CN104130143B - Method for preparing 3-methylamino-4-nitrophenoxyethanol - Google Patents
Method for preparing 3-methylamino-4-nitrophenoxyethanol Download PDFInfo
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Abstract
The invention relates to a method for preparing 3-methylamino-4-nitrophenoxyethanol. The method comprises the steps of performing methylamination reaction by using 2,4-dichloronitrobenzene as a raw material and using methanol as a solvent to obtain 3-methylamino-4-nitrochlorobenzene, performing nucleophilic substitution with a sodium hydroxide (or other alkaline matter) solution of ethylene glycol to substitute the remaining other chlorine group so as to obtain crude 3-methylamino-4-nitrophenoxyethanol, and performing re-crystallization to obtain high-purity 3-methylamino-4-nitrophenoxyethanol. The process of preparing the 3-methylamino-4-nitrochlorobenzene intermediate through a one-step method replaces a two-step method process of preparing the intermediate through high pressure ammonolysis of 2,4-dichloronitrobenzene and N-methylation reaction; in addition, methanol is adopted in the one-step method to replace a tetrahydrofuran solution, so that the purposes of reducing the recovery cost and reducing the cost of the solvent are achieved; the method has the characteristics of conventional equipment, simplicity in operation, cheap and readily available raw materials, low cost, high yield and the like.
Description
Technical field
The present invention relates to a kind of preparation method of nitro class dyestuff, especially relate to a kind of 3- methylamino -4- nitrobenzene oxygen
The preparation method of ethanol.
Background technology
In recent years, the pursuit to fashionable life with people, the ratio of hair dyeing increases increasingly.And in traditional hair dye
Directly chromophore component is p-phenylenediamine, and p-phenylenediamine is a kind of carcinogen, and easily allergy etc. occurs when contacting with skin, uncomfortable
Preferably long term frequent uses, therefore in the urgent need to developing low toxicity, hypoallergenic colour former.
3- methylamino -4- nitro Phenoxyethanol, a kind of nitro class dyestuff, CAS No.59820-63-2, it is a kind of direct
Hair coloring agents, 21 kinds of different colours hair dyes can be used in, concentration is up to 0.15%.It is applied to keratin fiber
During dyeing, wherein hair is attached to by cuticle contact and remaining color, rather than normal skin.Therefore no allergic or thorn
Swash and the problems such as toxicity is left, the cosmetics of super quality can be used for as hair dyed agent.The foreign trader's active demand having oriented, international
Domestic belong to new product, industrialization demand is big, and market and development prospect are wide.But directly obtain 3- methylamino -4- nitre
The technique of base Phenoxyethanol have not been reported, and what research was reported is only the synthesis of its intermediate 3- methylamino -4- nitro-chlorobenzene.
Chinese patent CN 102531923 A discloses a kind of production method of 3- methylamino -4- nitro-chlorobenzene, two between inciting somebody to action
Chlorobenzene is obtained 2,4- dichloronitrobenzene after adopting mixed acid nitrification, then 2,4- dichloronitrobenzene is added high pressure autoclave amination, is passed through liquid
Ammonia, 140～150 DEG C, 7.0～8.5MPa be incubated 5～6 hours, then through washing, suction filtration be obtained product 5- chloro-2-nitroaniline.
This method needs HTHP, and complex operation higher to equipment requirement.
Sergei Voskresensky etc.（Synthetic Communications, 2000, 30(19), 3523-
3526）It is raw material using 5- chloro-2-nitroaniline, toluene is solvent, Bu4N+HSO4 -Or Bu4N+Br-For catalyst, through sulfuric acid two
Methyl ester methylization is obtained product 3- methylamino -4- nitro-chlorobenzene, and its preparation process is as follows：
The method has that step is many, high pressure ammonolysis and methylating reagent dimethyl suflfate toxicity are big, yield is low asks
Topic.
