CN107021966B - The synthetic method of improved penoxsuam - Google Patents
The synthetic method of improved penoxsuam Download PDFInfo
- Publication number
- CN107021966B CN107021966B CN201710232100.0A CN201710232100A CN107021966B CN 107021966 B CN107021966 B CN 107021966B CN 201710232100 A CN201710232100 A CN 201710232100A CN 107021966 B CN107021966 B CN 107021966B
- Authority
- CN
- China
- Prior art keywords
- penoxsuam
- sulfonamide
- tetrafluoro
- difluoroethanol
- strong
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
- C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
- C07D487/04—Ortho-condensed systems
Abstract
The invention discloses a kind of synthetic methods of improved penoxsuam, with strong alkaline substance, difluoroethanol and the fluoro- 6- trifluoromethyl-N-(5 of 2-, 8- dimethoxy [1,2,4] triazol [1,5-c] pyrimidine -2-base) benzsulfamide (hereinafter referred to as tetrafluoro sulfonamide) is raw material, first reacts strong alkaline substance with difluoroethanol, it prepares and alkaline weaker contains F2CH1CH2O‑A liquid (while should there is also difluoroethanols) after, then add tetrafluoro sulfonamide and prepare penoxsuam, therefore, each raw material of the present invention sequentially adds and temperature of reaction system control, side reaction can be effectively reduced, reduce impurity content, improve product purity or reduce purification step.
Description
Technical field
The present invention relates to a kind of synthetic method of penoxsuam, especially a kind of improvement penoxsuam synthesis step
In, the synthetic method of etherification step.
Background technique
Penoxsuam (Peoxsulam) is the personnel such as the W.A.Kleschick of The Dow Agrosciences, LLC. with life
A kind of sulfonamides herbicide that rows' relationship such as object is developed.Its main mechanism is the same as current sulfonylurea and imidazolone one
Sample is acetolactate synthestase (ALS) inhibitor.They in the further investigation Jing Guo system, find 1,2,4- triazol [1,
5-a] there is row's activity such as good biology between pyrimidine ring and sulfonylureas, in terms of comprehensively considered synthesis after factor
W.A.Kleschick et al. has successfully been made that azoles is phonetic and some column compounds of sulfonamides after exchanging sulfonyl and amino.
Penoxsuam (penoxsulam) is Miao Houyong herbicide, by inhibiting acetolactate synthestase (ALS) to reach
To herbicidal effect.It is mainly used for agent for removing grass in paddy field.Chemical name is 3- (2,2- difluoroethoxy)-N- (5,8- dimethoxy
[1,2,4] triazol [1,5-c] pyrimidine -2-base)-α, α, α-benzotrifluoride -2- sulfonamide.Molecular structural formula is as follows:
Penoxsuam was registered in 2004 in Environmental Protection Agency's official register, was pushed away in southern US rice region within 2005
Wide listing application is broadcast with transplanting rice field bud rear defence for dry sowing, water except Echinochloa and many broadleaf weeds, nutgrass flatsedge and aquatic miscellaneous
Grass.2006, penoxsuam was in Spain, Brazil, Colombia, South Korea, Thailand's listing, for preventing and kill off rice weed.
2007, penoxsuam was registered and is listed in Japan, and the same year registers in China, prevented and kill off barnyard grass, annual Sha for rice
Grass, broadleaf weeds enter Chinese market in 2009.By development in recent years, application of the penoxsuam in world market
It is concentrated mainly on rice, global marketing volume increases year by year.
Penoxsuam also has noticeable market manifestation in non-agricultural use, and it is non-agricultural to be suitable for medicine fertilizer, lawn, orchard etc.
With the weeding in field.2013, it was more than to be used for that penoxsuam, which is about 1.4 hundred million dollars in the sales volume of non-agricultural use,
1.1 hundred million dollars of the sales volume of paddy field.Once had been reported that the patent protection of penoxsulam amine compounds will be in September, 2016
It expires within 22nd, keeps the enterprise being much locked in sight on penoxsuam already mad with joy, by verification, penoxsulam
Amine raw medicine patent of invention is on September 23rd, 1997 in the applying date of China, and expiry date is in September, 2017
22 days.For it is such a it is expected following there is strong market to show and i.e. by the product of Patent expiry, had numerous
Agricultural chemicals enterprise sets about applying for agriculture chemical registration and carries out correlation test.It is reported that it is related to the product of penoxsuam field trial, it is single
Agent has 261, and compound preparation has 182, and according to the average cost of registration, all these single doses and compounding agent are registered
Expense reaches 200,000,000 yuan, and these registration products are suitable on rice.
