CN109867601A - The preparation method of one kind (R) -2- (4- hydroxyphenoxy) butyl propionate - Google Patents
The preparation method of one kind (R) -2- (4- hydroxyphenoxy) butyl propionate Download PDFInfo
- Publication number
- CN109867601A CN109867601A CN201910115652.2A CN201910115652A CN109867601A CN 109867601 A CN109867601 A CN 109867601A CN 201910115652 A CN201910115652 A CN 201910115652A CN 109867601 A CN109867601 A CN 109867601A
- Authority
- CN
- China
- Prior art keywords
- hydroquinone
- hydroxyphenoxy
- butyl propionate
- reaction
- content
- 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.)
- Granted
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses it is a kind of (R) -2- (4- hydroxyphenoxy) butyl propionate preparation method, using immiscible binary organic solvent system, with (S) -2- chloropropionic acid butyl ester, excessive hydroquinone be raw material under acid binding agent and catalyst action, synthesis under normal pressure prepare (R) -2- (4- hydroxyphenoxy) butyl propionate.Present invention employs the modes of reaction, extraction, reduce side reaction, and product content is high and catechol content is low, and yield is greater than 95.0%(in terms of hydroquinone), while avoiding generating a large amount of phenol wastewater, reduce environmental protection pressure, is suitable for industrialized production.
Description
Technical field
The present invention relates to it is a kind of (R) -2- (4- hydroxyphenoxy) butyl propionate preparation method, have in particular by binary
Solvent prepare (R) -2- (4- hydroxyphenoxy) butyl propionate method.
Background technique
(R) -2- (4- hydroxyphenoxy) butyl propionate (compound 1) be synthesizing efficient chirality herbicide cyhalofop-butyl pass
Key intermediate, structural formula are as follows:
(R) -2- (4- hydroxyphenoxy) butyl propionate synthetic route is mainly hydroquinone method, i.e., with hydroquinone,
(S) -2- chloropropionic acid butyl ester be raw material be etherified under the action of acid binding agent using water, DMF or glycol monoethyl ether as solvent
Reaction obtains, Main By product be (R) -2- (4- hydroxyphenoxy) butyl propionate with (S) -2- chloropropionic acid butyl ester continue occur ether
Change reaction obtain bis ether by-product 2,2 '-(1,4- phenyl (dioxygen)) (2R, 2’RThe double butyl esters (2) of)-dipropionic acid.This method
Simply, but there are following common problems: ensure that product selectivity must sacrifice conversion per pass, since hydroquinone is oxidizable and
Difficulty is separated with product and byproduct, product quality is poor；Improving conversion per pass by-product can increase, and cost improves, economical
Property is poor；Using water for a large amount of effluent brines containing phenol can be generated when solvent, immense pressure is generated to environmental protection treatment.Its reaction equation is as follows:
Zhang Jixu etc. (" pesticide " the 5th phase in 2010) uses hydroquinone and potassium hydroxide for raw material, first in DMSO and first
Reflux water-dividing obtains sylvite in benzene, after redistillation removes toluene, then is added dropwise to 3, and the DMSO solution of 4- difluorobenzonilyile is etherified,
Obtain the similar etherified product of content 94%.This method can not inhibit bis ether by-product, bis ether separated with product it is more difficult,
Product purity is lower, influences downstream product quality.
Hong Xiaodong etc. (CN104803883) generates condensation product using butyl lactate and paratoluensulfonyl chloride reaction, then uses
DMF is solvent, reacts with hydroquinone, washes under alkaline condition after reaction, and organic layer vacuum distillation removes solvent, is not had
There is the report of yield and product quality.This method can not inhibit bis ether by-product, and bis ether separates more difficult with product.
Although in addition bis ether by-product 2, reaction solution can be reduced using the large excess of conventional method of hydroquinone
In remaining hydroquinone it is very more, due to hydroquinone and (R) -2- (4- hydroxyphenoxy) butyl propionate contains phenol hydroxyl
Base need to be controlled hydroquinone content in product by complicated post-processing and be lower than 0.1%, generated a large amount of phenol wastewater, cause huge
Big environmental protection pressure.
Summary of the invention
Thinking of the present invention: it is readily soluble in intensive polar solvent according to hydroquinone, in the property of nonpolar solvent indissoluble,
(R) -2- (4- hydroxyphenoxy) butyl propionate is soluble in nonpolar solvent, and etherification reaction need to carry out in intensive polar solvent
The characteristics of, the monoether stage, which is rested on, from control etherification reaction starts with, the polar solvent and nonpolarity for selecting being mutually dissolved property poor
Solvent is reaction dissolvent, is used as catalyst using the large excess of feeding mode of hydroquinone and 18- crown ether -6, is extracted by reaction
It takes, is extracted to nonpolar solvent phase after generating product at once, realize that concentration of the product in polar solvent remains one
A very low level and hydroquinone concentration are maintained at a higher level, and raising etherification reaction is selective in this way and reduces double
It is etherified the generation of by-product, realizes selected mono-etherification purpose, the reaction mechanism mechanism of reaction is shown in Figure of description.
