CN108164469A - A kind of method for preparing trione compounds - Google Patents
A kind of method for preparing trione compounds Download PDFInfo
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- CN108164469A CN108164469A CN201611115010.5A CN201611115010A CN108164469A CN 108164469 A CN108164469 A CN 108164469A CN 201611115010 A CN201611115010 A CN 201611115010A CN 108164469 A CN108164469 A CN 108164469A
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- 0 CN(c(ccc(C(C(C(CCC1)=O)C1=O)=O)c1*)c1C(N1c2c(*)cccc2I)=O)C1=O Chemical compound CN(c(ccc(C(C(C(CCC1)=O)C1=O)=O)c1*)c1C(N1c2c(*)cccc2I)=O)C1=O 0.000 description 6
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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
- C07D239/70—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings condensed with carbocyclic rings or ring systems
- C07D239/72—Quinazolines; Hydrogenated quinazolines
- C07D239/95—Quinazolines; Hydrogenated quinazolines with hetero atoms directly attached in positions 2 and 4
- C07D239/96—Two oxygen atoms
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Abstract
The present invention relates to field of pesticide preparation, disclose a kind of method for preparing trione compounds, which has the structure shown in formula (1), and this method includes：(1) under alkaline condition, in the presence of the first catalyst, formula (2) compound represented and 1,3 cyclohexanediones and CO is reacted, obtain the product shown in formula (3)；(2) under the conditions of rearrangement reaction, the product shown in formula (3) with the second catalyst and alkaline matter is contacted, obtains the trione compounds shown in formula (1).The preceding method of the present invention can be inexpensive and obtains trione compounds in high yield.It is also, high by the purity of trione compounds that the method for the present invention obtains.
Description
Technical field
The present invention relates to field of pesticide preparation, and in particular, to a kind of method for preparing trione compounds.
Background technology
P-hydroxyphenypyruvate dioxydenase (4-HPPD) is the effect of new herbicide found the 1980s
Target, it is widely present in various aerobic bioreactor bodies.The enzyme is a kind of containing ferrous double oxygenations by 2-ketoacid
Enzyme, Single-chip microcomputer can be catalytically converted into alcapton by it.The mechanism of action of 4-HPPD herbicides is to inhibit plant
Interior p-hydroxybenzene pyruvic acid (HPP) is converted into alcapton this process, in plant alcapton can further by living things catalysis into
Plastoquinone and tocopherol, and plastoquinone and tocopherol are substances necessary to electronic chain transmission in photosynthesis of plant, if suppression
4-HPPD will cause the biosynthesis block of alcapton in plant processed, and then influence photosynthesis electronic chain in plant and pass
It passs, plant is caused alphosis occur and dead.
Design is led with the hot spot that 4-HPPD inhibitor of the synthesis containing new structure is chemistry of pesticide research in recent years
One of domain.Up to the present, it has been found that the 4-HPPD inhibitor of 5 kinds or more different types of structure mainly has three ketones, pyrrole
Azole, isoxazole class, diketone cyanogen class and Benzophenones.There is efficient, low toxicity, to ring by the herbicide that target is developed of 4-HPPD
Border is friendly and to series of advantages such as succession crop safety.Therefore, 4-HPPD herbicides are a kind of very with researching value
With the herbicide of development prospect, more and more pesticide companies is also attracted to put into the research and development of 4-HPPD herbicides.City
The various types of the 4-HPPD inhibitor for the three ketones sold all contain there are one benzene ring structure in their molecule, such as have nitre sulphur
Humulone, sulphur humulone etc., wherein the effect of cutting weeds with mesotrione is best and safe.
According to 4-HPPD herbicide systematic researches, CN104557739A designs, which have synthesized, a kind of novel contains quinoline azoles
The three ketones 4-HPPD compounds of quinoline diketone structure.And it specifically discloses its trione compounds and passes through in rearrangement reaction condition
Under, the compound of structure shown in formula (II) with catalyst in the presence of alkali and solvent is contacted and is obtained.However, this is existing
The compound of structure is commercially available of high cost shown in formula (II) in the method for technology；During autonomous synthesis, and there are process routes to answer
The shortcomings that miscellaneous and yield is very low.
To sum up, it needs to find a kind of method that can obtain to low cost and high yield trione compounds in the art.
Invention content
The defects of the purpose of the present invention is overcoming the prior art, provide it is a kind of it is new can low cost and in high yield with it is high-purity
The method that degree ground obtains trione compounds.
To achieve these goals, in a first aspect, the present invention provides a kind of method for preparing trione compounds, the triketone
Class compound has the structure shown in formula (1), wherein, R1、R2And R3It is each independently selected from H, C1-6Alkyl, this method packet
It includes：
(1) under alkaline condition, in the presence of the first catalyst, by formula (2) compound represented and 1, hydroresorcinol
It is reacted with CO, obtains the product shown in formula (3)；
(2) under the conditions of rearrangement reaction, the product shown in formula (3) is contacted with the second catalyst and alkaline matter,
Obtain the trione compounds shown in formula (1).
Second aspect, the present invention provide a kind of method for preparing trione compounds, which has formula (1)
Shown structure, wherein, R1、R2And R3It is each independently selected from H, C1-6Alkyl, this method includes：
(1) it is the progress of formula (2) compound represented is cyanalation, obtain formula (4) compound represented；
(2) it is the progress of formula (4) compound represented is Carboxylation, obtain formula (5) compound represented；
(3) formula (5) compound represented is subjected to chloride, obtains formula (6) compound represented；
(4) formula (6) compound represented is esterified, obtains formula (3) compound represented；And
(5) under the conditions of rearrangement reaction, formula (3) compound represented is connect with the second catalyst and alkaline matter
It touches, obtains the trione compounds shown in formula (1).