In conjunction with the synthetic method that existing The Dow Agrosciences, LLC.'s patent (CN 1471532A) is reported, reported at present
The etherification technology of this step penoxsuam is mainly with the fluoro- 6- trifluoromethyl-N- of 2- (5,8- dimethoxys-[ 1,2,4 ] triazole
And [ 1,5-c ] pyrimidine -2)-benzsulfamide (abbreviation tetrafluoro sulfonamide) and difluoroethanol be that raw material, sodium hydride make the anti-of alkali progress
It answers, reaction equation is as follows:
Since sodium hydride easily fires, effective component is dispersed in mineral oil with 30 ~ 80%.This makes after completion of the reaction, institute
It obtains penoxsulam amine product packet to add mineral oil and product purity is caused not reach requirement, removes mineral oil in advance and not only increase behaviour
Make step, and the sodium hydride activity of processed mineral oil is higher, easily spontaneous combustion, danger coefficient improves.Increase penoxsuam
Purification step can improve cost again.
There is the idea for referring to and carrying out the step synthesis using sodium oxide molybdena as alkali in the country, but the idea is first with sodium oxide molybdena and tetrafluoro sulphur
Difluoroethanol is added in amide under low temperature mode after being mixed is synthesized.But it can be synthesized in etherificate in the synthetic method
Moisture content is generated in preceding and etherification procedure, the moisture content of generation is unfavorable for the progress of reaction, while the content of by-product impurities also can
Increase, is unfavorable for obtaining the product for requiring content.Therefore, it can not be obtained in the synthetic method satisfactory as a result, this is thought
Method still has obvious shortcoming and deficiency.
So considering adding in etherification procedure when making alkali using oxygen-containing/hydroxyl inorganic strong alkali in this step synthetic reaction
The removing of the moisture generated in material sequence and reaction is that the critical issue of experiment production is carried out using such alkali.
Therefore, the penoxsuam synthesis technology for probing into high-efficiency low energy consumption has great importance.
Summary of the invention
The present invention in view of the deficiencies of the prior art, improves the etherified step of existing tetrafluoro sulfonamide and forms penoxsuam
Synthesis technology, specifically: first prepare under strongly alkaline conditions difluoroethanol sodium/potassium method replacement the NaH containing mineral oil
Carry out etherificate synthesis, while in etherificate synthetic reaction, difluoroethanol sodium/potassium makees the dosage of alkali also by NaH usage amount 3.5 ~ 5
Equivalent drops to 2 equivalents.Difluoroethanol sodium/potassium of formation does not contain mineral oil, so greatly improves penoxsulam amine product
Purity, save purification step, substantially increase combined coefficient.
The specific technical solution of the present invention is as follows:
A kind of synthetic method of improved penoxsuam is with strong alkaline substance, difluoroethanol and tetrafluoro sulfonamide
Raw material, comprising the following steps:
I, the preparation of A liquid
Under nitrogen protection, firstly, dispersing strong alkaline substance in the glycol dimethyl ether under the conditions of ice-water bath,
Obtain strong basicity suspension；Then, difluoroethanol, and the dropwise addition speed for passing through control difluoroethanol are added dropwise into strong basicity suspension
Degree is to control temperature of reaction system at 10 DEG C hereinafter, to prepare containing F2CH1CH2O-A liquid, F2CH1CH2O-Corresponding structure
Formula is as follows:
The synthesis of II, penoxsuam
It is slowly added to tetrafluoro sulfonamide in batches into A liquid, and is controlled by the addition speed of control tetrafluoro sulfonamide
Temperature of reaction system is at 10 DEG C ~ 15 DEG C；
After the completion of the charging of tetrafluoro sulfonamide, after the system that is stirred to react is stablized to temperature, ice-water bath is cancelled, allows reaction system
After being to slowly warm up to 25 DEG C of room temperatures, keep the temperature under stirring condition to reaction system fully reacting；
The collection of III, penoxsuam
Water is added in the system completed to reaction to be diluted, lower use salt acid for adjusting pH is sufficiently stirred to 4 ~ 5, is sufficiently stirred
It is filtered after 1 ~ 2 hour, after obtained solid is washed, drained, dried, penoxsuam can be obtained.
