CN109796398A - A kind of preparation method of paraquat list pyridone iodide - Google Patents

A kind of preparation method of paraquat list pyridone iodide Download PDF

Info

Publication number
CN109796398A
CN109796398A CN201910140481.9A CN201910140481A CN109796398A CN 109796398 A CN109796398 A CN 109796398A CN 201910140481 A CN201910140481 A CN 201910140481A CN 109796398 A CN109796398 A CN 109796398A
Authority
CN
China
Prior art keywords
paraquat
pyridone
list
iodide
reaction
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.)
Pending
Application number
CN201910140481.9A
Other languages
Chinese (zh)
Inventor
贠克明
贾娟
马红娟
王颖
路玉平
王显连
苏红亮
张潮
尉志文
王乐乐
王锐利
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shanxi Medical University
Original Assignee
Shanxi Medical University
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Shanxi Medical University filed Critical Shanxi Medical University
Priority to CN201910140481.9A priority Critical patent/CN109796398A/en
Publication of CN109796398A publication Critical patent/CN109796398A/en
Pending legal-status Critical Current

Links

Landscapes

  • Pyridine Compounds (AREA)

Abstract

The invention discloses a kind of preparation methods of paraquat list pyridone iodide; the following steps are included: the bromo- 1- picoline -2- ketone of 4- and 4- pyridine boronic acid are dissolved in the aqueous solution of dioxane by (1); it is stirring evenly and then adding into potassium carbonate and four triphenyl phosphorus palladium chlorides, is reacted overnight under nitrogen protection;Compound I is post-processed to obtain after reaction;(2) compound I is dissolved in acetonitrile by what step (1) obtained, iodomethane is added at room temperature, is heated under nitrogen protection, reflux state reaction handles to obtain paraquat list pyridone iodide after reaction;Preparation process in the present invention is simple, and purpose product production cost is low, and the rate of recovery is high.

