CN103613517B

CN103613517B - A kind of method preparing taurine

Info

Publication number: CN103613517B
Application number: CN201310664018.7A
Authority: CN
Inventors: 孙华君; 刘年金; 张邦国; 王平; 张军桥
Original assignee: HUANGGANG FUCHI PHARMACEUTICAL Co Ltd
Current assignee: Hubei Yuanda life science and Technology Co Ltd
Priority date: 2013-12-10
Filing date: 2013-12-10
Publication date: 2016-01-20
Anticipated expiration: 2033-12-10
Also published as: CN103613517A

Abstract

The invention provides a kind of method preparing taurine newly: with Nitromethane 99Min. and formaldehyde for raw material, synthesizing nitryl ethanol, then with bisulfite reaction, then through reduction, sulfuric acid acidation obtains taurine; This preparation method's raw material is easy to get, easy and simple to handle, is particularly suitable for large-scale industrial production.

Description

A kind of method preparing taurine

Technical field

The invention belongs to pharmaceutical synthesis field, being specifically related to take Nitromethane 99Min. as the novel method that starting raw material produces taurine.

Background technology

Taurine extracted gained because of 1827 from oxgall, therefore by scientist's called after Taurine (material from ox courage), domestic translated name is taurine.Taurine is a kind of sulfur-containing amino acid with simple chemical structure, and chemical name is 2-aminoethyl sulfonic acid, structural formula NH2CH2CH2SO3H.People think that it is a kind of nonfunctional last meta-bolites eventually of sulfur-containing amino acid always for a long time, are not taken seriously.Until Hayes in 1975 etc. report that cat lacks taurine and can cause blind, Rfilha etc. propose the taurine levels of agalactous baby for want of in taurine and blood plasma and urine can not maintain normal after, side causes people to the great interest of taurine.

Taurine is the important nutrient of people and animal, is also the main component of rare Chinese medicine cow-bezoar, and it is present in the nearly all internal organs of Mammals in a free form, and in central nervous system, content is especially abundant.Taurine has important physiological action, can promote that brain cell is grown, improve immunizing power, alleviating fatigue, adjustment nerve conduction.Taurine also has important pharmacological action, has anti-inflammatory, antipyretic, analgesia, antiviral effect.Taurine also can be applicable to the fields such as medicine, health care, food, washing composition, white dyes, pH buffer reagent, also can be used as the intermediate of biochemical reagents and other organic syntheses.

The production method of taurine generally has two kinds: a kind of method extracts from natural resources (such as pluck); Another kind method is chemical synthesis process.Because the natural taurine extracted from pluck can not meet current needs far away, thus, become the inexorable trend of Developing heavily through chemical process synthesized taurine.

Because taurine plays very important role in the life of people, also have much new purposes being constantly found, its consumption, also in continuous growth, has attracted a lot of people constantly to remove to explore the approach of its synthetic.So far, about the synthetic method nearly tens of kinds of taurine.Wherein more valuable synthetic method roughly has more than ten to plant, and what have actual application value concentrates on girbotol process, epoxyethane method.Girbotol process is very long for reaction time, and wherein sulfonation reaction needs more than 30h, and high expensive, will be eliminated gradually in face of the market competition of fierceness.Epoxyethane method raw materials cost is lower than girbotol process.Current domestic industryization reaches certain scale.But full scale plant cost is high, and energy consumption is high, reaction needed High Temperature High Pressure, raw material transport, stores and production process unsafe factor and be restricted more.Raw material oxyethane (EO) is only second to poly important Organic chemical products in ethylene industry derivative, the direct oxidation method that it is main raw material that current China almost all adopts with ethene and oxygen.Because the processing unit major part in EO production system has inflammable and explosive, the feature such as poisonous and harmful, high temperature, high pressure, deep cooling low temperature, the safety problem of production is even more important.Oxyethane is a kind of chemical substance of inflammable, explosive and easy polymerization reaction take place.Oxyethane flash-point <-17.8 DEG C (open loop), boiling point 10.4 DEG C, under 1 atmospheric pressure, limits of explosion is 3% ~ 100% (V), and hazard level is A-grade in the first class's class.Oxyethane is a kind of strong narcotic, can cause acute poisoning and chronic poisoning, belong to and highly endanger chemical mediator.Oxyethane chemical property is very active, and contact basic metal, oxyhydroxide or high activated catalyst such as the oxide compound of the anhydrous chloride of iron, tin and aluminium and iron and aluminium can heat release in a large number, and can set off an explosion.