The preceding method of the present invention can be inexpensive and obtains trione compounds in high yield.Also, by the present invention's
The purity for the trione compounds that method obtains is high.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Description of the drawings
Attached drawing is to be used to provide further understanding of the present invention, and a part for constitution instruction, with following tool
Body embodiment is used to explain the present invention, but be not construed as limiting the invention together.In the accompanying drawings：
Fig. 1 is according to a kind of synthetic route chart of preferred embodiment formula (5) compound represented.
Fig. 2 is the synthetic route according to the trione compounds shown in a kind of preferred embodiment formula (1)
Figure.
Fig. 3 is the synthesis road according to the trione compounds shown in another preferred embodiment formula (1)
Line chart.
Specific embodiment
The specific embodiment of the present invention is described in detail below.It is it should be understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or
Value should be understood to comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively
It between the endpoint value of a range and individual point value and can be individually combined with each other between point value and obtain one or more
New numberical range, these numberical ranges should be considered as specific open herein.
In the present invention, in case of no particular description, first haptoreaction, the second haptoreaction, first
" first ", " second " in catalyst, second catalyst etc. are not expression precedence, merely to distinguishing.This field skill
Art personnel should not be construed as limiting the scope of the invention.
In a first aspect, the present invention provides provide a kind of method for preparing trione compounds, trione compounds tool
There is the structure shown in formula (1), wherein, R1、R2And R3It is each independently selected from H, C1-6Alkyl, this method includes：
(1) under alkaline condition, in the presence of the first catalyst, by formula (2) compound represented and 1, hydroresorcinol
It is reacted with CO, obtains the product shown in formula (3)；
(2) under the conditions of rearrangement reaction, the product shown in formula (3) is contacted with the second catalyst and alkaline matter,
Obtain the trione compounds shown in formula (1).
Preferably, in the present invention, R1、R2And R3It is each independently selected from H, C1-3Alkyl；It is highly preferred that R1、R2And R3
It is each independently selected from H, methyl, ethyl, n-propyl and isopropyl, and R1、R2And R3It is asynchronously H.
First catalyst is the catalyst that can be catalyzed slotting carbonyl reaction.
Second catalyst carries out the catalyst of rearrangement reaction for product that can be shown in catalysis type (3).
Preferably, in step (1), containing component A and component B in first catalyst, the component A for palladium and/
Or palladium bichloride；The component B is selected from bis- (2- diphenylphosphines phenyl) ethers and/or the bis- diphenylphosphine -9,9- dimethyl oxygens of 4,5-
The ligand of miscellaneous anthracene.
Preferably, in first catalyst, dosages of the component A in terms of palladium element and the content of the component B
Molar ratio is 1：(1-2)；It is highly preferred that dosage and the content molar ratio of the component B that the component A is counted using palladium element is 1：
(1.05-1.4)。
It was found by the inventors of the present invention that in first catalyst, the component A is palladium and/or palladium bichloride；And institute
Component B is stated as the ligand selected from bis- (2- diphenylphosphines phenyl) ethers and/or the bis- diphenylphosphine -9,9- xanthphos of 4,5-；
The dosage and the content molar ratio of the component B that the component A is counted using palladium element is 1：When (1.05-1.4), first urged using this
Agent and obtain trione compounds purity and yield it is very high.
Preferably, in step (1), formula (2) compound represented and 1, the condition that hydroresorcinol is reacted includes：
Reaction temperature is 30-100 DEG C, reaction time 0.2-48h, reaction pressure 0.1-2.5MPa.
It was found by the inventors of the present invention that control formula (2) compound represented and 1, the pressure that hydroresorcinol is reacted
During for 0.6-2.5MPa, the purity higher of the product of the present invention is enabled to.
Preferably, in step (1), formula (2) compound represented in terms of the precious metal element wherein contained
The dosage molar ratio of first catalyst is 1：(0.05-0.15).
Preferably, in step (1), the alkaline condition is formed by the substance for being selected from triethylamine and/or sodium bicarbonate.
Preferably, in step (1), the reaction carries out in the presence of a phase transfer catalyst；It is highly preferred that the phase turns
Shifting catalyst is tetrabutylammonium bromide.
Preferably, in step (2), second catalyst is selected from Cymag, potassium cyanide, acetone cyanohydrin, trimethyl cyanogen
At least one of silane, 1,2,4- triazoles and benzo 1,2,4- triazoles.
Preferably, in step (2), the alkaline matter is selected from potassium carbonate, sodium carbonate, cesium carbonate, triethylamine and pyridine
At least one of.
Preferably, in step (2), the product shown in formula (3) is contacted with the second catalyst and alkaline matter
Condition includes：Contact Temperature is 5-50 DEG C；Time of contact is 5-30h.
Second aspect, the present invention provides a kind of method for preparing trione compounds, which has formula
(1) structure shown in, wherein, R1、R2And R3It is each independently selected from H, C1-6Alkyl, this method includes：
(1) it is the progress of formula (2) compound represented is cyanalation, obtain formula (4) compound represented；
(2) it is the progress of formula (4) compound represented is Carboxylation, obtain formula (5) compound represented；
(3) formula (5) compound represented is subjected to chloride, obtains formula (6) compound represented；
(4) formula (6) compound represented is esterified, obtains formula (3) compound represented；And
(5) under the conditions of rearrangement reaction, formula (3) compound represented is connect with the second catalyst and alkaline matter
It touches, obtains the trione compounds shown in formula (1).
Preferably, it in step (1), carries out cyanalation condition and includes：It carries out, flows back in the presence of cyanalation catalyst
React 3-48h.
In step (1), formula (2) compound represented is carried out cyanalation concrete operations to include：By formula (2) institute
The compound shown is contacted with Cyan Donor.The Cyan Donor for example can be cuprous cyanide.
Preferably, it in step (2), carries out Carboxylation condition and includes：It carries out, flows back in the presence of Carboxylation catalyst
React 2-30h.
In step (2), formula (4) compound represented is carried out Carboxylation concrete operations to include：By formula (4) institute
The compound shown is contacted with carboxyl group donor.The carboxyl group donor for example can be：Acetic acid, formic acid etc..
