CN1057254A - Chinese gall Beihua tannin is synthetic produces 3,4, the 5-TMB - Google Patents

Abstract

A kind of synthetic 3,4 from Chinese gall Beihua tannin, the production technology of 5-TMB.It is mainly used in and produces synthetic antibiotic synergistic agent (TMP).The present invention is divided into esterification, hydrazine reaction and three production processes of oxidizing reaction, critical process is the esterification that contains greater than the doubly flower tannin of 60-65% tannin, adopt alkali hydrolysis method esterification 3,4,5-tri-methoxybenzoate yield can reach 106-110%, 3,4,5-trimethoxy benzhydrazide yield 84-87%; 3,4,5-TMB yield 77-81%.Product purity is 90-91%.Adopting the present invention is low 2.8579 ten thousand yuan/ton of raw material production cost with tripe times Weibull, and economic benefit is remarkable unusually, has vast market prospect.

Description

Chinese gall Beihua tannin is synthetic produces 3,4, the 5-TMB

The present invention relates to a kind of organic synthesis industrial production, specifically produce 3,4, the 5-TMB by Chinese gall Beihua tannin is synthetic.

3,4,5-TMB (3,4,5-Trimethoxybenzaldehyde is called for short TMB), molecular formula is C ₁₀H ₁₂O ₄, molecular weight is 196.2, it is mainly used in the raw material of producing synthetic antibiotic synergistic agent (TMP).Quite popular on the market at home and abroad, in TMB produces, one of critical process is preparation 3,4, the 5-tri-methoxybenzoate, pharmaceutical industry has the production process route that maturation is general both at home and abroad, each factory is similar on controlling of production process, all adopts acid-hydrolysis method to carry out esterification, and most of factory is a raw material with tripe times Weibull all, minority producer adopts the Turkey-galls vat liquor that is concentrated to a certain degree, also has to adopt the tara tannin vat liquor that is concentrated to a certain degree.

Utilize the synthetic production 3,4 of Chinese gall Beihua tannin alkali hydrolysis method, the 5-TMB is not seen so far the domestic and foreign literature report.And when utilizing tripe times Weibull to produce this product for raw material by acid hydrolysis, per ton cost reaches 12.9429 ten thousand yuan, the cost height, and cause environmental pollution serious, economic benefit is lower.

Task of the present invention is in order to reduce cost, to increase economic efficiency, open up raw material sources, utilize domestic Chinese gall Beihua tannin more than needed, alleviating the strained market supply problem of tripe times Weibull.

Finishing task of the present invention is to be raw material with the Chinese gall Beihua tannin, produces the fine product with alkali hydrolysis method through esterification, hydrazine reaction, oxidizing reaction.

Produce 10.0850 ten thousand yuan of product costs per ton by the present invention, product cost per ton was low 2.8579 ten thousand yuan when ratio was raw material by tripe times Weibull, that is to say so that doubly the flower tannin is synthetic and produce per ton 3,4, the 5-TMB can save 2.8579 ten thousand yuan, economic benefit is remarkable unusually, has vast market prospect, and also yield height than with tripe times Weibull time of the product yield of esterification, hydrazine reaction, oxidizing reaction three operations, product purity is also high, environmental pollution is also little, and this is because the reasonable corollary of operational path of the present invention.In addition, also can utilize original acid system production unit, need not increase new installation in addition, press alkali hydrolysis method and produce 3,4, the 5-TMB.

The production process route that the present invention determines is as follows:

(1) 3,4, the preparation of 5-tri-methoxybenzoate and production process

Pay reaction:

The sodium salt that free phenolic hydroxyl group forms under alkaline condition in the tannic acid molecule reacts with methyl-sulfate again, and this is a nucleophilic substitution reaction, and the band oxygen anion is to the carbonium atom attack of methyl-sulfate in the molecule.

