CN105237488A - Synthesis method of benzotriazole - Google Patents
Synthesis method of benzotriazole Download PDFInfo
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- CN105237488A CN105237488A CN201510774530.6A CN201510774530A CN105237488A CN 105237488 A CN105237488 A CN 105237488A CN 201510774530 A CN201510774530 A CN 201510774530A CN 105237488 A CN105237488 A CN 105237488A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
- C07D249/16—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms condensed with carbocyclic rings or ring systems
- C07D249/18—Benzotriazoles
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Abstract
The invention relates to a synthesis method of benzotriazole. The benzotriazole is synthesized in one step through an o-phenylenediamine pressurization method. The synthesis method particularly comprises the following steps that 1, material feeding is conducted, wherein o-phenylenediamine, sodium nitrite and water are added into a stainless steel reaction kettle according to the proportion of 1 to 1.1-1.2 to 10-15; 2, heating and pressurization are conducted, wherein stirring is started, the temperature is increased to range from 240 DEG C to 260 DEG C, the pressure is controlled to range from 3.0 MPa to 4.0 MPa, and heat preservation reaction is conducted for 3-3.5 h; 3, the reacted mixture is transferred to an acidification kettle, wherein the temperature is decreased to range from 120 DEG C to 130 DEG C, and a reaction product is transferred to the acidification kettle; 4, pH adjustment and delamination are conducted, the PH value is adjusted from 11.7 to 5.0 through concentrated sulfuric acid, and delamination is conducted; 5, purification and collection are conducted, wherein the delaminated oil layer enters a rectifying kettle for decompression purification, and distillate products at 202-204 DEG C/15 mmHg are collected. The synthesis method of the benzotriazole has the advantages that acetic acid is not needed, side reactions are few, pollution is less, the yield is high, the reaction time is short, and continuous production can be achieved.
Description
Technical field
The present invention relates to organic synthesis field, particularly a kind of synthesis side of benzotriazole
Method.
Background technology
(English name Benzotriazole, is called for short BTA to benzotriazole; Also known as benzotriazole, benzotriazole, 124 Triazole, benzo triazole, benzothiophene) be a kind of important fine chemical product.
Having many uses of benzotriazole, the main inhibiter as copper and copper alloy, metal antirusting agent, photograph antifogging agent and organic synthesis intermediate; Also be widely used in paint additive, the sanitas of synthetic detergent, antithrombotics, lubricating oil additive, synthetic dyestuff intermediate, Polymer material stabilizer, plant-growth regulator, anti-blushing agent, vapour-phase inhibitor and ultraviolet absorbers.Benzotriazole and multiple inhibiter with the use of, can corrosion mitigating effect be improved; It also can with multiple Scale inhibitors, Biocidal algae-killing agent with the use of, to closed recirculating cooling water system, can good corrosion mitigating effect be produced.As added benzotriazole in automobile frostproofer, coating, the effect of protecting materials can be played; In mechanical processing process, benzotriazole is added in machining oil, the copper nondiscoloration of processing can be made.
In recent years, along with saving process water energetically, water quality stabilizer is just widely applied at industrial circles such as chemical industry, chemical fertilizer, iron and steel, and consumption is increasing.Along with the development of various countries' chemical industry, automotive industry and metal-processing industry, and the improving constantly of living standards of the people, increasing to the demand of benzotriazole.
At present, mainly following methods is adopted to the synthesis of benzotriazole:
(1) O-Phenylene Diamine non-pressure process, is first dissolved in O-Phenylene Diamine in aqueous acetic acid, and configures the sodium nitrite in aqueous solution of about 40%; Hybrid reaction after two kinds of solution are chilled to 1 ~ 5 DEG C in advance, and remain in ice bath, rapid temperature increases to 80 DEG C closed loop generates benzotriazole subsequently, and cooled and filtered, washing obtain thick product; Distill under absolute pressure is 2000Pa, collect the cut of 201 ~ 204 DEG C, obtain product with benzene crystallization, yield is 70% ~ 80%.Existing domestic production producer mostly adopts this method, but this method have O-Phenylene Diamine toxicity large, consume the shortcomings such as a large amount of acetic acid, product purification difficulty, yield are low, severe reaction conditions.
(2) benzimidazolone method, benzimidazolone and sodium nitrite in aqueous solution, at 190 DEG C, react 75 minutes under high pressure, and through acidifying, washing, drying, obtaining product yield is 85.3%.Because benzimidazolone is prepared by O-Phenylene Diamine and urea reaction, so expensive, constrain the application of this synthetic method.
(3) ortho-nitrophenyl hydrazine method, ortho-nitrophenyl hydrazine is in ammoniacal liquor, Virahol and hexylene glycol mixed aqueous solution, and under 140 DEG C and high pressure, reaction 1.5 hours, generates 1-hydroxy benzo triazole (HBTA).Make catalyzer with copper-chromium sesquioxide, pass into hydrogen and nitrogen according to 92: 8 ratios, deoxidation hydrogenation reaction 1 hour under 160 ~ 170 DEG C and high pressure, HB2TA deoxidation hydrogenation generates BTA, and the yield of final benzotriazole is 89%.
(4) o-Nitrochlorobenzene method, first directly synthesizes HBTA by o-Nitrochlorobenzene and hydrazine hydrate, and then deoxidation hydrogenation generates BTA, and the highest total recovery can reach 98.6%.This method advantage is that yield is high, middle-chain is few, is a kind of very promising and very important method.
Comprehensive above synthetic method, research and development a kind of few without the need to acetic acid, side reaction, pollute little, yield is high and the reaction times is short, can the synthetic method of quantity-produced to benzotriazole be necessary.
Summary of the invention
The technical problem to be solved in the present invention be to provide a kind of few without the need to acetic acid, side reaction, pollute little, yield is high and the reaction times is short, can the synthetic method of quantity-produced benzotriazole.
For solving the problems of the technologies described above, technical scheme of the present invention is: a kind of synthetic method of benzotriazole, and its innovative point is: by the pressurization one-step synthesis benzotriazole of O-Phenylene Diamine, concrete steps are as follows:
(1) feed intake: O-Phenylene Diamine, Sodium Nitrite and water are put in stainless steel cauldron in the ratio of 1:1.1 ~ 1.2:10 ~ 15;
(2) heat up pressurization: open stir, heat up, temperature is risen to 240 ~ 260 DEG C, pressure-controlling between 3.0 ~ 4.0MPa, insulation reaction 3 ~ 3.5 hours;
(3) be transferred to acidifying still: be cooled to 120 ~ 130 DEG C, reaction product be transferred to acidifying still; (4) pH and layering is adjusted: with the vitriol oil, pH value is adjusted to 5.0 from 11.7, layering;
(5) purify and collect: the oil reservoir after layering enters rectifying still to carry out decompression and purify, collection 202-204 DEG C/15mmHg cut product.
The invention has the advantages that: the synthetic method of benzotriazole of the present invention, by the pressurization one-step synthesis benzotriazole of O-Phenylene Diamine, do not need in this synthetic method to add acetic acid, and the method side reaction is little, pollute little, yield is high and the reaction times is short, can continuous seepage benzotriazole, and then enhance productivity.
Embodiment
The following examples can make the present invention of professional and technical personnel's comprehend, but therefore do not limit the present invention among described scope of embodiments.
embodiment 1
The synthetic method of the present embodiment benzotriazole, by the pressurization one-step synthesis benzotriazole of O-Phenylene Diamine, concrete steps are as follows:
(1) feed intake: 100g O-Phenylene Diamine, 110g Sodium Nitrite and 1000g water are put in 3000L stainless steel cauldron;
(2) heat up pressurization: open stir, heat up, temperature is risen to 240 DEG C, pressure-controlling between 3.0MPa, insulation reaction 3 hours;
(3) be transferred to acidifying still: be cooled to 120 DEG C, reaction product be transferred to acidifying still;
(4) pH and layering is adjusted: with the vitriol oil, pH value is adjusted to 5.0 from 11.7, layering;
(5) purify and collect: the oil reservoir after layering enters rectifying still to carry out decompression and purify, collection 202 DEG C/15mmHg cut product.
embodiment 2
The synthetic method of the present embodiment benzotriazole, by the pressurization one-step synthesis benzotriazole of O-Phenylene Diamine, concrete steps are as follows:
(1) feed intake: 100g O-Phenylene Diamine, 120g Sodium Nitrite and 1500g water are put in 3000L stainless steel cauldron;
(2) heat up pressurization: open stir, heat up, temperature is risen to 260 DEG C, pressure-controlling between 4.0MPa, insulation reaction 3.5 hours;
(3) be transferred to acidifying still: be cooled to 130 DEG C, reaction product be transferred to acidifying still;
(4) pH and layering is adjusted: with the vitriol oil, pH value is adjusted to 5.0 from 11.7, layering;
(5) purify and collect: the oil reservoir after layering enters rectifying still to carry out decompression and purify, collection 204 DEG C/15mmHg cut product.
embodiment 3
The synthetic method of the present embodiment benzotriazole, by the pressurization one-step synthesis benzotriazole of O-Phenylene Diamine, concrete steps are as follows:
(1) feed intake: 100g O-Phenylene Diamine, 115g Sodium Nitrite and 1250g water are put in 3000L stainless steel cauldron;
(2) heat up pressurization: open stir, heat up, temperature is risen to 250 DEG C, pressure-controlling between 3.5MPa, insulation reaction 3.2 hours;
(3) be transferred to acidifying still: be cooled to 125 DEG C, reaction product be transferred to acidifying still;
(4) pH and layering is adjusted: with the vitriol oil, pH value is adjusted to 5.0 from 11.7, layering;
(5) purify and collect: the oil reservoir after layering enters rectifying still to carry out decompression and purify, collection 203 DEG C/15mmHg cut product.
Following table is content and the yield situation of benzotriazole in embodiment 1 ~ 3 sintetics:
| Product | Embodiment 1 | Embodiment 2 | Embodiment 3 |
| Benzotriazole content | 99.6% | 99.5% | 99.7% |
| Yield | 98.6% | 98.5% | 98.7% |
As can be seen from the above table, the product synthesized by synthetic method of the present invention, in product, the content of benzotriazole can reach 99.5%, and yield reaches 98.5%, and compared with the product synthesized with prior synthesizing method, yield substantially increases.
The technician of the industry should understand; the present invention is not restricted to the described embodiments; what describe in above-described embodiment and specification sheets just illustrates principle of the present invention; without departing from the spirit and scope of the present invention; the present invention also has various changes and modifications, and these changes and improvements all fall in the claimed scope of the invention.Application claims protection domain is defined by appending claims and equivalent thereof.
Claims (1)
1. a synthetic method for benzotriazole, is characterized in that: by the pressurization one-step synthesis benzotriazole of O-Phenylene Diamine, concrete steps are as follows:
(1) feed intake: O-Phenylene Diamine, Sodium Nitrite and water are put in stainless steel cauldron in the ratio of 1:1.1 ~ 1.2:10 ~ 15;
(2) heat up pressurization: open stir, heat up, temperature is risen to 240 ~ 260 DEG C, pressure-controlling between 3.0 ~ 4.0MPa, insulation reaction 3 ~ 3.5 hours;
(3) be transferred to acidifying still: be cooled to 120 ~ 130 DEG C, reaction product be transferred to acidifying still;
(4) pH and layering is adjusted: with the vitriol oil, pH value is adjusted to 5.0 from 11.7, layering;
(5) purify and collect: the oil reservoir after layering enters rectifying still to carry out decompression and purify, collection 202-204 DEG C/15mmHg cut product.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106588794A (en) * | 2016-11-30 | 2017-04-26 | 南通波涛化工有限公司 | Preparation method for 5-tolytriazole |
| CN107382885A (en) * | 2017-07-27 | 2017-11-24 | 潍坊奥通药业有限公司 | The preparation method of the triazoles of 1H 1,2,3 |
| CN108586365A (en) * | 2018-03-21 | 2018-09-28 | 南通波涛化工有限公司 | A kind of preparation method of high-purity 4- methyl benzotriazazoles |
| CN110016001A (en) * | 2019-05-30 | 2019-07-16 | 武汉创新特科技有限公司 | A kind of continuous synthetic method of benzotriazole |
| CN110041277A (en) * | 2019-04-26 | 2019-07-23 | 江苏扬农化工集团有限公司 | A kind of method and apparatus of benzotriazole Synthesis liquid serialization post-processing |
| CN110105296A (en) * | 2019-05-10 | 2019-08-09 | 江苏扬农化工集团有限公司 | The synthetic method of benzotriazole sodium salt and benzotriazole |
| CN110156705A (en) * | 2019-05-28 | 2019-08-23 | 江苏扬农化工集团有限公司 | A kind of method of benzotriazole Synthesis liquid acidification tail gas resource utilization |
| CN110590687A (en) * | 2019-11-07 | 2019-12-20 | 山东豪迈化工技术有限公司 | Preparation method of benzotriazole |
| CN111116502A (en) * | 2018-10-30 | 2020-05-08 | 中国石油化工股份有限公司 | One-step method for synthesizing benzotriazole |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106588794A (en) * | 2016-11-30 | 2017-04-26 | 南通波涛化工有限公司 | Preparation method for 5-tolytriazole |
| CN107382885A (en) * | 2017-07-27 | 2017-11-24 | 潍坊奥通药业有限公司 | The preparation method of the triazoles of 1H 1,2,3 |
| CN107382885B (en) * | 2017-07-27 | 2020-05-12 | 潍坊奥通药业有限公司 | Preparation method of 1H-1,2, 3-triazole |
| CN108586365A (en) * | 2018-03-21 | 2018-09-28 | 南通波涛化工有限公司 | A kind of preparation method of high-purity 4- methyl benzotriazazoles |
| CN111116502A (en) * | 2018-10-30 | 2020-05-08 | 中国石油化工股份有限公司 | One-step method for synthesizing benzotriazole |
| CN110041277A (en) * | 2019-04-26 | 2019-07-23 | 江苏扬农化工集团有限公司 | A kind of method and apparatus of benzotriazole Synthesis liquid serialization post-processing |
| DE112020002120T5 (en) | 2019-04-26 | 2022-01-27 | Jiangsu Yangnong Chemical Group Co., Ltd. | Process and apparatus for the continuous aftertreatment of a benzotriazole synthetic fluid |
| CN110105296A (en) * | 2019-05-10 | 2019-08-09 | 江苏扬农化工集团有限公司 | The synthetic method of benzotriazole sodium salt and benzotriazole |
| CN110156705A (en) * | 2019-05-28 | 2019-08-23 | 江苏扬农化工集团有限公司 | A kind of method of benzotriazole Synthesis liquid acidification tail gas resource utilization |
| CN110016001A (en) * | 2019-05-30 | 2019-07-16 | 武汉创新特科技有限公司 | A kind of continuous synthetic method of benzotriazole |
| CN110590687A (en) * | 2019-11-07 | 2019-12-20 | 山东豪迈化工技术有限公司 | Preparation method of benzotriazole |
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Effective date of registration: 20160526 Address after: 226500, 2, Xiangjiang Road, Changjiang town (Rugao port area), Nantong, Jiangsu, Rugao Applicant after: NANTONG BOTAO CHEMICAL CO., LTD. Address before: Jiang town Rugao City, Jiangsu province 226500 Nantong City Village Liaison Applicant before: Rugao Jinling Chemical Co., Ltd. |
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Application publication date: 20160113 |