Preferably, in step (3), the condition for carrying out chloride includes：It is carried out in the presence of chloride reagent, reaction temperature
It is 0-80 DEG C to spend, reaction time 0.5-24h.
In step (3), formula (5) compound represented is carried out to the concrete operations of chloride to be included：Such as two
In the presence of chloromethanes is as solvent, haptoreaction will be carried out under the conditions of 0-25 DEG C of formula (5) compound represented and acyl chlorides compound, so
DMF is added in backward system and is heated up with back flow reaction.The acyl chlorides compound for example can be thionyl chloride.
Preferably, in step (4), the condition being esterified includes：Reaction temperature is subzero 10 DEG C to 25 DEG C above freezing, instead
It is 0.2-12h between seasonable.
In step (4), the concrete operations that formula (6) compound represented is esterified can be included：Solvent (such as
DCM in the presence of), under alkaline condition, by formula (6) compound represented and 1, hydroresorcinol carries out haptoreaction.
Preferably, in step (5), second catalyst is selected from Cymag, potassium cyanide, acetone cyanohydrin, trimethyl cyanogen
At least one of silane, 1,2,4- triazoles and benzo 1,2,4- triazoles.
Preferably, in step (5), the alkaline matter is selected from potassium carbonate, sodium carbonate, cesium carbonate, triethylamine and pyridine
At least one of.
Preferably, in step (5), formula (3) compound represented is contacted with the second catalyst and alkaline matter
Condition include：Contact Temperature is 5-50 DEG C；Time of contact is 5-30h.
In the first aspect of the present invention and second aspect, formula (2) compound represented can be commercially available,
The synthetic method of the prior art can also be used to synthesize to obtain.
Formula (2) compound represented can be by formula (7) compound represented (R3It is defined as described above) it is prepared into
It arrives, specifically：In the alkaline environment for example formed by alkaline matters such as pyridines, by formula (7) compound represented and by C1-6's
The substituted or unsubstituted phenyl isocyanate of at least one of alkyl substituent group carries out the first haptoreaction, and will contact anti-
Should after obtained product carry out second in the alkaline environment formed by alkaline matters such as such as potassium carbonate with dimethyl suflfate and connect
Touch reaction.The first catalytic condition can include：Temperature is 50-150 DEG C, time 4-48h.Second contact
The condition of reaction can include：Temperature is 20-80 DEG C, time 2-48h.
Formula (4) compound represented can also be by formula (8) compound represented (R3It is defined as described above) it prepares
It obtains, specifically：In the alkaline environment for example formed by alkaline matters such as pyridines, by formula (8) compound represented and by C1-6
The substituted or unsubstituted phenyl isocyanate of at least one of alkyl substituent group carry out third haptoreaction, and will contact
The product obtained after reaction carries out the 4th with dimethyl suflfate in the alkaline environment formed by alkaline matters such as such as potassium carbonate
Haptoreaction.The catalytic condition of third can include：Temperature is 50-150 DEG C, time 4-48h.Described 4th connects
Touching the condition of reaction can include：Temperature is 20-80 DEG C, time 2-48h.
Also, in the present invention, formula (8) compound represented can carry out cyano by formula (7) compound represented
Change and obtain, specifically：In the presence of solvent, formula (7) compound represented and Cyan Donor such as cuprous cyanide are carried out the
Five haptoreactions, the 5th catalytic condition can include：Temperature be back flow reaction temperature, time 4-48h.
Formula (7) compound represented can be prepared by formula (9) compound represented, specifically：Organic molten
In the presence of agent such as carbon tetrachloride, formula (9) compound represented and bromine are subjected to the 6th haptoreaction, the 6th contact is anti-
The condition answered can include：Temperature is 0-50 DEG C, time 3-400min.
According to a kind of preferred embodiment, the formula (5) compound represented of the invention can be as shown in Figure 1
Synthetic route be prepared, specifically, include the following steps：
(1) under the alkaline environment formed by alkaline matters such as potassium hydroxide, by formula (5-1) compound represented and Gao Meng
Sour potassium carries out the 7th haptoreaction, and then products therefrom is placed in acidic environment to obtain formula (5-2) compound represented, institute
The 7th catalytic condition is stated to include：Temperature is 50-150 DEG C, time 1-10h；
(2) in the presence of organic solvent such as dichloromethane, formula (5-2) compound represented and thionyl chloride are carried out
8th haptoreaction, obtains formula (5-3) compound represented, and the 8th catalytic condition includes：Temperature is anti-for reflux
Answer temperature, time 1-18h；
(3) in the presence of organic solvent such as methanol, formula (5-3) compound represented and palladium-carbon catalyst are carried out the 9th
Haptoreaction, obtains formula (5-4) compound represented, and the 9th catalytic condition includes：Temperature is 0-80 DEG C, the time
For 4-48h；
(4) in the presence of alkaline matter such as pyridine, by formula (5-4) compound represented and by C1-6Alkyl in extremely
A kind of few substituted or unsubstituted phenyl isocyanate of substituent group carries out the tenth haptoreaction, and will be obtained after haptoreaction
Product carries out the 11st haptoreaction with iodomethane in the alkaline environment formed by alkaline matters such as such as potassium carbonate, obtains formula
(5-5) compound represented；The tenth catalytic condition can include：Temperature is 50-150 DEG C, time 4-48h；
The 11st catalytic condition can include：Temperature is 10-80 DEG C, time 2-48h；And
It (5), will be formula (5-5) Suo Shi in the presence of solvent such as water and in the presence of the acidic materials such as concentrated sulfuric acid
Compound and carboxyl group donor such as acetic acid carry out the 12nd haptoreaction；Obtain formula (5) compound represented；Described 12nd
Catalytic condition can include：Temperature is 60-200 DEG C, time 2-48h.