Detailed description of the invention: Fig. 1 is the reaction mechanism mechanism of reaction 1, and Fig. 2 is the reaction mechanism mechanism of reaction 2, and Fig. 3 is the reaction mechanism mechanism of reaction 3, and Fig. 4 is the reaction mechanism mechanism of reaction 4.
By early-stage study it has been found that hydroquinone and (R) -2- (4- hydroxyphenoxy) butyl propionate mixture not
With Distribution dynamics in dual solvent system, above invention thinking may be implemented.By 50% hydroquinone and 50% (R) -2- (4- hydroxyl
Phenoxyl) polar solvent and nonpolar solvent is added is 1:1 in the mixed solvent for the mixture of butyl propionate, standing is stirred at room temperature
Layering, it is separately sampled, using the composition in gas spectrum analysis two-phase.
Technical solution of the present invention: immiscible binary organic solvent system as reaction dissolvent, with (S) -2- chloropropionic acid
Butyl ester, excessive hydroquinone be raw material under acid binding agent and catalyst action, synthesis under normal pressure prepare (R) -2- (4- hydroxy benzenes oxygen
Base) butyl propionate method.Immiscible dual solvent system is made of polar solvent and nonpolar solvent.Reaction knot
Polar solvent after the beam mutually direct reuse after filtering desalination；The nonpolar solvent mutually direct circulation after simple distillation is recycled
Use, mother liquor obtain through rectification under vacuum (R) -2- (4- hydroxyphenoxy) butyl propionate.This technology uses the side of reaction, extraction
Case, therefore selectivity is high, yield is greater than 95.0%(in terms of hydroquinone).
The present invention reacts molar excess 50~100% using hydroquinone in the first batch, applies the equimolar feeding method of batch,
The polar solvent is one kind of ethylene glycol or glycerine, and dosage is 5~10 times of hydroquinone quality；Nonpolar solvent is
One of petroleum ether, toluene, dimethylbenzene or isopropylbenzene, dosage are 5~10 times of hydroquinone quality.
Acid binding agent of the present invention is one of potassium hydroxide, sodium hydroxide, and dosage is hydroquinone mole
0.50~0.75 times.
Reaction temperature is 90~120 DEG C, and the reaction time is 3~8h.
Catalyst is crown ether -6 18-, and dosage is the 0.1~0.3% of hydroquinone quality.
Compared with other synthetic methods, the invention has the following advantages that 1) simple process, reaction condition are mild, it is used
Solvent adapts to industrial requirement；2) after gas producing formation rectifying, the content of hydroquinone is lower than 0.1%, and liquid spectrum analysis product content is greater than
99%, it reduces rectifying difficulty and shortens the production cycle；3) selectivity improves, high income；4) a large amount of phenol wastewater are not generated,
Energy consumption and quantity of three wastes is greatly reduced, energy-saving and emission-reduction and environmental benefit are significant.
Specific embodiment
Below in conjunction with specific preferred embodiment, the invention will be further described, but not thereby limiting the invention
Protection scope.
1 33g(0.3 mol of embodiment) hydroquinone, 13.1g(0.21mol) 95% potassium hydroxide, 200mL ethylene glycol,
300mL petroleum ether, 0.005 g catalyst 18- crown ether -6 are added in 1000 mL three-necked flasks, and stirring is warming up to 80 DEG C, will
33.2g(0.2 mol) (S) -2- chloropropionic acid butyl ester is added in 4 h, the reaction was continued after adding 4h, Bi Jiangwen is reacted, negative pressure is taken out
Filter, filter cake are potassium chloride, split-phase after filtrate stands, and upper phase is nonpolar solvent phase, (R) -2- (4- hydroxyphenoxy) propionic acid fourth
Ester content is 97.3%(liquid area under spectrum normalizing), hydroquinone content is 1.7 %(liquid area under spectrum normalizings).Split-phase, upper layer reaction solution
After recovered solvent, high vacuum rectification obtain 98.5% (R) -2- (4- hydroxyphenoxy) butyl propionate (liquid spectrum external standard method), to benzene
Two phenol content 0.42%；Lower phase is polar solvent phase, and hydroquinone content is 85.7 %(liquid area under spectrum normalizings), (R) -2- (4- hydroxyl
Phenoxyl) butyl propionate content be 14.4 %(liquid area under spectrum normalizings), can be used directly as Recycling Mother Solution.It is secondary in reaction solution
2 content of compound is produced less than 0.5%.
