CN101717342A - Method for synthesizing 2,5-diamino phenyl ethanol - Google Patents
Method for synthesizing 2,5-diamino phenyl ethanol Download PDFInfo
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- CN101717342A CN101717342A CN200910253209A CN200910253209A CN101717342A CN 101717342 A CN101717342 A CN 101717342A CN 200910253209 A CN200910253209 A CN 200910253209A CN 200910253209 A CN200910253209 A CN 200910253209A CN 101717342 A CN101717342 A CN 101717342A
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Abstract
The invention discloses a method for synthesizing 2,5-diamino phenyl ethanol, which comprises the following steps: reacting 2-amino-5-nitro phenyl ethanol with a magnetic solid base, heating the reactants and adding hydrazine hydrate, wherein the reaction temperature is kept between 0 and 100 DEG C and the reaction time is 0.5 to 20 hours; and filtering hot reaction liquid, cooling the filtrate, standing the filtrate till white crystals precipitate, filtering the reaction liquid and drying the precipitate to obtain the product. The novel green process for synthesizing the 2,5-diamino phenyl ethanol provided by the invention has the advantages that: the magnetic solid base is used as a catalyst; the hydrazine hydrate is used to reduce the nitro groups; the emission of three wastes is reduced in a reaction process; the process is simplified; the cost is reduced; the product yield and purity are improved; and industry production is easy.
Description
(1) technical field
The present invention relates to a kind of 2, the synthetic method of 5-diamino benzene ethanol, especially a kind of applied magnetic solid alkali is raw material as catalyzer with 2-amino-5-oil of mirbane ethanol, utilizes the hydrazine hydrate reduction legal system to be equipped with 2, the novel environment-friendly process of 5-diamino benzene ethanol.
(2) background technology
2, the 5-diamino benzene ethanol is the xanchromatic solids at normal temperatures, is easy to oxidation, and generally the form with hydrochloride or vitriol exists, and its hydrochloride or vitriol are the solid of white, 222～224 ℃ of fusing points.2,5-diamino benzene ethanol and salt thereof are widely used in dyestuff, pigment, agricultural chemicals and the polymer, use mainly as a kind of hair dye of oxidized form efficiently.
2, the synthetic method of 5-diamino benzene ethanol has two kinds: one, be that starting raw material comes Synthetic 2 with the o-chlorobenzene acetic acid, the 5-diamino benzene ethanol has two technological lines in this synthetic method.1) temperature is controlled at below 5 ℃, in the process that stirs, o-chlorobenzene acetic acid is joined in the vitriol oil, it is fully dissolved, with the cryosel bath solution is cooled to below 0 ℃, under this temperature, slowly drip nitrosonitric acid, after dropwising, restir is about 1 hour, stopped reaction, reaction solution is poured in the frozen water, have a large amount of white solid to produce, water with white solid thing thorough washing after, oven dry promptly obtains 2-chloro-5-nitrophenyl-acetic acid.The product that obtains is dissolved in the methyl alcohol, and is catalyzer, under the condition that refluxes with the vitriol oil, reacted 2～3 hours, stopped reaction steams and removes part methyl alcohol, after the cooling, in reaction solution, add a large amount of water, have a large amount of crystal to separate out, filtering drying promptly gets 2-chloro-5 mononitro-benzene methyl acetates, joins in the dimethylbenzene then, fully stirring is dissolved it fully, adds reductive agent NaBH again in solution
4, under cooling, dripping diethylene glycol dimethyl ether, temperature is controlled at below 30 ℃, and after dropwising, temperature is controlled at about 30 ℃, reacts 24 hours, after reaction finishes, water and saturated aqueous common salt thorough washing reaction solution, organic layer anhydrous Na
2SO
