CN106083668A - A kind of preparation method of 3 bromomethyl 2 halo 4 alkyl sulphonyl benzoate - Google Patents
A kind of preparation method of 3 bromomethyl 2 halo 4 alkyl sulphonyl benzoate Download PDFInfo
- Publication number
- CN106083668A CN106083668A CN201610443995.8A CN201610443995A CN106083668A CN 106083668 A CN106083668 A CN 106083668A CN 201610443995 A CN201610443995 A CN 201610443995A CN 106083668 A CN106083668 A CN 106083668A
- Authority
- CN
- China
- Prior art keywords
- formula
- reducing agent
- compound shown
- consumption
- compound
- 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
Links
- 0 CI(C(CC*)I=CC[C@](C*)N)O Chemical compound CI(C(CC*)I=CC[C@](C*)N)O 0.000 description 2
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C315/00—Preparation of sulfones; Preparation of sulfoxides
- C07C315/04—Preparation of sulfones; Preparation of sulfoxides by reactions not involving the formation of sulfone or sulfoxide groups
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to field of compound preparation, disclose the preparation method of a kind of 3 bromomethyl 2 halo 4 alkyl sulphonyl benzoate, the method includes: in the presence of reducing agent and initiator, and substrate compounds and bromate carry out haptoreaction.The method, using bromate as bromating agent, obtains target product under reducing agent effect.Wherein, bromate and reducing agent are cheap.The method of the invention has low cost, yield advantages of higher, it is adaptable to large-scale industrial production.
Description
Technical field
The present invention relates to field of compound preparation, in particular it relates to a kind of 3-bromomethyl-2-halo-4-alkyl sulphonyl
The preparation method of benzoate.
Background technology
3-bromomethyl-2-halo-4-alkyl sulphonyl benzoate, is a kind of centre preparing pesticide herbicide ring sulphur ketone
Body.
WO2000021924A1 discloses the preparation side of a kind of 3-bromomethyl-2-chloro-4-methyl sulphonyl essence of Niobe
Method, the method is with 3-methyl-2-chloro-4-methyl sulphonyl essence of Niobe and bromating agent NBS (N-bromo-succinimide)
Reaction obtains 3-bromomethyl-2-chloro-4-methyl sulphonyl essence of Niobe.It addition, CN02817704.5 discloses a kind of 3-bromine
Methyl-2-chloro-4-benzoic the preparation method of methyl sulphonyl, the method is with compound 3-methyl-2-chloro-4-sulfonyloxy methyl
Yl benzoic acid and bromating agent NBS react and obtain 3-bromomethyl-2-chloro-4-sulfonyloxy methyl yl benzoic acid.In these bromination process, though
So yield is the highest, can reach 87～90%, but owing to NBS price is high, causes preparation cost higher.
Summary of the invention
It is an object of the invention to overcome employing prior art to prepare 3-bromomethyl-2-halo-4-alkyl sulfonyl yl benzoic acid
The defect that the cost of ester is high, it is provided that the preparation method of a kind of 3-bromomethyl-2-halo-4-alkyl sulphonyl benzoate.
To achieve these goals, the present invention provides the 3-bromomethyl-2-halo-4-alkyl sulfonyl shown in a kind of formula (1)
The preparation method of yl benzoic acid ester, wherein, the method includes: in the presence of reducing agent and initiator, by the change shown in formula (2)
Compound and the compound haptoreaction shown in formula (3)；
Wherein, R1For C1-C7Straight or branched alkyl；R2For the one in Li, Na and K；R3For in F, Cl and Br
Kind；R4For C1-C5Alkyl.
Using bromate as bromating agent in the present invention, under reducing agent effect, obtain target product.Wherein, bromate and also
Former dose cheap.The method of the invention has low cost, (yield can reach more than 80% to yield height, according to the present invention's
Preferred implementation, yield can reach 88-90%) etc. advantage, it is adaptable to large-scale industrial production.