It is raw material that patent WO2005080388 A1 adopts 2,4- dichloronitrobenzene, and oxolane is solvent, is initially charged three second
Amine and methylamine react 6 hours for lower 40 DEG C in argon gas atmosphere, are further continued for adding 40 DEG C of the methylamine-tetrahydrofuran solution of two equivalents anti-
Answer 16 hours prepared product 3- methylamino -4- nitro-chlorobenzenes, its preparation process is as follows：
The method has that solvents tetrahydrofurane valency is high, recovery difficult is big, the low problem of yield.
Therefore, improve intermediate 3- methylamino -4- nitro-chlorobenzene synthesis technique, reach production feasible, especially
Exploitation 3- methylamino -4- nitro-chlorobenzene carries out nucleophilic displacement of fluorine preparation 3- methylamino -4- nitrobenzene in the basic conditions with ethylene glycol
Oxyethanol is to obtain the new technology of high-quality product, extremely urgent.
Content of the invention
In order to overcome the deficiencies in the prior art, the invention provides one kind can be used as low toxicity, hypoallergenic color development
Agent, and may be used to prepare the preparation method of the 3- methylamino -4- nitro Phenoxyethanol of safety non-toxic hair dye.
A kind of preparation method of 3- methylamino -4- nitro Phenoxyethanol, comprises the steps：
（1）2,4- dichloronitrobenzene and mass concentration be 30～45% methylamine water solution in methanol solvate through methylamine
Reaction is obtained 3- methylamino -4- nitro chlorobenzene；Wherein, 2,4- dichloronitrobenzene, methylamine water solution, the weight ratio of methyl alcohol are：
1：095～1.25：2.12～3.02；
（2）3- methylamino -4- nitro chlorobenzene carries out nucleophilic substitution with ethylene glycol under alkali effect and obtains 3- first ammonia
Base -4- nitro Phenoxyethanol crude product；Wherein, 3- methylamino -4- nitro chlorobenzene, ethylene glycol, the weight ratio of alkali are：1：4.2～
6.0：0.34～0.40；
（3）3- methylamino -4- nitro Phenoxyethanol crude product carries out purification process and obtains 3- methylamino -4- nitro Phenoxyethanol
Sterling.
The present invention adopts formula（II）Shown 2,4- dichloronitrobenzene is raw material, and methanol as solvent is obtained formula through methylamine
（III）3- methylamino -4- nitro chlorobenzene, then the NaOH with ethylene glycol（Or other alkaline matters）Solution carries out nucleophilic and takes
For another chlorine remaining, prepared formula（I）Shown 3- methylamino -4- nitro Phenoxyethanol crude product, after through recrystallization preparation
High-purity 3- methylamino -4- nitro Phenoxyethanol.Synthetic route is as follows：
Preferably, step（1）In, the time for adding of methylamine water solution controls in 0.75～1.5h, and methylamine reaction is being returned
Carry out at a temperature of stream, the reaction time is 15～21h.
Preferably, obtain 3- methylamino -4- nitro chlorobenzene crude product after crystallizing, filter, being dried after methylamine reaction terminates,
Gained crude product rinses through methyl alcohol again, obtains intermediate 3- methylamino -4- nitro chlorobenzene after filtering drying.
Preferably, step（2）In, described alkali is KOH, NaOH, K2CO3、Na2CO3One of.
Preferably, described alkali is using being dividedly in some parts, and the weight of first alkali and second batch alkali is than for 1.5～2：1.
Preferably, step（2）Concrete operations be：First first alkali is heated to 90～100 DEG C so as to be dissolved in
After in ethylene glycol, control temperature at 100～105 DEG C, add 3- methylamino -4- nitro chlorobenzene, then be warming up to 110～115 DEG C
Add second batch alkali again after reaction 1～3h, control and add in 15～30min, then proceed to react 0.5～2.5h, be cooled to
Add deionized water stirred crystallization 30min after 70 DEG C, then be cooled to 40 DEG C of filtrations, gained filter cake obtains after deionized water rinsing
3- methylamino -4- nitro Phenoxyethanol crude product.