As a further improvement of the present invention, the strong alkaline substance is that can react with difluoroethanol to be dissolved in second
Strong basicity alkali metal, strong basicity inorganic base or the strong basicity organic base of glycol dimethyl ether.
As a further improvement of the present invention, the strong basicity alkali metal is metallic sodium；Strong basicity inorganic base is hydrogen-oxygen
Change sodium or potassium hydroxide；Strong basicity organic base is potassium tert-butoxide.
As a further improvement of the present invention, when strong alkaline substance is strong basicity inorganic base, the reaction in step III is produced
Object is before baking, it is also necessary to pass through recrystallized from acetonitrile purification process.
As a further improvement of the present invention, when strong alkaline substance is strong basicity inorganic base, delaying in batches into A liquid
Before slow addition tetrafluoro sulfonamide, need first to carry out dehydration, it is specific as follows: to be first added in A liquid obtained in step I de-
Aqua carries out stirring dehydration in 1 ~ 2 hour, and dehydrating agent is then removed by filtration.
As a further improvement of the present invention, dehydrating agent is 4 molecular sieves, anhydrous sodium sulfate, one in anhydrous magnesium sulfate
Kind.
As a further improvement of the present invention, the mole dosage ratio of the mole dosage of difluoroethanol and tetrafluoro sulfonamide is not
Lower than 2:1.
As a further improvement of the present invention, the mole dosage of difluoroethanol and the mole dosage ratio of tetrafluoro sulfonamide are
2:1。
As a further improvement of the present invention, the use equivalent for being greater than difluoroethanol using equivalent of alkaline matter.
As a further improvement of the present invention, the use equivalent for using equivalent proportion difluoroethanol of alkaline matter is big by 10%.
According to above-mentioned technical solution, compared with the existing technology for, the present invention have it is following the utility model has the advantages that
1, the present invention makees alkali without using the NaH of the mutually difficult valuableness of price, instead more cheap using Na, NaOH, KOH etc.
Alkali, while saving the purification process of mineral oil, make to reduce on the certain Cheng Du of cost.
2, post-reaction treatment step is simple, and the dosage of alkali declines to a great extent, and remaining alkali is few after reaction, and post-processing step is opposite
It is safer；
3, reduce purification process, product loss is few；
4, reaction can be greater than 98% purity and 95% yield obtains product, purity and yield >=NaH makees alkali effect, excellent
Matter is obvious.
In addition, the present invention first reacts strong alkaline substance with difluoroethanol, prepare alkalinity it is weaker contain F2CH1CH2O-
A liquid (while should there is also difluoroethanols) after, then add tetrafluoro sulfonamide and prepare penoxsuam, can be effectively avoided
Side reaction caused by tetrafluoro sulfonamide is added directly in strong alkali solution (it was found that under strongly alkaline conditions, temperature once reaches
To 35 degrees centigrades, tetrafluoro sulfonamide will start to generate side reaction, generate impurity, meanwhile, the higher side reaction of temperature is faster,
It is more obvious, and adds difluoroethanol at this moment to prepare penoxsuam, due to being exothermic reaction, it will usually cause local temperature
Height is spent, the generation of impurity is improved), therefore, each raw material of the present invention sequentially adds, the control of combination anchor temperature, can be with
Side reaction is efficiently reduced, impurity yield is reduced, improve product purity or reduces purification step.
Further more, the present invention using strong basicity inorganic base preparation A liquid when, since water can be generated in reaction process, into
Before the synthesis of row penoxsuam (i.e. to before being slowly added to tetrafluoro sulfonamide in batches into A liquid), need first to carry out dehydration step
Suddenly, impurity is otherwise easily generated in the synthesis process, while also will affect going on smoothly for reaction.