Other features and advantages of the present invention will be described in detail in detailed description of the invention part subsequently.
Detailed description of the invention
Hereinafter the detailed description of the invention of the present invention is described in detail.It should be appreciated that described herein specifically
Embodiment is merely to illustrate and explains the present invention, is not limited to the present invention.
The end points of scope disclosed in this article and any value are not limited to this accurate scope or value, these scopes or
Value should be understood to the value comprised close to these scopes or value.For numerical range, between the endpoint value of each scope, respectively
Between endpoint value and the single point value of individual scope, and can obtain one or more between single point value with combination with one another
New numerical range, these numerical rangies should be considered the most specifically to disclose.
The invention provides the preparation of the 3-bromomethyl-2-halo-4-alkyl sulphonyl benzoate shown in a kind of formula (1)
Method, wherein, the method includes: in the presence of reducing agent and initiator, shown in the compound shown in formula (2) and formula (3)
Compound haptoreaction；
In formula (2), R1For C1-C7Straight or branched alkyl, can be such as methyl, ethyl, n-pro-pyl, isopropyl,
Normal-butyl, isobutyl group, the tert-butyl group, n-pentyl or n-hexyl.Under preferable case, R1For C1-C3Straight or branched alkyl, such as
Can be methyl, ethyl or isopropyl.
In formula (2), R3For F, Cl or Br；Preferably, R3For Cl or Br；It is highly preferred that R3For Cl.
In formula (2), R4For C1-C5Alkyl, can be such as methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, different
Butyl, the tert-butyl group, n-pentyl, isopentyl, neopentyl or tertiary pentyl；Preferably, R4For C1-C3Alkyl, can be such as first
Base, ethyl, n-pro-pyl or isopropyl；It is highly preferred that R4For methyl.
In the present invention, the compound shown in formula (3) is bromate, and it is as the bromating agent needed for reaction.Described bromate
Can be commercially available.In formula (3), R2For Li, Na or K；Preferably, R2For Na or K.
In the present invention, the most special to the consumption of the compound shown in formula (3) and the consumption of the compound shown in formula (2)
Limit, but, in order to make full use of the compound shown in formula (3) and the compound shown in formula (2), to improve reaction efficiency, to subtract
Few production cost, it is preferable that the consumption of the compound shown in formula (3) with the mol ratio of the consumption of the compound shown in formula (2) is
0.8-3:1, preferably 1-1.5:1.
In the present invention, described catalytic reaction principle is that the compound shown in formula (3) is raw under the effect of reducing agent
Viability simple substance bromine；Under the effect of initiator, described simple substance bromine and the compound shown in formula (2) carry out bromination reaction.
In the present invention, described reducing agent can be conventional use of reducing agent in this area, under preferable case, described reduction
Agent is at least one in sodium sulfite, sodium sulfite, sodium peroxydisulfate and sodium thiosulfate；In the case of preferred, described
Reducing agent is sodium sulfite and/or sodium sulfite；In the case of You Xuan, described reducing agent is sodium sulfite.The present invention
The consumption of described reducing agent is had no particular limits, as long as the consumption of described reducing agent can by the compound shown in formula (3) also
Former, under preferable case, the consumption of described reducing agent is 0.8-4:1 with the mol ratio of the consumption of the compound shown in formula (2),
More preferably 1.2-2:1.
In the present invention, the selection to described initiator has no particular limits, and can be conventional use of in this area drawing
Sending out agent, under preferable case, described initiator is azodiisobutyronitrile and/or benzoyl peroxide.The present invention is to described initiator
Consumption have no particular limits, as long as the consumption of described initiator can make the compound shown in formula (2) and the change shown in formula (3)
Compound reacts completely, under preferable case, and the weight ratio of the consumption of the consumption of described initiator and the compound shown in formula (2)
For 0.005-0.5:1, preferably 0.01-0.2:1, more preferably 0.03-0.1:1.