According to another preferred embodiment, the synthetic route of trione compounds of the invention as shown in Figure 2
It is prepared, specifically, includes the following steps：
(1) in the presence of organic solvent such as carbon tetrachloride, formula (9) compound represented is carried out the 6th with bromine and is contacted
Reaction, obtains formula (7) compound represented, the 6th catalytic condition can include：Temperature is 0-50 DEG C, and the time is
3-400min；
(2) in the alkaline environment for example formed by alkaline matters such as pyridines, by formula (7) compound represented and by C1-6
The substituted or unsubstituted phenyl isocyanate of at least one of alkyl substituent group carry out the first haptoreaction, and will contact
The product obtained after reaction carries out second with dimethyl suflfate in the alkaline environment formed by alkaline matters such as such as potassium carbonate
Haptoreaction obtains formula (2) compound represented；The first catalytic condition can include：Temperature is 50-150 DEG C,
Time is 4-48h.The second catalytic condition can include：Temperature is 20-80 DEG C, time 2-48h；
(3) under alkaline condition, in the presence of the first catalyst, by formula (2) compound represented and 1, hydroresorcinol
It is reacted with CO, obtains the product shown in formula (3)；And
(4) under the conditions of rearrangement reaction, the product shown in formula (3) is contacted with the second catalyst and alkaline matter,
Obtain the trione compounds shown in formula (1).
According to the third preferred embodiment, the synthetic route of trione compounds of the invention as shown in Figure 3
It is prepared, specifically, includes the following steps：
(1) in the presence of organic solvent such as carbon tetrachloride, formula (9) compound represented is carried out the 6th with bromine and is contacted
Reaction, obtains formula (7) compound represented, the 6th catalytic condition can include：Temperature is 0-50 DEG C, and the time is
3-400min；
(2) in the alkaline environment for example formed by alkaline matters such as pyridines, by formula (7) compound represented and by C1-6
The substituted or unsubstituted phenyl isocyanate of at least one of alkyl substituent group carry out the first haptoreaction, and will contact
The product obtained after reaction carries out second with dimethyl suflfate in the alkaline environment formed by alkaline matters such as such as potassium carbonate
Haptoreaction obtains formula (2) compound represented；The first catalytic condition can include：Temperature is 50-150 DEG C,
Time is 4-48h.The second catalytic condition can include：Temperature is 20-80 DEG C, time 2-48h；
(3) it is the progress of formula (2) compound represented is cyanalation, obtain formula (4) compound represented；
(4) it is the progress of formula (4) compound represented is Carboxylation, obtain formula (5) compound represented；
(5) formula (5) compound represented is subjected to chloride, obtains formula (6) compound represented；
(6) formula (6) compound represented is esterified, obtains formula (3) compound represented；And
(5) under the conditions of rearrangement reaction, formula (3) compound represented is connect with the second catalyst and alkaline matter
It touches, obtains the trione compounds shown in formula (1).
It may be used in the reaction that the first aspect of the present invention and second aspect are related in the art conventional use of each
Kind post-processing approach post-processes obtained product.The method of the post processing includes but not limited to：Extraction is tied again
Brilliant, washing, dry, filtering etc..Details are not described herein, and the post-processing approach involved in embodiment is only for showing by the present invention
Enumerate to example property, it is the operation that must be used to be not offered as that, those skilled in the art may be used conventional other means into
Row substitutes.
It below will the present invention will be described in detail by embodiment and preparation example.
In following embodiment and preparation example, in case of no particular description, the various raw materials used are all from commercially available.
Preparation example 1：Formula (5) compound represented is synthesized using route shown in FIG. 1, wherein, R3For H, R1And R2For methyl
1st, Jiang Shui (500mL) is added in the four-hole boiling flask of 1000mL, opens stirring, system is cooled to 5 with brine ice
DEG C, then potassium hydroxide (553mmol) is slowly added into the four-hole boiling flask of 100mL, after addition, brine ice is removed,
It is slowly dropped into 2,4- dimethyl nitrobenzenes (3311mmol) again, after being added dropwise, reaction system is heated to 90 DEG C.Treat reactant
After system is raised to 90 DEG C, potassium permanganate (1659mmol) is added in four-hole boiling flask in batches in 0.5h, it will be anti-after addition
System is answered to keep the temperature 3h at 90 DEG C, is tracked and reacted with HPLC.It treats to filter while hot after completion of the reaction and be washed with the hot water (70 DEG C) of 500mL
Wash filter cake.5 DEG C are cooled the filtrate to, and concentrated hydrochloric acid (36 weight %, 100mL) is slowly dropped into it.Filtering, with 500mL's
Water wash filter cake dries filter cake to get to white solid, purity 97.8%, yield 80%.
2nd, the product (237mmol) that dichloromethane (500mL), step 1 obtain is added in the four-hole boiling flask of 1L, fed
After temperature of reaction system is down to 5 DEG C with brine ice again, then start that thionyl chloride (1422mmol) is slowly added dropwise, treat chlorine
Change sulfoxide, which is added dropwise, to be continued to stir 10min, and DMF (23.7mmol) is then slowly added dropwise again, 30min is stirred after being added dropwise,
Then reaction system is slowly heated to the 6h that flows back and keep the temperature, is tracked and reacted with HPLC.It treats reaction system after completion of the reaction
It drops to 25 DEG C and depressurizes precipitation again.The reaction solution after precipitation is dissolved with 250mL dichloromethane and is rapidly added drop-wise to 0 DEG C of methanol
In (500mL) solution.Continue to stir 10min after being added dropwise, monitored and reacted with HPLC.It treats after completion of the reaction, precipitation, to precipitation
200mL water and 600mL ethyl acetate are added in reaction solution afterwards, is stirred, layering.Then it is added to 200mL water to organic, and to
It wherein adds in sodium bicarbonate and so that pH is adjusted to neutrality, stratification dries organic phase with anhydrous sodium sulfate, and precipitation is to get to white
Color solid, purity 98.5%, yield 85%.
3rd, the product (167.2mmol) that methanol (400mL), step 2 obtain is added in the single port bottle of 1000mL.It opens
Stirring adds in palladium charcoal (10 weight %) into single port bottle.Hydrogen is passed through after exhaust, reaction system is slowly warming up to 45 DEG C
Incubated overnight is tracked with HPLC and reacted.It treats after completion of the reaction, while hot filtering reacting liquid, the methanol (50 DEG C) of filter cake heat washs
And it filters.By filtrate precipitation, when methanol stripper is to 1/3, eaten to the saturation of its interior ethyl acetate for adding in 600mL and 200mL
Brine, stirring, stratification dry organic phase with anhydrous sodium sulfate, and precipitation to get to white solid, receive by purity 97.8%
Rate is 95.4%.
4th, by pyridine (250mL), the product (144mmol) that step 3 obtains is added in the four-hole boiling flask of 500mL, is opened
Stirring, adds 2,6- dimethylphenyl isocyanates (179mmol), reaction system is warming up to 100 DEG C of guarantors after addition
Temperature overnight, is tracked with HPLC and reacted.It treats after completion of the reaction, reaction solution is poured into the water of 1L, and stir 30min while hot, mistake
Filter, filter cake is washed twice with isopropyl ether 100mL, obtained solid is dried, by obtained solid (103.6mmol) and DMF
(350mLl), potassium carbonate (124mmol) are added in the single port bottle of 500mL, and stirring is opened after addition, by reaction system plus
Heat is to 45 DEG C and keeps the temperature 30min, then starts that dimethyl suflfate (412mmol) is added dropwise.Continue stirring heat preservation after being added dropwise
For 24 hours, it is tracked and reacted with HPLC.It treats after completion of the reaction to pour into reaction system in the ice water of 500mL and stirs 30min, filter, use
The isopropyl ether washing filter cake of 200mL, filter cake is dried to get to white solid, purity 97.5%, yield 60%.
5th, the product (59mmol) that Jiang Shui (89mL), glacial acetic acid (120mL), step 4 obtain is added to four mouthfuls of burnings of 500mL
In bottle, stirring is opened, and the concentrated sulfuric acid (120mL) is slowly added dropwise, reaction system is warming up to reflux after being added dropwise and keeps the temperature 6h,
It is tracked and reacted with HPLC.It treats after completion of the reaction to be poured into reaction solution in the mixture of ice and water of 500mL while hot, stirs 30min, mistake
Filter, filter cake is washed twice with the isopropyl ether of 200mL, obtained solid is dried to get to white solid, purity 97.5%,
Yield is 90%.
Preparation example 2：Formula (2) compound represented, and R1And R2For methyl, R3For H
Carbon tetrachloride (100mL) and 2- Methyl anthranilates (149mmol) the 1, are added to the four-hole boiling flask of 250mL
It is interior, stirring is opened, starts that bromine (156.45mmol) is added dropwise, sampling HPLC tracking reaction after being added dropwise.Treat that reaction finishes
Filtering reacting liquid afterwards, filter cake are eluted with 200mL isopropyl ethers, drying, you can obtain yellow solid, purity 96.5%, yield is
90%.
2nd, by pyridine (250mL), the product (144mmol) that step 1 obtains is added in the four-hole boiling flask of 500mL, is opened
Stirring, adds 2,6- dimethylphenyl isocyanates (179mmol), reaction system is warming up to 100 DEG C of guarantors after addition
Temperature overnight, is tracked with HPLC and reacted.It treats after completion of the reaction, reaction solution is poured into the water of 1L, and stir 30min while hot, mistake
Filter, filter cake are washed twice with isopropyl ether 100mL, obtained solid are dried.Then by obtained solid (116mmol), DMF
(400mL), potassium carbonate (139mmol) are added in the single port bottle of 1L, and stirring is opened after addition, reaction system is heated to
45 DEG C and 30min is kept the temperature, after keeping the temperature 30min, start that dimethyl suflfate (464mmol) is slowly added dropwise.Continue after being added dropwise
Stirring heat preservation for 24 hours, is tracked with HPLC and reacted.It treats after completion of the reaction to pour into reaction system in the ice water of 1L and stirs 30min, mistake
Filter, washs filter cake with the isopropyl ether of 200mL, filter cake is put drying, obtain product, purity 96.8%, yield 72%.
Preparation example 3：Formula (4) compound represented, and R1And R2For methyl, R3For H
DMF (300mL), 2- amino -5- methyl-bromobenzoates (130.4mmol) are added in the single port bottle of 1000mL,
Stirring is opened, adds cuprous cyanide (2260.8mmol).Reaction system is warming up to reflux and incubated overnight after addition,
It is tracked and reacted with HPLC.It treats that reaction solution first is dropped to 25 DEG C after completion of the reaction, the water for then adding in 500mL into reaction solution again stirs
30min is mixed, the ethyl acetate of 300mL is then added in into it again, is filtered after stirring, by filtrate stratification, water phase
It is extracted respectively three times with the ethyl acetate of 600mL, dries organic phase with anhydrous sodium sulfate, precipitation is to get to white solid, purity
It is 95.6%, yield 90%.
2nd, by pyridine (167mL), the product (113.6mmol) that step 1 obtains is added in the four-hole boiling flask of 500mL, opens
Stirring is opened, 2,6- dimethylphenyl isocyanates (126.32mmol) is added, reaction system is warming up to 100 after addition
DEG C incubated overnight is tracked with HPLC and reacted.It treats after completion of the reaction, reaction solution is poured into the water of 1L, and stir while hot
30min, filtering, filter cake are washed twice with isopropyl ether 100mL, obtained solid are dried.Then by obtained solid (83mmol),
DMF (260mL), potassium carbonate (99.6mmol) are added in the single port bottle of 500mL, stirring are opened after addition, by reactant
System is heated to 45 DEG C and keeps the temperature 30min, then starts that dimethyl suflfate (332mmol) is slowly added dropwise, continues after being added dropwise
It stirring 24 hours of heat preservation, is tracked and reacted with HPLC.It treats after completion of the reaction to pour into reaction system in the ice water of 500mL and stir
30min, filtering, filter cake is washed with the isopropyl ether of 100mL, and filter cake is dried to get product, purity 97%, yield 72%.
Preparation example 4：Formula (2) compound represented, and R1And R3For methyl, R2For H
This preparation example is prepared using the method similar to preparation example 2, the difference is that using equimolar amounts in this preparation example
2- amino -6- methyl toluates replace preparation example 2 in 2- Methyl anthranilates and the 2- first with equimolar amounts
Base phenyl isocyanate replaces the 2,6- dimethylphenyl isocyanates in preparation example 2.Remaining is identical with preparation example 2, obtains
To product, purity 96.5%, yield 73%.
Embodiment 1：Trione compounds shown in shown reaction equation formula (1) according to fig. 2, R3For H, R1And R2For
Methyl
Add in the dioxane (400mL) 6- bromo- 3- (2,6- 3,5-dimethylphenyls) -1- methylquinazolins -2,4 (1H,
3H)-diketone (0.1mol), hydroresorcinol (0.12mol), palladium bichloride (10mmol), bis- (2- diphenylphosphines phenyl) ethers
(11mmol), triethylamine (0.35mol), tetrabutylammonium chloride (0.12mol), are then passed through carbon monoxide into reaction system,
Control pressure is 2MPa, is heated to 60 DEG C of reaction 5h.Reaction finishes, and filtering, filtrate is extracted with ethyl acetate after adding water, organic phase
With organic phase dry after the salt acid elution to neutrality of 25 weight %, it is concentrated to give crude compound.Crude product is directly used without further purification
It is reacted in next step.
Above-mentioned crude product 40g is added in acetonitrile (400mL), is added with stirring triethylamine (0.15mol), acetone cyanohydrin
(0.01mol).Reaction system is stirred to react 15 hours at 30 DEG C.Reaction finishes stirring, and pH is acidified to the hydrochloric acid of 25 weight %
=1.Obtained solid filter, washing, with recrystallizing methanol to get light yellow solid 3- (2,6- 3,5-dimethylphenyl) -6- (2- hydroxyls
Base -6- oxocyclohex -1- alkene carboxyl) -1- methylquinazolins -2,4 (1H, 3H)-diketone, purity 99.8%, yield is
96.0%.
Embodiment 2：Trione compounds shown in shown reaction equation formula (1) according to fig. 2, R3For H, R1And R2For
Methyl
Add in the dioxane (400mL) 6- bromo- 3- (2,6- 3,5-dimethylphenyls) -1- methylquinazolins -2,4 (1H,
3H)-diketone (0.1mol), hydroresorcinol (0.12mol), palladium bichloride (10mmol), the bis- diphenylphosphine -9,9- diformazans of 4,5-
Base xanthene (12mmol), triethylamine (0.35mol), tetrabutylammonium chloride (0.12mol), are then passed through one into reaction system
Carbonoxide, control pressure 1.6MPa are heated to 80 DEG C of reaction 4h.Reaction finishes, and filtering, filtrate is extracted after adding water with ethyl acetate
It takes, dry organic phase, is concentrated to give crude compound after the organic phase salt acid elution to neutrality of 25 weight %.Crude product is without pure
Change is directly used in reacts in next step.
Above-mentioned crude product is added in acetonitrile (400mL), is added with stirring triethylamine (0.15mol), acetone cyanohydrin
(0.01mol).Reaction system is stirred to react 15 hours at 30 DEG C.Reaction finishes stirring, and pH is acidified to the hydrochloric acid of 25 weight %
=1.Obtained solid filter, washing, with recrystallizing methanol to get light yellow solid 3- (2,6- 3,5-dimethylphenyl) -6- (2- hydroxyls
Base -6- oxocyclohex -1- alkene carboxyl) -1- methylquinazolins -2,4 (1H, 3H)-diketone, purity 99.5%, yield is
96.0%.
Embodiment 3：Trione compounds shown in shown reaction equation formula (1) according to fig. 2, R3And R1For methyl, R2
For H
5- methyl -6- bromo- 3- (2- aminomethyl phenyls) -1- methylquinazolins -2,4 are added in dioxane (400mL)
(1H, 3H)-diketone (0.1mol), hydroresorcinol (0.12mol), palladium bichloride (10mmol), bis- (2- diphenylphosphines phenyl)
Ether (14mmol), triethylamine (0.35mol), tetrabutylammonium chloride (0.12mol), are then passed through an oxidation into reaction system
Carbon, control pressure 1.2MPa are heated to 60 DEG C of reaction 5h.Reaction finishes, and filtering, filtrate is extracted with ethyl acetate after adding water,
Dry organic phase, is concentrated to give crude product after the organic phase salt acid elution to neutrality of 25 weight %.Crude product is directly used without further purification
It is reacted in next step.
Above-mentioned crude product is added in acetonitrile (400mL), is added with stirring triethylamine (0.15mol), acetone cyanohydrin
(0.01mol).Reaction system is stirred to react 15 hours at 30 DEG C.Reaction finishes stirring, and pH is acidified to the hydrochloric acid of 25 weight %
=1.Obtained solid filter, washing, with recrystallizing methanol to get light yellow solid 3- (2,6- 3,5-dimethylphenyl) -6- (2- hydroxyls
Base -6- oxocyclohex -1- alkene carboxyl) -1- methylquinazolins -2,4 (1H, 3H)-diketone, purity 98.7%, yield 72%.
Embodiment 4：Trione compounds shown in shown reaction equation formula (1) according to fig. 2, R3For H, R1And R2For
Methyl
The present embodiment is carried out using method same as Example 1, the difference is that in the present embodiment, to reaction system
In be passed through carbon monoxide, control pressure 0.3MPa, remaining is in the same manner as in Example 1.
As a result gained 3- (2,6- 3,5-dimethylphenyls) -6- (2- hydroxyl -6- oxocyclohex -1- alkene carboxyl) -1- methyl quinoline azoles
Quinoline -2,4 (1H, 3H)-diketone, purity 67.6%, yield 96.0%.
Embodiment 5：Trione compounds shown in shown reaction equation formula (1) according to fig. 2, R3For H, R1And R2For
Methyl
The present embodiment is carried out using method same as Example 1, the difference is that in the present embodiment, bis- (2- diphenyl
Phosphorus phenyl) ether dosage for 25mmol, remaining is in the same manner as in Example 1.
As a result gained 3- (2,6- 3,5-dimethylphenyls) -6- (2- hydroxyl -6- oxocyclohex -1- alkene carboxyl) -1- methyl quinoline azoles
Quinoline -2,4 (1H, 3H)-diketone, purity 90.69%, yield 89.6%.
Embodiment 6：Trione compounds shown in shown reaction equation formula (1) according to fig. 2, R3For H, R1And R2For
Methyl
The present embodiment is carried out using method same as Example 1, the difference is that in the present embodiment, using equimolar
The PdCl of amount2(PPh3)2Palladium bichloride in alternative embodiment 1, remaining is in the same manner as in Example 1.
As a result gained 3- (2,6- 3,5-dimethylphenyls) -6- (2- hydroxyl -6- oxocyclohex -1- alkene carboxyl) -1- methyl quinoline azoles
Quinoline -2,4 (1H, 3H)-diketone, purity 90.69%, yield 68.9%.
Embodiment 7：Trione compounds shown in shown reaction equation formula (1) according to fig. 3, R3For H, R1And R2For
Methyl
1st, DMF (300mL), bromide (83.6mmol) are sequentially added into the single port bottle of 1000mL, unlatching is stirred
It mixes, adds load weighted cuprous cyanide (167.1mmol).Reaction system is warming up to reflux after addition and was kept the temperature
Night is tracked with HPLC and reacted.It treats that reaction solution first is dropped to 25 DEG C after completion of the reaction, then adds in 500mL's into reaction solution again
Water is stirred 30 minutes, is then filtered after stirring to the ethyl acetate that 300mL is added in it again, by filtrate stratification,
Its water phase is extracted three times respectively with the ethyl acetate of 600mL, dries organic phase with anhydrous sodium sulfate, precipitation is to get solid to white
Body, purity 96.4%, yield 90%.
2nd, the cyano object for obtaining glacial acetic acid (150mL), water (620mL), trifluoromethanesulfonic acid (37mL) and step 1
(146.6mmol) is added in the four-hole boiling flask of 1000mL, opens stirring, reaction system is cooled to 10 DEG C of left sides with brine ice
The right side, is then slowly added dropwise the concentrated sulfuric acid (500mL), and reaction system is slowly warmed to flow back and be protected by the concentrated sulfuric acid after being added dropwise
Temperature overnight, is tracked with HPLC and reacted.It treats cooling reaction system after completion of the reaction, reaction solution is poured into the ice water of 1L and stirred
30min, filtering.Filter cake is washed with the isopropyl ether of 200mL, is dried to get to gray solid, purity 97.8%, yield is
70%.
3rd, the product (77mmol) and dichloromethane (300mL) that obtain step 2 are added to the four-hole boiling flask of 500mL
It is interior, reaction system is cooled to 5 DEG C or so and starts that thionyl chloride (231mmol) is added dropwise, continues to stir 10min after being added dropwise.
Then DMF (4mmol) is added dropwise again, is added dropwise and continues to stir 30min, reaction system is warming up to reflux and keeps the temperature 6 hours,
It is tracked and reacted with HPLC.It treats that reaction system cooled to 25 DEG C after completion of the reaction, precipitation is to get to brown solid, purity
98.9%, yield 100%.
4th, by 1, hydroresorcinol (85mmol), DCM (200mL) is added in the single port bottle of 500mL, with cool brine to anti-
System is answered to be cooled to 0 DEG C and instills triethylamine (155mmol), continues low temperature stirring 1h after being added dropwise, then will contain 50mL
The acyl chlorides compound (77mmol) that is prepared of abovementioned steps 3 of dichloromethane be added drop-wise in low-temp reaction system, time for adding
Control continues low temperature stirring 30min within 10min, after being added dropwise, and is tracked and reacted with HPLC.Treating after completion of the reaction will reaction
System is washed respectively with the hydrochloric acid of 2mol/L (30mL × 2), the sodium carbonate liquor of 5 weight % (60mL × 2) washing, finally with full
It is washed with saline solution (30mL).Gained organic layer is dried with anhydrous sodium sulfate, to get to white solid, purity is precipitation
97.85%, yield 76%.
5th, the product (48mmol) and acetonitrile 200mL that obtain step 4 are added sequentially to the four-hole boiling flask of 1000mL
It is interior, stirring is opened, then triethylamine (72mmol), acetone cyanohydrin (0.48mmol) are added sequentially in reaction system, is fed
After reaction system be warming up to 30 DEG C under the protection of nitrogen and keep the temperature 12h, tracked and reacted with HPLC.It treats after completion of the reaction
Precipitation is depressurized at 40 DEG C, takes off after dry acetonitrile to 40 DEG C of the water that 250mL is added in it, opens stirring, then three are added in into it
Reaction system is kept the temperature 30min by ethamine (100mmol) after being added dropwise at 40 DEG C, and then filtering reacting liquid, gained filtrate is dropped
For temperature to 5 DEG C, the salt acid for adjusting pH value for adding in 2mol/L into it while stirring is 1.Obtained solid is filtered, wash, uses methanol
Recrystallization is to get to light yellow solid, purity 98.9%, yield 70%.
The preceding method of the present invention can be inexpensive and obtains three ketones chemical combination in high yield it can be seen from aforementioned result
Object.It is also, high by the purity of trione compounds that the method for the present invention obtains.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above
Detail, within the scope of the technical concept of the present invention, a variety of simple variants can be carried out to technical scheme of the present invention, this
A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy no longer separately illustrates.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should also be regarded as the disclosure of the present invention.
Claims (10)
1. a kind of method for preparing trione compounds, which has the structure shown in formula (1), wherein, R1、R2
And R3It is each independently selected from H, C1-6Alkyl, this method includes：
(1) under alkaline condition, in the presence of the first catalyst, by formula (2) compound represented and 1, hydroresorcinol and CO
It is reacted, obtains the product shown in formula (3)；
(2) under the conditions of rearrangement reaction, the product shown in formula (3) with the second catalyst and alkaline matter is contacted, is obtained
Trione compounds shown in formula (1).
2. according to the method described in claim 1, wherein, in step (1), component A and group are contained in first catalyst
It is palladium and/or palladium bichloride to divide B, the component A；The component B is selected from bis- (2- diphenylphosphines phenyl) ethers and/or 4,5- bis- two
The ligand of Phenylphosphine -9,9- xanthphos.
3. according to the method described in claim 2, wherein, in first catalyst, use of the component A in terms of palladium element
Amount and the content molar ratio of the component B are 1：(1-2)；Preferably,
The dosage and the content molar ratio of the component B that the component A is counted using palladium element is 1：(1.05-1.4).
4. according to the method described in any one in claim 1-3, wherein, in step (1), formula (2) compound represented
The condition reacted with hydroresorcinol includes：Reaction temperature is 30-100 DEG C, reaction time 0.2-48h, reaction pressure
Power is 0.1-2.5MPa.
5. according to the method described in any one in claim 1-4, wherein, in step (1), the change shown in the formula (2)
Object and the dosage molar ratio of first catalyst counted using the precious metal element wherein contained are closed as 1：(0.05-0.15).
6. according to the method described in any one in claim 1-5, wherein, in step (1), the alkaline condition is by being selected from
The substance of triethylamine and/or sodium bicarbonate is formed.
7. according to the method described in any one in claim 1-6, wherein, in step (1), the reaction is urged in phase transfer
It is carried out in the presence of agent；Preferably,
The phase transfer catalyst is tetrabutylammonium bromide.
8. according to the method described in any one in claim 1-7, wherein, in step (2), second catalyst is selected from
At least one in Cymag, potassium cyanide, acetone cyanohydrin, trimethylsilyl cyanide, 1,2,4- triazoles and benzo 1,2,4- triazoles
Kind；Preferably,
In step (2), the alkaline matter in potassium carbonate, sodium carbonate, cesium carbonate, triethylamine and pyridine at least one
Kind；Preferably,
In step (2), the product shown in formula (3) is included with the condition that the second catalyst and alkaline matter contact：It connects
It is 5-50 DEG C to touch temperature；Time of contact is 5-30h.
9. a kind of method for preparing trione compounds, which has the structure shown in formula (1), wherein, R1、R2
And R3It is each independently selected from H, C1-6Alkyl, this method includes：
(1) it is the progress of formula (2) compound represented is cyanalation, obtain formula (4) compound represented；
(2) it is the progress of formula (4) compound represented is Carboxylation, obtain formula (5) compound represented；
(3) formula (5) compound represented is subjected to chloride, obtains formula (6) compound represented；
(4) formula (6) compound represented is esterified, obtains formula (3) compound represented；And
(5) under the conditions of rearrangement reaction, formula (3) compound represented with the second catalyst and alkaline matter is contacted, is obtained
To the trione compounds shown in formula (1).
10. according to the method described in claim 9, wherein,
In step (1), carry out cyanalation condition and include：It is carried out in the presence of cyanalation catalyst, back flow reaction 3-48h；
Preferably,
In step (2), carry out Carboxylation condition and include：It is carried out in the presence of Carboxylation catalyst, back flow reaction 2-30h；
Preferably,
In step (3), the condition for carrying out chloride includes：It being carried out in the presence of chloride reagent, reaction temperature is 0-80 DEG C,
Reaction time is 0.5-24h；Preferably,
In step (4), the condition being esterified includes：Reaction temperature is subzero 10 DEG C to 25 DEG C above freezing, and the reaction time is
0.2-12h；Preferably,
In step (5), second catalyst is selected from Cymag, potassium cyanide, acetone cyanohydrin, trimethylsilyl cyanide, 1,2,4-
At least one of triazole and benzo 1,2,4- triazoles；Preferably, the alkaline matter is selected from potassium carbonate, sodium carbonate, carbon
At least one of sour caesium, triethylamine and pyridine；Preferably, by formula (3) compound represented and the second catalyst and basic species
The condition that matter is contacted includes：Contact Temperature is 5-50 DEG C；Time of contact is 5-30h.
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| CN110669016A (en) * | 2018-09-29 | 2020-01-10 | 山东先达农化股份有限公司 | Triketone compound, preparation method and application thereof, and herbicide |
| CN113845452A (en) * | 2020-06-28 | 2021-12-28 | 沈阳中化农药化工研发有限公司 | Synthetic method of triketone compound |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110669016A (en) * | 2018-09-29 | 2020-01-10 | 山东先达农化股份有限公司 | Triketone compound, preparation method and application thereof, and herbicide |
| WO2020063981A1 (en) * | 2018-09-29 | 2020-04-02 | 山东先达农化股份有限公司 | Triketone compound, preparation method therefor and use thereof, and herbicide |
| CN110669016B (en) * | 2018-09-29 | 2021-05-25 | 山东先达农化股份有限公司 | Triketone compound, preparation method and application thereof, and herbicide |
| CN113845452A (en) * | 2020-06-28 | 2021-12-28 | 沈阳中化农药化工研发有限公司 | Synthetic method of triketone compound |
| CN113845452B (en) * | 2020-06-28 | 2024-03-12 | 沈阳中化农药化工研发有限公司 | Synthesis method of trione compounds |
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