Preferably, step（3）In, described purification process is：3- methylamino -4- nitro Phenoxyethanol crude product is first in acetic acid second
Carry out activated carbon decolorizing process in ester solvent, then recrystallized in deionized water, obtain 3- methylamino -4- nitrobenzene oxygen
Ethanol；Wherein, ethyl acetate, activated carbon, the weight ratio of 3- methylamino -4- nitro Phenoxyethanol crude product are：3.5～6.0：0.05
～1：1, deionized water with the weight ratio of 3- methylamino -4- nitro Phenoxyethanol crude product is：5～7：1.
Preferably, step（3）Concrete operations be：Add ethyl acetate, 3- methylamino -4- nitrobenzene oxygen in the reactor
Ethanol crude product, is passed through nitrogen and stirs and be warming up to 60～65 DEG C, after solid is entirely molten, puts into activated carbon, after continuing stirring 1～2h
Stop heating, filter and pour filtrate in deionized water into, be heated to 60～65 DEG C, then be cooled to 10～15 DEG C, filter, filter cake
3- methylamino -4- nitro Phenoxyethanol is obtained final product after drying.
Preferably, the preparation method of described 3- methylamino -4- nitro Phenoxyethanol comprises the steps：
（1）Add 50g 2,4- dichloronitrobenzene, 150g methyl alcohol in four-hole boiling flask, after stirring is warming up to backflow, drip
47.6g mass concentration is 40% methylamine water solution, after completion of dropping in 1h, after maintaining the reflux for thermotonus 15h, is passed through cryosel
Water is cooled to 10 DEG C, insulation crystallization 30min, then obtains 3- methylamino -4- nitro chlorobenzene crude product, gained crude product after filtering drying
Use 60g methyl alcohol to pull an oar again, filter, after 70 DEG C of dryings, obtain 3- methylamino -4- nitro chlorobenzene；
（2）Add 5.5gNaOH, 105g ethylene glycol in four-hole boiling flask, stirring is warming up to 100 DEG C, is completely dissolved to NaOH
Afterwards, add 25g 3- methylamino -4- nitro chlorobenzene, after being warming up to 110 DEG C of reaction 2h, add 3g NaOH, continue reaction 2.5h
After be cooled to 70 DEG C, add 105g deionized water, stirred crystallization 30min at 70 DEG C, then be cooled to 40 DEG C of filtrations, gained filter cake
3- methylamino -4- nitro Phenoxyethanol crude product is filtered to obtain again after deionized water rinsing；
（3）Add 100g ethyl acetate, 20g 3- methylamino -4- nitro Phenoxyethanol crude product in four-hole boiling flask, be passed through
Nitrogen simultaneously stirs and is warming up to 65 DEG C, after solid is entirely molten, puts into 1.18g activated carbon, stops heating, filter simultaneously after continuing stirring 1h
Filtrate is poured in 115g deionized water, is heated to 65 DEG C, then be cooled to 10 DEG C, filter, filter cake obtains final product 3- first ammonia after drying
Base -4- nitro Phenoxyethanol.
The beneficial effects of the present invention is：
（1）The compound 3- methylamino -4- nitro Phenoxyethanol that the present invention prepares, can effectively sending out as hair dye
Color composition, has the advantages that toxicity is low, good to skin adaptability, has wide market prospects；
（2）The present invention is adopted 2,4- dichloronitrobenzene in methanol solvate, carries out the selection MMA of normal pressure with methylamine
Change reaction, the technique preparing intermediate 3- methylamino -4- nitro-chlorobenzene by one-step method, instead of 2,4- dichloronitrobenzene
Carry out the two-step process that N- methylation reaction prepares intermediate again after first high pressure ammonolysis；In addition, adopting methyl alcohol in one-step method
Substituted tetrahydrofuran solvent, the purpose reducing reclaimer operation expense and reducing solvent cost；
（3）3- methylamino -4- nitro Phenoxyethanol preparation method provided by the present invention has equipment routine, operation letter
Single, raw material is cheap and easy to get, low cost, high income the features such as.