Specific embodiment
The synthetic method of penoxsuam of the present invention is specifically related to tetrafluoro sulfonamide by etherificate preparation five
The improvement of the etherification step of penoxsulam, the etherification step (are five fluorine with strong alkaline substance, difluoroethanol and tetrafluoro sulfonamide
Sulphur grass amine synthesis technology intermediate 2- fluoro- 6- trifluoromethyl-N- (5,8- dimethoxys-[ 1,2,4 ] triazol [ 1,5-c ] pyrimidine-
2)-benzsulfamide abbreviation) be raw material, specific synthesis procedure the following steps are included:
I, the preparation of A liquid
Under nitrogen protection, firstly, being dissolved in strong alkaline substance in the glycol dimethyl ether under the conditions of ice-water bath,
Obtain strong alkali solution；Then, be added dropwise difluoroethanol into strong alkali solution, and the rate of addition by controlling difluoroethanol come
Temperature of reaction system is controlled at 10 DEG C hereinafter, to prepare containing F2CH1CH2O-A liquid, at this point, should be there are also part in A liquid
Difluoroethanol, F2CH1CH2O-Corresponding structural formula is as follows:
The synthesis of II, penoxsuam
It is slowly added to tetrafluoro sulfonamide into A liquid, and reactant is controlled by the addition speed of control tetrafluoro sulfonamide
It is temperature at 10 DEG C ~ 15 DEG C；And tetrafluoro sulfonamide is slowly added in batches.
After the completion of the charging of tetrafluoro sulfonamide, after the system that is stirred to react is stablized to temperature, ice-water bath is cancelled, allows reaction system
After being to slowly warm up to 25 DEG C of room temperatures, keep the temperature under stirring condition to reaction system fully reacting；
The collection of III, penoxsuam
Water is added in the system completed to reaction to be diluted, lower use salt acid for adjusting pH is sufficiently stirred to 4 ~ 5, is sufficiently stirred
It is filtered after 1 ~ 2 hour, after obtained solid is washed, drained, dried, penoxsuam can be obtained.
The strong alkaline substance be the strong basicity alkali metal that can be dissolved in glycol dimethyl ether, strong basicity inorganic base or
Person's strong basicity organic base.Wherein: strong basicity alkali metal is metallic sodium；Strong basicity inorganic base is sodium hydroxide or potassium hydroxide；
Strong basicity organic base is potassium tert-butoxide.
When strong alkaline substance is strong basicity inorganic base, the reaction product in step III is after the drying, it is also necessary to pass through second
The processing of nitrile recrystallization purifying, can just obtain the penoxsuam of high-purity (> 98%).In other words, the strong basicity that the present invention uses
When substance is metallic sodium or potassium tert-butoxide, then it is not necessarily to recrystallized from acetonitrile purification process, the five of high-purity (> 98%) can be obtained
Penoxsulam.The mole dosage of difluoroethanol and the mole dosage ratio of tetrafluoro sulfonamide are not less than 2:1, that is to say, that this hair
The dosage of the bright difluoroethanol, can be down to 2.0eq.
When strong alkaline substance is strong basicity inorganic base, before being slowly added to tetrafluoro sulfonamide in batches into A liquid, need
Dehydration is first carried out, it is specific as follows: the stirring that dehydrating agent carries out 1 ~ 2 hour being first added in A liquid obtained in step I and takes off
Then dehydrating agent is removed by filtration in water；Wherein: dehydrating agent is 4 molecular sieves, in anhydrous sodium sulfate, anhydrous magnesium sulfate
It is a kind of.Using dehydration, the moisture content in A liquid can be removed, be effectively prevented from side reaction, reduced impurity and generate, together
When can effectively guarantee going on smoothly for reaction system.
Alkaline matter using equivalent slightly larger than difluoroethanol use equivalent, the present invention in, the use of alkaline matter is worked as
It measures bigger by 10% using equivalent than difluoroethanol.
