chloride hexahydrate mmole: triethylamine mmole: the ratio of toluene milliliter is the ratio of 0.4: 1.0: 0.4: 2, oil bath temperature rises to 85 DEG C, and Keep agitation carries out oxidizing reaction 3.5 hours;
In step (2), elutriant is ethyl acetate: the ratio of sherwood oil is 1: the mixed solution of (70 ~ 100), obtains faint yellow solid 4,4 '-(N, N, N ', N '-tetramethyl-) diaminodiphenylmethane.
3. according to a kind of N according to claim 1, N-dialkyl aniline derivative self-assembled synthesis 4,4 '-diaminodiphenylmethane derivative, it is characterized in that: in step (1), raw material is methylphenylamine, oxygenant is Iron(III) chloride hexahydrate, additive is triethylamine, in toluene solvant, according to methylphenylamine mmole: Iron(III) chloride hexahydrate mmole: triethylamine mmole: the ratio of toluene milliliter is the ratio of 0.4: 1.0: 0.4: 2, oil bath temperature rises to 85 DEG C, and Keep agitation carries out oxidizing reaction 3.5 hours;
In step (2), elutriant is ethyl acetate: the ratio of sherwood oil is 1: the mixed solution of (70 ~ 100), obtains faint yellow solid 4,4 '-(N, N '-dimethyl) diaminodiphenylmethane.
4. according to a kind of N according to claim 1, N-dialkyl aniline self assembly 4,4 '-diaminodiphenylmethane derivative, it is characterized in that: in step (1), raw material is the chloro-N of 3-, accelerine, oxygenant is Iron(III) chloride hexahydrate, additive is triethylamine, in toluene solvant, according to the chloro-DMA mmole of 3-: Iron(III) chloride hexahydrate mmole: triethylamine mmole: the ratio of toluene milliliter is the ratio of 0.4: 1.0: 0.4: 2, oil bath temperature rises to 85 DEG C, and Keep agitation carries out oxidizing reaction 3.5 hours;
In step (2), elutriant is ethyl acetate: the ratio of sherwood oil is 1: the mixed solution of (70 ~ 100), obtains faint yellow solid 3,3 '-two chloro-4,4 '-(N, N, N ', N '-tetramethyl-) diaminodiphenylmethane.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107501524A (en) * | 2017-08-30 | 2017-12-22 | 景县本源精化有限公司 | N, N ' it is alkylated diaminodiphenyl-methane class curing agent and preparation method |
-
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Non-Patent Citations (1)
| Title |
|---|
| XUEGE LING ET AL.: "Synthesis of Benzidine Derivatives via FeCl3.6H2O-Promoted Oxidative Coupling of Anilines", 《THE JOURNAL OF ORGANIC CHEMISTRY》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107501524A (en) * | 2017-08-30 | 2017-12-22 | 景县本源精化有限公司 | N, N ' it is alkylated diaminodiphenyl-methane class curing agent and preparation method |
| CN107501524B (en) * | 2017-08-30 | 2020-05-12 | 本源精化环保科技有限公司 | N, N' -alkylated diaminodiphenyl methane curing agent and preparation method thereof |
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