Recycling Mother Solution derived above is used: 33 g(0.3 mol) hydroquinone, 12.4g(0.2mol) 95% hydrogen-oxygen
Changing potassium, 0.005 g catalyst 18- crown ether -6, circulating mother liquor, all about tri- mouthfuls of 1000 mL burnings are added in 200mL, 300mL petroleum ether
Bottle in, stirring be warming up to 80 DEG C, by 33.2g(0.2 mol) (S) -2- chloropropionic acid butyl ester is added in 4 h, continue after adding anti-
4h is answered, Bi Jiangwen, negative pressure leaching are reacted, filter cake is potassium chloride, and split-phase after filtrate stands, upper phase is nonpolar solvent phase, monoether
Content is 98.1%(liquid area under spectrum normalizing), hydroquinone content is 1.2 %(liquid area under spectrum normalizings).Split-phase, upper layer reaction solution warp
After recycling design, high vacuum rectification obtain 45.3g 99.0% (R) -2- (4- hydroxyphenoxy) butyl propionate (liquid spectrum external standard method),
Hydroquinone content 0.10%, reaction yield are 94.2% (in terms of hydroquinone)；Lower phase is polar solvent phase, and hydroquinone contains
Amount is 92.5 %(liquid area under spectrum normalizings), (R) -2- (4- hydroxyphenoxy) butyl propionate content be 7.0 %(liquid area under spectrum return
One) use, can be continued cycling through directly as mother liquor.
2 44g(0.4 mol of embodiment) hydroquinone, 9.2g(0.22mol) 95% sodium hydroxide, 300mL ethylene glycol,
200mL toluene, 0.013 g catalyst 18- crown ether -6 are added in 1000 mL three-necked flasks, and stirring is warming up to 100 DEG C, by 33.2g
(0.2 mol) (S) -2- chloropropionic acid butyl ester is added in 3 h, the reaction was continued after adding 3h, react Bi Jiangwen, negative pressure leaching, filter
Cake is sodium chloride, split-phase after filtrate stands, and upper phase is nonpolar solvent phase, (R) -2- (4- hydroxyphenoxy) butyl propionate content
For 98.7%(liquid area under spectrum normalizing), hydroquinone content is 0.4 %(liquid area under spectrum normalizing).Split-phase, upper layer reaction solution are recovered
After solvent, high vacuum rectification obtain 99.4% (R) -2- (4- hydroxyphenoxy) butyl propionate (liquid spectrum external standard method), hydroquinone contains
Amount 0.07%；Lower phase is polar solvent phase, and hydroquinone content is 91.0 %(liquid chromatography area normalizings), (R) -2- (4- hydroxyl
Phenoxy group) butyl propionate content be 7.3 %(liquid area under spectrum normalizings), can be used directly as Recycling Mother Solution.By-product in reaction solution
2 content of compound is less than 0.3%.
Recycling Mother Solution derived above is used: 22 g(0.2 mol) hydroquinone, 8.4g(0.2mol) 95% hydroxide
All about 300mL, 200mL toluene are added in 1000 mL three-necked flasks for sodium, 0.01 g catalyst 18- crown ether -6, circulating mother liquor,
Stirring be warming up to 100 DEG C, by 33.2g(0.2 mol) (S) -2- chloropropionic acid butyl ester is added in 3 h, the reaction was continued after adding 3h,
Bi Jiangwen is reacted, negative pressure leaching, filter cake is sodium chloride, split-phase after filtrate stands, and upper phase is nonpolar solvent phase, (R)-2-(4-
Hydroxyphenoxy) butyl propionate content be 98.4%(liquid area under spectrum normalizing), hydroquinone content be 0.5 %(liquid area under spectrum return
One).Split-phase, after the recovered solvent of upper layer reaction solution, high vacuum rectification obtain 44.9g 99.3% (R) -2- (4- hydroxyphenoxy)
Butyl propionate (liquid spectrum external standard method), hydroquinone content 0.03%, reaction yield are 93.6% (in terms of hydroquinone)；Lower phase is
Polar solvent phase, hydroquinone content are 91.7 %(liquid chromatography area normalizings), (R) -2- (4- hydroxyphenoxy) propionic acid fourth
Ester content is 7.9 %(liquid area under spectrum normalizings), use can be continued cycling through directly as mother liquor.