Description

A kind of preparation method of paraquat list pyridone iodide
Technical field
The invention belongs to pesticide production technology fields, and in particular to a kind of preparation side of paraquat list pyridone iodide Method.
Background technique
Paraquat is a kind of quick steriland herbicide of double amidopyridine salt class, has action of contace poison and certain systemic action, energy Kill most of grass family and broadleaf weeds, greenery just start withered after contact medical fluid a few hours, being administered latter hour meets rain, medicine It imitates unaffected.Medical fluid has no adverse effects to mature or brown bark, climing rattan.It is passivated rapidly after contact soil, does not influence crop Root.Various annual grassy weeds can be prevented and kill off, is primarily adapted for use in and prevents and kill off orchard, mulberry field, plantation, corn, sugarcane, soybean and nursery The weeds of crop.Due to having the advantage that, this pesticide is widely used at home at present.Due to special with excellent weeding Property, paraquat is the Pesticidal products of world's sales volume second.
Currently, the production technology of paraquat is mainly two kinds.First is that sodium method, i.e., need to use metallic sodium.The method has many disadvantages End, especially high/medium temperature sodium method, yield is lower, and objectionable impurities is more, and quantity of three wastes is big, and equipment easily blocks, inflammable and explosive etc.;Second is that Cyanide process need to use hydrogen cyanide or cyanide.For the method compared with sodium method, yield is higher, and objectionable impurities is few, simple process, behaviour Make safety.Cyanamide process especially therein, product purity is high, does not generate harmful substance, yield can reach 95% or more.But disadvantage It is to need to use hydrogen cyanide or cyanide in production process, needs strictly to handle these extremely toxic substances.
Therefore, in order to further reach the production of China's paraquat herbicide safety and the requirement used, paraquat is explored It novel processing step and researches and develops its derivative and is of great significance.
Summary of the invention
To solve the above technical problem, the present invention provides a kind of preparation method of paraquat list pyridone iodide, the system Standby simple process, purpose product production cost is low, and the rate of recovery is high.
Technical solution provided by the invention is as follows:
A kind of preparation method of paraquat list pyridone iodide, comprising the following steps:
(1) the bromo- 1- picoline -2- ketone of 4- and 4- pyridine boronic acid are dissolved in the aqueous solution of dioxane, are stirred evenly Potassium carbonate and four triphenyl phosphorus palladium chlorides are added afterwards, are reacted overnight under nitrogen protection;It is cooled to room temperature after reaction, it is rear to locate Manage to obtain compound I;
(2) compound I is dissolved in acetonitrile by what step (1) obtained, iodomethane is added at room temperature, adds under nitrogen protection Heat, reflux state reaction, is cooled to room temperature after reaction, post-processes to obtain paraquat list pyridone iodide.
Preferably, the bromo- 1- picoline -2- ketone of 4-, 4- pyridine boronic acid, potassium carbonate and four triphenyl phosphorus palladium chlorides Between mass ratio be (0.8~1.2): (0.7~1): (2~2.5): (0.1~0.2).
Preferably, the mass concentration of dioxane is 75~85% in the aqueous solution of the dioxane;Every 10ml dioxy The amount of the bromo- 1- picoline -2- ketone of the 4- being added in the aqueous solution of six rings and 4- pyridine boronic acid is 0.5~0.7g.
Preferably, post-processing concrete operation method described in step (1) are as follows: (1) reaction solution is filtered to take into its filtrate, stood Water phase and organic phase are separated afterwards;(2) gained water phase adopts to be extracted with dichloromethane takes organic phase three times;(3) merge step (1) and step Suddenly the organic phase that (2) obtain, Rotary Evaporators concentration are spin-dried for obtaining crude product, and after crude product is using ethyl acetate mashing, filtration drying is obtained Compound I.
Preferably, the amount that compound I is added in step (2) in the acetonitrile of every 1ml is 0.1~0.2g;The iodomethane of every 1ml The middle amount that compound I is added is 0.15~0.2g.
Preferably, post-processing concrete operation method described in step (2) are as follows: reaction solution is filtered to take into filter residue, filter residue uses Acetonitrile washs three times, and dry obtained solid object is up to paraquat list pyridone iodide.
Preferably, the overnight temperature of reaction is 90~100 DEG C in step (1);In step (2) back flow reaction temperature be 50~ 60 DEG C, the reaction time is 25~40min.
Preferably, in step (2), the tail gas generated in reaction process, which is passed through in ammonium hydroxide, to be recycled.
Compared with prior art, the present invention has following technical advantage:
(1) present invention synthesizes the paraquat list pyridine containing different alkyl substituents by the type of change synthesis material Ketone iodide have widened the route of synthesis of paraquat derivatives, and practical.
(2) the paraquat list pyridone iodide rate of recovery produced by the present invention is 60% or more, and purpose product is crystalline state, Purity is very high, reduces production cost and energy consumption;
(3) the synthetic method device in the present invention is simple, and preparation process is simple, and raw material sources are extensive, cheap and easy to get, and anti- It answers the period short, improves workshop appliance utilization rate.
Detailed description of the invention
Fig. 1 is the synthetic route chart of the 1 gained purpose product of embodiment in the present invention
Fig. 2 is the mass-spectrogram of the 1 gained purpose product of embodiment in the present invention
Fig. 3 is the nuclear magnetic resonance map of the 1 gained purpose product of embodiment in the present invention
Specific embodiment
First in conjunction with specific embodiments, the present invention will be further described.
Embodiment 1
A kind of preparation method of paraquat list pyridone iodide, comprising the following steps:
(1) the bromo- 1- picoline -2- ketone of 1.0g 4- and 790mg 4- pyridine boronic acid are dissolved in the dioxane water of 30mL In solution (mass concentration 75% of dioxane), after mixing evenly, 2.2g potassium carbonate and tetra- triphenyl phosphorus dichloro of 100mg is added Change palladium, is heated to 90 DEG C under nitrogen protection, is stirred overnight;It is cooled to room temperature after reaction, reaction solution is filtered to take into its filtrate, Water phase and organic phase are separated after standing;Gained water phase adopts to be extracted with dichloromethane takes organic phase three times;Merge all organic phases, Rotary Evaporators concentration is spin-dried for obtaining crude product, and after crude product is using ethyl acetate mashing, filtration drying obtains compound I 700mg;
(2) it takes 700mg compound I to be dissolved in the acetonitrile of 5mL, 4mL iodomethane is added at room temperature, is heated under nitrogen protection Reaction solution is filtered to take filter residue by 50 DEG C of back flow reaction 30min, and filter residue is washed three times using acetonitrile, and dry obtained solid object to obtain the final product Paraquat list pyridone iodide 800mg, measures its rate of recovery 64.8%.
The sterling compound obtained using mass spectrum (ESI-MS) analytical procedure (2), measured result: [M+H]+It is 201.3, sees Fig. 2;Using nuclear-magnetism1The sterling that H-NMR (400MHz, DMSO) analytical procedure (2) obtains, data be δ 9.10 (d, 2H), 8.52 (d, 2H), 8.00 (d, 1H), 7.12 (s, 1H), 6.81 (d, 1H), 4.37 (s, 3H), 3.51 (s, 3H) are shown in Fig. 3.
Embodiment 2
A kind of preparation method of paraquat list pyridone iodide, comprising the following steps:
(1) dioxane for the bromo- 1- picoline -2- ketone of 2.2g 4- and 1.6g 4- pyridine boronic acid being dissolved in 60mL is water-soluble In liquid (mass concentration 80% of dioxane), after mixing evenly, 4g potassium carbonate and tetra- triphenyl phosphorus dichloride of 200mg is added Palladium is heated to 95 DEG C under nitrogen protection, is stirred overnight;It is cooled to room temperature after reaction, reaction solution is filtered to take into its filtrate, it is quiet Postpone separation water phase and organic phase;Gained water phase adopts to be extracted with dichloromethane takes organic phase three times;Merge all organic phases, revolves Turn evaporimeter concentration and be spin-dried for obtaining crude product, after crude product is using ethyl acetate mashing, filtration drying obtains compound I 1.5g;
(2) it takes 1.2g compound I to be dissolved in the acetonitrile of 10mL, 8mL iodomethane is added at room temperature, is heated under nitrogen protection Reaction solution is filtered to take filter residue by 55 DEG C of back flow reaction 25min, and filter residue is washed three times using acetonitrile, and dry obtained solid object to obtain the final product Paraquat list pyridone iodide 1.5g, measures its rate of recovery 68.2%.
The sterling compound obtained using mass spectrum (ESI-MS) analytical procedure (2), measured result: [M+H]+It is 201.4, adopts The sterling obtained with nuclear-magnetism 1H-NMR (400MHz, DMSO) analytical procedure (2), data be δ 9.11 (d, 2H), 8.53 (d, 2H), 8.01 (d, 1H), 7.11 (s, 1H), 6.80 (d, 1H), 4.34 (s, 3H), 3.53 (s, 3H), because embodiment 2 identification map with Embodiment 1 is similar, therefore does not upload.
Embodiment 3
A kind of preparation method of paraquat list pyridone iodide, comprising the following steps:
(1) dioxane for the bromo- 1- picoline -2- ketone of 3.6g 4- and 3g 4- pyridine boronic acid being dissolved in 100mL is water-soluble In liquid (mass concentration 85% of dioxane), after mixing evenly, 7.2g potassium carbonate and tetra- triphenyl phosphorus dichloride of 0.6g is added Palladium is heated to 100 DEG C under nitrogen protection, is stirred overnight;It is cooled to room temperature after reaction, reaction solution is filtered to take into its filtrate, Water phase and organic phase are separated after standing;Gained water phase adopts to be extracted with dichloromethane takes organic phase three times;Merge all organic phases, Rotary Evaporators concentration is spin-dried for obtaining crude product, and after crude product is using ethyl acetate mashing, filtration drying obtains compound I 2.2g;
(2) it takes 2g compound I to be dissolved in the acetonitrile of 15mL, 12mL iodomethane is added at room temperature, is heated under nitrogen protection Reaction solution is filtered to take filter residue by 60 DEG C of back flow reaction 40min, and filter residue is washed three times using acetonitrile, and dry obtained solid object to obtain the final product Paraquat list pyridone iodide 2.5mg, measures its rate of recovery 67.5%.
The sterling compound obtained using mass spectrum (ESI-MS) analytical procedure (2), measured result: [M+H]+It is 201.7, adopts The sterling obtained with nuclear-magnetism 1H-NMR (400MHz, DMSO) analytical procedure (2), data be δ 9.13 (d, 2H), 8.51 (d, 2H), 8.05 (d, 1H), 7.13 (s, 1H), 6.79 (d, 1H), 4.31 (s, 3H), 3.52 (s, 3H), because embodiment 3 identification map with Embodiment 1 is similar, therefore does not upload.

Claims (8)

1. a kind of preparation method of paraquat list pyridone iodide, it is characterised in that the following steps are included:
(1) the bromo- 1- picoline -2- ketone of 4- and 4- pyridine boronic acid are dissolved in the aqueous solution of dioxane, after mixing evenly plus Enter potassium carbonate and four triphenyl phosphorus palladium chlorides, is reacted overnight under nitrogen protection;It is cooled to room temperature, post-processes after reaction Compound I;
(2) compound I is dissolved in acetonitrile by what step (1) obtained, iodomethane is added at room temperature, is heated under nitrogen protection, returned Stream mode reaction, is cooled to room temperature after reaction, post-processes up to paraquat list pyridone iodide.
2. a kind of preparation method of paraquat list pyridone iodide according to claim 1, it is characterised in that: 4- is bromo- Mass ratio between 1- picoline -2- ketone, 4- pyridine boronic acid, potassium carbonate and four triphenyl phosphorus palladium chlorides be (0.8~ 1.2): (0.7~1): (2~2.5): (0.1~0.2).
3. a kind of preparation method of paraquat list pyridone iodide according to claim 1, it is characterised in that: described two The mass concentration of dioxane is 75~85% in the aqueous solution of six ring of oxygen;The 4- being added in the aqueous solution of every 10ml dioxane The amount of bromo- 1- picoline -2- ketone and 4- pyridine boronic acid is 0.5~0.7g.
4. a kind of preparation method of paraquat list pyridone iodide according to claim 1, it is characterised in that: step (1) the post-processing concrete operation method described in are as follows: (1) reaction solution is filtered to take into its filtrate, separate water phase and organic phase after standing; (2) gained water phase adopts to be extracted with dichloromethane takes organic phase three times;(3) merge the organic phase that step (1) and step (2) obtains, Rotary Evaporators concentration is spin-dried for obtaining crude product, and after crude product is using ethyl acetate mashing, filtration drying obtains compound I.
5. a kind of preparation method of paraquat list pyridone iodide according to claim 1, it is characterised in that: step (2) amount that compound I is added in the acetonitrile of every 1ml is 0.1~0.2g;The amount of addition compound I is in the iodomethane of every 1ml 0.15~0.2g.
6. a kind of preparation method of paraquat list pyridone iodide according to claim 1, it is characterised in that: step (2) the post-processing concrete operation method described in are as follows: reaction solution is filtered to take into filter residue, filter residue is washed three times using acetonitrile, dry institute Solids is obtained up to paraquat list pyridone iodide.
7. a kind of preparation method of paraquat list pyridone iodide according to claim 1, it is characterised in that: step (1) the overnight temperature of reaction is 90~100 DEG C in;In step (2) back flow reaction temperature be 50~60 DEG C, the reaction time be 25~ 40min。
8. a kind of preparation method of paraquat list pyridone iodide according to claim 1, it is characterised in that: step (2) in, the tail gas generated in reaction process, which is passed through in ammonium hydroxide, to be recycled.
CN201910140481.9A 2019-02-18 2019-02-18 A kind of preparation method of paraquat list pyridone iodide Pending CN109796398A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201910140481.9A CN109796398A (en) 2019-02-18 2019-02-18 A kind of preparation method of paraquat list pyridone iodide

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201910140481.9A CN109796398A (en) 2019-02-18 2019-02-18 A kind of preparation method of paraquat list pyridone iodide

Publications (1)

Publication Number Publication Date
CN109796398A true CN109796398A (en) 2019-05-24

Family

ID=66562370

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201910140481.9A Pending CN109796398A (en) 2019-02-18 2019-02-18 A kind of preparation method of paraquat list pyridone iodide

Country Status (1)

Country Link
CN (1) CN109796398A (en)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008214307A (en) * 2007-03-07 2008-09-18 Chisso Corp Electron transport material and organic electroluminescent element using the same
CN106083708A (en) * 2016-06-30 2016-11-09 浙江大学 2 aminopyrazole derivatives containing 2 pyridone ring side chains and preparation and application
CN107698494A (en) * 2017-11-15 2018-02-16 山东潍坊润丰化工股份有限公司 A kind of preparation method of 4,4 ' bipyridyl
CN107935918A (en) * 2017-11-15 2018-04-20 山东潍坊润丰化工股份有限公司 A kind of preparation method of paraquat
CN108290858A (en) * 2015-12-01 2018-07-17 日本农药株式会社 3H- pyrrolopyridine compounds or its N- oxide or their salt and the salt, garderning pesticide containing the compound and its application method