Specific embodiment
With reference to specific embodiment, the invention will be further described, but protection scope of the present invention is not limited to this.
Embodiment 1
（1）The preparation of 3- methylamino -4- nitro chlorobenzene
50g is added in four-hole boiling flask（0.260mol）2,4- dichloronitrobenzenes, 150g methyl alcohol, stirring is warming up to backflow,
Dropping 47.6g（0.613mol）Concentration is the methylamine water solution of 40w%, and time for adding controls after 1h, completion of dropping, keeps back
Stream thermotonus 15h, reactant liquor is orange transparent liquid, is passed through brine ice slow cooling to 10 DEG C, insulation crystallization 30min, then warp
Orange 3- methylamino -4- nitro chlorobenzene crude product is obtained, gained crude product uses 60g methyl alcohol to pull an oar, through 70 after filtration again after filtering drying
DEG C dry 34.5g orange intermediate 3- methylamino -4- nitro chlorobenzene, HPLC purity is 99.65%, and yield is 71.00%.
（2）The preparation of 3- methylamino -4- nitro Phenoxyethanol crude product
5.5gNaOH is added in 250mL four-hole boiling flask（First alkali）、105g（1.692mol）Ethylene glycol, stirring heats up
To 100 DEG C until NaOH is completely dissolved, add 25g（0.134mol）Purity is 99.65% 3- methylamino -4- nitro chlorination
Benzene, after being warming up to 110 DEG C of reaction 2h, adds 3g NaOH（Second batch alkali）, continue reaction 2.5h and be cooled to 70 DEG C, be slowly added to
105g deionized water, stirred crystallization 30min at 70 DEG C, then it is cooled to 40 DEG C of filtrations, gained filter cake is after deionized water rinsing
Filter to obtain 23.8g 3- methylamino -4- nitro Phenoxyethanol crude product again, HPLC purity is 95.28%, yield is 83.31%.
（3）3- methylamino -4- nitro Phenoxyethanol refined
100g ethyl acetate, 20g 3- methylamino -4- nitro Phenoxyethanol crude product is added in four-hole boiling flask（Purity is
95.28%）, it is passed through nitrogen and stirs and be warming up to 65 DEG C, after solid is entirely molten, put into 1.18g activated carbon, stop after continuing stirring 1h
Only heat, filter and pour filtrate in 115g deionized water into, be heated to 65 DEG C, then slow cooling, to 10 DEG C, filters, filter cake dries
It is 16.60g 3- methylamino -4- nitro Phenoxyethanol after dry, HPLC purity is 99.39%, and refined yield is 83.0%.
Embodiment 2～4
Using with embodiment 1 step（1）Middle same operation, except for the difference that select the methyl alcohol of different amounts, methylamine water solution,
Variable concentrations methylamine water solution and differential responses time, embodiment 1～4 the data obtained is as shown in table 1：
Table 1
According to table 1 as can be seen that using the methyl alcohol of different amounts, methylamine water solution, variable concentrations methylamine water solution and
The differential responses time, all the purity of 3- methylamino -4- nitro chlorobenzene and yield can be existed significantly affects, thus impact is
The purity of end-product 3- methylamino -4- nitro Phenoxyethanol and yield.
Embodiment 5～8
Using with embodiment 1 step（2）Middle same operation, except for the difference that selects the ethylene glycol of different amounts, NaOH and not
Same reaction time, embodiment 1 and embodiment 5～8 the data obtained are as shown in table 2：
Table 2
Wherein, in embodiment 6, NaOH is disposable addition, and other embodiment is and is dividedly in some parts.