Explain the synthesis of penoxsuam of the present invention in detail below with reference to each embodiment.Each embodiment is related to
Penoxsuam synthetic reaction formula it is as follows:
Example one
In the four round flask of the 2000mL equipped with thermometer, nitrogen ball and rubber stopper, glycol dimethyl ether is added
The 30.4g metallic sodium (1.32 mol, 2.2eq) removed the peel under nitrogen protection, is cut fritter and system is added, filled under ice-water bath by 700g
Divide stirring to be cooled to 5 DEG C or so, difluoroethanol 49.2g(0.6 mol, 2.0eq be slowly added dropwise to system), notice that dropwise addition process is put
Hot obvious, and generate with bulk gas, the temperature of reaction system is controlled at 10 DEG C hereinafter, adjusting difluoro with temperature change
The rate of addition of ethyl alcohol.After being added dropwise to complete, in 10 DEG C or so in batches slowly into system be added tetrafluoro sulfonamide (126g,
0.3mol, 1.0eq).It is still generated with bulk gas in adition process and apparent exothermic phenomenon, control is added speed, makes
System temperature is controlled at 10 ~ 15 DEG C or so.After the completion of charging, stirred under nitrogen atmosphere to temperature is stablized (to heat up there is no obvious
Phenomenon), ice-water bath is removed, environment temperature is to slowly warm up to, is not higher than 25 DEG C, is stirred insulation reaction 3 hours, sampling tracks to original
Expect fully reacting.
500mL water is added in the system completed to reaction, the salt acid for adjusting pH with 1mol/L is sufficiently stirred down to 4 ~ 5, fills
It being filtered after 1 ~ 2 hour after dividing stirring, solid is washed with 100mL, and after draining, solid product is collected, is dried, HPLC assay >
98%, yield 95%.
Example two
Metallic sodium is replaced with potassium tert-butoxide, specific embodiment is referring to example one.Product drying, HPLC assay >
98%, yield 93.5%.
Example three
In the four round flask of the 2000mL equipped with thermometer, nitrogen ball and rubber stopper, glycol dimethyl ether is added
78g potassium hydroxide (95%, 1.32 mol, 2.2eq) powder under nitrogen protection, is added system, is slowly added dropwise to system by 100g
Difluoroethanol 49.2g(0.6 mol, 2.0eq), it is sufficiently stirred, notices that dropwise addition process heat release is obvious.It finishes, 50 DEG C of heating stirrings
It is completely dissolved to solid potassium hydroxide, 4 molecular sieve of 10g is added after dissolving completely, dehydration in 1 ~ 2 hour is sufficiently stirred, pull molecule out
Sieve activation reuse.Solution is sufficiently stirred under ice-water bath is cooled to 5 DEG C or so, in 5 ~ 10 DEG C or so in batches slowly into system
It is added tetrafluoro sulfonamide (126g, 0.3mol, 1.0eq).Still with apparent exothermic phenomenon in adition process, speed is added in control
Degree, makes system temperature at 10 ~ 15 DEG C or so.After the completion of charging, stirred under nitrogen atmosphere to temperature is stablized (to heat up there is no obvious
Phenomenon), ice-water bath is removed, environment temperature is to slowly warm up to, oil bath keeps the temperature at 25 DEG C, stirs insulation reaction 3 hours, sampling tracking
To raw material fully reacting.
500mL water is added in the system completed to reaction, the salt acid for adjusting pH with 1mol/L is sufficiently stirred down to 4 ~ 5, fills
It being filtered after 1 ~ 2 hour after dividing stirring, solid is washed with 100mL, and after draining, solid product is collected, is dried, HPLC assay >
90%, yield 85%.After the drying, by recrystallized from acetonitrile purification process, products obtained therefrom HPLC assay > 98%.
Example four
Potassium hydroxide is replaced with sodium hydroxide, specific embodiment is referring to example three.Product drying, HPLC assay >
90%, yield 82%.Before baking, by recrystallized from acetonitrile purification process, products obtained therefrom HPLC assay > 98%.