So when methylating with methyl-sulfate, need under alkaline medium, to carry out, to increase anionic charge reactivity on the Sauerstoffatom, the dimethyl ester reactive behavior is big, be suitable for reacting under the low temperature, if the too high easy decomposition of temperature, simultaneously, gallic acid is a polyatomic phenol, it is very unstable during high temperature under alkalescence, oxidizing reaction easily takes place, and the temperature that therefore methylates is unsuitable too high, is controlled at 80-85 ℃, question response is finished again, and intensification is hydrolyzed, and constantly water is steamed, so that improve temperature of reaction, will help hydrolysis reaction and carry out.Can get 3 after the hydrolysis, 4,5-trimethoxy benzoic acid sodium and 3-hydroxyl-4-5-mesitylenic acid sodium, the two proceeds esterification under alkalescence, and the latter is in the esterified while of hydroxyl, go up hydroxyl for 3 and also carry out methylation reaction, in weakly alkaline solution, carry out the esterification of carboxyl with dimethyl ester, be an esterification that is of little use, but yield is very high, can think that methyl-sulfate by carboxylate anion's hydrolysis esterification is taken place:

Dropwise liquid is with control reaction solution alkalescence when esterification, and this is very crucial operation, and strict being controlled in the PH=8-9 scope reacted during the PH meta-acid not exclusively, and the carboxylate that then generates when crossing alkali easily is hydrolyzed.

The production process of esterification is roughly: add the water measure in reactor, stir and drop into Chinese gall Beihua tannin next time, add liquid caustic soda the 10-12 ℃ of first time, in the control warm 30-35 ℃, till not having an insolubles, drip (CH for the first time ₃) ₂SO ₄, the remaining methyl-sulfate and the second time are also flowed the liquid caustic soda that adds control PH=8-8.5, temperature 80-85 ℃, insulation reaction half an hour, add liquid caustic soda for the second time, make the PH=10-11 hydrolysis that heats up, boil off water in 100-105 ℃, steam and added tributyl phosphate for preventing to spume before the water and carry out froth breaking, steaming water needs 2-3 hour approximately, frozen cooling is to 40-45 ℃, drip methyl-sulfate for the third time, still surplus dimethyl ester and the 4th adding liquid caustic soda also flow, and make PH=8-8.5 constant, 1.5 hours time, add 36 ℃ of water, stir half an hour, repetition measurement PH is constant, dehydration, be washed to neutrality, centrifuging plays the material pack.

(2) 3,4, the preparation and the production process thereof of 5-trimethoxy benzhydrazide

Be the material input amount in hydrazine reaction post with esterification post quantum of output, in reaction by weight 1: 0.5-0.6 adds 3,4,5-tri-methoxybenzoate and hydrazine hydrate carry out the hydrazine reaction, should select a kind of solvent treatment of organic solvents such as toluene, benzene, ethanol, methyl alcohol for use.After being warming up to 68 ℃ and begin to stir, be warming up to 95 ℃ naturally, keep refluxing and reacted 3 hours down, a large amount of (50kg) boiling water of adding, the dissolving 1 hour that refluxes, naturally cooling 2 hours are finished in reaction, then be water-cooled to 30 ℃, standing over night, dehydration next day, and wash to PH=7-7.5 with massive laundering again, whizzer separates, collecting precipitation thing-3,4,5-trimethoxy benzhydrazide.

(3) 3,4, the preparation of 5-TMB and production process thereof

In the oxidizing reaction post, in hydrazine chemical industry preface gained hydrazine compound: ammoniacal liquor: red prussiate of potash: toluene: hydrochloric acid: yellow soda ash: water: the ratio of gac=1: 4.5-5.0: 2.5-3.5: 9.0-10.5: 0.1-0.2: 0.03-0.04: 12.0-13.0: 0.05-0.06, add toluene earlier, ammoniacal liquor, the hydrazine compound of reaction gained, in 10-15 minute, drip red prussiate of potash liquid in 25 ℃, in 42-45 ℃ of insulation reaction 40 minutes, leave standstill and made its layering in 20 minutes, after 85 ℃ of concentrated deammoniations, this is after filtration under diminished pressure, the layering jar is interior through pickling, alkali cleaning, washing, at temperature 95-120 ℃ filtration under diminished pressure, after steaming toluene, remaining liquid cooling, solidify and product 3,4, the 5-TMB.In order to remove colloid, in the reaction beginning or reaction finishes or the water washing product is optional adds the processing of decolouring of a gac, product color is shoaled.

