CN104356163A - Water-soluble 1-phenyl-5-tetrazole-thione organic phosphate derivative - Google Patents
Water-soluble 1-phenyl-5-tetrazole-thione organic phosphate derivative Download PDFInfo
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- CN104356163A CN104356163A CN201410518905.8A CN201410518905A CN104356163A CN 104356163 A CN104356163 A CN 104356163A CN 201410518905 A CN201410518905 A CN 201410518905A CN 104356163 A CN104356163 A CN 104356163A
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Abstract
The invention discloses a water-soluble 1-phenyl-5-tetrazole-thione organic phosphate derivative. A sulfuric acid solution is taken as a solvent; 1-phenyl-5-tetrazole-thione and alpha-alkenyl acid react; the compound generated by the reaction passes through suction filtration and a filter cake, is resolved by alkali water solution, and is treated with secondary suction filtration, filter liquor acidation for purification, and reacts with hydroxyalkyl secondary amine; esterification reaction between amidate product generated by the reaction and phosphorus pentoxide is carried out. The compound is good in water-solubility, is tetrazole carboxylic acid amide organic phosphate, has the characteristics that a plurality of slow release perssads and metal are bound, can play excellent function of rust prevention, has extreme pressure property, and is high in property, simple in technology, and suitable for industrialized production.
Description
Technical field
The present invention relates to organic inhibition additive synthesis technical field, espespecially a kind of water-soluble 1-phenyl-5-mercapto tetrazole phosphate derivative.
Background technology
Inhibiter is a kind of important additive in intermetallic composite coating, in the process of metal working such as metal cutting, grinding, calendering, punching press and tapping, adding of inhibiter not only can make workpiece not corrode at inter process, and the equipment such as lathe, cutter that simultaneously workpiece can be made again to contact with it in the course of processing does not produce corrosion.Along with the development and application of organic rust preventing additive, inorganic salts rust-inhibiting additive is substituted gradually, and carboxyl is the size of the essential groups of natural organic ligand and melts combine, 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 phosphate derivative of synthesis 1-phenyl-5-mercapto tetrazole; make in its molecule containing multiple 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 phosphate 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 α-thiazolinyl acid are reacted, the compound that its reaction generates is after suction filtration, the dissolving of filter cake aqueous sodium hydroxide solution, the again purification such as suction filtration, acidification of filtrate, react with hydroxy-alkyl secondary again, the amidated products that its reaction generates, then carry out esterification with Vanadium Pentoxide in FLAKES further, specifically comprise following steps:
1) .1-phenyl-5-mercapto tetrazole (I) is dissolved in sulphuric acid soln, add α-thiazolinyl acid (II) on a small quantity in batches, react 3 ~ 4 hours at 50 DEG C ~ 60 DEG C temperature, be cooled to less than 30 DEG C, generate intermediate compound (III), its main chemical reactions is:
2). the above-mentioned reaction mass of thin up, suction filtration, the filter cake aqueous sodium hydroxide solution of 5% ~ 10% dissolves, suction filtration removing insolubles again, it is 1 ~ 2 that filtrate acid solution is acidified to pH, and object is separated out again, suction filtration, washing, obtain the intermediate compound (III) of purification;
3). take tetrahydrofuran (THF) as solvent, the intermediate compound (III) of purifying and hydroxy-alkyl secondary (IV) react, at 90 ~ 110 DEG C, carry out back flow reaction 4 ~ 5 hours, reaction mixture is lowered the temperature, underpressure distillation is except desolventizing, and obtain 1-phenyl tetrazole carboxamide derivative (V), its main chemical reactions is:
4) .1-phenyl tetrazole carboxamide derivative (V) and the Vanadium Pentoxide in FLAKES be dissolved in sherwood oil react; under 70 ~ 80 DEG C and nitrogen protection; carry out back flow reaction 2 ~ 3 hours; after completion of the reaction; reaction mixture is lowered the temperature; distillation removing sherwood oil, obtained water-soluble 1-phenyl-5-mercapto tetrazole phosphate derivative (VI) and (VII), its main chemical reactions is:
（Ⅵ） （Ⅶ）
In formula, R
1and R
2separate hydrogen atom, methyl, ethyl, propyl group, sec.-propyl, butyl or isobutyl-, R
3and R
4separate ethylidene, propylidene, isopropylidene or butylidene.
Further, the mol ratio of described 1-phenyl-5-mercapto tetrazole, α-thiazolinyl acid, diethanolamine and Vanadium Pentoxide in FLAKES is 1 ﹕ 1 ~ 1.1 ﹕ 1 ~ 1.4 ﹕ 1 ~ 1.2.
Described acid solution is dilution heat of sulfuric acid or dilute hydrochloric acid solution.
The water-soluble 1-phenyl of the present invention-5-mercapto tetrazole phosphate derivative, its feature and advantage are: synthetics good water solubility; Be a kind of carboxylic acid amide phosphoric acid ester of tetrazole, there is the characteristic of multiple eluting group and melts combine, excellent rust inhibition can be played; Synthetics also has extreme pressure property; Performance 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 120ml of 70%, add the 1-phenyl-5-mercapto tetrazole of 33 grams, it is made to dissolve in sulphuric acid soln, add 19 grams of α-pentenoic acids on a small quantity in batches, react 3 ~ 4 hours at 50 DEG C ~ 60 DEG C temperature, be cooled to less than 30 DEG C, the above-mentioned reaction mass of thin up, suction filtration, the filter cake aqueous sodium hydroxide solution of 7% dissolves, suction filtration removing insolubles again, it is 1 ~ 2 that filtrate dilute hydrochloric acid is acidified to pH, object is separated out again, suction filtration, washing, the intermediate compound that must purify, the intermediate compound of purifying loads in four-hole bottle, add 100 grams of tetrahydrofuran (THF)s and 27 grams of diethanolamine, at 90 ~ 110 DEG C, carry out back flow reaction 4 ~ 5 hours, reaction mixture is lowered the temperature, underpressure distillation is except desolventizing, obtained 1-phenyl tetrazole carboxamide derivative, 100 grams of sherwood oils and 29 grams of Vanadium Pentoxide in FLAKESs are added in four-hole bottle, dissolve, under 70 ~ 80 DEG C and nitrogen protection, carry out back flow reaction 2 ~ 3 hours, after completion of the reaction, reaction mixture is lowered the temperature, distillation removing sherwood oil, obtained water-soluble 1-phenyl-5-mercapto tetrazole phosphate derivative.
Embodiment 2
In the there-necked flask that whipping appts and thermometer are housed, add the sulfuric acid 100ml of 70%, add the 1-phenyl-5-mercapto tetrazole of 36 grams, it is made to dissolve in sulphuric acid soln, add 18.5 grams of methacrylic acids on a small quantity in batches, react 3 ~ 4 hours at 50 DEG C ~ 60 DEG C temperature, be cooled to less than 30 DEG C, the above-mentioned reaction mass of thin up, suction filtration, the filter cake aqueous sodium hydroxide solution of 10% dissolves, suction filtration removing insolubles again, it is 1 ~ 2 that filtrate dilution heat of sulfuric acid is acidified to pH, object is separated out again, suction filtration, washing, the intermediate compound that must purify, the intermediate compound of purifying loads in four-hole bottle, add 100 grams of tetrahydrofuran (THF)s and 10.5 grams of diethanolamine and 14 grams of diisopropanolamine (DIPA), at 90 ~ 110 DEG C, carry out back flow reaction 4 ~ 5 hours, reaction mixture is lowered the temperature, underpressure distillation is except desolventizing, obtained 1-phenyl tetrazole carboxamide derivative, 100 grams of sherwood oils and 28.8 grams of Vanadium Pentoxide in FLAKESs are added in four-hole bottle, dissolve, under 70 ~ 80 DEG C and nitrogen protection, carry out back flow reaction 2 ~ 3 hours, after completion of the reaction, reaction mixture is lowered the temperature, distillation removing sherwood oil, obtained water-soluble 1-phenyl-5-mercapto tetrazole phosphate derivative.
Embodiment 3
In the there-necked flask that whipping appts and thermometer are housed, add the sulfuric acid 150ml of 70%, add the 1-phenyl-5-mercapto tetrazole of 39 grams, it is made to dissolve in sulphuric acid soln, add 20.7 grams of alpha-butylene acid on a small quantity in batches, react 3 ~ 4 hours at 50 DEG C ~ 60 DEG C temperature, be cooled to less than 30 DEG C, the above-mentioned reaction mass of thin up, suction filtration, the filter cake aqueous sodium hydroxide solution of 5% dissolves, suction filtration removing insolubles again, it is 1 ~ 2 that filtrate dilute hydrochloric acid solution is acidified to pH, object is separated out again, suction filtration, washing, the intermediate compound that must purify, the intermediate compound of purifying loads in four-hole bottle, add 100 grams of tetrahydrofuran (THF)s and 36 grams of diisopropanolamine (DIPA), at 90 ~ 110 DEG C, carry out back flow reaction 4 ~ 5 hours, reaction mixture is lowered the temperature, underpressure distillation is except desolventizing, obtained 1-phenyl tetrazole carboxamide derivative, 120 grams of sherwood oils and 37 grams of Vanadium Pentoxide in FLAKESs are added in four-hole bottle, dissolve, under 70 ~ 80 DEG C and nitrogen protection, carry out back flow reaction 2 ~ 3 hours, after completion of the reaction, reaction mixture is lowered the temperature, distillation removing sherwood oil, obtained water-soluble 1-phenyl-5-mercapto tetrazole phosphate derivative.
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 (3)
1. a water-soluble 1-phenyl-5-mercapto tetrazole phosphate derivative, is characterized in that: described water-soluble 1-phenyl-5-mercapto tetrazole phosphate derivative is the compound with following (VI) and (VII) two kind of structure:
（Ⅵ）
（Ⅶ）
In formula, R
1and R
2separate hydrogen atom, methyl, ethyl, propyl group, sec.-propyl, butyl or isobutyl-, R
3and R
4separate ethylidene, propylidene, isopropylidene or butylidene.
2. the water-soluble 1-phenyl of one according to claim 1-5-mercapto tetrazole phosphate derivative, it is characterized in that: the preparation method of described water-soluble 1-phenyl-5-mercapto tetrazole phosphate derivative is: take sulphuric acid soln as solvent, 1-phenyl-5-mercapto tetrazole and α-thiazolinyl acid are reacted, the compound that its reaction generates is through suction filtration, filter cake aqueous sodium hydroxide solution dissolves, suction filtration again, after acidification of filtrate etc. are purified, react with hydroxy-alkyl secondary again, the amidated products that its reaction generates, esterification is carried out further again with Vanadium Pentoxide in FLAKES, specifically comprise following steps:
1) .1-phenyl-5-mercapto tetrazole is dissolved in sulphuric acid soln, adds α-thiazolinyl acid on a small quantity in batches, reacts 3 ~ 4 hours, be cooled to less than 30 DEG C, generate intermediate compound at 50 DEG C ~ 60 DEG C temperature;
2). the above-mentioned reaction mass of thin up, suction filtration, the filter cake aqueous sodium hydroxide solution of 5% ~ 10% dissolves, again suction filtration removing insolubles, and it is 1 ~ 2 that filtrate acid solution is acidified to pH, and object is separated out again, suction filtration, washing, obtains the intermediate compound of purification;
3). take tetrahydrofuran (THF) as solvent, the intermediate compound of purification and hydroxy-alkyl secondary react, and at 90 ~ 110 DEG C, carry out back flow reaction 4 ~ 5 hours, are lowered the temperature by reaction mixture, and underpressure distillation, except desolventizing, obtains 1-phenyl tetrazole carboxamide derivative;
4) .1-phenyl tetrazole carboxamide derivative and the Vanadium Pentoxide in FLAKES be dissolved in sherwood oil react; under 70 ~ 80 DEG C and nitrogen protection; carry out back flow reaction 2 ~ 3 hours; after completion of the reaction; reaction mixture is lowered the temperature; distillation removing sherwood oil, obtained water-soluble 1-phenyl-5-mercapto tetrazole phosphate derivative.
3. the water-soluble 1-phenyl of one according to claim 1-5-mercapto tetrazole phosphate derivative, is characterized in that: the mol ratio of described 1-phenyl-5-mercapto tetrazole, α-thiazolinyl acid, diethanolamine and Vanadium Pentoxide in FLAKES is 1 ﹕ 1 ~ 1.1 ﹕ 1 ~ 1.4 ﹕ 1 ~ 1.2; Described acid solution is dilution heat of sulfuric acid or dilute hydrochloric acid solution.
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| CN201410518905.8A CN104356163A (en) | 2014-10-06 | 2014-10-06 | Water-soluble 1-phenyl-5-tetrazole-thione organic phosphate derivative |
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| CN201410518905.8A CN104356163A (en) | 2014-10-06 | 2014-10-06 | Water-soluble 1-phenyl-5-tetrazole-thione organic phosphate derivative |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113789651A (en) * | 2021-09-10 | 2021-12-14 | 苏州泰克银纤维科技有限公司 | Preparation method of antioxidant chinlon DTY type fiber fabric |
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2014
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113789651A (en) * | 2021-09-10 | 2021-12-14 | 苏州泰克银纤维科技有限公司 | Preparation method of antioxidant chinlon DTY type fiber fabric |
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Application publication date: 20150218 |