4Drying removes solvent under reduced pressure and obtains white solid 2-chloro-5-oil of mirbane ethanol; Again white solid 2-chloro-5-oil of mirbane ethanol is joined in the benzylamine, fully stir and make its dissolving, under protection of nitrogen gas; be heated to backflow, under refluxad, reacted 5 hours; stopped reaction, most of benzylamine is removed in decompression, obtains dope; recrystallization joins in the methyl alcohol after obtaining xanchromatic solid 2-benzamido group-5-oil of mirbane ethanol, and adds 5% palladium carbon as catalyzer; under 50 ℃; hydrogenating reduction 5 hours obtains xanchromatic solid 2 through aftertreatment, the 5-diamino benzene ethanol.2) temperature is controlled at below 5 ℃, and in the process that stirs, o-chlorobenzene acetic acid is joined in the vitriol oil, it is fully dissolved, bathe with cryosel and go to below 0 ℃ solution is cold, under this temperature, slowly drip nitrosonitric acid, after dripping fully, restir is about 1 hour, stopped reaction, reaction solution is poured in the frozen water, obtain the solid product of white, behind the solids thorough washing, oven dry promptly obtains 2-chloro-5-nitrophenyl-acetic acid; The white solid that obtains is joined in the autoclave, and the ammoniacal liquor with 25% is solvent, and CuCl is a catalyzer, under 95 ℃, compressive reaction 30 hours is after the cooling, under protection of nitrogen gas, reaction solution is extruded, remove most of ammonia,, have a large amount of light yellow solids to separate out with hydrochloric acid adjust pH 3～4, behind the filtration and recrystallization, get xanchromatic solid 2-amino-5-nitrophenyl-acetic acid; The yellow solid that obtains is joined in the diethylene glycol dimethyl ether solution of sodium borohydride, fully stir and make its dissolving, heat temperature raising under this temperature, drips the diethylene glycol dimethyl ether solution of aluminum chloride to 750C, after dripping, reacted 4 hours, and used ethyl acetate extraction, and water and saturated aqueous common salt thorough washing organic layer, removal of solvent under reduced pressure obtains xanchromatic solids 2-amino-5-oil of mirbane ethanol; The solids that obtains is joined in the methyl alcohol again, and add 5% palladium carbon as catalyzer, under 50 ℃, hydrogenating reduction 5 hours obtains xanchromatic solid 2 through aftertreatment, the 5-diamino benzene ethanol.Two, be that starting raw material comes Synthetic 2 with adjacent amino-benzene ethanol, the 5-diamino benzene ethanol.Acetic anhydride is added drop-wise in the adjacent amino-benzene ethanol, then under 80 ℃, stirring reaction 1 hour is cooled to 10 ℃, adds 98% the vitriol oil, maintain the temperature under 0～10 ℃, slowly drip nitrosonitric acid, after dropwising, restir reaction 1 hour, after reaction finishes, the water that adds capacity in the reaction solution, heat temperature raising to 100 ℃, stirring reaction is after 3 hours, be cooled to 10 ℃, add sodium hydroxide with neutralisation of sulphuric acid, then, use ethyl acetate extraction, solvent is removed in decompression, obtains xanchromatic solid 2-amino-5-oil of mirbane ethanol; Join in the methyl alcohol then, and add 5% palladium carbon,, obtain xanchromatic solid 2 through aftertreatment, the 5-diamino benzene ethanol 50 ℃ of hydrogenating reductions 5 hours as catalyzer.
For developing new clean production technology, develop new and effective catalyzer, simplify reactions steps, reduce disposal of pollutants, realize chemical reaction efficiently, reach the purpose of zero release.The present invention is with reference to the method for Zhejiang University's master thesis " 2,5-diamino benzene ethanol synthetic, 2005 ", being starting raw material with adjacent amino-benzene ethanol at first, is catalyzer with the vitriol oil, in toluene solvant with urea generation ring-closure reaction, making solid benzo [1, the 3] oxaza heptan-2-ketone of white, is solvent again with the vitriol oil, carry out nitration reaction at low temperatures, make nitration product, 2-amino-5-oil of mirbane ethanol, last, by hydrazine hydrate reduction preparation 2,5-diamino benzene ethanol.This is an industrial economically viable Synthetic 2, the new technology route of 5-diamino benzene ethanol, and stable yield, raw material is cheap and easy to get, and production cost is low, has good industrialized application prospect.
(3) summary of the invention
The invention provides a kind of green Synthetic 2, the novel process of 5-diamino benzene ethanol, select magnetic solid base as catalyzer, utilize hydrazine hydrate that nitryl group is reduced, reduce the three waste discharge in the reaction process, simplify technology simultaneously, improve product yield and purity, make synthetic technology be easy to industrialization.