Claims (8)
1. a kind of synthetic method of improved penoxsuam is original with strong alkaline substance, difluoroethanol and tetrafluoro sulfonamide
Material, tetrafluoro sulfonamide are the fluoro- 6- trifluoromethyl-N- of 2- (5,8- dimethoxys [1,2,4] triazol [1,5-c] pyrimidine -2-base)
The abbreviation of benzsulfamide, which comprises the following steps:
I, the preparation of A liquid
Under nitrogen protection, it firstly, dispersing strong alkaline substance in the glycol dimethyl ether under the conditions of ice-water bath, obtains
Strong basicity suspension；Then, difluoroethanol is added dropwise into strong basicity suspension, strong alkaline substance is greater than difluoro second using equivalent
Alcohol uses equivalent, and controls temperature of reaction system at 10 DEG C hereinafter, to prepare by the rate of addition of control difluoroethanol
Contain F out2CH1CH2O-A liquid, F2CH1CH2O-Corresponding structural formula is as follows:
The synthesis of II, penoxsuam
It is slowly added to tetrafluoro sulfonamide in batches into A liquid, and the addition speed by controlling tetrafluoro sulfonamide is reacted to control
System temperature is at 10 DEG C~15 DEG C；
After the completion of the charging of tetrafluoro sulfonamide, after the system that is stirred to react is stablized to temperature, ice-water bath is cancelled, makes reaction system slow
After being warming up to 25 DEG C of room temperatures, keep the temperature under stirring condition to reaction system fully reacting；
The mole dosage of difluoroethanol and the mole dosage ratio of tetrafluoro sulfonamide are not less than 2:1；
The collection of III, penoxsuam
Water is added in the system completed to reaction to be diluted, be sufficiently stirred it is lower with salt acid for adjusting pH to 4~5, be sufficiently stirred 1~
It is filtered after 2 hours, after obtained solid is washed, drained, dried, penoxsuam can be obtained.
2. the synthetic method of penoxsuam according to claim 1, it is characterised in that: the strong alkaline substance is energy
It is enough to react organic to be dissolved in the strong basicity alkali metal of glycol dimethyl ether, strong basicity inorganic base or strong basicity with difluoroethanol
Alkali.
3. the synthetic method of penoxsuam according to claim 2, it is characterised in that: the strong basicity alkali metal is
Metallic sodium；Strong basicity inorganic base is sodium hydroxide or potassium hydroxide；Strong basicity organic base is potassium tert-butoxide.
4. the synthetic method of penoxsuam according to claim 3, it is characterised in that: when strong alkaline substance is strong basicity
When inorganic base, the reaction product in step III is before baking, it is also necessary to pass through recrystallized from acetonitrile purification process.
5. the synthetic method of penoxsuam according to claim 1, it is characterised in that: when strong alkaline substance is strong basicity
When inorganic base, before being slowly added to tetrafluoro sulfonamide in batches into A liquid, need first to carry out dehydration, it is specific as follows: first to exist
The stirring dehydration that dehydrating agent carries out 1~2 hour is added in step I in obtained A liquid, dehydrating agent is then removed by filtration i.e.
It can.
6. the synthetic method of penoxsuam according to claim 5, it is characterised in that: dehydrating agent isMolecular sieve, nothing
One of aqueous sodium persulfate, anhydrous magnesium sulfate.
7. the synthetic method of penoxsuam according to claim 1, it is characterised in that: the mole dosage of difluoroethanol with
The mole dosage ratio of tetrafluoro sulfonamide is 2:1.