3 44g(0.4 mol of embodiment) hydroquinone, 12.5g(0.3mol) 95% sodium hydroxide, 400mL ethylene glycol,
300mL dimethylbenzene, 0.01 g catalyst 18- crown ether -6 are added in 1000 mL three-necked flasks, and stirring is warming up to 110 DEG C, will
33.2g(0.2 mol) (S) -2- chloropropionic acid butyl ester is added in 2 h, the reaction was continued after adding 2h, Bi Jiangwen is reacted, negative pressure is taken out
Filter, filter cake are sodium chloride, split-phase after filtrate stands, and upper phase is nonpolar solvent phase, (R) -2- (4- hydroxyphenoxy) propionic acid fourth
Ester content is 99.0%(liquid area under spectrum normalizing), hydroquinone content is 0.3 %(liquid area under spectrum normalizing).Split-phase, upper layer reaction solution
After recovered solvent, high vacuum rectification obtain 99.5% (R) -2- (4- hydroxyphenoxy) butyl propionate (liquid spectrum external standard method), to benzene
Two phenol content 0.08%；Lower phase is polar solvent phase, and hydroquinone content is 91.7 %(liquid chromatography area normalizings), (R)-2-
(4- hydroxyphenoxy) butyl propionate content is 6.5 %(liquid area under spectrum normalizings), it can be used directly as Recycling Mother Solution.Reaction solution
Middle 2 content of by-product compound is less than 0. 3%.
Recycling Mother Solution derived above is used: 22 g(0.2 mol) hydroquinone, 8.4g(0.2mol) 95% hydroxide
All about 1000 mL three-necked flasks are added in 400mL, 300mL dimethylbenzene for sodium, 0.01 g catalyst 18- crown ether -6, circulating mother liquor
In, stirring be warming up to 110 DEG C, by 33.2g(0.2 mol) (S) -2- chloropropionic acid butyl ester is added in 2 h, the reaction was continued after adding
2h reacts Bi Jiangwen, and negative pressure leaching, filter cake is sodium chloride, split-phase after filtrate stands, and upper phase is nonpolar solvent phase, (R)-2-
(4- hydroxyphenoxy) butyl propionate content is 99.1%(liquid area under spectrum normalizing), hydroquinone content is that 0.5%(liquid area under spectrum is returned
One).Split-phase, after the recovered solvent of upper layer reaction solution, high vacuum rectification obtain 45.7g 99.2% (R) -2- (4- hydroxyphenoxy)
Butyl propionate (liquid spectrum external standard method), hydroquinone content 0.03%, reaction yield are 95.2% (in terms of hydroquinone)；Lower phase is
Polar solvent phase, hydroquinone content are 92.8 %(liquid chromatography area normalizings), (R) -2- (4- hydroxyphenoxy) propionic acid fourth
Ester content is 7.3 %(liquid area under spectrum normalizings), use can be continued cycling through directly as mother liquor.
4 44g(0.4 mol of embodiment) hydroquinone, 12.5g(0.3mol) 95% sodium hydroxide, 400mL ethylene glycol,
400mL isopropylbenzene, 0.01 g catalyst 18- crown ether -6 are added in 1000 mL three-necked flasks, and stirring is warming up to 120 DEG C, will
33.2g(0.2 mol) (S) -2- chloropropionic acid butyl ester is added in 2 h, the reaction was continued after adding 1h, Bi Jiangwen is reacted, negative pressure is taken out
Filter, filter cake are sodium chloride, split-phase after filtrate stands, and upper phase is nonpolar solvent phase, (R) -2- (4- hydroxyphenoxy) propionic acid fourth
Ester content is 99.1%(liquid area under spectrum normalizing), hydroquinone content is 0.2 %(liquid area under spectrum normalizing).Split-phase, upper layer reaction solution
After recovered solvent, high vacuum rectification obtain 99.6% (R) -2- (4- hydroxyphenoxy) butyl propionate (liquid spectrum external standard method), to benzene
Two phenol content 0.05%；Lower phase is polar solvent phase, and hydroquinone content is 92.0 %(liquid chromatography area normalizings), (R)-2-
(4- hydroxyphenoxy) butyl propionate content is 5.8 %(liquid area under spectrum normalizings), it can be used directly as Recycling Mother Solution.Reaction solution
Middle 2 content of by-product compound is less than 0. 5%.
Recycling Mother Solution derived above is used: 22 g(0.2 mol) hydroquinone, 8.4g(0.2mol) 95% hydroxide
All about 1000 mL three-necked flasks are added in 400mL, 400mL isopropylbenzene for sodium, 0.01 g catalyst 18- crown ether -6, circulating mother liquor
In, stirring be warming up to 120 DEG C, by 33.2g(0.2 mol) (S) -2- chloropropionic acid butyl ester is added in 2 h, the reaction was continued after adding
1h reacts Bi Jiangwen, and negative pressure leaching, filter cake is sodium chloride, split-phase after filtrate stands, and upper phase is nonpolar solvent phase, (R)-2-
(4- hydroxyphenoxy) butyl propionate content is 99.4%(liquid area under spectrum normalizing), hydroquinone content is that 0.2%(liquid area under spectrum is returned
One).Split-phase, after the recovered solvent of upper layer reaction solution, high vacuum rectification obtain 45.9g 99.6% (R) -2- (4- hydroxyphenoxy)
Butyl propionate (liquid spectrum external standard method), hydroquinone content 0.03%, reaction yield are 96.0% (in terms of hydroquinone)；Lower phase is
Polar solvent phase, hydroquinone content are 93.0 %(liquid chromatography area normalizings), (R) -2- (4- hydroxyphenoxy) propionic acid fourth
Ester content is 6.1 %(liquid area under spectrum normalizings), use can be continued cycling through directly as mother liquor.
