CN110734407A - method for preparing triazine ring by pot method - Google Patents
method for preparing triazine ring by pot method Download PDFInfo
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- CN110734407A CN110734407A CN201911313269.4A CN201911313269A CN110734407A CN 110734407 A CN110734407 A CN 110734407A CN 201911313269 A CN201911313269 A CN 201911313269A CN 110734407 A CN110734407 A CN 110734407A
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- triazine ring
- pot
- methanol
- solvent methanol
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D253/00—Heterocyclic compounds containing six-membered rings having three nitrogen atoms as the only ring hetero atoms, not provided for by group C07D251/00
- C07D253/02—Heterocyclic compounds containing six-membered rings having three nitrogen atoms as the only ring hetero atoms, not provided for by group C07D251/00 not condensed with other rings
- C07D253/06—1,2,4-Triazines
- C07D253/065—1,2,4-Triazines having three double bonds between ring members or between ring members and non-ring members
- C07D253/07—1,2,4-Triazines having three double bonds between ring members or between ring members and non-ring members with hetero atoms, or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D253/075—Two hetero atoms, in positions 3 and 5
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- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for preparing triazine ring by a pot method of , which comprises the following steps of (1) carrying out cyclization reaction on 2-methyl thiosemicarbazide, dimethyl oxalate and sodium methoxide in solvent methanol, (2) recovering the solvent methanol by distillation after the cyclization reaction is finished, (3) adding water for continuous distillation after the methanol is distilled, and taking out residual solvent methanol by water, (4) supplementing water, adding hydrochloric acid for acidification to separate out crystals, (5) carrying out solid-liquid separation after cooling, and drying the solids to obtain the triazine ring.
Description
Technical Field
The invention belongs to the technical field of organic chemical synthesis, and particularly relates to a method for synthesizing triazine ring by - pot method.
Background
At present, a plurality of triazine ring synthesis process methods are provided, each company has a unique process for preparing triazine ring, but in order to improve the yield and quality of triazine ring, the triazine ring intermediate sodium salt is filtered, and due to the limitation of equipment or filter cloth, when the triazine ring sodium salt solid is filtered, part of sodium salt is dissolved in mother liquor, so that the yield loss is caused, wherein the yield is and is less than 70 percent, in the process of filtering the sodium salt, because a plurality of solvents exist in the sodium salt, the solvent smell is serious, the air environment is polluted, an alarm always gives an alarm, unnecessary property loss is caused, and a large amount of three wastes are generated.
For example, chinese CN101701012A discloses a synthesis method of triazine rings, which includes filtration of intermediate sodium salt of triazine ring, and the yield is only about 70%.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides methods for preparing triazine ring by pot method, wherein the pot method is adopted to synthesize triazine ring, so that the defects of material loss and environmental pollution caused by sodium salt produced in the intermediate process are overcome, and the yield and quality of triazine ring are improved.
The process route of the invention is as follows:
the technical scheme of the invention is as follows:
A pot method for preparing triazine ring, comprising the following steps:
(1) performing cyclization reaction on 2-methyl thiosemicarbazide, dimethyl oxalate and sodium methoxide in a solvent methanol;
(2) after the cyclization reaction is finished, recovering the solvent methanol by distillation;
(3) adding water for continuous distillation after the methanol distillation is finished, and taking out residual solvent methanol through water;
(4) adding water, adding hydrochloric acid, and acidifying to separate out crystal;
(5) and (4) cooling, carrying out solid-liquid separation, and drying the solid to obtain the triazine ring.
, in the step (1), the mass ratio of the 2-methyl thiosemicarbazide, the dimethyl oxalate and the sodium methoxide is 1 (1.8-2.1) to (3.7-4).
, in the step (1), the cyclization reaction is controlled at 38-48 ℃ and kept for 4.5-6 h.
, in the step (1), the using amount of the methanol is 6 to 8.5 times of the mass of the 2-methyl thiosemicarbazide.
, in the step (1), after mixing 2-methyl thiosemicarbazide, dimethyl oxalate and a part of solvent methanol, cooling to 10-20 ℃, slowly adding sodium methoxide, controlling the temperature not to exceed 20 ℃, adding the rest solvent methanol, heating to 38-48 ℃, and keeping the temperature for 4.5-6 h, wherein the mass ratio of the part solvent methanol to the rest solvent methanol is 35-40: 150-.
, in the step (2), the distillation is carried out under reduced pressure, and the vacuum degree is not lower than-0.08 MPa.
, in the step (3), the water addition amount is 0.9-1.1 times of the solvent methanol amount, the distilled water amount is 40-55% of the water addition amount, and the distillation adopts reduced pressure distillation, wherein the vacuum degree is controlled to be-0.045 Mpa to-0.055 Mpa, and the temperature is controlled to be 70-75 ℃.
And , in the step (4), the added water amount is 40-55% of the added water amount in the step (3).
In the step (4), , adding hydrochloric acid to adjust pH to 0.8-1.2, and further , wherein the hydrochloric acid is 30% by mass of hydrochloric acid, and the addition amount of the hydrochloric acid is 1.8-2.0 times of the mass of the 2-methyl thiosemicarbazide.
And , cooling to 10-15 ℃ for solid-liquid separation in the step (5).
Compared with the prior art, the synthesis method adopts steps, namely, the triazine ring is directly synthesized by pot method from raw material reaction, so that the process cost is reduced, the environmental protection benefit is improved, the problem of environmental pollution and air pollution caused by the formation of the sodium salt of the triazine ring is effectively solved, the triazine ring loss caused by intermediate links such as filtration and the like is avoided in the synthesis process, the yield of the triazine ring is improved, the total yield is 80-85%, and the purity is more than or equal to 99.5%.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further illustrated in detail below with reference to the following embodiments.
Example 1
Putting 24.2g of 2-methyl thiosemicarbazide into a 500ml four-neck bottle, adding 45g of dimethyl oxalate and 38g of methanol, adding ice water with the temperature of 10-15 ℃ into a water bath kettle, and cooling the raw materials; dropwise adding 90g of sodium methoxide at about 15 ℃ by a thermometer in the reaction liquid, stirring and dropwise adding, controlling the dropwise adding amount of the sodium methoxide, wherein the dropwise adding time is about 25min, and controlling the temperature to be not more than 20 ℃; after the dropwise addition is finished, 150g of methanol is added, and the temperature of a water bath kettle is raised to 38-48 ℃ for heat preservation; after the heat preservation time is 5 hours, cooling to 25-30 ℃, installing a distillation device, opening a vacuum pump, regulating the vacuum to be more than-0.08 MPa, and evaporating methanol; adding 180g of purified water after the methanol is evaporated, adjusting the temperature of a water bath to 70-75 ℃, adjusting a vacuum pump to-0.05 Mpa, evaporating 80g to 100g of water, and adding 80ml of water; then, the temperature is reduced, 44g of hydrochloric acid (30%) is used for adjusting the pH value to 0.8, and the water bath kettle is removed; and after crystals are separated out, cooling to 10-15 ℃ by using ice water, filtering to obtain the triazine ring, and drying to obtain the finished product triazine ring, wherein the calculated yield is 82%, and the purity is 99.6%.
Example 2
Putting 24.2kg 2-methyl thiosemicarbazide into a 1000L glass lined kettle, adding 50kg dimethyl oxalate and 39kg methanol, opening an ice brine valve , dropwise adding 96kg sodium methoxide at about 15 ℃ by a thermometer, dropwise adding for about 25min, controlling the temperature to be not higher than 20 ℃, adding 160kg methanol after dropwise adding, closing an ice brine valve , opening a steam valve , closing a stop valve after steam is emitted from a steam pipeline, heating, closing steam for heat preservation for 6h when the temperature is raised to 38 ℃ to 48 ℃, opening a methanol tank valve , opening a vacuum pump, evaporating methanol, opening a pure water pump after evaporation, opening a pure water valve , adding 200L purified water, closing a methanol tank pipeline valve , opening a wastewater tank pipeline valve , opening a vacuum pump, opening a steam valve , heating the kettle to 70 ℃ to 75 ℃, evaporating 100L water, adding 100L purified water, adding 48kg hydrochloric acid (30%), adjusting the pH to 0.9, closing a steam valve , opening a steam valve, opening a water valve, opening a ring cooling stop valve, opening a double-cone ring triazine ring condensing reaction kettle, drying, discharging the temperature of the kettle to 70 ℃ to reach 3615-85 ℃, and drying to obtain a qualified finished product.
The present invention is not limited to the above-described embodiments, and various changes can be made within the knowledge of those skilled in the art without departing from the gist of the present invention, and the contents of the changes still fall within the scope of the present invention.
Claims (10)
1, method for preparing triazine ring by pot method, which is characterized by comprising the following steps:
(1) performing cyclization reaction on 2-methyl thiosemicarbazide, dimethyl oxalate and sodium methoxide in a solvent methanol;
(2) after the cyclization reaction is finished, recovering the solvent methanol by distillation;
(3) adding water for continuous distillation after the methanol distillation is finished, and taking out residual solvent methanol through water;
(4) adding water, adding hydrochloric acid, and acidifying to separate out crystal;
(5) and (4) cooling, carrying out solid-liquid separation, and drying the solid to obtain the triazine ring.