In the present invention, described haptoreaction is carried out the most in a solvent.Preferably, described solvent is 1,2-dichloroethanes
And/or chlorobenzene.In the present invention, the consumption to described solvent has no particular limits, but, in order to be able to make the chemical combination shown in formula (2)
Thing is dissolved completely in solvent, under preferable case, and the weight ratio of the consumption of the consumption of described solvent and the compound shown in formula (2)
For 0.5-10:1, preferably 2-6:1, more preferably 3-5:1.
When described solvent is 1, during the mixture of 2-dichloroethanes and chlorobenzene, the present invention to 1,2-dichloroethanes and chlorobenzene
There is no particular limitation for consumption.Under preferable case, the weight ratio of the consumption of 1,2-dichloroethanes and the consumption of chlorobenzene is 0.2-5:
1。
In the present invention, the compound shown in formula (2) and the catalytic process of compound shown in formula (3) preferably include with
Lower step:
(1) by the compound dissolution shown in formula (2) in described solvent to obtain solution, then by the chemical combination shown in formula (3)
Thing adds in described solution, obtains mixture；
(2) mixture that step (1) obtains is reacted under the effect of reducing agent and initiator.
In step (1), the compound shown in formula (3) adds in form of an aqueous solutions, it is preferable that the change shown in formula (3)
The concentration of the aqueous solution of compound is 5-60 weight %, more preferably 20-50 weight %, more preferably 20-35 weight %.
In step (2), described reducing agent adds in form of an aqueous solutions, it is preferable that dripped by the aqueous solution of reducing agent
In described mixture；It is highly preferred that the concentration of the aqueous solution of described reducing agent is 5-50 weight %, more preferably 20-
40 weight %.
In the present invention, after dripping reducing agent, continue to be incubated at a temperature of the aqueous solution dripping described reducing agent
Stirring reaction.The temperature dripping the reaction described in the temperature of the aqueous solution of described reducing agent and step (2) is 30-130 DEG C, excellent
Elect 60-100 DEG C as, more preferably 70-90 DEG C；Time for adding is 1-20 hour, preferably 2-15 hour, further preferably
For 3-8 hour.After dripping the aqueous solution of described reducing agent, in order to make reaction complete, continue to be stirred at said temperatures
Reaction 0.5-3h, preferably 1-2h.
In the present invention, after described haptoreaction terminates, by stratification, aqueous phase is separated with organic facies, isolate
Organic facies with sodium sulfite aqueous solution drip washing once, reclaim organic solvent, i.e. obtain the compound shown in formula (1), according to need
Want, recrystallization purification processes can be carried out with ethanol.
To be described the present invention by embodiment below.
In following example, by the target product in liquid chromatography for measuring product；
Yield is calculated by following formula:
In following example, Potassium bromate., sodium bromate and lithium bromate are purchased from Beijing chemical reagents corporation；
Chlorobenzene, 1,2-dichloroethanes, azodiisobutyronitrile are purchased, benzoyl peroxide, sodium sulfite are purchased from Beijing
Learn Reagent Company；
2,6-dichlorotoleune, 2,6-dibromomethylbenzene, sodium methyl mercaptide are purchased from Beijing coupling Science and Technology Ltd.；
2-chloro-3-methyl-4-methyl sulphonyl essence of Niobe, 2-chloro-3-methyl-4-sulfonyloxy methyl yl benzoic acid second
Ester, 2-chloro-3-methyl-4-methyl sulphonyl isopropyl benzoate and 2-bromo-3-methyl-4-ethylsulfonyl essence of Niobe are equal
For self-control, preparation method is as follows:
The method of compound III, IV, V, VI reference literature WO2000021924A1 is prepared: with hexamethyl phosphoramide
For solvent, compound I is reacted with anhydrous compound II, obtain compound III；Compound III again with aluminum trichloride (anhydrous) and
Excess acetyl chloride, obtains compound IV, then with hydroperoxidation, obtain compound V；Compound V again with sodium hypochlorite reaction,
Obtain compound VI；
The preparation of compound VII: add two chloroethenes of 4 times of weight of compound VI50g and compound VI in reaction bulb
Alkane, is warming up to 60 DEG C, and the thionyl chloride of 1.5 times of moles of dropping compound VI, after dripping off, at 70 DEG C, insulation reaction 3 is little
Time, the thionyl chloride of negative pressure abjection excess and dichloroethanes, residue is compound VII；
The preparation of compound shown in formula (2): add 4 times of weight of compound VII in the material that last step obtains
The compound VIII of 2 times of moles of new dichloroethanes and compound VII, drips 1.5 times of compound VII at 20-30 DEG C
The triethylamine of mole.After dripping off triethylamine, at 40 DEG C, stirring reaction 3 hours, are subsequently adding 3 times of weight of compound VII
Water, with HCl adjust pH to 2, stand, branch vibration layer, organic layer wash once, after the organic layer negative pressure desolventizing obtained, to obtain final product
To compound shown in formula (2).
During preparation 2-chloro-3-methyl-4-methyl sulphonyl essence of Niobe, R1For methyl, R3For Cl, R4For methyl；
During preparation 2-chloro-3-methyl-4-methyl sulphonyl ethyl benzoate, R1For ethyl, R3For Cl, R4For methyl；
During preparation 2-chloro-3-methyl-4-methyl sulphonyl isopropyl benzoate, R1For isopropyl, R3For Cl, R4For methyl；
During preparation 2-bromo-3-methyl-4-ethylsulfonyl essence of Niobe, R1For methyl, R3For Br, R4For ethyl.
Embodiment 1
The present embodiment is for illustrating the preparation method of 3-bromomethyl-2-chloro-4-methyl sulphonyl essence of Niobe.
30g (0.112mol) 2-chloro-3-methyl-4-methyl sulphonyl essence of Niobe and 120g chlorobenzene are added 500mL
Four mouthfuls of reaction bulbs in；25.6g (0.168mol) sodium bromate is dissolved in 100g water, obtains sodium bromate aqueous solution, by obtain
Sodium bromate aqueous solution adds in four mouthfuls of reaction bulbs of 500mL；85 DEG C it are warming up to, by 0.93g (0.006mol) azo two under stirring
Isopropyl cyanide adds in four mouthfuls of reaction bulbs of 500mL；At 85 DEG C, drip 40% aqueous solution of sodium bisulfite 59g while stirring
(0.224mol), dropping in 3 hours is complete；After dripping off, it is maintained at 85 DEG C stirring reaction 1 hour, stratification the most while hot, divides
Go out aqueous phase；Adding a small amount of aqueous solution of sodium bisulfite in organic facies and wash once, after separating water layer, organic facies negative pressure reclaims molten
Agent, the solid obtained adds ethyl alcohol recrystallization, obtains 35.3g 3-bromomethyl-2-chloro-4-methyl sulphonyl essence of Niobe, purity
Being 97.8%, yield is 90.3%.
Embodiment 2
The present embodiment is for illustrating the preparation method of 3-bromomethyl-2-chloro-4-methyl sulphonyl ethyl benzoate.
31.57g (0.112mol) 2-chloro-3-methyl-4-methyl sulphonyl ethyl benzoate and 94.71g chlorobenzene are added
In four mouthfuls of reaction bulbs of 500mL；17.07g (0.112mol) sodium bromate is dissolved in 39.83g water, obtains sodium bromate aqueous solution,
The sodium bromate aqueous solution obtained is added in four mouthfuls of reaction bulbs of 500mL；90 DEG C it are warming up to, by 3.16g under stirring
(0.019mol) in azodiisobutyronitrile adds four mouthfuls of reaction bulbs of 500mL；At 90 DEG C, drip 20% sulfurous acid while stirring
Hydrogen sodium water solution 70g (0.134mol), dropping in 5 hours is complete；After dripping off, it is maintained at 90 DEG C stirring reaction 1.5 hours, then
Stratification while hot, separates aqueous phase；In organic facies, add a small amount of aqueous solution of sodium bisulfite wash once, after separating water layer, have
Machine phase negative pressure recycling design, the solid obtained adds ethyl alcohol recrystallization, obtains 3-bromomethyl-2-chloro-4-sulfonyloxy methyl yl benzoic acid
Ethyl ester, purity is 98.1%, and yield is 88.3%.
Embodiment 3
The present embodiment is for illustrating the preparation method of 3-bromomethyl-2-chloro-4-methyl sulphonyl isopropyl benzoate.
By 33.1g (0.112mol) 2-chloro-3-methyl-4-methyl sulphonyl isopropyl benzoate and 165.7g1,2-dichloro
Ethane adds in four mouthfuls of reaction bulbs of 500mL；24.32g (0.146mol) Potassium bromate. is dissolved in 45.16g water, obtains Potassium bromate.
Aqueous solution, adds the Potassium bromate. aqueous solution obtained in four mouthfuls of reaction bulbs of 500mL；70 DEG C it are warming up to, by 2.32g under stirring
(0.01mol) in benzoyl peroxide adds four mouthfuls of reaction bulbs of 500mL；At 70 DEG C, drip 30% sulfurous acid while stirring
Hydrogen sodium water solution 58.67g (0.168mol), dropping in 8 hours is complete；After dripping off, it is maintained at 70 DEG C stirring reaction 2 hours, so
After stratification while hot, separate aqueous phase；In organic facies, add a small amount of aqueous solution of sodium bisulfite wash once, after separating water layer,
Organic facies negative pressure recycling design, the solid obtained adds ethyl alcohol recrystallization, obtains 35.7g 3-bromomethyl-2-chloro-4-sulfonyloxy methyl
Yl benzoic acid isopropyl ester, purity is 98.2%, and yield is 89.0%.
Embodiment 4
The present embodiment is for illustrating the preparation method of 3-bromomethyl-2-bromo-4-ethylsulfonyl essence of Niobe.
According to the method for embodiment 1, except for the difference that, reaction substrate is 2-bromo-3-methyl-4-ethylsulfonyl benzoic acid first
Ester.The purity of product 3-bromomethyl-2-bromo-4-ethylsulfonyl essence of Niobe is 95.7%, and yield is 80.2%.
Embodiment 5
The present embodiment is for illustrating the preparation method of 3-bromomethyl-2-chloro-4-methyl sulphonyl essence of Niobe.
According to the method for embodiment 1, except for the difference that, bromating agent is lithium bromate.The purity of product is 97.2%, and yield is
86.3%.
Embodiment 6
The present embodiment is for illustrating the preparation method of 3-bromomethyl-2-chloro-4-methyl sulphonyl essence of Niobe.
According to the method for embodiment 1, except for the difference that, the consumption of sodium bromate is 0.224mol.The purity of product is 90.5%,
Yield is 84.3%.
Embodiment 7
The present embodiment is for illustrating the preparation method of 3-bromomethyl-2-chloro-4-methyl sulphonyl essence of Niobe.
According to the method for embodiment 1, except for the difference that, solvent is 1,2-dichloroethanes and the mixture of chlorobenzene, 1,2-dichloro
The weight ratio of the consumption of ethane and the consumption of chlorobenzene is 0.5:1.The purity of product is 94.6%, and yield is 84.9%.
Comparative example 1
This comparative example prepares 3-bromomethyl-2-chloro-4-sulfonyloxy methyl yl benzoic acid first using NBS as bromating agent for explanation
The yield of ester.
According to the method for embodiment 1, except for the difference that, bromating agent is NBS (N-bromo-succinimide).The purity of product is
93.8%, yield is 87.5%.