8. the synthetic method of penoxsuam according to claim 1, it is characterised in that: strong alkaline substance uses equivalent
It is bigger by 10% using equivalent than difluoroethanol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710232100.0A CN107021966B (en) | 2017-04-11 | 2017-04-11 | The synthetic method of improved penoxsuam |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710232100.0A CN107021966B (en) | 2017-04-11 | 2017-04-11 | The synthetic method of improved penoxsuam |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107021966A CN107021966A (en) | 2017-08-08 |
| CN107021966B true CN107021966B (en) | 2019-04-19 |
Family
ID=59527767
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710232100.0A Active CN107021966B (en) | 2017-04-11 | 2017-04-11 | The synthetic method of improved penoxsuam |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107021966B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2555635B (en) * | 2016-11-07 | 2022-04-13 | Rotam Agrochem Int Co Ltd | A novel form of penoxsulam, a process for its preparation and use of the same |
| CN113563347A (en) * | 2021-08-19 | 2021-10-29 | 安徽华星化工有限公司 | Purification method of penoxsulam technical |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1471532A (en) * | 2000-09-26 | 2004-01-28 | �ݶ�ũ������˾ | Process for the preparation of z-alkoxy-6-trifluoromethyl-N-[(C1,2,4] triazolo[1,5-C] pyrimidin-2-yl) benzensulfonamides |
| CN103044431A (en) * | 2012-10-22 | 2013-04-17 | 中国药科大学 | Novel preparation method of penoxsulam |
| CN103724353A (en) * | 2013-12-12 | 2014-04-16 | 江苏富鼎化学有限公司 | Improved synthesis method of penoxsulam |
| CN104402890A (en) * | 2014-11-10 | 2015-03-11 | 常州大学 | Preparation method of penoxsulam |
-
2017
- 2017-04-11 CN CN201710232100.0A patent/CN107021966B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1471532A (en) * | 2000-09-26 | 2004-01-28 | �ݶ�ũ������˾ | Process for the preparation of z-alkoxy-6-trifluoromethyl-N-[(C1,2,4] triazolo[1,5-C] pyrimidin-2-yl) benzensulfonamides |
| CN103044431A (en) * | 2012-10-22 | 2013-04-17 | 中国药科大学 | Novel preparation method of penoxsulam |
| CN103724353A (en) * | 2013-12-12 | 2014-04-16 | 江苏富鼎化学有限公司 | Improved synthesis method of penoxsulam |
| CN104402890A (en) * | 2014-11-10 | 2015-03-11 | 常州大学 | Preparation method of penoxsulam |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107021966A (en) | 2017-08-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106243046B (en) | A kind of preparation method of mesosulfuron | |
| TWI287539B (en) | Uracil substituted phenyl sulfamoyl carboxamides | |
| CN102395569B (en) | E-type phenyl acrylic ester compounds containing substituted anilino pyrimidine group and uses thereof | |
| EP2970123B1 (en) | Salt of omecamtiv mecarbil and process for preparing salt | |
| CN102020647B (en) | Preparation method of 1-(2,2-difluoroethoxy)-6-trifluoromethyl-N-([1,2,4]triazolezol[1,5-C] pyrimidine-2-)benzsulfamide | |
| CN103724353B (en) | The improvement synthetic method of penoxsuam | |
| JPH02501831A (en) | heterocyclic compound | |
| CN107021966B (en) | The synthetic method of improved penoxsuam | |
| SK14742000A3 (en) | Pyridazinone hydrochloride compound and method for producing the same | |
| CN103044431A (en) | Novel preparation method of penoxsulam | |
| CN104045602A (en) | Improved method for preparing tetrazole for valsartan | |
| KR20040004427A (en) | N-([1,2,4]Triazoloazinyl) thiophenesulfonamide compounds as herbicides | |
| CN109776442B (en) | Method for preparing high-purity 3-isoxazolidinone compound crystal, crystal form and application thereof | |
| CA2002671C (en) | Process for the production of 4,5-dichloro-6-ethyl-pyrimidine | |
| JP2003533497A (en) | Method for producing aniline compound | |
| CN109006823A (en) | Application of the 2- aryl substituted pyrroles class compound in snail-killing medicine | |
| CN108069915A (en) | A kind of pyrazinamide class compound and its preparation method and application and a kind of fungicide | |
| CN109232442A (en) | Acceptable salt, preparation method, herbicidal composition on aryi-uracile class compound or its Pesticide Science | |
| CN111303073B (en) | Method for preparing pesticide mefenacet by using benzothiazolone and 2-halogenated-N-methyl-N-phenyl acetamide | |
| JP2002519409A (en) | Method for producing 2-nitro-5- (phenylthio) -aniline | |
| CN109983011A (en) | The manufacturing method of polymerizable compound | |
| JPS63258462A (en) | 2-phenoxypyrimidine derivative and herbicide | |
| CN115974729B (en) | Preparation method of 2- (2, 2-difluoroethoxy) -6-trifluoromethyl benzenesulfonyl chloride | |
| JP4761602B2 (en) | Purification method for guanidine derivatives | |
| CN108864063A (en) | A kind of drug solvent for the treatment of cancer closes object and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |