CN1202487A - Two-step process for synthesizing anabasine - Google Patents
Two-step process for synthesizing anabasine Download PDFInfo
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- CN1202487A CN1202487A CN 97111398 CN97111398A CN1202487A CN 1202487 A CN1202487 A CN 1202487A CN 97111398 CN97111398 CN 97111398 CN 97111398 A CN97111398 A CN 97111398A CN 1202487 A CN1202487 A CN 1202487A
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Abstract
The present invention relates to two-step synthesis process to synthesize triazine group insect growth regulator, especially anabasine. the synthesis process includes the first step of preparing 2-cyclopropylamino-4,6-dichloro triazine and the second step of preparing anabasine in dioxolane or tetrahydrofuran solvent at 70-130 deg.C. It has yield of 60-70%, solvent amount of 2-6 times that of cyanuric chloride in weight ratio, liquid ammonia amount of 4-9 times that of cyanuric chloride in molar ratio, short flow path and technological period, and low product cost.
Description
The present invention relates to the technology of technology, the especially synthesizing anabasine of the synthetic triazine insect growth regulator(IGR) of a kind of two-step approach.
Anabasine is called fly eradication amine again, and its common name Cyroaazine, chemical name are R-cyclopropyl-1,3,5-triazines-2,4, the 6-triamine.United States Patent (USP) (us4225598,1980), U.S. chemical abstract (CA94:52939y etc.) have all disclosed physical and chemical performance, application and its preparation method etc. of this product.
Anabasine has special activity to Diptera larvae, inhales conduction in having, and can lure that Diptera larvae distorts on form into, and adult eclosion is not entirely or suppressed.According to the pertinent data record, if impose the anabasine of low effective dose, can be to lucilia, louse, Liriomyza have the better prevention effect.At present, in New Zealand, states such as Australia are applied to prevent and treat Diptera larvae on ox, the chimera, receive very good effect, and raising ox, woolfell quality are had active effect.
The technology of existing synthesizing anabasine mainly comprises following three step building-up processes:
The first step is synthetic to be preparation 2-cyclopropyl amino-4, the process of 6-dichloro sym-trinitrobenzene:
This step process mainly is that cyanuric chloride is suspended in the chlorobenzene solvent, with cyclopropylamine, sodium hydroxide reaction, removes chlorobenzene through static, washing, drying, filtration, underpressure distillation at a lower temperature, makes product 2-cyclopropyl amino-4,6-dichloro sym-trinitrobenzene.
Second step is synthetic to be the process of preparation 2-cyclopropyl amino-4-amino-6-chlorine sym-trinitrobenzene:
The synthetic 2-cyclopropyl amino-4 that mainly will in the first step building-up process, make of this step, 6-dichloro sym-trinitrobenzene, in the mixed solvent of dioxane and ether, react with ammoniacal liquor, its reaction solution makes product 2-cyclopropyl amino-4-amino-6-chlorine sym-trinitrobenzene through vacuum distilling, washing, filtration, drying etc.
The 3rd step is synthetic to be the process of preparation anabasine (N-cyclopropyl-1,3,5-triazines-2,4,6-triamine):
This step is synthetic mainly to be to synthesize the 2-cyclopropyl amino-4-amino-6-chlorine sym-trinitrobenzene that makes by above-mentioned second step, arise from reacting by heating in the dioxane solvent with ammonia one, its reaction solution removes solvent through cooling, underpressure distillation, the anabasine crude product that makes through washing, suction strainer, drying again, behind the boiling ethyl alcohol recrystallization, make final purpose product anabasine again.
The technology of above-mentioned synthesizing anabasine mainly is synthetic and corresponding treating processess of three steps, exists process many, and flow process and reaction time are long, the low problems such as (about 49.12%) of product once through yield; The solvent species of selecting for use is many, needs underpressure distillation to reclaim the product cost height.
The objective of the invention is to change the technology of three step synthesizing anabasines into two steps,, optimize processing condition, improve the product once through yield with minimizing process, shortening flow process and reaction time.
The present invention is based on improvement to synthesizing anabasine technology, all multifactor to technological process, temperature of reaction, solvent species and consumption thereof, material and the proportioning etc. that influence synthesizing anabasine, carry out exploratory experiment, on the repeated screening basis, carried out repeatedly stability test again.
Task of the present invention is achieved through the following technical solutions:
The two-step approach synthesizing anabasine, its the first step is synthetic to be in trichloroethylene solvent, cyanuric chloride and cyclopropylamine, sodium hydroxide reaction, collect product 2-cyclopropyl amino-4,6-dichloro sym-trinitrobenzene, its characteristics be second step synthetic be product (2-cyclopropyl amino-4,6-dichloro sym-trinitrobenzene) that the first step building-up process is collected in dioxolane or tetrahydrofuran solvent, under 70 ℃～130 ℃ temperature, produce anabasine with the liquefied ammonia reaction.
Synthetic used solvent dioxolane or tetrahydrofuran (THF) of second step in the technique scheme, its consumption is 2～6 times (weight ratios) of cyanuric chloride.