Comparative example 2
This comparative example prepares 3-bromomethyl-2-chloro-4-sulfonyloxy methyl yl benzoic acid using bromine as bromating agent for explanation
The yield of methyl ester.
30g (0.112mol) 2-chloro-3-methyl-4-methyl sulphonyl essence of Niobe and 120g chlorobenzene are added 500mL
Four mouthfuls of reaction bulbs in；27.4g (0.17mol) bromine is dissolved in 107g water, obtains the aqueous solution of bromine, the water of bromine that will obtain
Solution adds in four mouthfuls of reaction bulbs of 500mL；It is warming up to 85 DEG C under stirring, 0.93g (0.006mol) azodiisobutyronitrile is added
Enter in four mouthfuls of reaction bulbs of 500mL；At 85 DEG C, drip 40% aqueous solution of sodium bisulfite 59g (0.224mol) while stirring,
Dropping in 3 hours is complete；After dripping off, it is maintained at 85 DEG C stirring reaction 1 hour, stratification the most while hot, separates aqueous phase；Xiang You
The machine a small amount of aqueous solution of sodium bisulfite of middle addition mutually is washed once, after separating water layer, and organic facies negative pressure recycling design, the solid obtained
Add ethyl alcohol recrystallization, the product purity obtained is 81.4%, and yield is 51.8%.
By the comparison of embodiment 1 and comparative example 1 it can be seen that the present invention uses than the bromate of NBS low cost as bromine
Agent, the yield of 3-bromomethyl-2-halo-4-alkyl sulphonyl benzoate and employing NBS are as yield phase during bromating agent
When；By the comparison of embodiment 1 and comparative example 2 it can be seen that use the method for the invention to prepare 3-bromomethyl-2-halo-4-
The yield of alkyl sulphonyl benzoate is significantly higher.
By the result of above-described embodiment it can be seen that the present invention provide 3-bromomethyl-2-halo-4-alkyl sulphonyl benzene
The preparation method step of formic acid esters is simple, (yield can reach more than 80% to mild condition, low cost, product yield height, according to this
The preferred implementation of invention, yield can reach 88-90%), it is adaptable to large-scale industrial production.
The preferred embodiment of the present invention described in detail above, but, the present invention is not limited in above-mentioned embodiment
Detail, in the technology concept of the present invention, technical scheme can be carried out multiple simple variant, this
A little simple variant belong to protection scope of the present invention.
It is further to note that each the concrete technical characteristic described in above-mentioned detailed description of the invention, at not lance
In the case of shield, can be combined by any suitable means, the present invention is to various possible compound modes the most separately
Explanation.
Additionally, combination in any can also be carried out between the various different embodiment of the present invention, as long as it is without prejudice to this
The thought of invention, it should be considered as content disclosed in this invention equally.
Claims (10)
1. a preparation method for the 3-bromomethyl-2-halo-4-alkyl sulphonyl benzoate shown in formula (1), its feature exists
In, the method includes: in the presence of reducing agent and initiator, by the compound shown in formula (2) and the compound shown in formula (3)
Haptoreaction；
Wherein, R1For C1-C7Straight or branched alkyl；R2For Li, Na or K；R3For F, Cl or Br；R4For C1-C5Alkyl.
Method the most according to claim 1, wherein, R1For C1-C4Straight or branched alkyl；R2For Na or K；R3For Cl or
Br, preferably Cl；R4For C1-C3Alkyl, preferably methyl.
Method the most according to claim 1 and 2, wherein, described haptoreaction is carried out in a solvent, the consumption of described solvent
It is 0.5-10:1, preferably 2-6:1 with the weight ratio of the consumption of the compound shown in formula (2)；
Preferably, described solvent is 1,2-dichloroethanes and/or chlorobenzene.
Method the most according to claim 1 and 2, wherein, the consumption of the compound shown in formula (3) and the change shown in formula (2)
The mol ratio of the consumption of compound is 0.8-3:1, preferably 1-1.5:1.
Method the most according to claim 1, wherein, the consumption of described initiator and the consumption of the compound shown in formula (2)
Weight ratio be 0.005-0.5:1, preferably 0.01-0.2:1；
Preferably, described initiator is azodiisobutyronitrile and/or benzoyl peroxide.
Method the most according to claim 1, wherein, the consumption of described reducing agent and the consumption of the compound shown in formula (2)
Mol ratio be 0.8-4:1, preferably 1.2-2:1；
Preferably, at least one during described reducing agent is sodium sulfite, sodium sulfite, sodium peroxydisulfate and sodium thiosulfate.
Method the most according to claim 3, wherein, the compound shown in formula (2) contacts instead with the compound shown in formula (3)
The process answered comprises the following steps:
(1) by the compound dissolution shown in formula (2) in described solvent to obtain solution, then the compound shown in formula (3) is added
Enter in described solution, obtain mixture；
(2) mixture that step (1) obtains is reacted under the effect of reducing agent and initiator.
Method the most according to claim 7, wherein, in step (1), the compound shown in formula (3) is with the shape of aqueous solution
Formula adds；
Preferably, the concentration of the aqueous solution of the compound shown in formula (3) is 5-60 weight %, preferably 20-50 weight %.
Method the most according to claim 7, wherein, in step (2), described reducing agent adds in form of an aqueous solutions,
Preferably the aqueous solution of reducing agent is added drop-wise in described mixture；
It is highly preferred that the concentration of the aqueous solution of described reducing agent is 5-50 weight %, more preferably 20-40 weight %.
Method the most according to claim 9, wherein, drips temperature and step (2) institute of the aqueous solution of described reducing agent
The temperature of the reaction stated is 30-130 DEG C, preferably 60-100 DEG C；
Preferably, time for adding is 1-20 hour, preferably 3-8 hour.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610443995.8A CN106083668A (en) | 2016-06-20 | 2016-06-20 | A kind of preparation method of 3 bromomethyl 2 halo 4 alkyl sulphonyl benzoate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610443995.8A CN106083668A (en) | 2016-06-20 | 2016-06-20 | A kind of preparation method of 3 bromomethyl 2 halo 4 alkyl sulphonyl benzoate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106083668A true CN106083668A (en) | 2016-11-09 |
Family
ID=57237167
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610443995.8A Pending CN106083668A (en) | 2016-06-20 | 2016-06-20 | A kind of preparation method of 3 bromomethyl 2 halo 4 alkyl sulphonyl benzoate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106083668A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108409616A (en) * | 2017-02-09 | 2018-08-17 | 北京颖泰嘉和生物科技股份有限公司 | A kind of preparation method of the halogenated -4- alkyl sulphonyls benzoic ethers of 3- bromomethyls -2- |
| CN113024455A (en) * | 2019-12-25 | 2021-06-25 | 北京颖泰嘉和生物科技股份有限公司 | Preparation method of 5-methoxymethyl-2, 3-pyridine dimethyl dicarboxylate |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0894792A1 (en) * | 1996-03-26 | 1999-02-03 | Nippon Soda Co., Ltd. | Heterocycle-substituted benzene derivatives and herbicides |
| CN1553891A (en) * | 2001-09-11 | 2004-12-08 | �Ϻ���ͨ��ѧ | Method for producing 3-bromomethylbenzoic acids |
| CN105601548A (en) * | 2016-01-18 | 2016-05-25 | 黑龙江大学 | Benzoyl compound, composition containing benzoyl compound and application of benzoyl compound |
-
2016
- 2016-06-20 CN CN201610443995.8A patent/CN106083668A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0894792A1 (en) * | 1996-03-26 | 1999-02-03 | Nippon Soda Co., Ltd. | Heterocycle-substituted benzene derivatives and herbicides |
| CN1553891A (en) * | 2001-09-11 | 2004-12-08 | �Ϻ���ͨ��ѧ | Method for producing 3-bromomethylbenzoic acids |
| CN105601548A (en) * | 2016-01-18 | 2016-05-25 | 黑龙江大学 | Benzoyl compound, composition containing benzoyl compound and application of benzoyl compound |
Non-Patent Citations (1)
| Title |
|---|
| 兰世林等: "邻硝基苄基溴的合成研究", 《精细化工中间体》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108409616A (en) * | 2017-02-09 | 2018-08-17 | 北京颖泰嘉和生物科技股份有限公司 | A kind of preparation method of the halogenated -4- alkyl sulphonyls benzoic ethers of 3- bromomethyls -2- |
| CN108409616B (en) * | 2017-02-09 | 2021-10-01 | 北京颖泰嘉和生物科技股份有限公司 | Preparation method of 3-bromomethyl-2-halo-4-alkylsulfonylbenzoate |
| CN113024455A (en) * | 2019-12-25 | 2021-06-25 | 北京颖泰嘉和生物科技股份有限公司 | Preparation method of 5-methoxymethyl-2, 3-pyridine dimethyl dicarboxylate |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108409616A (en) | A kind of preparation method of the halogenated -4- alkyl sulphonyls benzoic ethers of 3- bromomethyls -2- | |
| CN103833723A (en) | Method for producing cyclic sulfonic acid ester and intermediate thereof | |
| US11932613B2 (en) | Process for preparing 1,1,3-trioxo-1,2-benzothiazole-6-carboxamide | |
| CN102942524B (en) | Preparation method of quinoline derivative | |
| CN106083668A (en) | A kind of preparation method of 3 bromomethyl 2 halo 4 alkyl sulphonyl benzoate | |
| CN117229187B (en) | Synthesis method of thioimine ester compound | |
| CN105985227A (en) | Preparation method and application of 4,4'-dihalide acetodiphenyl | |
| CN102690194B (en) | Preparation method of 3-cyclopropylmethoxy-4-difluoromethoxy-benzoic acid | |
| US10633352B2 (en) | Process for preparing 1,1,3-trioxo-1,2-benzothiazole-6-carboxamide | |
| CN105237445A (en) | Synthetic process of 4-[2-(5-chloro-2-methoxy benzamide)ethyl]benzsulfamide | |
| CN102516133A (en) | Preparation method of methanesulfonic acid derivative | |
| US20100185008A1 (en) | Method for Producing Fenofibrate | |
| CN102791678A (en) | Process for the preparation of 4-bromomethyl-[1,1'-biphenyl]-2'-carbonitrile | |
| CN100537530C (en) | Synthesis process of sulcoatrione | |
| CN104744337B (en) | The synthetic method of aryl sulfonic acid alkyl esters compound | |
| CN103467443B (en) | 2-alkyl-3-aminothiophene derivative and application thereof | |
| US10059654B2 (en) | Composition containing 3-chloro-4-methoxybenzylamine hydrochloride, and method for producing same | |
| NO136750B (en) | ||
| CN108727242A (en) | A kind of preparation method of the trans- -4- cyclohexyl-L-PROLINE of blood-pressure drug key intermediate | |
| CN104513182A (en) | Method for preparing (1R,2R)-1,2-cyclohexanedimethanol disulfonate | |
| JP2000143649A (en) | Production of 2-chloro-5-chloromethyl-1,3-thiazole | |
| CN103214406B (en) | Preparation method of besilate compound | |
| AU2019439692B2 (en) | Method for preparing 2-arylmalonic acid derivative, intermediate, and application thereof | |
| JP7364538B2 (en) | Method for preparing halogenated carboxylic acid anhydrides | |
| CN107382742A (en) | A kind of new synthetic method of fluorine 4 (trifluoromethyl) anilinechloride of 5 chlorine of fragrance intermediate containing trifluoromethyl 2 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20161109 |