CN108314619A - A kind of synthetic method of R- (+) -2- (4- hydroxyphenoxies) propionic acid - Google Patents
A kind of synthetic method of R- (+) -2- (4- hydroxyphenoxies) propionic acid Download PDFInfo
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- CN108314619A CN108314619A CN201711334123.9A CN201711334123A CN108314619A CN 108314619 A CN108314619 A CN 108314619A CN 201711334123 A CN201711334123 A CN 201711334123A CN 108314619 A CN108314619 A CN 108314619A
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- C07C51/43—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation
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Abstract
The invention discloses a kind of synthetic methods of 2 (4 hydroxyphenoxy) propionic acid of R (+), include the following steps：(1) hydroquinone is added portionwise in the sodium hydroxide solution containing organic solvent, in N2Para hydroxybenzene phenol sodium suspension is obtained by the reaction under atmosphere；(2) 2 chloropropionic acids of S () are dissolved in organic solvent, Na is slowly added under the conditions of ice-water bath2CO3Solid reaction obtains 2 chloropropionic acid sodium solutions of S ()；(3) solution of step (2) is slowly added dropwise into the suspension of step (1), obtained reaction solution is through being evaporated under reduced pressure, dissolving acidification, extract, be evaporated under reduced pressure to white solid, i.e. R (+) 2 (4 hydroxyphenoxy) propionic acid.Above-mentioned synthetic method has synthetic route simple, and reaction condition is mild, product yield high, and product optical purity ee values are high, and the hydroquinone rate of recovery is high, and " three wastes " of generation are few, low power consumption and other advantages.
Description
Technical field
The invention belongs to pesticide intermediates to synthesize field, and in particular to a kind of R- (+) -2- (4- hydroxyphenoxies) propionic acid
Synthetic method.
Background technology
R- (+) -2- (4- hydroxyphenoxies) propionic acid is a kind of important pesticide intermediate, is widely used in synthesizing benzene oxygen third
Acid herbicides.R-Phenoxypropionate herbicide is the novel herbicidal with optically active to grow up after the seventies in last century
Agent has high efficiency, highly selective, environment compatibility, the various advantages energy such as safety.The chemical structure pair of such herbicide
Bioactivity influences very big, the high hundred times of the bioactivity ratio S configurations of usual R configurations, by the herbicide of R and S mixed types
The waste of invalid body can not only be caused but also pollute the environment by launching into farmland, therefore the preparation of the R type herbicides of high-optical-purity
Just it is particularly important.Thus, the synthesis of R- (+) -2- (4- hydroxyphenoxies) propionic acid just has important research and applies valence
Value.
The principal synthetic routes of industrial R- (+) -2- (4- hydroxyphenoxies) propionic acid are by 6.4 equivalents to benzene two at present
Phenol, which is dissolved in equimolar sodium hydrate aqueous solution, is warming up to 72 DEG C, is then reacted with S- (-) -2- chloropropionic acids, product is through acid
Change, MIBK extractions, distillation is recrystallized to give, but it has " three wastes " total amount is more, and yield is relatively low, and the hydroquinone rate of recovery is low etc.
Insufficient (Green Chem, 2014,16,3993).
Invention content
It is an object of the invention to solve the defect of above-mentioned technique, new synthesis R- (+) -2- (4- hydroxyl is provided
Phenoxy group) propionic acid method.
The present invention adopts the following technical scheme that realization above-mentioned purpose：
A kind of synthetic method of R- (+) -2- (4- hydroxyphenoxies) propionic acid, specifically includes following steps：
(1) sodium hydrate solid and organic solvent are added into reaction vessel, in N2Hydroquinone is added portionwise under protection,
Control temperature reacts 20-25min at 12-20 DEG C, obtains para hydroxybenzene phenol sodium suspension；
(2) S- (-) -2- chloropropionic acids are dissolved in organic solvent, Na is slowly added under the conditions of ice-water bath2CO3Solid, reaction
Obtain S- (-) -2- chloropropionic acid sodium solutions；Na is added2CO3Solid ensures that S- (-) -2- chloropropionic acids form S- (-) -2- chloropropionic acid sodium,
It avoids reacting with para hydroxybenzene phenol sodium, improves reaction yield；Reaction equation is as follows：
(3) S- (-) -2- chloropropionic acid sodium solutions obtained in step (2) are slowly added dropwise into step (1) obtained to hydroxyl
It in base sodium phenate suspension, controls and is reacted at 30-40 DEG C of temperature, the reaction was complete up to S- (-) -2- chloropropionic acids sodium solution, stops
Reaction, obtains R- (+) -2- (4- hydroxyphenoxies) propionic acid sodium solution；
(4) propionic acid sodium solution is post-treated obtains white solid by R- (+) -2- (4- hydroxyphenoxies) that step (3) obtains,
As target product R- (+) -2- (4- hydroxyphenoxies) propionic acid；Reaction equation is as follows：
Hydroquinone described in step (1)：The molar ratio of sodium hydroxide is 1：1-1：3, preferably 1：1-1：1.5；
Preferred 14-16 DEG C of the temperature of hydroquinone and sodium hydroxide reaction described in step (1)；
Enter hydroquinone in batches described in step (1), preferably divides 3 batches or 4 batches, but the present invention is not limited thereto；
S- (-) -2- chloropropionic acids described in step (2)：Na2CO3Molar ratio be 1：1-1：2.5, preferably 1:1-1：1.2；
Organic solvent described in step (1), (2) is CH3OH、CH3CH2At least one of OH, DMF, DMSO, preferably
DMSO；The present invention is using dipole solvents such as organic solvent DMF, DMSO to SN2 react more advantageous, CH3OH、CH3CH2OH can make
Organic Sodium Salt slow mechanism dissolved in reaction system reduces byproduct of reaction, avoids using H2The reaction of the inorganic solvents such as O generates
By-product is more, and product yield is low；
Hydroquinone described in step (3)：The molar ratio of S- (-) -2- chloropropionic acids is 2：1-2.5：1, preferred molar ratio is
2.2：1-2.5：1；
S- (-) -2- chloropropionic acids and the reaction temperature of para hydroxybenzene phenol sodium described in step (3) are preferably 33-36 DEG C；
The detailed process of post-processing is in step (4)：R- (+) -2- (4- hydroxyphenoxies) propionic acid sodium solution is first through decompression
Be distilled to recover organic solvent, residue is dissolved in water, and adjusts pH, through organic solvent extract the organic phase containing hydroquinone and
Water phase containing R- (+) -2- (4- hydroxyphenoxies) propionic acid recycles the hydroquinone in organic phase, adjusts water phase pH, passes through again
Organic solvent extracts to contain the organic phase of R- (+) -2- (4- hydroxyphenoxies) propionic acid, and vacuum distillation obtains R- (+) -2- (4-
Hydroxyphenoxy) propionic acid.
Step (4) adjust pH method be：Originally titration adjusting is carried out using the concentrated hydrochloric acid that molar concentration is 12mol/L,
The hydrochloric acid that molar concentration is 6mol/L is reused when close to titration end-point to be adjusted, and required pH value is arrived until adjusting；
It is ethyl acetate, dichloromethane, methyl iso-butyl ketone (MIBK) that organic solvent used is extracted in step (4) post-processing
(MIBK), preferably MIBK；
The present invention has the advantage that compared with prior art：
1. providing the synthetic method of new R- (+) -2- (4- hydroxyphenoxies) propionic acid, this route has raw material letter
It is singly easy to get, synthetic route is simple, and reaction condition is mild.
2. synthetic method of the present invention is carried out using substep, so that hydroquinone is initially formed phenol negative oxygen ion, enhance its nucleophilic energy
Power, and use the organic solvents such as DMSO as solvent, the formation of byproduct of reaction is reduced, the yield of product is increased, to benzene two
The phenol rate of recovery is high, has high industrial value.
3. synthetic route " three wastes " is few, safe, low energy consumption, belongs to green chemistry.
Specific implementation mode
Below in conjunction with specific embodiment, the present invention is further described, and but the scope of the present invention is not limited thereto：
Embodiment 1
4.2g NaOH (0.1mol) solid is added in four neck round-bottom flasks of 100mL, 30mL CH are added3OH is added
Magneton is inserted into Inner temperature thermometers, loads onto spherical condensation tube, vacuumize, N2Under protection, point 3 batches of addition 11.1g hydroquinones
(0.1mol), finishes, and is cooled to 18-20 DEG C of reaction 20min；
5.6gS- (-) -2- chloropropionic acids are weighed in 100mL flasks, 20mL CH are added3OH makes it dissolve completely, by S-
(-) -2- chloropropionic acid methanol solutions are placed in ice-water bath, are slowly added to 5.4g Na2CO3, stir to bubble-free and generate, obtain S- (-)-
2- chloropropionic acid sodium solutions；
S- (-) -2- chloropropionic acid sodium solutions are slowly added dropwise into four neck round-bottom flasks, drop finishes, and is to slowly warm up to 30-32
DEG C, the reaction was continued.By TLC plates and HPLC monitoring reactions, waits for that the reaction was complete for raw material S- (-) -2- chloropropionic acids, stop reaction；
Reaction solution is evaporated under reduced pressure, CH is recycled3OH, residue are dissolved in water, and first concentrated hydrochloric acid (12M) are used to adjust pH,
It is adjusted using 6M hydrochloric acid when close to terminal, until pH=6.0, is extracted 3 times with MIBK, obtained containing the organic of hydroquinone
Phase and the water phase for containing R- (+) -2- (4- hydroxyphenoxies) propionic acid, recycle the hydroquinone 5.0g in organic phase, and the rate of recovery is
89%, water phase pH to 2.0 is adjusted, it is identical as the first time adjusting method of pH, it is extracted 3 times, is obtained containing R- (+) -2- (4- with MIBK
Hydroxyphenoxy) propionic acid organic phase, it is evaporated under reduced pressure, recycling design MIBK, obtains R- (+) -2- (4- hydroxy benzenes oxygen
Base) propionic acid quality be 7.6g, yield 83%, chiral HPLC measure its ee value be 98.3%.
Embodiment 2
6.2g NaOH (0.15mol) solid is added in four neck round-bottom flasks of 100mL, 30mL DMF are added, magnetic is added
Son is inserted into Inner temperature thermometers, loads onto spherical condensation tube, vacuumize, N2Under protection, point 3 batches of addition 11.1g hydroquinones
(0.1mol), finishes, and is cooled to 14-16 DEG C of reaction 20min；
5.6gS- (-) -2- chloropropionic acids are weighed in 100mL flasks, 20mL DMF are added, are dissolved completely, by S-
(-) -2- chloropropionic acid DMF solutions are placed in ice-water bath, are slowly added to 8.0g Na2CO3, stir to bubble-free and generate, obtain S- (-)-
2- chloropropionic acid sodium solutions；
S- (-) -2- chloropropionic acid DMF solutions are slowly added dropwise into four neck round-bottom flasks, drop finishes, and is to slowly warm up to 33-36
DEG C, the reaction was continued.By TLC plates and HPLC monitoring reactions, waits for that the reaction was complete for raw material S- (-) -2- chloropropionic acids, stop reaction；
Reaction solution is evaporated under reduced pressure, DMF is recycled, residue is dissolved in water, and first concentrated hydrochloric acid (12M) is used to adjust pH,
It is adjusted close to when terminal using 6M hydrochloric acid, until pH=6.0, is extracted with ethyl acetate 3 times, obtains having containing hydroquinone
Machine phase and the water phase for containing R- (+) -2- (4- hydroxyphenoxies) propionic acid recycle the hydroquinone 5.2g in organic phase, the rate of recovery
It is 93%, adjusts water phase pH to 2.0, it is identical as the first time adjusting method of PH, it is extracted with ethyl acetate 3 times, R- must be contained
The organic phase of (+) -2- (4- hydroxyphenoxies) propionic acid, is evaporated under reduced pressure it, recycling design ethyl acetate, R- (+) -2-
(4- hydroxyphenoxies) propionic acid quality is 7.7g, and yield 85%, it is 98.2% that chiral HPLC, which measures its ee value,.
Embodiment 3
5.2g NaOH (0.125mol) solid is added in four neck round-bottom flasks of 100mL, 40mL DMSO are added, is added
Magneton is inserted into Inner temperature thermometers, loads onto spherical condensation tube, vacuumize.N2Under protection, point 4 batches of addition 13.9g hydroquinones
(0.125mol), finishes, and is cooled to 10-12 DEG C of reaction 25min；
5.6gS- (-) -2- chloropropionic acids are weighed in 100mL flasks, 20mL DMSO are added, are dissolved completely, by S-
(-) -2- chloropropionic acid DMSO solutions are placed in ice-water bath, are slowly added to 5.4g Na2CO3, stir to bubble-free and generate, obtain S- (-)-
2- chloropropionic acid sodium solutions；
S- (-) -2- chloropropionic acid DMSO solutions are slowly added dropwise into four neck round-bottom flasks, drop finishes, and is to slowly warm up to 38-40
DEG C, the reaction was continued.By TLC plates and HPLC monitoring reactions, waits for that the reaction was complete for raw material S- (-) -2- chloropropionic acids, stop reaction；
Reaction solution is evaporated under reduced pressure, DMSO is recycled, residue is dissolved in water, and first concentrated hydrochloric acid (12M) is used to adjust pH,
It is adjusted close to when terminal using 6M hydrochloric acid, until pH=6.0, is extracted with ethyl acetate 3 times, obtains organic containing hydroquinone
Phase and the water phase for containing R- (+) -2- (4- hydroxyphenoxies) propionic acid, recycle the hydroquinone 7.1g in organic phase, and the rate of recovery is
86%, water phase pH to 2.0 is adjusted, it is identical as the first time adjusting method of pH, it is extracted with ethyl acetate 3 times, obtains containing R- (+)-
2- (4- hydroxyphenoxies) propionic acid organic phase, is evaporated under reduced pressure it, recycling design ethyl acetate, R- (+) -2- (4- hydroxyls
Phenoxy group) propionic acid quality be 8.4g, yield 92%, chiral HPLC measure its ee value be 98.5%.
Embodiment 4
5.2g NaOH (0.125mol) solid is added in four neck round-bottom flasks of 100mL, 40mL DMSO are added, is added
Magneton is inserted into Inner temperature thermometers, loads onto spherical condensation tube, vacuumize, N2Under protection, point 3 batches of addition 13.9g hydroquinones
(0.125mol), finishes, and is cooled to 14-16 DEG C of reaction 25min；
5.6gS- (-) -2- chloropropionic acids are weighed in 100mL flasks, 20mL DMSO are added, are dissolved completely, it will
5.6gS- (-) -2- chloropropionic acid DMSO solutions are placed in ice-water bath, are slowly added to 5.4g Na2CO3, stir to bubble-free and generate, obtain
S- (-) -2- chloropropionic acid sodium solutions；
S- (-) -2- chloropropionic acid DMSO solutions are slowly added dropwise into four neck round-bottom flasks, drop finishes, and is to slowly warm up to 33-36
DEG C, the reaction was continued.By TLC plates and HPLC monitoring reactions, waits for that the reaction was complete for raw material S- (-) -2- chloropropionic acids, stop reaction；
Reaction solution is evaporated under reduced pressure, and DMSO is recycled, and residue is dissolved in water, and first concentrated hydrochloric acid (12M) is used to adjust pH, connect
Be adjusted using 6M hydrochloric acid when nearly terminal, until pH=6.0, extracted 3 times with MIBK, obtain the organic phase containing hydroquinone and
Water phase containing R- (+) -2- (4- hydroxyphenoxies) propionic acid is recycled to the hydroquinone 8.1g in organic phase, and the rate of recovery is
97%, water phase pH to 2.0 is adjusted, it is identical as the first time adjusting method of pH, it is extracted 3 times, is obtained containing R- (+) -2- (4- with MIBK
Hydroxyphenoxy) propionic acid organic phase, it is evaporated under reduced pressure, recycling design MIBK, R- (+) -2- (4- hydroxyphenoxies)
Propionic acid quality is 8.7g, and yield 96%, it is 99.0% that chiral HPLC, which measures its ee value,.
Comparative example 1
5.2g NaOH (0.125mol) solids and 13.9g hydroquinones are added in four neck round-bottom flasks of 250mL
(0.125mol) is added 74mL water, magneton is added, and is inserted into Inner temperature thermometers, loads onto spherical condensation tube, vacuumize, N2Under protection,
5.6g S- (-) -2- chloropropionic acids (0.05mol) are added, then heat to 72 DEG C of reaction 3h.It is anti-by TLC plates and HPLC monitorings
It answers, the reaction was complete for raw material S- (-) -2- chloropropionic acids, stops reaction.Reaction solution adjusts pH to 6.0, is extracted 3 times, must be contained with MIBK
The organic phase of hydroquinone and the water phase for containing R- (+) -2- (4- hydroxyphenoxies) propionic acid adjust water phase pH to 1.0, use MIBK
Extraction 3 times, obtains the organic phase containing R- (+) -2- (4- hydroxyphenoxies) propionic acid, finally has to what is obtained after above-mentioned extraction twice
Machine is mutually evaporated under reduced pressure again, recycling design MIBK, recycles hydroquinone 5.0g, the rate of recovery 60%, R- (+) -2- (4- hydroxyls
Phenoxy group) propionic acid quality be 3.6g, yield 40% ((mostly becoming two substitution products).
Claims (10)
1. a kind of synthetic method of R- (+) -2- (4- hydroxyphenoxies) propionic acid, it is characterised in that specifically comprise the following steps：
(1), sodium hydrate solid and organic solvent are added into reaction vessel, in N2Hydroquinone is added portionwise under protection, in temperature
20-25min is reacted at 12-20 DEG C of degree, obtains para hydroxybenzene phenol sodium suspension；
(2), S- (-) -2- chloropropionic acids are dissolved in organic solvent, Na is slowly added under the conditions of ice-water bath2CO3Solid is obtained by the reaction
S- (-) -2- chloropropionic acid sodium solutions；
(3), S- (-) -2- chloropropionic acid sodium solutions made from step (2) are slowly added dropwise to para hydroxybenzene phenol made from step (1)
In sodium suspension, reacted at 30-40 DEG C of temperature, up to S- (-) -2- chloropropionic acids sodium solution, the reaction was complete, obtains R- (+) -2-
(4- hydroxyphenoxies) propionic acid sodium solution；
(4), step (3) obtains R- (+) -2- (4- hydroxyphenoxies) propionic acid sodium solution is post-treated to obtain white solid, i.e.,
For target product R- (+) -2- (4- hydroxyphenoxies) propionic acid.
2. synthetic method according to claim 1, it is characterised in that the molar ratio of the hydroquinone and sodium hydroxide
It is 1：1-1：3；Described S- (-) -2- chloropropionic acids and Na2CO3Molar ratio be 1：1-1：2.5；The hydroquinone and S-
The molar ratio of (-) -2- chloropropionic acids is 2：1-2.5：1.
3. synthetic method according to claim 2, it is characterised in that the molar ratio of the hydroquinone and sodium hydroxide
It is 1:1-1：1.5；Described S- (-) -2- chloropropionic acids and Na2CO3Molar ratio be 1：1-1：1.2；The hydroquinone and S-
The molar ratio of (-) -2- chloropropionic acids is 2.2：1-2.5：1.
4. synthetic method according to claim 1, it is characterised in that hydroquinone and sodium hydroxide react in step (1)
Temperature is 14-16 DEG C.
5. synthetic method according to claim 1, it is characterised in that the organic solvent described in step (1) is CH3OH、
CH3CH2At least one of OH, DMF, DMSO, preferably DMSO.
6. synthetic method according to claim 1, it is characterised in that in step (2), the organic solvent is CH3OH、
CH3CH2At least one of OH, DMF, DMSO, preferably DMSO.
7. synthetic method according to claim 1, it is characterised in that the reaction temperature in step (3) is 33-36 DEG C.
8. synthetic method according to claim 1, it is characterised in that in step (4), R- (+) -2- (4- hydroxyphenoxies)
Propionic acid sodium solution first recycles organic solvent through vacuum distillation, and residue is dissolved in water, and adjusts pH, extracts to contain through organic solvent
The organic phase of hydroquinone and the water phase for containing R- (+) -2- (4- hydroxyphenoxies) propionic acid adjust water phase pH, again through organic
Solvent extraction must contain the organic phase of R- (+) -2- (4- hydroxyphenoxies) propionic acid, and vacuum distillation obtains R- (+) -2- (4- hydroxyls
Phenoxy group) propionic acid.
9. synthetic method according to claim 8, it is characterised in that it is described adjust pH method be：Originally dense using mole
Degree be 12mol/L concentrated hydrochloric acid carry out titration adjusting, reused when close to titration end-point molar concentration be 6mol/L hydrochloric acid into
Row is adjusted, and required pH value is arrived until adjusting.
10. synthetic method according to claim 8, it is characterised in that it is acetic acid second to extract organic solvent used twice
Ester, dichloromethane, MIBK, preferably MIBK.
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| CN110105201A (en) * | 2018-10-29 | 2019-08-09 | 苏州开元民生科技股份有限公司 | A kind of R-(+) -2-(4- hydroxyphenoxy) propionic acid preparation method |
| CN110105201B (en) * | 2018-10-29 | 2022-05-31 | 苏州开元民生科技股份有限公司 | Preparation method of R- (+) -2- (4-hydroxyphenoxy) propionic acid |
| CN110803987A (en) * | 2019-11-07 | 2020-02-18 | 苏州开元民生科技股份有限公司 | Preparation method of R- (+) -2- (4-hydroxyphenoxy) propionic acid |
| CN110803987B (en) * | 2019-11-07 | 2022-10-14 | 苏州开元民生科技股份有限公司 | Preparation method of R- (+) -2- (4-hydroxyphenoxy) propionic acid |
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