According to table 2 as can be seen that adopting the ethylene glycol of different amounts, NaOH and differential responses time, all can be to 3- first ammonia
There is significantly impact, thus affecting final product 3- methylamino -4- nitre in the purity of base -4- nitro Phenoxyethanol crude product and yield
The purity of base Phenoxyethanol and yield.
Embodiment 9
Other steps are same as Example 1, using the subtractive process of 3- methylamino -4- nitro Phenoxyethanol crude product different as
Comparative example 1：330g dichloromethane, 20g 3- methylamino -4- nitro Phenoxyethanol crude product is added in four-hole boiling flask（Purity
95.28%）, it is passed through nitrogen and stirs and be warming up to 65 DEG C, solids cannot dissolve, filter in backward filter cake and add 105g methyl alcohol, plus
Heat, to 70 DEG C, puts into 1g activated carbon after solids all dissolves, and stops heating, filter and pour filtrate into after continuing stirring 1h
In 100g deionized water, it is heated to 65 DEG C, then slow cooling, to 15 DEG C, filters, be 3g 3- methylamino -4- nitre after filter cake drying
Base Phenoxyethanol, HPLC purity is 99.58%, and refined yield is 15.64%.
Embodiment 10～12
Using with embodiment 1 step（3）Middle same operation, except for the difference that selects the organic solvent of variety classes and consumption,
Embodiment 1 and embodiment 10～12 the data obtained are as shown in table 3：
Table 3
1, embodiment 9 and embodiment 10～12 in conjunction with the embodiments, it is recognised that variety classes and consumption is organic molten
Agent, for the very big impact of the refined presence of 3- methylamino -4- nitro Phenoxyethanol crude product, can affect final product 3- first ammonia
The purity of base -4- nitro Phenoxyethanol and yield.
Last in addition it is also necessary to it is noted that listed above be only the present invention several instantiations.Obviously, the present invention
It is not limited to above example, can also have many deformation.Those of ordinary skill in the art can be direct from present disclosure
The all deformation derived or associate, are all considered as protection scope of the present invention.
Claims (6)
1. a kind of preparation method of 3- methylamino -4- nitro Phenoxyethanol is it is characterised in that comprise the steps：
（1）2,4- dichloronitrobenzene and mass concentration are that 30～45% methylamine water solution reacts through methylamine in methanol solvate
Prepared 3- methylamino -4- nitro chlorobenzene；Wherein, 2,4- dichloronitrobenzene, methylamine water solution, the weight ratio of methyl alcohol are：1：
0.95～1.25：2.12～3.02；
（2）3- methylamino -4- nitro chlorobenzene carries out nucleophilic substitution with ethylene glycol under alkali effect and obtains 3- methylamino -4-
Nitro Phenoxyethanol crude product；Wherein, 3- methylamino -4- nitro chlorobenzene, ethylene glycol, the weight ratio of alkali are：1：4.2～6.0：
0.34～0.40；Described alkali is KOH, NaOH, K2CO3、Na2CO3One of；Described alkali using being dividedly in some parts, first alkali with
The weight of second batch alkali is than for 1.5～2：1；
（3）3- methylamino -4- nitro Phenoxyethanol crude product carries out purification process, and to obtain 3- methylamino -4- nitro Phenoxyethanol pure
Product；
Wherein, step（2）Concrete operations be：First first alkali is heated to 90～100 DEG C so as to be dissolved in ethylene glycol
In after, control temperature at 100～105 DEG C, add 3- methylamino -4- nitro chlorobenzene, then be warming up to 110～115 DEG C reaction 1～
Add second batch alkali again after 3h, control and add in 15～30min, then proceed to react 0.5～2.5h, after being cooled to 70 DEG C
Add deionized water stirred crystallization 30min, then be cooled to 40 DEG C of filtrations, gained filter cake obtains 3- first ammonia after deionized water rinsing
Base -4- nitro Phenoxyethanol crude product.
