CN104649991A

CN104649991A - Water-soluble 1-phenyl-5-mercaptotetrazole derivative and preparation method thereof

Info

Publication number: CN104649991A
Application number: CN201310597605.9A
Authority: CN
Inventors: 刘现梅
Original assignee: Individual
Current assignee: Individual
Priority date: 2013-11-25
Filing date: 2013-11-25
Publication date: 2015-05-27

Abstract

The invention discloses a water-soluble 1-phenyl-5-mercaptotetrazole derivative and a preparation method thereof. The method is characterized by: taking a sulfuric acid solution as the solvent, subjecting 1-phenyl-5-mercaptotetrazole and maleic anhydride to addition reaction, carrying out filtering, alkali dissolution, acidification and other purification on the reaction produced carboxyl containing intermediate compound, then carrying out amidation reaction with diethanol amine to generate the water-soluble 1-phenyl tetrazole derivative. The composition has good water solubility, is dicarboxylic acid amide of an organic heterlcyclic ring, has the characteristic that multiple sustained-release groups combine with metals, can play an excellent antirust role, and has resistance to hard water. Also, the yield is high, and the process is simple.

Description

A kind of water-soluble 1-phenyl-5-mercapto tetrazole derivative and preparation method thereof

Technical field

The present invention relates to organic inhibition additive synthesis technical field, espespecially a kind of water-soluble 1-phenyl-5-mercapto tetrazole derivative and preparation method thereof.

Background technology

Water-based metal working fluid is because having excellent cooling, cleaning, rust-preventing characteristic, the advantage such as economy and security, be developed rapidly, and be widely used in cutting, grinding, calendering, the metal processing sectors such as punching press and tapping, inhibiter is the important component part of water-based metal working fluid, along with the development and application of organic rust preventing additive, inorganic salts rust-inhibiting additive is substituted gradually, carboxyl is the essential groups of natural organic ligand and melts combine, the size of its corrosion inhibition, depend primarily on molecular structure, in metallic surface, keying action is played to molecular adsorption.

1-phenyl-5-mercapto tetrazole is a kind of heterocyclic inhibiter; but its poorly water-soluble; by functional group and reaction; the derivative of synthesis 1-phenyl-5-mercapto tetrazole; make in its molecule containing plural eluting group; the while of increasing water miscible, by physical adsorption be chemisorbed on metallic surface and form the protective membrane aligned, thus slow down and inhibit corrosion of metal.

Summary of the invention

The object of the present invention is to provide a kind of water-soluble 1-phenyl-5-mercapto tetrazole derivative and preparation method thereof.

Technical solution of the present invention is: to achieve these goals, technical solution of the present invention is: take sulphuric acid soln as solvent, 1-phenyl-5-mercapto tetrazole and MALEIC ANHYDRIDE carry out addition reaction, after the carboxylic intermediate compound that its reaction generates after filtration, alkali dissolution, acidifying etc. purify, amidate action is carried out again with diethanolamine, generate water-soluble 1-phenyl tetranitroazole derivative, specifically comprise following steps:

1). take sulphuric acid soln as solvent, 1-phenyl-5-mercapto tetrazole (I) is dissolved in sulphuric acid soln, at 40 DEG C ~ 60 DEG C, add MALEIC ANHYDRIDE in batches, react 2 ~ 4 hours, be cooled to less than 30 DEG C, generate carboxylic intermediate compound (III), its main chemical reactions is:

2). the above-mentioned reaction mass of thin up, filter, filter cake alkaline aqueous solution dissolves, and being adjusted to PH is 9 ~ 10, and again cross and filter insolubles, it is 1 ~ 3 that filtrate acid solution is acidified to PH, filters, washes, carboxylic intermediate compound (III) of purifying;

3). the carboxylic intermediate compound (III) of purification, with a small amount of water for solvent, react with diethanolamine (IV), at 110 ~ 140 DEG C, carry out back flow reaction 3 ~ 5 hours, reaction mixture is lowered the temperature, underpressure distillation removing moisture, obtained 1-phenyl tetranitroazole derivative rust-inhibiting additive (V), its main chemical reactions is:

Further, the mol ratio of described 1-phenyl-5-mercapto tetrazole, MALEIC ANHYDRIDE and diethanolamine is 1 ﹕ 1 ~ 1.2 ﹕ 2 ~ 2.5.

Described alkaline aqueous solution is one or both in sodium hydroxide solution and sodium carbonate solution.

Described acid solution is dilution heat of sulfuric acid.

A kind of water-soluble 1-phenyl-5-mercapto tetrazole derivative of the present invention and preparation method thereof, its feature and advantage are: synthetics good water solubility; Be a kind of dicarboxylic acid acid amides of organic heterocyclic, there is the characteristic of multiple eluting group and melts combine, excellent rust inhibition can be played; Synthetics has the performance of resistance to hard water; Productive rate is high, and technique is simple, is applicable to suitability for industrialized production.

Embodiment

Embodiment 1

In the there-necked flask that whipping appts and thermometer are housed, add the sulfuric acid 150ml of 75%, add the 1-phenyl-5-mercapto tetrazole of 36 grams, it is made to dissolve in sulphuric acid soln, at 40 DEG C ~ 60 DEG C, add the MALEIC ANHYDRIDE of 20 grams in batches, react 2 ~ 4 hours, be cooled to less than 30 DEG C, generate carboxylic intermediate compound, the above-mentioned reaction mass of thin up, filter, filter cake aqueous sodium carbonate dissolves, being adjusted to PH is 9 ~ 10, again cross and filter insolubles, it is 1 ~ 3 that filtrate dilution heat of sulfuric acid is acidified to PH, filter, washing, carboxylic intermediate compound of purifying loads in four-hole bottle, add 10 grams of water and 43 grams of diethanolamine, at 100 ~ 120 DEG C, carry out reaction 3 ~ 5 hours, reaction mixture is lowered the temperature, underpressure distillation removing moisture, obtained water-soluble 1-phenyl-5-mercapto tetrazole derivative rust-inhibiting additive.

Embodiment 2

In the there-necked flask that whipping appts and thermometer are housed, add the sulfuric acid 160ml of 75%, add the 1-phenyl-5-mercapto tetrazole of 38 grams, it is made to dissolve in sulphuric acid soln, at 40 DEG C ~ 60 DEG C, add the MALEIC ANHYDRIDE of 25 grams in batches, react 2 ~ 4 hours, be cooled to less than 30 DEG C, generate carboxylic intermediate compound, the above-mentioned reaction mass of thin up, filter, filter cake aqueous sodium hydroxide solution dissolves, being adjusted to PH is 9 ~ 10, again cross and filter insolubles, it is 1 ~ 3 that filtrate dilution heat of sulfuric acid is acidified to PH, filter, washing, carboxylic intermediate compound of purifying loads in four-hole bottle, add 11 grams of water and 43 grams of diethanolamine, at 120 ~ 130 DEG C, carry out reaction 3 ~ 5 hours, reaction mixture is lowered the temperature, underpressure distillation removing moisture, obtained water-soluble 1-phenyl-5-mercapto tetrazole derivative rust-inhibiting additive.

Embodiment 3

In the there-necked flask that whipping appts and thermometer are housed, add the sulfuric acid 200ml of 75%, add the 1-phenyl-5-mercapto tetrazole of 50 grams, it is made to dissolve in sulphuric acid soln, at 40 DEG C ~ 60 DEG C, add the MALEIC ANHYDRIDE of 30 grams in batches, react 2 ~ 4 hours, be cooled to less than 30 DEG C, generate carboxylic intermediate compound, the above-mentioned reaction mass of thin up, filter, filter cake aqueous sodium carbonate dissolves, being adjusted to PH is 9 ~ 10, again cross and filter insolubles, it is 1 ~ 3 that filtrate dilution heat of sulfuric acid is acidified to PH, filter, washing, carboxylic intermediate compound of purifying loads in four-hole bottle, add 16 grams of water and 70 grams of hydroxy-alkyl secondary, at 130 ~ 140 DEG C, carry out reaction 3 ~ 5 hours, reaction mixture is lowered the temperature, underpressure distillation removing moisture, obtained water-soluble 1-phenyl-5-mercapto tetrazole derivative rust-inhibiting additive.

The above; embodiment is only be described the preferred embodiment of the present invention; not scope of the present invention is limited; under the prerequisite of spirit not departing from the technology of the present invention; the various distortion that this area engineering technical personnel make technical scheme of the present invention and improvement, all should fall in protection domain that claims of the present invention determine.

Claims

1. water-soluble 1-phenyl-5-mercapto tetrazole derivative and preparation method thereof, it is characterized in that: take sulphuric acid soln as solvent, 1-phenyl-5-mercapto tetrazole and MALEIC ANHYDRIDE carry out addition reaction, after the carboxylic intermediate compound that its reaction generates after filtration, alkali dissolution, acidifying etc. purify, amidate action is carried out again with diethanolamine, generate water-soluble 1-phenyl tetranitroazole derivative, specifically comprise following steps:

1). take sulphuric acid soln as solvent, 1-phenyl-5-mercapto tetrazole is dissolved in sulphuric acid soln, at 40 DEG C ~ 60 DEG C, adds MALEIC ANHYDRIDE in batches, reacts 2 ~ 4 hours, is cooled to less than 30 DEG C, generates carboxylic intermediate compound;

2). the above-mentioned reaction mass of thin up, filter, filter cake alkaline aqueous solution dissolves, and being adjusted to PH is 9 ~ 10, and again cross and filter insolubles, it is 1 ~ 3 that filtrate acid solution is acidified to PH, filters, washes, carboxylic intermediate compound of purifying;

3). the carboxylic intermediate compound of purification, with a small amount of water for solvent, reacts with diethanolamine, at 110 ~ 140 DEG C, carry out back flow reaction 3 ~ 5 hours, reaction mixture is lowered the temperature, underpressure distillation removing moisture, obtained 1-phenyl tetranitroazole derivative rust-inhibiting additive.

2. the water-soluble 1-phenyl of one according to claim 1-5-mercapto tetrazole derivative and preparation method thereof, is characterized in that: the mol ratio of described 1-phenyl-5-mercapto tetrazole, MALEIC ANHYDRIDE and diethanolamine is 1 ﹕ 1 ~ 1.2 ﹕ 2 ~ 2.5; Described alkaline aqueous solution is one or both in sodium hydroxide solution and sodium carbonate solution; Described acid solution is dilution heat of sulfuric acid.