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008214307A (en) * 2007-03-07 2008-09-18 Chisso Corp Electron transport material and organic electroluminescent element using the same
CN108290858A (en) * 2015-12-01 2018-07-17 日本农药株式会社 3H- pyrrolopyridine compounds or its N- oxide or their salt and the salt, garderning pesticide containing the compound and its application method
CN106083708A (en) * 2016-06-30 2016-11-09 浙江大学 2 aminopyrazole derivatives containing 2 pyridone ring side chains and preparation and application
CN107698494A (en) * 2017-11-15 2018-02-16 山东潍坊润丰化工股份有限公司 A kind of preparation method of 4,4 ' bipyridyl
CN107935918A (en) * 2017-11-15 2018-04-20 山东潍坊润丰化工股份有限公司 A kind of preparation method of paraquat

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
A. CALDERBANK,ET AL.: ""Bipyridylium Quaternary Salts and Related Compounds. Part IV. Pyridones derived from Paraquat and Diquat"", 《JOURNAL OF THE CHEMICAL SOCIETY》 *
邹华生 等: ""2-甲基吡啶的合成工艺"", 《华南理工大学学报(自然科学版)》 *

Similar Documents

Publication Publication Date Title
CN102432561A (en) Method for preparing neonicotine pesticide clothianidin
CN103450170B (en) Containing 1,3,4-oxadiazole derivative and preparation method thereof and the application of pyridine
CN104302629B (en) The pyrimidine salicylic acid compounds of weeding activity, its preparation method and the purposes as weedicide thereof
CN112094243A (en) Compound containing benzotriazine structure, preparation method and application thereof, and herbicide
CN109796398A (en) A kind of preparation method of paraquat list pyridone iodide
CN104177321B (en) A kind of copper ion fluorescence probe based on chromene diketone and preparation method thereof
CN104610267B (en) Method for efficiently synthesizing 6-alkyl pyrazolo [1,5-c ] quinazoline framework compound under non-catalytic condition
CN103319343B (en) Pyrethroid compound, and preparation method and applications thereof
CN102070610A (en) 1,4-dihydropyridine ring-containing cis-neonicotinoid compounds and preparation thereof
US4065290A (en) Herbicidal β-phenyl-4-piperidinones
CN103880832B (en) A kind of preparation method of Diacloden
CN105254621A (en) Triazinone compound containing thiazole rings and preparation method and application thereof
CN100503585C (en) Second anabasine insecticide JT-L001 and chemical synthesis method thereof
CN110078673A (en) A kind of aryi-uracile class compound and preparation method thereof and composition pesticide
CN102030710A (en) Method for synthesizing 14 C-labeled compound of pyraoxystrobin serving as bactericide
CN105153013A (en) Synthesis method of 6-bromoisoindolinyl-1-one
CN107089939A (en) A kind of synthetic method of the bromopyridine of 2,5 dimethyl 3
CN105085255B (en) A kind of synthesis technique of the oxo succinate of 2 alkoxy of imidazolinone herbicide intermediate 3
CN101597256B (en) Preparation method of paraquat derivatives
CN103709175A (en) One-step synthesis method of 6-chlorine-3H-oxazole [4,5-b] pyridine-2-ketone
CN114133356B (en) Pyridazine compound and application thereof
CN106316861B (en) A kind of method for preparing double benzene bacterium amine
CN109134218A (en) Ingredient 4- oxo-trans- 2- hexenoic aldehyde synthetic method is lured in a kind of fleahopper sex pheromone
CN110330422A (en) A kind of preparation method of 2,6- diethyl -4- methylphenyl acetic acid
CN104910154A (en) 3-Bromo-6-chloro-imidazo [1,2-a] pyridine synthetic method

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
DD01 Delivery of document by public notice
DD01 Delivery of document by public notice

Addressee: Yuan Keming

Document name: Notice of Review Opinion

DD01 Delivery of document by public notice
DD01 Delivery of document by public notice

Addressee: SHANXI MEDICAL University Person in charge of patentsThe principal of patent

Document name: Notice of Approval of Claim for Restoration of Rights

DD01 Delivery of document by public notice
DD01 Delivery of document by public notice

Addressee: Yuan Keming

Document name: Notice of Conformity

RJ01 Rejection of invention patent application after publication
RJ01 Rejection of invention patent application after publication

Application publication date: 20190524