Synthetic preparation of second step anabasine in the technical solution of the present invention, its liquefied ammonia consumption is 4～9 times (mol ratios) of cyanuric chloride.
The present invention compares with existing three-step approach synthesis technique owing to adopted the two-step approach synthesizing anabasine, and following advantage is arranged:
1, reduced building-up process, shortened technical process and reaction time, the product once through yield brings up to 60～70% by 49.12% of former three-step approach synthesis technique;
2, used solvent dioxolane or the tetrahydrofuran (THF) of the synthesizing anabasine second step reaction process, its boiling point is lower than dioxane, be easy to distillation recovery under the normal pressure, and price is lower than the dioxane of import, can reduce product cost.
Accompanying drawing is the process flow diagram of two-step approach synthesizing anabasine.
Now wait in conjunction with the accompanying drawings and embodiments the present invention is further described as follows:
Accompanying drawing represents to improve the technological process that the two-step approach synthesizing anabasine is adopted in the back.Dotted line is the first step synthesis technique flow process with top among the figure, i.e. 2-cyclopropyl amino-4, the synthetic and product processing process of 6-dichloro sym-trinitrobenzene; Dotted line is the second step synthesis technique flow process with the lower section among the figure, promptly with above-mentioned the first step building-up process preparation and the product 2-cyclopropyl amino of collecting-4,6-dichloro sym-trinitrobenzene is a raw material, with the liquefied ammonia reaction, makes final purpose product anabasine in dioxolane or tetrahydrofuran solvent.
From top accompanying drawing as can be seen the present invention reduced the process of Synthetic 2-cyclopropyl amino-4-amino-6-chlorine sym-trinitrobenzene and processing thereof than the technology of existing three-step approach synthesizing anabasine.
From following table 1 as seen, the present invention selects for use dioxolane or tetrahydrofuran (THF) to make solvent, and the purpose product anabasine color that makes is better, and the boiling point of solvent for use is lower than dioxane, is easy to adopt air distillation to reclaim, and domestic production is arranged, and price is lower; With other dioxane mixed solvents, the appearance color of the final purpose product anabasine that makes is not ideal, color jaundice etc., and solvent is difficult to be reclaimed, and loss amount is big.Make solvent with single dioxane, though the anabasine yield that makes is also higher, 2-cyclopropyl amino-4,6-dichloro sym-trinitrobenzene dissolves slower therein, also needs underpressure distillation to reclaim dioxane, and the rate of recovery is low, therefore this products production of domestic nothing needs import, and costs an arm and a leg.
The used liquefied ammonia amount of synthesizing anabasine is that 4～9 times (mol ratios) of cyanuric chloride are advisable, and is more serious to equipment corrosion if consumption is low excessively, when consumption is too high, can make the reaction process hypertonia, and operation is not easy control.
Embodiment 1:
The first step is synthetic, promptly prepares 2-cyclopropyl amino-4,6-dichloro sym-trinitrobenzene and treating processes thereof:
One agitator is housed, condenser, in the four-hole boiling flask of the 3000ml of thermometer and dropping funnel, add the 2000ml trieline, start agitator, the cyanuric chloride of 420g 99.00% is suspended wherein, temperature is controlled at-9～-6 ℃ with the cryosel water-bath, drip the cyclopropylamine of 158.9ml, the time was controlled at more than 30 minutes, dripped the aqueous sodium hydroxide solution of 277.3g 35.00% then, the front reaction mixture was stirred 1.5 hours, under the normal temperature static 10 hours, then 1250ml water is added in the mixed solution, through shaking, static layering, collect product, use excessive anhydrous sodium sulfate drying, filter, its solution reclaims trieline through underpressure distillation, just make the 2-cyclopropyl amino-4 of 418.60g, 6-dichloro sym-trinitrobenzene, its content are 95.20%, and this step yield is 86.67%.
Second step is synthetic, promptly prepares anabasine and treating processes thereof:
It with the above-mentioned the first step synthetic content 2-cyclopropyl amino-4 of 95.20% 418.60g, 6-dichloro sym-trinitrobenzene is dissolved in the 1200ml dioxolane solvent, then this solution is moved on in 21 voltage-resistant reactors, feeds 279, the liquefied ammonia of 00g, temperature rises to 130 ℃ from room temperature; Constant temperature 20 hours, cool but to room temperature, reclaim dioxolane through the normal pressure distillation, remaining solid adds 1000ml water washing, filtration, collection solid, and drying makes the white powder of 253.70g, and promptly content is 94.50% anabasine, and this step yield is 73.85%.
Embodiment 2～4:
The first step is synthetic, promptly prepares 2-cyclopropyl amino-4, and 6-dichloro sym-trinitrobenzene and treating processes are all identical with the method for the first step synthetic (preparing identical product) among the embodiment 1.
Second step is synthetic, promptly prepares anabasine and treating processes.The required material of this step synthesizing anabasine, solvent, temperature of reaction, constant temperature time etc. have been provided in the table 2, as long as carry out according to the embodiment synthetic method that provides of 1 second step, just can make corresponding final purpose product anabasine, it must amount, content and this step yield are also all listed (referring to table 2) corresponding to each embodiment sequence number one by one in table 2.</entry></row></tbody></tgroup></table></tables>Annotate: 1. table internal solvent title back adds the * symbol, the solvent that expression the present invention selects for use.