2. The pot-process triazine ring preparation method as claimed in claim 1, wherein in the step (1), the mass ratio of 2-methyl thiosemicarbazide, dimethyl oxalate and sodium methoxide is 1 (1.8-2.1) to (3.7-4).
3. The pot-method triazine ring preparation method according to claim 1, characterized in that in the step (1), the cyclization reaction is controlled at 38-48 ℃ and kept for 4.5-6 h.
4. The pot-process triazine ring preparation method according to claim 1, wherein in step (1), methanol is used in an amount of 6-8.5 times the mass of 2-methyl thiosemicarbazide.
5. The pot-method triazine ring preparation method as claimed in claim 1, wherein in the step (1), 2-methyl thiosemicarbazide, dimethyl oxalate and part of solvent methanol are mixed, then the temperature is reduced to 10-20 ℃, then sodium methoxide is slowly added, the temperature is controlled not to exceed 20 ℃, then the rest solvent methanol is added, the temperature is increased to 38-48 ℃, the temperature is kept for 4.5-6 h, and the mass ratio of the part solvent methanol to the rest solvent methanol is 35-40: 150-.
6. The pot method for preparing triazine ring according to claim 1, wherein in the step (2), the distillation is performed under reduced pressure with the vacuum degree not lower than-0.08 MPa.
7. The pot-method triazine ring preparation method according to claim 1, characterized in that in step (3), the water addition amount is 0.9-1.1 times of the solvent methanol amount, the distilled water is 40-55% of the water addition amount, reduced pressure distillation is adopted for distillation, the vacuum degree is controlled to be-0.045 MPa to-0.055 MPa, the temperature is controlled to be 70 ℃ -75 ℃, and in step (4), the water addition amount is 40-55% of the water addition amount in step (3).
8. The pot process for preparing triazine ring according to claim 1, wherein hydrochloric acid is added to adjust pH to 0.8-1.2 in step (4).
9. The pot-process triazine ring preparation method according to claim 1, wherein the hydrochloric acid is 30% by mass and is added in an amount of 1.8-2.0 times the mass of 2-methylaminothiourea.
10. The pot-process triazine ring preparation method of claim 1, wherein in the step (5), the temperature is reduced to 10-15 ℃ for solid-liquid separation.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112759558A (en) * | 2020-12-30 | 2021-05-07 | 山东金城柯瑞化学有限公司 | Process for the preparation of triazine rings |
| CN113214176A (en) * | 2021-05-17 | 2021-08-06 | 山东汇海医药化工有限公司 | Preparation method of triazine ring product |
| CN113735790A (en) * | 2021-09-24 | 2021-12-03 | 山东汇海医药化工有限公司 | Method for recovering triazine ring from triazine ring cyclization mother liquor |
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| CN101701012A (en) * | 2009-11-20 | 2010-05-05 | 南通市纳百园化工有限公司 | Method for synthesizing triazine ring |
| CN101817789A (en) * | 2010-04-14 | 2010-09-01 | 如皋市信宇兽药原料有限公司 | Process for producing sulfamethoxydiazine |
| CN109485614A (en) * | 2017-09-11 | 2019-03-19 | 西安格瑞德化工新材料有限公司 | The synthesis piperazine technique of tricyclic |
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2019
- 2019-12-19 CN CN201911313269.4A patent/CN110734407A/en active Pending
Patent Citations (3)
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| CN101701012A (en) * | 2009-11-20 | 2010-05-05 | 南通市纳百园化工有限公司 | Method for synthesizing triazine ring |
| CN101817789A (en) * | 2010-04-14 | 2010-09-01 | 如皋市信宇兽药原料有限公司 | Process for producing sulfamethoxydiazine |
| CN109485614A (en) * | 2017-09-11 | 2019-03-19 | 西安格瑞德化工新材料有限公司 | The synthesis piperazine technique of tricyclic |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112759558A (en) * | 2020-12-30 | 2021-05-07 | 山东金城柯瑞化学有限公司 | Process for the preparation of triazine rings |
| CN112759558B (en) * | 2020-12-30 | 2022-06-14 | 山东金城柯瑞化学有限公司 | Process for the preparation of triazine rings |
| CN113214176A (en) * | 2021-05-17 | 2021-08-06 | 山东汇海医药化工有限公司 | Preparation method of triazine ring product |
| CN113735790A (en) * | 2021-09-24 | 2021-12-03 | 山东汇海医药化工有限公司 | Method for recovering triazine ring from triazine ring cyclization mother liquor |
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Application publication date: 20200131 |