The technical solution used in the present invention is as follows:
A kind of suc as formula 2 shown in (II), the synthetic method of 5-diamino benzene ethanol, under the magnetic solid base catalyst effect that magnetic mg_al hydrotalcite makes, reacted 1～20 hour at 0～60 ℃ suc as formula 2-amino-5-oil of mirbane ethanol shown in (I) and hydrazine hydrate, reaction solution gets described product 2 through aftertreatment, 5-diamino benzene ethanol (II); Reaction equation is as follows:
The magnetic solid base that described magnetic mg_al hydrotalcite makes is magnesium aluminum-hydrotalcite to be carried out magnetic modify, and makes it have magnetic and catalysis dual-use function, reaches the purpose that improves catalytic activity.Particularly, the preparation method of described magnetic solid base catalyst is as follows: get a certain amount of magnetic colloidal sol and join in the reaction flask, add distilled water again, stirring at room, magnesium nitrate and the aluminum nitrate getting the magnalium ratio and be 1: 2 are mixed with solution, and other joins the sodium hydroxide solution of pH=10～13, two kinds of solution are added in the reaction flask, 110 ℃ of stirrings, washing and drying makes magnetic mg_al hydrotalcite, forms magnetic solid base 450～500 ℃ of high-temperature roastings then.Magnetic colloidal sol is to adopt chemical coprecipitation, with Fe
3+And Fe
2+Vitriol or muriate in excessive alkali, mix to stir in 1: 1 ratio and make.Specifically can be with reference to the 29th volume the 3rd phase (in March, 2002) " preparation of magnetic mg_al hydrotalcite solid alkali and sign " of applicating technology.
Described temperature of reaction is carried out at 0 ℃～70 ℃, is preferably 30 ℃～50 ℃.
The described reaction times is 0.5～20 hour, preferred 3～8 hours.
The consumption of described magnetic solid base catalyst is that 2-amino-5-oil of mirbane alcoholic acid molar weight ratio is 1～10%, preferred 5%.
The consumption of described hydrazine hydrate is that 2-amino-5-oil of mirbane alcoholic acid molar weight ratio is 1: 2～10, preferred 1: 3.
Described aftertreatment is: reacting liquor while hot is filtered, and the filtrate cooling is left standstill, and treats that white crystal separates out after-filtration, after the drying product.
Concrete recommend described synthetic method to carry out according to following steps: in the reactor that return line, thermometer and whipping appts are housed, according to 2-amino-5-oil of mirbane ethanol: hydrazine hydrate: the molar weight ratio of the material of catalyzer is 1: 1～10: 1～10% to feed intake.The reaction solution heat temperature raising drips hydrazine hydrate, is reflected at 0 ℃～100 ℃ and carries out, and react 0.5～20 hour, and reacting liquor while hot is filtered, and the filtrate cooling is left standstill, and treats that white crystal separates out after-filtration, must product after the drying.
In this reaction, described magnetic solid base catalyst can recycle after reclaiming.
The magnetic solid base that the present invention utilizes magnetic mg_al hydrotalcite to make carries out 2 as catalyzer, synthesizing of 5-diamino benzene ethanol, compared with the prior art, its advantage is embodied in: this magnetic solid base catalyst is applied to 2, in 5-diamino benzene ethanol synthetic, make 2, the preparation of 5-diamino benzene ethanol with respect to technology in the past become simple, easy to operate, reaction yield is high, good product purity, environmental pollution is little, the suitability for industrialized production that is suitable for certain scale is a green clean synthetic route.
(4) embodiment:
Below with specific embodiment technical scheme of the present invention is described, but protection scope of the present invention is not limited thereto.
Embodiment 1
In the there-necked flask of 1000mL, add 2-amino-5-oil of mirbane ethanol 182g (1 mole), ethanol 300mL, 10% mole of magnetic solid base catalyst, stir, heating makes 2-amino-5-oil of mirbane dissolve with ethanol, is warming up to 50 ℃, slowly drip hydrazine hydrate 96g (3 moles), drip after 1 hour insulation reaction 5 hours, filtered while hot, be cooled to 0 ℃, drip the sulfuric acid salify, have a large amount of solids to separate out, filter, drying under reduced pressure, obtain the solid 129g of white, productive rate is 85% (with 2, the 5-diamino benzene ethanol calculates).Fusing point: 222～224 ℃ of consistent with literature value [CAS No.] 93841-24-8.
Embodiment 2
In the there-necked flask of 1000mL, add 2-amino-5-oil of mirbane ethanol 182g (1 mole), ethanol 300mL, 5% mole of magnetic solid base catalyst, stir, heating makes 2-amino-5-oil of mirbane dissolve with ethanol, is warming up to 100 ℃, slowly drip hydrazine hydrate 64g (2 moles), drip after 1 hour insulation reaction 10 hours, filtered while hot, be cooled to 0 ℃, drip the sulfuric acid salify, have a large amount of solids to separate out, filter, drying under reduced pressure, obtain the solid 125g of white, productive rate is 82% (with 2, the 5-diamino benzene ethanol calculates).