5 44g(0.4 mol of embodiment) hydroquinone, 18.7g(0.3mol) 95% potassium hydroxide, 400mL glycerine,
500mL petroleum ether, 0.01 g catalyst 18- crown ether -6 are added in 1000 mL three-necked flasks, and stirring is warming up to 80 DEG C, by 33.2g
(0.2 mol) (S) -2- chloropropionic acid butyl ester is added in 4 h, the reaction was continued after adding 4h, react Bi Jiangwen, negative pressure leaching, filter
Cake is potassium chloride, split-phase after filtrate stands, and upper phase is nonpolar solvent phase, (R) -2- (4- hydroxyphenoxy) butyl propionate content
For 98.3%(liquid area under spectrum normalizing), hydroquinone content is 0.9%(liquid area under spectrum normalizing).Split-phase, upper layer reaction solution are recovered
After solvent, high vacuum rectification obtain 99.2% (R) -2- (4- hydroxyphenoxy) butyl propionate (liquid spectrum external standard method), hydroquinone contains
Amount 0.1%；Lower phase is polar solvent phase, and hydroquinone content is 90.6%(liquid area under spectrum normalizing), (R) -2- (4- hydroxy benzenes oxygen
Base) butyl propionate content be 9.5%(liquid area under spectrum normalizing), can be used directly as Recycling Mother Solution.By-product compound in reaction solution
2 contents are less than 0.6%.
Recycling Mother Solution derived above is used: 22 g(0.2 mol) hydroquinone, 12.4g(0.2mol) 95% hydrogen-oxygen
Changing potassium, 0.01g catalyst 18- crown ether -6, circulating mother liquor, all about 1000 mL three-necked flasks are added in 400mL, 500mL petroleum ether
In, stirring be warming up to 80 DEG C, by 33.2g(0.2 mol) (S) -2- chloropropionic acid butyl ester is added in 4 h, the reaction was continued after adding
4h reacts Bi Jiangwen, negative pressure leaching, and filter cake is potassium chloride, and split-phase after filtrate stands, upper phase is nonpolar solvent phase, and monoether contains
Amount is 98.8%(liquid area under spectrum normalizing), hydroquinone content is 0.8 %(liquid area under spectrum normalizing).Split-phase, upper layer reaction solution pass through back
Receive solvent after, high vacuum rectification obtain 45.0g 98.9% (R) -2- (4- hydroxyphenoxy) butyl propionate (liquid spectrum external standard method),
Hydroquinone content 0.11%, reaction yield are 93.5% (in terms of hydroquinone)；Lower phase is polar solvent phase, and hydroquinone contains
Amount is 92.7 %(liquid area under spectrum normalizings), (R) -2- (4- hydroxyphenoxy) butyl propionate content be 6.6 %(liquid area under spectrum return
One) use, can be continued cycling through directly as mother liquor.
6 44g(0.4 mol of embodiment) hydroquinone, 9.2g(0.22mol) 95% sodium hydroxide, 400mL glycerine,
400mL toluene, 0.01 g catalyst 18- crown ether -6 are added in 1000 mL three-necked flasks, and stirring is warming up to 100 DEG C, by 33.2g
(0.2 mol) (S) -2- chloropropionic acid butyl ester is added in 3 h, the reaction was continued after adding 3h, react Bi Jiangwen, negative pressure leaching, filter
Cake is sodium chloride, split-phase after filtrate stands, and upper phase is nonpolar solvent phase, (R) -2- (4- hydroxyphenoxy) butyl propionate content
For 99.0%(liquid area under spectrum normalizing), hydroquinone content is 0.2 %(liquid area under spectrum normalizing).Split-phase, upper layer reaction solution are recovered
After solvent, high vacuum rectification obtain 99.5% (R) -2- (4- hydroxyphenoxy) butyl propionate (liquid spectrum external standard method), hydroquinone contains
Amount 0.05%；Lower phase is polar solvent phase, and hydroquinone content is 91.9 %(liquid chromatography area normalizings), (R) -2- (4- hydroxyl
Phenoxy group) butyl propionate content be 7.4 %(liquid area under spectrum normalizings), can be used directly as Recycling Mother Solution.By-product in reaction solution
2 content of compound is less than 0.2%.