2. 3- methylamino -4- nitro Phenoxyethanol according to claim 1 preparation method it is characterised in that：Step（1）
In, the time for adding of methylamine water solution controls in 0.75～1.5h, and methylamine reaction is carried out at a reflux temperature, and the reaction time is
15～21h.
3. 3- methylamino -4- nitro Phenoxyethanol according to claim 2 preparation method it is characterised in that：Methylamine
Reaction obtains 3- methylamino -4- nitro chlorobenzene crude product after terminating after crystallizing, filter, being dried, and gained crude product rinses through methyl alcohol again,
Intermediate 3- methylamino -4- nitro chlorobenzene is obtained after filtering drying.
4. 3- methylamino -4- nitro Phenoxyethanol according to claim 1 preparation method it is characterised in that：Step（3）
In, described purification process is：3- methylamino -4- nitro Phenoxyethanol crude product first carries out activated carbon decolorizing in ethyl acetate solvent
Process, then recrystallized in deionized water, obtain 3- methylamino -4- nitro Phenoxyethanol；Wherein, ethyl acetate, work
Property charcoal, the weight ratio of 3- methylamino -4- nitro Phenoxyethanol crude product are：3.5～6.0：0.05～1：1, deionized water and 3- first
The weight ratio of amino -4- nitro Phenoxyethanol crude product is：5～7：1.
5. 3- methylamino -4- nitro Phenoxyethanol according to claim 4 preparation method it is characterised in that：Step
（3）Concrete operations be：Add ethyl acetate, 3- methylamino -4- nitro Phenoxyethanol crude product in the reactor, be passed through nitrogen simultaneously
Stirring be warming up to 60～65 DEG C, after solid is entirely molten, put into activated carbon, continue stirring 1～2h after stop heating, filter and will
Filtrate is poured in deionized water, is heated to 60～65 DEG C, then is cooled to 10～15 DEG C, filters, and filter cake obtains final product 3- first ammonia after drying
Base -4- nitro Phenoxyethanol.
6. the preparation method of 3- methylamino -4- nitro Phenoxyethanol according to claim 1 is it is characterised in that include following
Step：
（1）Add 50g 2,4- dichloronitrobenzene, 150g methyl alcohol in four-hole boiling flask, after stirring is warming up to backflow, drip 47.6g
Mass concentration is 40% methylamine water solution, and time for adding controls after 1h, completion of dropping, after maintaining the reflux for thermotonus 15h,
It is passed through brine ice and be cooled to 10 DEG C, insulation crystallization 30min, then obtain 3- methylamino -4- nitro chlorobenzene crude product after filtering drying,
Gained crude product uses 60g methyl alcohol to pull an oar again, filters, and obtains 3- methylamino -4- nitro chlorobenzene after being dried；
（2）Add 5.5gNaOH, 105g ethylene glycol in four-hole boiling flask, stirring is warming up to 100 DEG C, after being completely dissolved to NaOH,
Add 25g 3- methylamino -4- nitro chlorobenzene, after being warming up to 110 DEG C of reaction 2h, add 3gNaOH, drop after continuing reaction 2.5h
Temperature, to 70 DEG C, adds 105g deionized water, stirred crystallization 30min at 70 DEG C, then is cooled to 40 DEG C of filtrations, gained filter cake is through going
Ionized water filters to obtain 3- methylamino -4- nitro Phenoxyethanol crude product after rinsing again；
（3）Add 100g ethyl acetate, 20g 3- methylamino -4- nitro Phenoxyethanol crude product in four-hole boiling flask, be passed through nitrogen
And stir and be warming up to 65 DEG C, after solid is entirely molten, put into 1.18g activated carbon, stop heating after continuing stirring 1h, filter and will filter
Liquid is poured in 115g deionized water, is heated to 65 DEG C, then is cooled to 10 DEG C, filters, and filter cake obtains final product 3- methylamino -4- after drying
Nitro Phenoxyethanol.
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