CN110357774A - A method of 2,5- dimethyl phenyl acetic acid is prepared by raw material of 2,5- dimethyl halobenzene - Google Patents
A method of 2,5- dimethyl phenyl acetic acid is prepared by raw material of 2,5- dimethyl halobenzene Download PDFInfo
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- CN110357774A CN110357774A CN201910644793.3A CN201910644793A CN110357774A CN 110357774 A CN110357774 A CN 110357774A CN 201910644793 A CN201910644793 A CN 201910644793A CN 110357774 A CN110357774 A CN 110357774A
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/36—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
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- C—CHEMISTRY; METALLURGY
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Abstract
The present invention relates to organic synthesis field, more particularly to a kind of method for preparing 2,5- dimethyl phenyl acetic acid with 2,5- dimethyl halobenzene for raw material, includes the following steps: that 2,5- dimethyl halobenzene is reacted with magnesium and generate Grignard Reagent 2,5- 3,5-dimethylphenyl magnesium halide；2,5- 3,5-dimethylphenyl magnesium halide and reacting ethylene oxide generate 2,5- dimethyl benzene ethyl alcohol；2,5- dimethyl benzene ethyl alcohol uses NaClO and NaClO under TEMPO or 4-OH TEMPO catalyst2It is oxidized to 2,5- dimethyl phenyl acetic acid.The invention has the advantages that 2, the use of the cyanating reagent of expensive noble metal catalyst and severe toxicity is avoided in the synthesis process of 5- dimethyl phenyl acetic acid, agents useful for same is environmentally friendly, it reduces costs, simplify technique, yield is higher, overcomes the deficiencies in the prior art, is suitable for large-scale industrial production.
Description
Technical field
It is that raw material prepares 2,5- diformazan that the present invention relates to organic synthesis fields, more particularly to one kind with 2,5- dimethyl halobenzene
The method of base phenylacetic acid.
Background technique
2,5- dimethyl phenyl acetic acids are a kind of important fine-chemical intermediates, it is widely used in medicine and pesticide neck
Domain, particularly, it is the key intermediate of novel pesticide spiral shell worm ethyl ester, which is only so far with two-way interior suction biography
Lead the insecticide of performance.
About the synthetic technology of 2,5- dimethyl phenyl acetic acid, method is mainly the following with reference to domestic and foreign literature:
1, Kazuhiko et al. is in Bulletin of the Chemical Society of Japan 1975,48 (2),
With 2,5- dimethyl benzyl chloride for initial feed in 497-504, the reaction mechanism mechanism of reaction is as follows, through cyaniding, hydrolysis two-step reaction synthesis 2,5-
Dimethyl phenyl acetic acid.Three step total recovery of this method is 38%, and yield is lower, and cyanating reagent severe toxicity.
2, the synthetic method of 2,5- dimethyl phenyl acetic acid disclosed in Bayer patent CN1918103, the reaction mechanism mechanism of reaction is as follows, makes
Paraxylene is converted into the chloro- 1- of 2- (2,5- xylyl) ethyl ketone (I) with chloracetyl chloride, with the glycol of logical formula (II) by the ketone
It is prepared into the ketal of corresponding logical formula (III), the ketal of logical formula (III) is then made to reset to obtain the 2,5- of corresponding logical formula (IV)
The mixture of dimethyl phenyl acetic acid hydroxy alkyl ester and bis- (2,5- dimethyl phenyl acetic acid) diester of logical formula (V) finally makes described mixed
Hydrate hydrolysis obtains 2,5- dimethyl phenyl acetic acid.This method synthesis step is longer, and technique is cumbersome.
3, a kind of preparation side for preparing 2,5- dimethyl phenyl acetic acid is disclosed in Japanese Daicel patent JP2008291008
Method.The reaction mechanism mechanism of reaction is as follows, with 2,5- dimethyl acetophenone for initial feed, synthesizes 2,5- dimethyl through overcoupling, hydrolysis
Phenylacetic acid.This method generates a large amount of sulfur-bearing waste, it is also possible to volatile sulfide with very foul odour is generated, it is right
Environment is very unfriendly.
4, it is disclosed in Lianhe Chemical Technology Co., Ltd.'s patent CN102140062A and a kind of prepares 2,5- dimethyl benzene second
The preparation method of acid.The reaction mechanism mechanism of reaction is as follows, using paraxylene as initial feed, closes through chloromethylation, palladium chtalyst CO addition reaction
At 2,5- dimethyl phenyl acetic acid.This method needs to use the valuable catalysts such as tetraphenylphosphonium palladium, and higher cost is industrialized feasible
Property is little.
5, a kind of preparation method for preparing 2,5- dimethyl phenyl acetic acid is disclosed in Southeast University, Patent CN103804176A.
The reaction mechanism mechanism of reaction is as follows, using paraxylene as initial feed, synthesizes 2,5- diformazan through bromomethylation, precious metal catalyst CO addition reaction
Base phenylacetic acid.This method also needs to use bis-triphenylphosphipalladium palladium dichloride, [RhCl (COD)2]2Equal noble metal catalysts, limitation
Industrialized production.
In conclusion the preparation method of existing 2,5- dimethyl phenyl acetic acid is respectively present, material toxicity is big, synthesizes step
The problems such as rapid more, reaction type is more complex, catalyst is expensive, synthetic product yield is low.
Summary of the invention
The technical problem to be solved by the present invention is providing, a kind of reaction is mild, step is brief, former without using valuableness/toxicity
The synthetic method of the 2,5- dimethyl phenyl acetic acid of material.
The technical scheme to solve the above technical problems is that
One kind includes the following steps: in the method that 2,5- dimethyl halobenzene is that raw material prepares 2,5- dimethyl phenyl acetic acid
(1) 2,5- dimethyl halobenzene is reacted with magnesium generates Grignard Reagent 2,5- 3,5-dimethylphenyl magnesium halide；
(2) 2,5- 3,5-dimethylphenyl magnesium halide and reacting ethylene oxide generate 2,5- dimethyl benzene ethyl alcohol；
(3) 2,5- dimethyl benzene ethyl alcohol uses NaClO and NaClO under TEMPO or 4-OH TEMPO catalyst2It is oxidized to 2,
5- dimethyl phenyl acetic acid；
Specific reaction equation is as follows:
Wherein X is chlorine or bromine.
Preferably, the molar ratio of 2,5- dimethylbenzyl halogen and magnesium is 1:0.8~2.0 in the step (1)；Further,
The molar ratio of 2,5- dimethylbenzyl halogen and magnesium is 1:1.0~2.0 in the step (1)；Further, in the step (1)
The molar ratio of 2,5- dimethylbenzyl halogen and magnesium is 1:1.05~1.2.
Preferably, it is also added into initiator iodine, 1,2- Bromofume or isopropyl Grignard Reagent etc. in the step (1),
The molar ratio of the initiator and 2,5- dimethylbenzyl halogen is 1:0.0001~0.05；Further, the initiator and 2,5-
The molar ratio of dimethylbenzyl halogen is 1:0.0005~0.01.
Preferably, solvent used in the step (1) includes the ethers such as tetrahydrofuran, 2- methyltetrahydrofuran, ether
The mixed solvent of solvent or ether solvent and toluene.
Preferably, 2,5- dimethylbenzyl halogen is added portionwise in remaining reaction reagent in the step (1), first additional amount
It is the 10~20% of 2,5- dimethylbenzyl halogen total amount, surplus is added after reaction solution becomes canescence.
Preferably, in the step (2) molar ratio of 2,5- 3,5-dimethylphenyl magnesium halide and ethylene oxide be 1:0.9~
20.0；The molar ratio of 2,5- 3,5-dimethylphenyl magnesium halide and ethylene oxide is 1:1.0~10.0 in the step (2)；More into one
Step, the molar ratio of 2,5- 3,5-dimethylphenyl magnesium halide and ethylene oxide is 1:2.0~8.0 in the step (2).
Preferably, the step (2).
Preferably, solvent used in the step (3) include the proton solvents such as water, methanol, ethyl alcohol or acetonitrile, acetone,
The nonpolar solvents such as the dipole solvents such as DMF or ethyl acetate, methylene chloride.
Preferably, the molar ratio of 2,5- dimethyl benzene ethyl alcohol and TEMPO or 4-OH TEMPO are 1 in the step (3):
0.005~0.1；Further, in the step (3) 2,5- dimethyl benzene ethyl alcohol and TEMPO or 4-OH TEMPO molar ratio
For 1:0.01~0.08.
Preferably, 2,5- dimethyl benzene ethyl alcohol and NaClO, NaClO in the step (3)2Molar ratio be 1:0.9~
5.0:0.9~5.0；Further, 2,5- dimethyl benzene ethyl alcohol and NaClO, NaClO in the step (3)2Molar ratio be 1:
1.1~2.0:1.1~2.0；Further, 2,5- dimethyl benzene ethyl alcohol and NaClO, NaClO in the step (3)2Rub
You are than being 1:1.1~1.5:1.1~1.5.
Preferably, NaClO is first added in the step (3), adds NaClO2。
The invention has the advantages that avoided in the synthesis process of 2,5- dimethyl phenyl acetic acid expensive noble metal catalyst and
The use of the cyanating reagent of severe toxicity, agents useful for same is environmentally friendly, reduces costs, and simplifies technique, and yield is higher, overcomes
The deficiencies in the prior art are suitable for large-scale industrial production.
The Chinese name of compound, which has with structural formula, in the present invention conflicts, and is subject to structural formula.
Specific embodiment
Illustrate the present invention below in conjunction with example, but does not limit the present invention.In the art, technical staff is the present invention
Simple replacement or improvement belong in the technical solution protected of the present invention.
Embodiment 1:
In 250mL dry four-hole bottle, vacuumizes and nitrogen replaces system three times, then successively add under nitrogen protection
Enter 60mL anhydrous tetrahydro furan, the magnesium chips (molecular weight 24.3,142.27mmol, 1.1eq) and a granule iodine (15mg) of 3.46g,
60 DEG C are warming up to, tetrahydrofuran solution [20g 2, the 5- dimethyl chloride of about 1/10th 2,5- dimethyl benzyl chloride is slowly added dropwise
Benzyl (molecular weight 154.64,129.33mmol, 1eq) is dissolved in 30mL tetrahydrofuran], temperature has no obvious rising, in this temperature
Lower stir about 20 minutes is observed temperature at this time and is obviously risen, reaches reflux state, while the yellow in solution is taken off, become ash
White.The tetrahydrofuran solution of remaining 2,5- dimethyl benzyl chloride is slowly added dropwise, drips off within about 40 minutes.Heat preservation 1 hour is dripped off, is seen
The magnesium chips in reaction solution is examined to vanish from sight substantially.Reacting liquid temperature is down to 5 DEG C, 28.49g ethylene oxide is slowly added to and (divides
44.05,646.82mmol, 5.0eq of son amount), 5 DEG C or so are kept after adding continues stirring 3 hours.50mL saturated ammonium chloride is added
Solution extracts reaction of going out, and water phase 40mL methylene chloride extracts three times after vacuum distillation removes tetrahydrofuran, merges methylene chloride phase,
Negative pressure is evaporated methylene chloride, obtains 18.70g (molecular weight 150.22, theory obtains 19.43g) white solid, detects through HPLC pure
Degree is 98.1%, as 2,5- dimethyl benzene ethyl alcohol, mass yield 94.41%.
(1H-NMR(CDCl3)δ:1.75(s,1H),2.32(s,3H),2.33(s,3H),2.88(t,2H),3.83(t,
2H),6.98(d,1H),7.01(s,1H),7.08(d,1H))
In 250mL four-hole bottle, 80mL ethyl acetate, the 18.3g 2 that upper step is reacted, 5- dimethyl are added at room temperature
Benzyl carbinol (molecular weight 150.22,121.82mmol, 1.0eq), 381.22mg TEMPO (molecular weight 156.24,2.44mmol,
0.02eq).Be cooled to 5 DEG C, be slowly added dropwise 98.93g mass fraction 11% liquor natrii hypochloritis (molecular weight 74.44,
146.19mmol, 1.2eq), about half an hour is added dropwise, drips and finishes stirring 30min.Water phase pH is adjusted to 5 with 30% hydrochloric acid, then will
Reaction solution is warming up to 27~33 DEG C, be slowly added dropwise sodium chlorite aqueous solution (sodium chlorite purity be 80%, molecular weight 90.44,
146.19mmol, 1.2eq, 16.53g sodium chlorite are dissolved in 49.6g water, are made into 25% solution), about half an hour drips off, and drips off guarantor
Temperature stirring 3h.Stratification, lower layer's water phase use 40mL ethyl acetate to extract again, merge organic phase negative pressure and are concentrated to dryness, obtain
19.53g white solid (molecular weight 164.2, theory obtains 19.62g) is 97.5% through HPLC detection purity, as 2,5- bis-
Methylphenyl acetic acid.Yield 97.05%.
(1H-NMR(CDCl3)δ:2.28(s,3H),2.31(s,3H),3.63(s,2H),7.01(m,2H),7.08(d,
1H))
Embodiment 2:
In 250mL dry four-hole bottle, vacuumizes and nitrogen replaces system three times, then successively add under nitrogen protection
Enter 60mL anhydrous ether, the magnesium chips (molecular weight 24.3,135.80mmol, 1.05eq) and a granule iodine (15mg) of 3.30g, heating
To 30 DEG C, be slowly added dropwise about 1/5th 2,5- dimethyl bromobenzyl diethyl ether solution [total amount be 25.75g 2,5- dimethyl
Bromobenzyl (molecular weight 199.09,129.33mmol, 1eq) is dissolved in 30mL ether], temperature has no obvious rising, at this temperature
Stir about 30 minutes, temperature was observed at this time and is obviously risen, reaches reflux state, while the yellow in solution is taken off, becomes greyish white
Color.The diethyl ether solution of remaining 2,5- dimethyl bromobenzyl is slowly added dropwise, drips off within about 40 minutes.Drip off heat preservation 1 hour, observing response
Magnesium chips in liquid is vanished from sight substantially.Reacting liquid temperature is down to 10 DEG C, is slowly added to 11.39g ethylene oxide (molecular weight
44.05,258.66mmol, 2.0eq), 10 DEG C or so are kept after adding continues stirring 3 hours.It is molten that 30mL saturated ammonium chloride is added
Liquid extracts reaction of going out, and three times with the extraction of 60mL ethyl acetate, combined ethyl acetate phase, negative pressure is evaporated ethyl acetate, obtains 18.72g
(molecular weight 150.22, theory obtains 19.43g) white solid is 97.7% through HPLC detection purity, as 2,5- dimethyl benzene
Ethyl alcohol, mass yield 94.13%.
(1H-NMR(CDCl3)δ:1.75(s,1H),2.32(s,3H),2.33(s,3H),2.88(t,2H),3.83(t,
2H),6.98(d,1H),7.01(s,1H),7.08(d,1H))
In 250mL four-hole bottle, 80mL ethyl acetate, the 18.3g 2 that upper step is reacted, 5- dimethyl are added at room temperature
Benzyl carbinol (molecular weight 150.22,121.82mmol, 1.0eq), 190.61mg TEMPO (molecular weight 156.24,1.22mmol,
0.01eq).Be cooled to 5 DEG C, be slowly added dropwise 90.68g mass fraction 11% liquor natrii hypochloritis (molecular weight 74.44,
134.00mmol, 1.1eq), about half an hour is added dropwise, drips and finishes stirring 30min.Water phase pH is adjusted to 5 with 30% hydrochloric acid, then will
Reaction solution is warming up to 27~33 DEG C, be slowly added dropwise sodium chlorite aqueous solution (sodium chlorite purity be 80%, molecular weight 90.44,
146.19mmol, 1.2eq, 16.53g sodium chlorite are dissolved in 49.6g water, are made into 25% solution), about half an hour drips off, and drips off guarantor
Temperature stirring 3h.Stratification, lower layer's water phase use 40mL ethyl acetate to extract again, merge organic phase negative pressure and are concentrated to dryness, obtain
19.70g white solid (molecular weight 164.2, theory obtains 19.54g) is 96.2% through HPLC detection purity, as 2,5- bis-
Methylphenyl acetic acid.Yield 96.99%.
(1H-NMR(CDCl3)δ:2.28(s,3H),2.31(s,3H),3.63(s,2H),7.01(m,2H),7.08(d,
1H))
Embodiment 3:
In 250mL dry four-hole bottle, vacuumizes and nitrogen replaces system three times, then successively add under nitrogen protection
Enter 60mL anhydrous ether, the magnesium chips (molecular weight 24.3,155.20mmol, 1.2eq) and a granule iodine (15mg) of 3.77g, heating
To 60 DEG C, be slowly added dropwise about 1/5th 2,5- dimethyl bromobenzyl diethyl ether solution [total amount be 25.75g 2,5- dimethyl
Bromobenzyl (molecular weight 199.09,129.33mmol, 1eq) is dissolved in 30mL ether], temperature has no obvious rising, at this temperature
Stir about 30 minutes, temperature was observed at this time and is obviously risen, reaches reflux state, while the yellow in solution is taken off, becomes greyish white
Color.The diethyl ether solution of remaining 2,5- dimethyl bromobenzyl is slowly added dropwise, drips off within about 40 minutes.Drip off heat preservation 1 hour, observing response
Magnesium chips in liquid is vanished from sight substantially.Reacting liquid temperature is down to 0 DEG C, is slowly added to 46.04g ethylene oxide (molecular weight
44.05,1034.6mmol, 8.0eq), 0 DEG C or so is kept after adding continues stirring 3 hours.70mL saturated ammonium chloride solution is added
Extract reaction of going out, the extraction of water phase 40mL methylene chloride three times, merges methylene chloride phase, negative pressure is evaporated after tetrahydrofuran is evaporated off in negative pressure
Methylene chloride obtains 18.87g (molecular weight 150.22, theory obtains 19.43g) white solid, is through HPLC detection purity
97.5%, as 2,5- dimethyl benzene ethyl alcohol, mass yield 94.69%.
(1H-NMR(CDCl3)δ:1.75(s,1H),2.32(s,3H),2.33(s,3H),2.88(t,2H),3.83(t,
2H),6.98(d,1H),7.01(s,1H),7.08(d,1H))
In 500mL four-hole bottle, 80mL ethyl acetate, the 18.3g 2 that upper step is reacted, 5- dimethyl are added at room temperature
Benzyl carbinol (molecular weight 150.22,121.82mmol, 1.0eq), 1.68g 4-OH TEMPO (molecular weight 172.24,2.44mmol,
0.08eq).Be cooled to 0 DEG C, be slowly added dropwise 123.66g mass fraction 11% liquor natrii hypochloritis (molecular weight 74.44,
182.73mmol, 1.5eq), about 40min is added dropwise, drips and finishes stirring 30min.Water phase pH is adjusted to 5 with 30% hydrochloric acid, then will
Reaction solution is warming up to 27~33 DEG C, be slowly added dropwise sodium chlorite aqueous solution (sodium chlorite purity be 80%, molecular weight 90.44,
182.73mmol, 1.5eq, 20.66g sodium chlorite are dissolved in 61.99g water, are made into 25% solution), about 40min is dripped off, and drips off guarantor
Temperature stirring 3h.Stratification, lower layer's water phase use 40mL ethyl acetate to extract again, merge organic phase negative pressure and are concentrated to dryness, obtain
19.53g white solid (molecular weight 164.2, theory obtains 19.50g), as 2,5- dimethyl phenyl acetic acid detect pure through HPLC
Degree is 97.0%, yield 97.15%.
(1H-NMR(CDCl3)δ:2.28(s,3H),2.31(s,3H),3.63(s,2H),7.01(m,2H),7.08(d,
1H))。
What has been described above is only a preferred embodiment of the present invention, it is noted that for those of ordinary skill in the art
For, without departing from the concept of the premise of the invention, various modifications and improvements can be made, these belong to the present invention
Protection scope.
Claims (10)
1. a kind of method for preparing 2,5- dimethyl phenyl acetic acid with 2,5- dimethyl halobenzene for raw material, it is characterised in that including as follows
Step:
(1) 2,5- dimethylbenzyl halogen is reacted with magnesium generates Grignard Reagent 2,5- dimethyl benzyl magnesium halide；
(2) 2,5- dimethyl benzyl magnesium halide and polyformaldehyde reaction generate 2,5- dimethyl benzene ethyl alcohol；
(3) 2,5- dimethyl benzene ethyl alcohol uses NaClO and NaClO under TEMPO or 4-OH TEMPO catalyst2It is oxidized to 2,5- bis-
Methylphenyl acetic acid；
The reaction equation of above-mentioned reaction is as follows:
Wherein X is chlorine or bromine.
2. it is as described in claim 1 the method for raw material preparation 2,5- dimethyl phenyl acetic acid with 2,5- dimethyl halobenzene, it is special
Sign is that the molar ratio of 2,5- dimethylbenzyl halogen and magnesium is 1:0.8~2.0 in the step (1).
3. it is as claimed in claim 2 the method for raw material preparation 2,5- dimethyl phenyl acetic acid with 2,5- dimethyl halobenzene, it is special
Sign is that the molar ratio of 2,5- dimethylbenzyl halogen and magnesium is 1:1.0~2.0 in the step (1).
4. it is as described in claim 1 the method for raw material preparation 2,5- dimethyl phenyl acetic acid with 2,5- dimethyl halobenzene, it is special
Sign is, is also added into initiator iodine, 1,2- Bromofume or isopropyl Grignard Reagent, the initiator in the step (1)
Molar ratio with 2,5- dimethylbenzyl halogen is 1:0.0001~0.05.
5. it is as described in claim 1 the method for raw material preparation 2,5- dimethyl phenyl acetic acid with 2,5- dimethyl halobenzene, it is special
Sign is that solvent used in the step (1) includes ether solvents or the ethers such as tetrahydrofuran, 2- methyltetrahydrofuran, ether
The mixed solvent of class solvent and toluene.
6. it is as described in claim 1 the method for raw material preparation 2,5- dimethyl phenyl acetic acid with 2,5- dimethyl halobenzene, it is special
Sign is that 2,5- dimethylbenzyl halogen is added portionwise in remaining reaction reagent in the step (1), first additional amount is 2,5- bis-
The 10~20% of methyl benzyl halogen total amount, surplus is added after reaction solution becomes canescence.
7. it is as described in claim 1 the method for raw material preparation 2,5- dimethyl phenyl acetic acid with 2,5- dimethyl halobenzene, it is special
Sign is that the molar ratio of 2,5- 3,5-dimethylphenyl magnesium halide and ethylene oxide is 1:0.9~20.0 in the step (2).
8. it is as described in claim 1 the method for raw material preparation 2,5- dimethyl phenyl acetic acid with 2,5- dimethyl halobenzene, it is special
Sign is that solvent used in the step (3) includes the dipoles such as the proton solvents such as water, methanol, ethyl alcohol or acetonitrile, acetone, DMF
The nonpolar solvents such as solvent or ethyl acetate, methylene chloride.
9. it is as claimed in claim 8 the method for raw material preparation 2,5- dimethyl phenyl acetic acid with 2,5- dimethyl halobenzene, it is special
Sign is, in the step (3) molar ratio of 2,5- dimethyl benzene ethyl alcohol and TEMPO or 4-OH TEMPO be 1:0.005~
0.1。
10. it is as claimed in claim 9 the method for raw material preparation 2,5- dimethyl phenyl acetic acid with 2,5- dimethyl halobenzene, it is special
Sign is, 2,5- dimethyl benzene ethyl alcohol and NaClO, NaClO in the step (3)2Molar ratio be 1:0.9~5.0:0.9~
5.0。
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113121341A (en) * | 2019-12-31 | 2021-07-16 | 江苏中旗科技股份有限公司 | Method for synthesizing 2, 6-diethyl-4-methyl phenylacetate |
| CN114790139A (en) * | 2021-01-26 | 2022-07-26 | 江苏中旗科技股份有限公司 | Method for synthesizing 2-chloro-4-fluorobenzoic acid by taking 2-chloro-4-amino bromobenzene as raw material |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109651068A (en) * | 2018-12-12 | 2019-04-19 | 江苏中旗科技股份有限公司 | The synthetic method of pinoxaden intermediate (2,6- diethyl -4- methyl) phenylacetic acid |
-
2019
- 2019-07-17 CN CN201910644793.3A patent/CN110357774A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109651068A (en) * | 2018-12-12 | 2019-04-19 | 江苏中旗科技股份有限公司 | The synthetic method of pinoxaden intermediate (2,6- diethyl -4- methyl) phenylacetic acid |
Non-Patent Citations (2)
| Title |
|---|
| MANGZHU ZHAO等: ""Oxidation of Primary Alcohols to Carboxylic Acids with Sodium Chlorite Catalyzed by TEMPO and Bleach"", 《J. ORG. CHEM.》 * |
| SONG LIN等: ""Intra/Intermolecular Direct Allylic Alkylation via Pd(II)-Catalyzed Allylic C-H Activation"", 《J. AM. CHEM. SOC.》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113121341A (en) * | 2019-12-31 | 2021-07-16 | 江苏中旗科技股份有限公司 | Method for synthesizing 2, 6-diethyl-4-methyl phenylacetate |
| CN114790139A (en) * | 2021-01-26 | 2022-07-26 | 江苏中旗科技股份有限公司 | Method for synthesizing 2-chloro-4-fluorobenzoic acid by taking 2-chloro-4-amino bromobenzene as raw material |
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