Recycling Mother Solution derived above is used: 22 g(0.2 mol) hydroquinone, 8.4g(0.2mol) 95% hydroxide
All about 400mL, 400mL toluene are added in 1000 mL three-necked flasks for sodium, 0.01 g catalyst 18- crown ether -6, circulating mother liquor,
Stirring be warming up to 100 DEG C, by 33.2g(0.2 mol) (S) -2- chloropropionic acid butyl ester is added in 3 h, the reaction was continued after adding 3h,
Bi Jiangwen is reacted, negative pressure leaching, filter cake is sodium chloride, split-phase after filtrate stands, and upper phase is nonpolar solvent phase, (R)-2-(4-
Hydroxyphenoxy) butyl propionate content be 99.0%(liquid area under spectrum normalizing), hydroquinone content be 0.33 %(liquid area under spectrum return
One).Split-phase, after the recovered solvent of upper layer reaction solution, high vacuum rectification obtain 45.4g 99.5% (R) -2- (4- hydroxyphenoxy)
Butyl propionate (liquid spectrum external standard method), hydroquinone content 0.02%, reaction yield are 94.9% (in terms of hydroquinone)；Lower phase is
Polar solvent phase, hydroquinone content are 92.9 %(liquid chromatography area normalizings), (R) -2- (4- hydroxyphenoxy) propionic acid fourth
Ester content is 6.7 %(liquid area under spectrum normalizings), use can be continued cycling through directly as mother liquor.
Embodiment 7
44g(0.4 mol) hydroquinone, 9.2g(0.22mol) 95% sodium hydroxide, 300mL glycerine, 400mL dimethylbenzene,
0.01g catalyst 18- crown ether -6 is added in 1000 mL three-necked flasks, and stirring is warming up to 110 DEG C, by 33.2g(0.2 mol)
(S) -2- chloropropionic acid butyl ester is added in 2h, the reaction was continued after adding 2h, reacts Bi Jiangwen, negative pressure leaching, filter cake is sodium chloride,
Filtrate stand after split-phase, upper phase be nonpolar solvent phase, (R) -2- (4- hydroxyphenoxy) butyl propionate content be 99.1%(liquid
Area under spectrum normalizing), hydroquinone content is 0.3%(liquid area under spectrum normalizing).Split-phase, after the recovered solvent of upper layer reaction solution, Gao Zhen
Empty rectifying obtain 99.2% (R) -2- (4- hydroxyphenoxy) butyl propionate (liquid spectrum external standard method), hydroquinone content 0.08%；Under
Mutually it is polar solvent phase, hydroquinone content is 91.6 %(liquid chromatography area normalizings), (R) -2- (4- hydroxyphenoxy) third
Acid butyl ester content is 7.7 %(liquid area under spectrum normalizings), it can be used directly as Recycling Mother Solution.By-product compound 2 contains in reaction solution
Amount is less than 0.4%.
Recycling Mother Solution derived above is used: 22 g(0.2 mol) hydroquinone, 8.4g(0.2mol) 95% hydroxide
All about 1000 mL three-necked flasks are added in 300mL, 400mL dimethylbenzene for sodium, 0.01 g catalyst 18- crown ether -6, circulating mother liquor
In, stirring be warming up to 110 DEG C, by 33.2g(0.2 mol) (S) -2- chloropropionic acid butyl ester is added in 2 h, the reaction was continued after adding
2h reacts Bi Jiangwen, and negative pressure leaching, filter cake is sodium chloride, split-phase after filtrate stands, and upper phase is nonpolar solvent phase, (R)-2-
(4- hydroxyphenoxy) butyl propionate content is 99.2%(liquid area under spectrum normalizing), hydroquinone content is 0.2 %(liquid area under spectrum
Normalizing).Split-phase, after the recovered solvent of upper layer reaction solution, high vacuum rectification obtain 46.0g 99.4% (R) -2- (4- hydroxy benzenes oxygen
Base) butyl propionate (liquid spectrum external standard method), hydroquinone content 0.04%, reaction yield is 96.0% (in terms of hydroquinone)；Under
Mutually it is polar solvent phase, hydroquinone content is 92.7 %(liquid chromatography area normalizings), (R) -2- (4- hydroxyphenoxy) third
Acid butyl ester content is 7.0 %(liquid area under spectrum normalizings), use can be continued cycling through directly as mother liquor.
