CN105294572A - Preparation method of mono-methoxyl pyrilamine - Google Patents
Preparation method of mono-methoxyl pyrilamine Download PDFInfo
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- CN105294572A CN105294572A CN201510656065.6A CN201510656065A CN105294572A CN 105294572 A CN105294572 A CN 105294572A CN 201510656065 A CN201510656065 A CN 201510656065A CN 105294572 A CN105294572 A CN 105294572A
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- preparation
- pyrimidine
- residual quantity
- temperature
- amine
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- ZDNWAKRJMZVACF-UHFFFAOYSA-N CN(C)c1nc(C=O)cc(Cl)n1 Chemical compound CN(C)c1nc(C=O)cc(Cl)n1 ZDNWAKRJMZVACF-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
- C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
- C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
- C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more 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, directly attached to ring carbon atoms
- C07D239/32—One oxygen, sulfur or nitrogen atom
- C07D239/42—One nitrogen atom
Abstract
The invention discloses a preparation method of mono-methoxyl pyrilamine. According to the method, dichloropyrimidine and sodium methoxide are used as raw materials for performing nucleophilic substitution reaction. The method comprises the steps including reaction decoloration, thermal filtration, crystallization, centrifugation and drying. The reaction and the decoloration are completed in one step, so that the synthesis steps are greatly reduced; the operation work procedure is simplified. Crude product refining is not needed. Compared with the existing preparation method, the preparation method has the obvious advantages in the aspects of reducing the production cost, reducing the environment harm, maintaining the human body health and the like.
Description
Technical field
The invention belongs to pesticide synthesis technical field, be specifically related to a kind of preparation method of a methoxy pyrimidine amine.
Background technology
One methoxy pyrimidine amine, chemistry is by name: 2-amino-4-chloro-6-methoxylpyrimidin, and English name is 2-Amino-4-chloro-6-methoxypyrimidine; No. CAS: 5734-64-5; Its structural formula as shown in the formula:
One methoxy pyrimidine amine is pesticide intermediate, and it can be used for synthesizing sulfonylurea pesticide, as benbbensulfuronmethyl, nicosulfuron, AC322140, ethoxysulfuron, rimsulfuron, amidosulfuron etc.
At present, the synthetic route of a methoxy pyrimidine amine is as follows:
In said synthesis route, main production operation process comprises:
1), in reactor drop into methyl alcohol, dichloro pyrimidine, after being warming up to backflow, drip sodium methylate, drip and terminate insulation reaction 2h; 2), be incubated and terminate, by solvent evaporate to dryness, then add water, stir 1h; The solvent methanol steamed can be applied mechanically; 3), stop stirring, filter squeezed into by material, and filtrate (waste water) enters sewage lagoon; Solid is sent from the heart, and the material after centrifugal is a methoxy pyrimidine amine crude product; 4), in decolouring still drop into toluene, methoxy pyrimidine amine crude product and a gac, be warming up to backflow, the moisture remained separated by water trap simultaneously in reactor; Divided material filtered while hot after water, filtrate enters crystallization kettle, and filter residue (waste active carbon) is collected, and regularly processes; 5), by material in crystallization kettle be cooled to normal temperature, then put into suction filtration tank and carry out suction filtration; Filtrate collection is applied mechanically, and solid is sent from the heart, and the material after centrifugal send drying; Control moisture and be not more than 0.3wt%, the material after oven dry is a methoxy pyrimidine amine.