Embodiment 3
In the there-necked flask of 500mL, add 2-amino-5-oil of mirbane ethanol 182g (1 mole), ethanol 300mL, 1% mole of magnetic solid base catalyst, stir, heating makes 2-amino-5-oil of mirbane dissolve with ethanol, is warming up to 50 ℃, slowly drip hydrazine hydrate 320g (10 moles), drip after 1 hour insulation reaction 20 hours, filtered while hot, be cooled to 0 ℃, drip the sulfuric acid salify, have a large amount of solids to separate out, filter, drying under reduced pressure, obtain the solid 132g of white, productive rate is 87% (with 2, the 5-diamino benzene ethanol calculates).
Embodiment 4
In the there-necked flask of 500mL, add 2-amino-5-oil of mirbane ethanol 182g (1 mole), ethanol 300mL, 10% mole of magnetic solid base catalyst, stir, heating makes 2-amino-5-oil of mirbane ethanol, is warming up to 50 ℃, slowly drip hydrazine hydrate 32g (1 mole), drip after 1 hour insulation reaction 20 hours, filtered while hot, be cooled to 0 ℃, drip the sulfuric acid salify, have a large amount of solids to separate out, filter, drying under reduced pressure, obtain the solid 122g of white, productive rate is 80% (with 2, the 5-diamino benzene ethanol calculates).
Embodiment 5
In the there-necked flask of 500mL, add 2-amino-5-oil of mirbane ethanol 182g (1 mole), ethanol 300mL, 10% mole of magnetic solid base catalyst, stir, heating makes 2-amino-5-oil of mirbane dissolve with ethanol, is warming up to 50 ℃, slowly drip hydrazine hydrate 160g (5 moles), drip after 1 hour insulation reaction 1 hour, filtered while hot, be cooled to 0 ℃, drip the sulfuric acid salify, have a large amount of solids to separate out, filter, drying under reduced pressure, obtain the solid 131g of white, productive rate is 86% (with 2, the 5-diamino benzene ethanol calculates).
Claims (4)
1. one kind 2, the synthetic method of 5-diamino benzene ethanol is characterized in that the step of method is as follows:
Select magnetic solid base as catalyzer, utilize hydrazine hydrate that nitryl group is reduced; According to 2-amino-5-oil of mirbane ethanol: hydrazine hydrate: the molar weight ratio of the material of catalyzer is 1: 1～10: 1～10%; The reaction solution heat temperature raising drips hydrazine hydrate, is reflected at 0 ℃～100 ℃ and carries out, and react 0.5～20 hour, and reacting liquor while hot is filtered, and the filtrate cooling is left standstill, and treats that white crystal separates out after-filtration, must product after the drying.
2. require described a kind ofly 2 according to right 1, the synthetic method of 5-diamino benzene ethanol is characterized in that: described to selecting magnetic solid base as catalyzer, and utilize hydrazine hydrate that nitryl group is reduced.
3. require described a kind ofly 2 according to right 1, the synthetic method of 5-diamino benzene ethanol is characterized in that: described to 2-amino-5-oil of mirbane ethanol: hydrazine hydrate: the molar weight ratio of the material of catalyzer is 1: 1～10: 1～10%.
4. require described a kind ofly 2 according to right 1, the synthetic method of 5-diamino benzene ethanol is characterized in that: described to the reaction solution heat temperature raising, drip hydrazine hydrate, and be reflected at 0 ℃～100 ℃ and carry out, reacted 0.5～20 hour.
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| CN200910253209A CN101717342A (en) | 2009-12-04 | 2009-12-04 | Method for synthesizing 2,5-diamino phenyl ethanol |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103242177A (en) * | 2013-04-28 | 2013-08-14 | 浙江工业大学 | Preparation method of 2,5-diaminophenethyl alcohol sulfate |
| CN111440077A (en) * | 2020-05-15 | 2020-07-24 | 上海舒尔发化妆品科技有限公司 | Synthesis method of 2, 5-diaminophenylethanol sulfate and application thereof in anti-allergic hair dye |
-
2009
- 2009-12-04 CN CN200910253209A patent/CN101717342A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103242177A (en) * | 2013-04-28 | 2013-08-14 | 浙江工业大学 | Preparation method of 2,5-diaminophenethyl alcohol sulfate |
| CN111440077A (en) * | 2020-05-15 | 2020-07-24 | 上海舒尔发化妆品科技有限公司 | Synthesis method of 2, 5-diaminophenylethanol sulfate and application thereof in anti-allergic hair dye |
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Application publication date: 20100602 |