Summary of the invention

The present invention relates to a kind of novel method of producing taurine, its object is to solve high etc. the problem of existing potential safety hazard, the energy consumption with oxyethane being the method for raw material exists.Taurine new process for producing provided by the invention raw material Nitromethane 99Min., hydrosulphite and the vitriol oil used is all easy to get; there is no the potential safety hazard of oxyethane; in addition, taurine new process for producing provided by the invention also has the advantages such as technique environmental protection, easy to operate, less energy-consumption, yield are higher, easy suitability for industrialized production.

The invention discloses a kind of method of synthesized taurine: take Nitromethane 99Min. as raw material, first synthesizing nitryl ethanol, then adds hydrosulphite; intermediate product is without separation, and catalytic hydrogen reduction nitro is amino, then by solution and catalyst separating; use sulfuric acid adjust pH, filtration drying obtains taurine.

The structural formula that structural formula [1] is taurine:

The preparation method of taurine comprises the steps:

(1) addition: by Nitromethane 99Min. (as Suo Shi structural formula [2]) and formaldehyde in the basic conditions addition obtain the nitroethyl alcohol shown in structural formula [3];

This step reaction formula is as follows:

(2) replace: nitroethyl alcohol and bisulfite reaction obtain the nitro-ethyl sulfonate shown in structural formula [4];

Wherein, M is basic metal, ammonium ion.

This step reaction formula is as follows:

(3) reduction, acidifying: through reduction, sulfuric acid acidation obtains the taurine shown in structural formula [1].

This step reaction formula is as follows:

Wherein: the temperature of reaction described in step (1) is 25 ~ 120 DEG C, reaction solvent is methyl alcohol, ethanol, propyl alcohol, Virahol, formic acid, acetic acid, water or their mixture, and also can be solvent-free, the reaction times be 2 ~ 21h.

Reaction described in step (1) alkali used is basic metal, alkaline earth metal hydroxides, acetate, carbonate, ammoniacal liquor, ammonium salt, triethylamine, pyridine or their mixture.

Hydrosulphite described in step (2) is its alkali metal salts or ammonium salt;

Replacement and reduction step solvent for use are methyl alcohol, ethanol, propyl alcohol, Virahol, formic acid, acetic acid, water or their mixture, and temperature of reaction is 20 ~ 90 DEG C, and the reaction times is 2.5 ~ 23h.

Reduction catalyst described in step (3) comprises RanneyNi, Pd/C or ferrous sulfate/hydrazine hydrate.

Accompanying drawing explanation

Fig. 1 represents the hydrogen spectrum of nitroethyl alcohol: dominant absorption peak-to-peak:

¹HNMR(400MHz,CDCl ₃):δ4.55(t,2H,J=4.4Hz),4.34(s,1H),4.14(s,2H)

Fig. 2 represents the hydrogen spectrum of nitro-ethyl sodium sulfonate: major absorbance peak:

¹HNMR(400MHz,D ₂O):δ4.73(t,2H,J=4.0Hz),3.47(t,2H,J=4.0Hz)

Fig. 3 represents the hydrogen spectrum of taurine: major absorbance peak:

¹HNMR(500MHz,D ₂O):δ3.34(t,2H,J=5.0Hz),3.17(t,2H,J=5.0Hz)

Embodiment:

The synthetic method one of embodiment 1:2-nitroethyl alcohol

At 30 DEG C, in 2000mL reactor, add paraformaldehyde (50g, 1.56mol), Nitromethane 99Min. (285.6g, 4.7mol, 253mL), acetic acid 2.5L opens stirring, adds Glacial acetic acid potassium (5g, 0.05mol), continue to stir 3h, then temperature rising reflux 30min.Unreacted Nitromethane 99Min. and solvent acetic acid are reclaimed in underpressure distillation, obtain 139.8g red oil, yield 92.1%, without purification, directly carry out next step reaction. ¹HNMR(400MHz,CDCl ₃):δ4.55(t,2H,J=4.4Hz),4.34(s,1H),4.14(s,2H)。

The synthetic method two of embodiment 2:2-nitroethyl alcohol

At room temperature, under agitation, in 20L reactor, Nitromethane 99Min. (762.5g is added, 12.5mol, 675mL), paraformaldehyde (100g, 3.12mol), add sodium hydroxide (3.2g, 0.08mol), methyl alcohol 8L continues to stir 5h, then temperature rising reflux 2h.Unreacted Nitromethane 99Min. and solvent methanol are reclaimed in underpressure distillation, obtain 286.6g pale yellow oil, yield 94.6%, without purification, directly carry out next step reaction.

Embodiment 3: the synthetic method one of taurine

At 20 DEG C, add 10% aqueous sodium hydroxide solution 500mL in 2000mL reactor, passing into sulfur dioxide gas to pH value is 5.8, then add nitroethyl alcohol (164g, 1.8mol), stir 18h, [concentrated, obtain nitro-ethyl sodium sulfonate white solid ¹hNMR (400MHz, D ₂o): δ 4.73 (t, 2H, J=4.0Hz); 3.47 (t, 2H, J=4.0Hz)]; add RanneyNi20g, pass into hydrogen, question response is complete; separate aqueous layer and catalyzer; with vitriol oil adjust pH to point of equivalent, separate out taurine, suction filtration, dry 180g taurine; yield 80%, fusing point 319 DEG C (dec). ¹HNMR(500MHz,D ₂O):δ3.34(t,2H,J=5.0Hz),3.17(t,2H,J=5.0Hz)。

Embodiment 4: the synthetic method two of taurine

At room temperature, in 5000mL reactor, sodium bisulfite (375g, 3.6mol) is added; the 2800mL that adds water dissolves, and then adds nitroethyl alcohol (273g, 3mol); stir 21h, add 10%Pd/C30g, pass into hydrogen; question response is complete; separate aqueous layer and catalyzer, with vitriol oil adjust pH to point of equivalent, separate out taurine; suction filtration, dry 308g taurine, yield 82.1%.

Embodiment 5: the synthetic method three of taurine

At room temperature, in 10L reactor, add Potassium hydrogen sulfite (869g, 7.2mol), the 3000mL that adds water dissolves, then add nitroethyl alcohol (546g, 6mol), stir 15h, add 3000mL ethanol, 85% hydrazine hydrate (384g, 12mol amount to into pure hydrazine), adds FeSO ₄7H ₂o (8.3g, 0.5mol%), temperature rising reflux, question response is complete, concentrated, with vitriol oil adjust pH to point of equivalent, separates out taurine, suction filtration, dry 597g taurine, yield 79.6%.

Claims

1. a preparation method for taurine, the method comprises the steps:

(1) at room temperature, under agitation, add Nitromethane 99Min. 762.5g, paraformaldehyde 100g, add sodium hydroxide 3.2g in 20L reactor, methyl alcohol 8L continues to stir 5h, then temperature rising reflux 2h; Unreacted Nitromethane 99Min. and solvent methanol are reclaimed in underpressure distillation, obtain pale yellow oil nitroethyl alcohol, without purification, directly carry out next step reaction;

(2) at room temperature; in 5000mL reactor, add sodium bisulfite 375g, the 2800mL that adds water dissolves, and then adds nitroethyl alcohol 273g; stir 21h; add 10%Pd/C30g, pass into hydrogen, question response is complete; separate aqueous layer and catalyzer; with vitriol oil adjust pH to point of equivalent, separate out taurine, suction filtration, to be drying to obtain.