2. yield means the second step building-up reactions yield.Required material, reaction conditions and product information slip in second step reaction of table 2 synthesizing anabasine
Annotate: this table anabasine yield is the second step synthetic yield among each embodiment.
| Embodiment | 2-cyclopropyl amino-4,6-dichloro sym-trinitrobenzene | Solvent | Temperature of reaction (℃) | Constant temperature time (hour) | Liquefied ammonia | Anabasine | |||||
| Consumption (g) | Content (%), W/W | The name of an article | Consumption (ml) | Consumption (g) | Content (%), W/W | Must measure (g) | Content (%), W/W | Yield (%) | |||
| ????2 | ??418.60 | ???95.20 | Tetrahydrofuran (THF) | 1000 | ????70 | ????20 | ?153.25 | ???99.00 | ??257.10 | ??95.00 | ?75.24 |
| ????3 | ??421.40 | ???94.75 | Dioxolane | 2377 | ????100 | ????20 | ?344.82 | ???99.00 | ??250.86 | ??93.24 | ?71.91 |
| ????4 | ??417.59 | ???96.17 | Tetrahydrofuran (THF) | 1275 | ????130 | ????20 | ?279.53 | ???99.00 | ??259.53 | ??94.11 | ?74.65 |
Claims (3)
1. the technology of a two-step approach synthesizing anabasine, comprise that mainly the first step is solvent with the trieline, cyanuric chloride and cyclopropylamine, sodium hydroxide reaction, collect 2-cyclopropyl amino-4,6-dichloro sym-trinitrobenzene product is characterized in that the product that second step was collected the preceding step, in dioxolane or tetrahydrofuran (THF), under 70～130 ℃ of temperature,, produce anabasine with the liquefied ammonia reaction.
2,, it is characterized in that dioxolane or tetrahydrofuran (THF) consumption are 2 to 6 times (weight ratio) of cyanuric chloride according to the technology of the described two-step approach synthesizing anabasine of claim 1.
3,, it is characterized in that the liquefied ammonia consumption is 4 to 9 times (mol ratio) of cyanuric chloride according to the technology of the described two-step approach synthesizing anabasine of claim 1.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97111398A CN1071321C (en) | 1997-06-18 | 1997-06-18 | Two-step process for synthesizing anabasine |
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| Application Number | Priority Date | Filing Date | Title |
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| CN97111398A CN1071321C (en) | 1997-06-18 | 1997-06-18 | Two-step process for synthesizing anabasine |
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| CN1202487A true CN1202487A (en) | 1998-12-23 |
| CN1071321C CN1071321C (en) | 2001-09-19 |
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| CN97111398A Expired - Fee Related CN1071321C (en) | 1997-06-18 | 1997-06-18 | Two-step process for synthesizing anabasine |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104876884A (en) * | 2014-11-24 | 2015-09-02 | 上海化工研究院 | Synthesis method of stable isotope-labeled cyromazine and its derivative |
| CN111777567A (en) * | 2020-07-27 | 2020-10-16 | 江西禾益化工股份有限公司 | Method for refining cyromazine technical product |
| CN112500360A (en) * | 2020-12-17 | 2021-03-16 | 浙江日出药业有限公司 | Safe and environment-friendly cyromazine synthesis method |
| CN112851594A (en) * | 2021-01-27 | 2021-05-28 | 山东道可化学有限公司 | High-yield synthesis method of cyromazine technical |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CH604517A5 (en) * | 1976-08-19 | 1978-09-15 | Ciba Geigy Ag | |
| US4187305A (en) * | 1978-02-17 | 1980-02-05 | Ciba-Geigy Corporation | Procedure for treating mammals to control parasitic diptera larvae |
| NL7905724A (en) * | 1979-07-24 | 1981-01-27 | Ciba Geigy | Cyclopropyl:amino di:amino triazine derivs. - useful for controlling parasitic diptera larvae in mammals |
-
1997
- 1997-06-18 CN CN97111398A patent/CN1071321C/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104876884A (en) * | 2014-11-24 | 2015-09-02 | 上海化工研究院 | Synthesis method of stable isotope-labeled cyromazine and its derivative |
| CN104876884B (en) * | 2014-11-24 | 2018-02-02 | 上海化工研究院有限公司 | A kind of synthetic method of cold labeling cyromazine and its derivative |
| CN111777567A (en) * | 2020-07-27 | 2020-10-16 | 江西禾益化工股份有限公司 | Method for refining cyromazine technical product |
| CN112500360A (en) * | 2020-12-17 | 2021-03-16 | 浙江日出药业有限公司 | Safe and environment-friendly cyromazine synthesis method |
| CN112851594A (en) * | 2021-01-27 | 2021-05-28 | 山东道可化学有限公司 | High-yield synthesis method of cyromazine technical |
| CN112851594B (en) * | 2021-01-27 | 2023-03-07 | 山东道可化学有限公司 | High-yield synthesis method of cyromazine technical |
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| CN1071321C (en) | 2001-09-19 |
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