Generally speaking, it is that raw material is that this product of raw material production is compared with acid-hydrolysis method tripe times tannin that alkali hydrolysis method is doubly spent tannin, although though the esterification yield is the same, be 100-105%, yet during the hydrazine reaction, product yield is respectively 90%, 85-87%, or alkali hydrolysis method height; During oxidizing reaction, product yield is respectively 85-86%, and 76-78% is still the alkali hydrolysis method height.Alkali hydrolysis method produces 3,4 with Chinese gall Beihua tannin, and 5-TMB production process route is reasonable, reliable, feasible.

Embodiment 1: product batch number 9008002

By aforesaid three production processes is raw material with the Chinese gall Beihua tannin, and through the production of esterification, hydrazineization, oxidation three operations, by aforesaid production control condition, it is qualified 3,4 to obtain, 5-trimethoxy-benzene first wine aldehyde product.In the esterification post, drop into Chinese gall Beihua tannin 275kg, methyl-sulfate 770kg, liquid caustic soda 742kg and water 450kg can obtain 3,4, the 5-tri-methoxybenzoate output 303kg that wets, yield is 109.8%, straight product amount 218.79kg, content are 88.7%, moisture 18.74%.In the hydrazine post, drop into esterification post gained carboxylate 204kg, hydrazine hydrate 112.2kg and water 50kg obtain 3,4,5-trimethoxy benzhydrazide product, its wet amount is 217.4kg, and is moisture 12.89%, content 93.26%, straight product amount 176.6kg; Yield 86.57%.In the oxidation post, drop into 3,4,5-trimethoxy benzhydrazide 60kg, ammoniacal liquor 300kg, red prussiate of potash 181kg, toluene 720l, hydrochloric acid 12kg, yellow soda ash 3kg and gac 4kg.Reaction gained 3,4, the 5-TMB is 40.0kg, content 90.6%, yield 76.86%.

Embodiment 2: product batch number 9008003

In the esterification post, drop into Chinese gall Beihua tannin 275kg, methyl-sulfate 770kg, liquid caustic soda 742kg and water 450kg by aforementioned production control condition, obtain the wet volume production thing 285kg of this operation the application carboxylate, moisture 16.02%, this carboxylate content 89.02%, pure carboxylate amount 213kg, yield is 106.7%.In the hydrazine post, drop into this carboxylate 213.0kg, hydrazine hydrate 112.9kg and water 60kg.Obtain the application's the wet volume production thing 228kg of benzhydrazide, moisture 13.67%, this hydrazides content 92.87%, the pure products amount is 182.8kg, yield 85.8%.In the oxidation post, feed intake by embodiment 1, and produce by the aforementioned operation process, get the application's aldehyde product 40.5kg, content 90.5%, yield are 77.8%.

Embodiment 3: product batch number 9008005

In the esterification post, feed intake by embodiment 1 charging capacity, and by aforementioned production control condition, obtain the wet volume production thing 302kg of the application's carboxylate, moisture 21.27%, this carboxylate content 89.48%, pure carboxylate content 213.0kg, yield 106.7%.In the hydrazine post, drop into this carboxylate 212.6kg, hydrazine hydrate 114kg, water 55kg obtain the application's the wet volume production thing 248kg of benzhydrazide, and be moisture 20.27%, benzhydrazide content 90.10%, pure products amount 178.15kg, yield 83.8%.In the oxidation post, charging capacity and working condition obtain the application's aldehyde product 42kg with embodiment 1, and content 89.9%, yield are 80.7%.

Claims (7)

1, a kind of 3,4, the production technology of 5-TMB (being called for short TMB) is characterized in that with the Chinese gall Beihua tannin being starting raw material, and through esterification, hydrazine reaction, oxidizing reaction three-procedure are finished production;

2, by claim 1 described 3,4,5-TMB production technology, it is characterized in that using Chinese gall Beihua tannin and methyl-sulfate (divide four the adding) reaction of tannin content greater than 60-65%, and divide and be added dropwise to liquid caustic soda four times, control PH=8-9, and the weight proportion of reaction mass is a Chinese gall Beihua tannin: sulfuric acid=methyl esters: liquid caustic soda: water=1: 2.5-3.0: 2.5-3.0: 1.5-2.0;

3, by claim 1 and 2 described 3,4,5-TMB production technology, it is characterized in that adding water, after adding Chinese gall Beihua tannin and adding the part liquid caustic soda, add the part of sulfuric acid dimethyl ester, control PH=8-8.5 is under temperature 80-85 ℃, insulation reaction half an hour, add liquid caustic soda control PH=10-11 intensification hydrolysis then, boil off water in 100-105 ℃, add the tributyl phosphate froth breaking before beginning to steam water, frozen cooling is to 40-45 ℃, add methyl-sulfate and liquid caustic soda again, PH=8-8.5 is constant in control, reacts 1.5 hours, add behind the big water gaging and stirring, keep PH=8-8.5 constant, be washed to neutrality, centrifuging, finish this esterification, yield can reach 106-110%;

4, described 3,4 by claim 1,5-TMB production technology is characterized in that 3,4, and 5-trimethoxy benzene methyl and hydrazine hydrate are proceeded the hydrazine reaction, and its ratio of components is 3,4,5-trimethoxy benzene methyl: hydrazine hydrate=1: 0.5-0.6;

5, by claim 1 and 4 described 3,4,5-TMB production technology, it is characterized in that adding in the reactor methyl esters and hydrazine hydrate 3,4, two kinds of reactants of 5-trimethoxybenzoic acid, being warming up to 68 ℃ begins to stir, stop to heat to 85 ℃, be warming up to 95 ℃ naturally, keep refluxing 3 hours, the complete boiling water that adds of reaction, reflux and dissolved 1 hour, naturally cooling 2 hours, logical water coolant are chilled to 30 ℃, standing over night, dehydration, massive laundering is to PH=7-7.5, and centrifuging plays material, get 3,4,5-trimethoxy benzhydrazide, yield are 84-87%;

6, by claim 1 described 3,4,5-TMB production technology, it is characterized in that 3,4,5-trimethoxy benzhydrazide continues with the red prussiate of potash oxidation, and the proportioning of its reactant is the hydrazine compound of gained: ammoniacal liquor: red prussiate of potash: toluene: hydrochloric acid: yellow soda ash: water: gac=1: 4.5-5.0: 2.5-3.5: 9-10.5: 0.1-0.2: 0.03-0.04: 12.0-13.0: 0.05-0.06

7, by claim 1 and 6 described 3,4,5-TMB production technology is characterized in that adding earlier toluene, ammoniacal liquor, reaction gained hydrazine compound, in the time of 25 ℃, drip red prussiate of potash in 10 minutes, in 42-45 ℃ of insulation reaction 40 minutes, standing demix, mother liquor concentrates deammoniation, this was after reduced pressure, the layering jar is interior through pickling, alkali cleaning, the washing, at temperature 95-120 ℃ filtration under diminished pressure, steam toluene after, remaining liquid cooling, solidify and product 3,4, the 5-TMB, the oxidizing reaction yield is 77-81%, product purity is 90-91%, and, reaction beginning reaction finishes or the water washing product after optionally add an activated carbon decolorizing and handle.