8 44g(0.4 mol of embodiment) hydroquinone, 12.5g(0.3mol) 95% sodium hydroxide, 300mL glycerine,
400mL isopropylbenzene, 0.013 g catalyst 18- crown ether -6 are added in 1000 mL three-necked flasks, and stirring is warming up to 120 DEG C, will
33.2g(0.2 mol) (S) -2- chloropropionic acid butyl ester is added in 2 h, the reaction was continued after adding 2h, Bi Jiangwen is reacted, negative pressure is taken out
Filter, filter cake are sodium chloride, split-phase after filtrate stands, and upper phase is nonpolar solvent phase, (R) -2- (4- hydroxyphenoxy) propionic acid fourth
Ester content is 99.4%(liquid area under spectrum normalizing), hydroquinone content is 0.2 %(liquid area under spectrum normalizing).Split-phase, upper layer reaction solution
After recovered solvent, high vacuum rectification obtain 99.6% (R) -2- (4- hydroxyphenoxy) butyl propionate (liquid spectrum external standard method), to benzene
Two phenol content 0.03%；Lower phase is polar solvent phase, and hydroquinone content is 94.0 %(liquid chromatography area normalizings), (R)-2-
(4- hydroxyphenoxy) butyl propionate content is 5.7 %(liquid area under spectrum normalizings), it can be used directly as Recycling Mother Solution.Reaction solution
Middle 2 content of by-product compound is less than 0.2%.
Recycling Mother Solution derived above is used: 22 g(0.2 mol) hydroquinone, 8.4g(0.2mol) 95% hydroxide
All about 1000 mL three-necked flasks are added in 300mL, 400mL isopropylbenzene for sodium, 0.01 g catalyst 18- crown ether -6, circulating mother liquor
In, stirring be warming up to 120 DEG C, by 33.2g(0.2 mol) (S) -2- chloropropionic acid butyl ester is added in 2 h, the reaction was continued after adding
2h reacts Bi Jiangwen, and negative pressure leaching, filter cake is sodium chloride, split-phase after filtrate stands, and upper phase is nonpolar solvent phase, (R)-2-
(4- hydroxyphenoxy) butyl propionate content is 99.0%(liquid area under spectrum normalizing), hydroquinone content is that 0.2%(liquid area under spectrum is returned
One).Split-phase, after the recovered solvent of upper layer reaction solution, high vacuum rectification obtain 46.2g 99.4% (R) -2- (4- hydroxyphenoxy)
Butyl propionate (liquid spectrum external standard method), hydroquinone content 0.02%, reaction yield are 96.4% (in terms of hydroquinone)；Lower phase is
Polar solvent phase, hydroquinone content are 95.1 %(liquid chromatography area normalizings), (R) -2- (4- hydroxyphenoxy) propionic acid fourth
Ester content is 4.3 %(liquid area under spectrum normalizings), use can be continued cycling through directly as mother liquor.
The above is only a preferred embodiment of the present invention, protection scope of the present invention is not limited merely to above-mentioned reality
Apply example.All technical solutions belonged under thinking of the present invention all belong to the scope of protection of the present invention.It is noted that being led for this technology
For the those of ordinary skill in domain, improvements and modifications without departing from the principle of the present invention, these improvements and modifications
It should be regarded as protection scope of the present invention.
Claims (7)
1. a kind of (R) -2- (4- hydroxyphenoxy) butyl propionate preparation method, it is characterised in that it is organic with immiscible binary
Dicyandiamide solution as reaction dissolvent, (S) -2- chloropropionic acid butyl ester is added to excessive in certain temperature and time to benzene two
In phenol, acid binding agent and catalyst system, insulation reaction obtain (R) -2- (4- hydroxyphenoxy) butyl propionate, after reaction
The polar solvent mutually direct reuse after filtering desalination；For nonpolar solvent mutually through simple distillation recycling design, solvent can be direct
Be recycled, mother liquor obtain through rectification under vacuum (R) -2- (4- hydroxyphenoxy) butyl propionate.
2. a kind of according to claim 1 (R) -2- (4- hydroxyphenoxy) butyl propionate preparation method, it is characterised in that
Immiscible dual solvent system is made of polar solvent and nonpolar solvent, and polar solvent is ethylene glycol or glycerine
One kind, dosage is 5~10 times of hydroquinone quality；Nonpolar solvent is petroleum ether, toluene, dimethylbenzene or isopropylbenzene
One of, dosage is 5~10 times of hydroquinone quality.
3. a kind of according to claim 1 (R) -2- (4- hydroxyphenoxy) butyl propionate preparation method, it is characterised in that
Acid binding agent is one of potassium hydroxide, sodium hydroxide, and dosage is 0.5~0.75 times of hydroquinone mole.
4. a kind of according to claim 1 (R) -2- (4- hydroxyphenoxy) butyl propionate preparation method, it is characterised in that
Catalyst is crown ether -6 18-, and dosage is the 0.1~0.3% of hydroquinone quality.