1), the first synthesis crude product that adopts of this technique the defect that above-mentioned technique exists has:, and then carries out the operational path refined, needs to change solvent in production, and relates to filtration, centrifugal for twice, and operating process is very loaded down with trivial details; 2), distillation adds water after terminating, its object is to the impurity, inorganic salt etc. that remove wherein, but produce the waste water that therefore 1 ton of crude product can produce about about 10 tons, and the methyl alcohol of this waste water containing the 2%wt that has an appointment and the sodium-chlor of about 3.6wt%, COD and salinity are all very high, and later stage cost for wastewater treatment is very large; 3), early stage methyl alcohol distillation and later stage one methoxy pyrimidine amine crude product cause because of moisture bleaching time extend 4-6h, all can cause a large amount of thermal waste; In above-mentioned two operations, often produce 1 ton of one methoxy pyrimidine amine meeting loss about 6.5 tons of steam; 4), this technique changes solvent and washing because relating to, and complex operation, cause a methoxy pyrimidine amine total recovery lower, generally at 86-90%; 5), because of this technological operation loaded down with trivial details, in operating process, material is easily exposed in air, and toluene smell is comparatively large, causes production environment poor, easily causes personnel's Nausea and vomiting, the symptom such as poisoning.
Summary of the invention
The object of this invention is to provide a kind of preparation method of a methoxy pyrimidine amine, the method solves the complex operation existed in existing synthetic method, the technical problem such as energy consumption is high, yield is low, environmental hazard is large preferably.
Above-mentioned purpose of the present invention is achieved by the following scheme:
The preparation method of one methoxy pyrimidine amine, carries out nucleophilic substitution reaction with dichloro pyrimidine and sodium methylate for raw material, comprises the steps:
(1) react, decolour
Methyl alcohol, dichloro pyrimidine and gac are put in reactor, is warming up to backflow; Sodium methylate is dripped after backflow insulation; Dropping is incubated after terminating, and then detects the residual quantity controlling dichloro pyrimidine in still by liquid phase chromatography, prepares heat filtering after continuing insulation;
(2) heat filtering
Material in still is squeezed into heat filtering machine, and filtrate enters crystallization kettle; Heat filtering machine remaining solid is waste active carbon, regularly processes separately after collection;
(3) crystallization
Crystallization kettle open water coolant carry out lowering the temperature, stir after prepare centrifugally operated;
(4) centrifugal
Automatic discharge centrifuge put into by crystallization kettle material, and filtrate collection repeatedly uses; Drying machine is sent after solid materials pack;
(5) dry
Start closed negative pressure formula drying plant and solvent reclaimer, regulate input speed and temperature, dry and control material moisture, the material after oven dry is a methoxy pyrimidine amine.
Further, the intensification of reactor and insulating process are in above-mentioned steps (1): reactor is warming up to 60 ~ 70 DEG C of backflows; Sodium methylate is dripped after backflow insulation 15min; Dropping terminates rear insulation 30min; The residual quantity controlling dichloro pyrimidine in still reaches the follow-up continuation of insurance temperature 3h of requirement.
In above-mentioned steps (1), the residual quantity of dichloro pyrimidine controls as follows: dichloro pyrimidine residual quantity > 0.5wt%, then add quantitative sodium methylate, until dichloro pyrimidine residual quantity < 0.5wt%.
Above-mentioned steps (3) crystallisation process is further: crystallization kettle is opened water coolant and lowered the temperature, and stops cooling after temperature is down to 30 DEG C, continues stirring and prepares centrifugally operated after 1 hour.
Material moisture < 0.3wt% is controlled in above-mentioned steps (5).
Compared with prior art, the beneficial effect that the present invention has is:
1, reaction of the present invention and decolouring are that a step completes, and substantially reduce synthesis step, simplify operation sequence; Adopt the mode of direct heat filtering to make whole process without the participation of water, thus avoid the generation of waste water, decrease the harm to environment.
2, the present invention does not produce a methoxy pyrimidine amine crude product, thus without the need to carrying out crude product refining, while decreasing operation steps, avoids the use of toluene equal solvent; Mother liquor can be applied mechanically continuously, and the total recovery of a methoxy pyrimidine amine can reach 92-95%.
3, this is simple to operate in the present invention, and it is little that material exposes probability, and without obvious smell, operating environment is better, decreases the Health hazard to personnel.
Accompanying drawing explanation
Fig. 1 is process schematic representation of the present invention.
Embodiment
For ease of understanding the present invention, it is as follows that the present invention enumerates embodiment.Those skilled in the art should understand, described embodiment only understands the present invention for helping, and should not be considered as concrete restriction of the present invention.
As no specific instructions, various raw material of the present invention all can be obtained by commercially available; Or prepare according to the ordinary method of this area.Unless otherwise defined or described herein, all specialties used herein and scientific words and art technology skillfully the person of entering the same meaning be familiar with.In addition any method similar or impartial to described content and material all can be applicable in the inventive method.
An a kind of methoxy pyrimidine amine Preparation Method, with dichloro pyrimidine and sodium methylate for raw material carries out nucleophilic substitution reaction, specific operation process is:
(1) reaction and decolouring: methyl alcohol, dichloro pyrimidine and gac are put in reactor in the lump, is warming up to backflow (about 67 DEG C); Sodium methylate is dripped after backflow insulation 15min; Drip and terminate insulation 30min, then detect the residual quantity of dichloro pyrimidine in still by liquid phase chromatography; If residual quantity > is 0.5wt%, then add quantitative sodium methylate; Continue insulation 3h, prepare heat filtering.
(2) heat filtering: after insulation terminates, material in still is squeezed into heat filtering machine, and filtrate enters crystallization kettle; Heat filtering machine remaining solid is waste active carbon, regularly process after collecting.
(3) crystallization: crystallization kettle is opened water coolant and lowered the temperature, and stops cooling after temperature is down to 30 DEG C, continues to stir 1h; Prepare centrifugally operated.
(4) centrifugal: automatic discharge centrifuge put into by crystallization kettle material, and filtrate collection repeatedly uses; Drying machine is sent after solid materials pack.
(5) dry: to start closed negative pressure formula drying plant and solvent reclaimer, regulate input speed and temperature; Control material containing wet < 0.3wt%, the material after oven dry is a methoxy pyrimidine amine.
The quantity of above-mentioned main reaction still, strainer, crystallization kettle is configured by 2:1:2, and whizzer and drying machine day output are not less than 2d output; Centrifuge filtrate feeds intake when reaching two reactor feed amounts immediately; Two main reaction still operation rhythm are consistent, and carry out heat filtering simultaneously, farthest can shorten the operating time.Meanwhile, the present invention is without the need to carrying out crude product refining, and mother liquor can be applied mechanically continuously, and the total recovery of product can reach 92-95%.Preparation method provided by the invention compared with original preparation method, at reduction production cost, reduce environmental hazard, safeguard health of human body etc. in have obvious advantage.
Applicant states, person of ordinary skill in the field is on the basis of above-described embodiment, by the concrete content point value of above-described embodiment component, combined with the technical scheme of summary of the invention part, thus the new numerical range produced, also be one of record scope of the present invention, the application, for making specification sheets simple and clear, no longer enumerates these numerical ranges.
Claims (5)
1. the preparation method of a methoxy pyrimidine amine, carries out nucleophilic substitution reaction with dichloro pyrimidine and sodium methylate for raw material, it is characterized in that comprising the steps:
(1) react, decolour
Methyl alcohol, dichloro pyrimidine and gac are put in reactor, is warming up to backflow; Sodium methylate is dripped after backflow insulation; Dropping is incubated after terminating, and then detects the residual quantity controlling dichloro pyrimidine in still by liquid phase chromatography, prepares heat filtering after continuing insulation;
(2) heat filtering
Material in still is squeezed into heat filtering machine, and filtrate enters crystallization kettle; Heat filtering machine remaining solid is waste active carbon, otherwise processed after collecting;
(3) crystallization
Crystallization kettle open water coolant carry out lowering the temperature, stir after prepare centrifugally operated;
(4) centrifugal
Automatic discharge centrifuge put into by crystallization kettle material, and filtrate collection repeatedly uses; Drying machine is sent after solid materials pack;
(5) dry
Start closed negative pressure formula drying plant and solvent reclaimer, regulate input speed and temperature, dry and control material moisture, the material after oven dry is a methoxy pyrimidine amine.
2. the preparation method of a methoxy pyrimidine amine as claimed in claim 1, is characterized in that, intensification and the insulating process of the middle reactor of described step (1) are: reactor is warming up to 60 ~ 70 DEG C of backflows; Sodium methylate is dripped after backflow insulation 15min; Dropping terminates rear insulation 30min; The residual quantity controlling dichloro pyrimidine in still reaches the follow-up continuation of insurance temperature 3h of requirement.
3. the preparation method of a methoxy pyrimidine amine as claimed in claim 1, it is characterized in that, in described step (1), the residual quantity of dichloro pyrimidine controls as follows: dichloro pyrimidine residual quantity > 0.5wt%, then add quantitative sodium methylate, until dichloro pyrimidine residual quantity < 0.5wt%.
4. the preparation method of a methoxy pyrimidine amine as claimed in claim 1, is characterized in that, described step (3) is: crystallization kettle is opened water coolant and lowered the temperature, and stops cooling after temperature is down to 30 DEG C, prepares centrifugally operated after continuing to stir 1h.
5. the preparation method of a methoxy pyrimidine amine as claimed in claim 1, is characterized in that, controls material moisture < 0.3wt% in described step (5).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201510656065.6A CN105294572A (en) | 2015-10-13 | 2015-10-13 | Preparation method of mono-methoxyl pyrilamine |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201510656065.6A CN105294572A (en) | 2015-10-13 | 2015-10-13 | Preparation method of mono-methoxyl pyrilamine |
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| CN105294572A true CN105294572A (en) | 2016-02-03 |
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| CN201510656065.6A Pending CN105294572A (en) | 2015-10-13 | 2015-10-13 | Preparation method of mono-methoxyl pyrilamine |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106053691A (en) * | 2016-07-19 | 2016-10-26 | 安徽广信农化股份有限公司 | Method for measuring content of 4,6-dichloropyrimidine |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4547215A (en) * | 1983-03-24 | 1985-10-15 | E. I. Du Pont De Nemours And Company | Herbicidal sulfonamides |
| US20060035913A1 (en) * | 2002-10-26 | 2006-02-16 | Sylvia Huber | Method for the production of 2-amino-4-chloro-6-alkoxypyrimidines |
| CN101711241A (en) * | 2007-02-06 | 2010-05-19 | 诺瓦提斯公司 | PI 3-kinase inhibitors and methods of their use |
| CN102603651A (en) * | 2012-02-27 | 2012-07-25 | 安徽丰乐农化有限责任公司 | Novel synthesis process of high-purity pesticide intermediate |
-
2015
- 2015-10-13 CN CN201510656065.6A patent/CN105294572A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4547215A (en) * | 1983-03-24 | 1985-10-15 | E. I. Du Pont De Nemours And Company | Herbicidal sulfonamides |
| US20060035913A1 (en) * | 2002-10-26 | 2006-02-16 | Sylvia Huber | Method for the production of 2-amino-4-chloro-6-alkoxypyrimidines |
| CN101711241A (en) * | 2007-02-06 | 2010-05-19 | 诺瓦提斯公司 | PI 3-kinase inhibitors and methods of their use |
| CN102603651A (en) * | 2012-02-27 | 2012-07-25 | 安徽丰乐农化有限责任公司 | Novel synthesis process of high-purity pesticide intermediate |
Non-Patent Citations (2)
| Title |
|---|
| 孔繁蕾，等: "2-氨基嘧啶类系列化合物的合成", 《化学世界》 * |
| 朱路，等: "2-氨基-4-氯-6-甲氧基嘧啶的合成", 《郑州大学学报(自然科学版)》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106053691A (en) * | 2016-07-19 | 2016-10-26 | 安徽广信农化股份有限公司 | Method for measuring content of 4,6-dichloropyrimidine |
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