5. a kind of according to claim 1 (R) -2- (4- hydroxyphenoxy) butyl propionate preparation method, it is characterised in that
First batch of reaction raw materials molar ratio is hydroquinone: (S) -2- chloropropionic acid butyl ester=1.5~2:1, applying material molar ratio in batch is
Hydroquinone: (S) -2- chloropropionic acid butyl ester=1:1.
6. a kind of according to claim 1 (R) -2- (4- hydroxyphenoxy) butyl propionate preparation method, it is characterised in that
Dropping temperature and holding temperature are 90 ~ 120 DEG C.
7. a kind of according to claim 1 (R) -2- (4- hydroxyphenoxy) butyl propionate preparation method, it is characterised in that
Having the reaction time is 3 ~ 8h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910115652.2A CN109867601B (en) | 2019-02-15 | 2019-02-15 | Preparation method of (R) -2- (4-hydroxyphenoxy) butyl propionate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910115652.2A CN109867601B (en) | 2019-02-15 | 2019-02-15 | Preparation method of (R) -2- (4-hydroxyphenoxy) butyl propionate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109867601A true CN109867601A (en) | 2019-06-11 |
| CN109867601B CN109867601B (en) | 2021-05-28 |
Family
ID=66918705
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910115652.2A Active CN109867601B (en) | 2019-02-15 | 2019-02-15 | Preparation method of (R) -2- (4-hydroxyphenoxy) butyl propionate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109867601B (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4489207A (en) * | 1981-12-18 | 1984-12-18 | Basf Aktiengesellschaft | Preparation of 2-(hydroxyphenoxy)-carboxylates |
| CN1340497A (en) * | 2000-08-30 | 2002-03-20 | 中国科学院大连化学物理研究所 | Process for synthesizing 2-(4-hydroxylphenoxyl) butyl propionate |
-
2019
- 2019-02-15 CN CN201910115652.2A patent/CN109867601B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4489207A (en) * | 1981-12-18 | 1984-12-18 | Basf Aktiengesellschaft | Preparation of 2-(hydroxyphenoxy)-carboxylates |
| CN1340497A (en) * | 2000-08-30 | 2002-03-20 | 中国科学院大连化学物理研究所 | Process for synthesizing 2-(4-hydroxylphenoxyl) butyl propionate |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109867601B (en) | 2021-05-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| WO2021078239A1 (en) | Gas-liquid bubbling bed reactor, reaction system and method for synthesizing carbonate | |
| CN106588589A (en) | Purification method for polyoxymethylene dimethyl ether(PODE) | |
| CN104628545B (en) | A kind of preparation method of P-methoxybenzal-dehyde | |
| CN110372512B (en) | Separation and purification process of dimethyl carbonate | |
| WO2009063487A2 (en) | An improved process for manufacture of epoxides, particularly epichlorohydrin | |
| CN106588599A (en) | Purification method of PODE (polyoxymethylene dimethyl ether) | |
| CN108067012A (en) | A kind of extractant for being used for separation of extractive distillation methanol and dimethyl carbonate azeotrope and application thereof and processing method | |
| CN112142574B (en) | Synthesis method of 9, 9-bis [4- (2-hydroxyethoxy) phenyl ] fluorene | |
| ES2660223T3 (en) | Methyl Lactate Preparation Procedure | |
| CN108164388B (en) | Preparation method of high-content 2-methyl allyl chloride | |
| CN101781172B (en) | Novel process for efficiently and continuously synthesizing 2-naphthol | |
| WO2018135016A1 (en) | Acetic acid production method | |
| CN105985224A (en) | Synthetic method of semi-hindered bisphenol-type antioxidant | |
| CN110003154A (en) | A method of preparing high purity butylene phthalide | |
| CN109180490A (en) | The lithium electricity homogeneous production technology of high-purity diethyl carbonate | |
| CN105032473B (en) | A kind of method using the sulfuric acid modified catalyst preparation dialkoxy methanes for the treatment of nanoscale HZSM 5 | |
| CN109867601A (en) | The preparation method of one kind (R) -2- (4- hydroxyphenoxy) butyl propionate | |
| CN103012131B (en) | Method for preparing 4-acetoxy-2-methyl-2-butenal | |
| CN108569996A (en) | A kind of synthetic method of high-efficiency polymerization inhibitor 701 | |
| JP5356455B2 (en) | Method for separating glycol mono-tert-butyl ether and glycol di-tert-butyl ether | |
| CN106588597A (en) | Method for purifying polyoxyethene dimethyl ether | |
| TWI311987B (en) | Process for production of dialkyl carbonate and diol | |
| CN106588657A (en) | Method for synthesizing dimethyl carbonate | |
| CN103467264B (en) | A kind of method being prepared 9-Fluorenone by Industrial fluorene | |
| AU2018446483A1 (en) | Process and system for producing alkyl nitrites |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |