CN106432109A - Preparation method of quizalofop-P-ethyl - Google Patents
Preparation method of quizalofop-P-ethyl Download PDFInfo
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- CN106432109A CN106432109A CN201610835358.5A CN201610835358A CN106432109A CN 106432109 A CN106432109 A CN 106432109A CN 201610835358 A CN201610835358 A CN 201610835358A CN 106432109 A CN106432109 A CN 106432109A
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- OSUHJPCHFDQAIT-GFCCVEGCSA-N CCOC([C@@H](C)Oc(cc1)ccc1Oc1cnc(cc(cc2)Cl)c2n1)=O Chemical compound CCOC([C@@H](C)Oc(cc1)ccc1Oc1cnc(cc(cc2)Cl)c2n1)=O OSUHJPCHFDQAIT-GFCCVEGCSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D241/00—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings
- C07D241/36—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems
- C07D241/38—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems with only hydrogen or carbon atoms directly attached to the ring nitrogen atoms
- C07D241/40—Benzopyrazines
- C07D241/44—Benzopyrazines with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to carbon atoms of the hetero ring
Abstract
The invention provides a preparation method of quizalofop-P-ethyl. Ethyl S(-)-tosyllactate is prepared from p-toluenesulfonyl chloride and L-ethyl lactate through a reaction, and quizalofop-P-ethyl is prepared from ethyl S(-)-tosyllactate and 6-chloro-2-(4-hydroxyphenoxy) quinoxaline through a reaction. Ethyl S(-)-tosyllactate is prepared from liquid organic tertiary amine as alkali through reaction in a solvent-free and desiccant-free system, and hydrolysis of L-ethyl lactate is avoided, so that the content of impurities in p-toluenesulfonyl chloride is reduced, the content of impurities in quizalofop-P-ethyl is further reduced, and the chemical content of obtained quizalofop-P-ethyl is 98% or higher, the optical purity is high (R/S is larger than 99/1); operating procedures are simplified, and the production cost is reduced.
Description
Technical field
The invention belongs to pesticide synthesis technical field is and in particular to a kind of preparation method of Quizalotop-ethyl, the smart quinoline of acquisition
Standing grain spirit chemical content more than 98%, R/S ＞ 99/1.
Background technology
Quizalotop-ethyl (quizalofop-P-ethyl), also known as smart quizalofopethyl, are to be opened by Japanese Nissan chemical industrial company
The aryloxyphenoxypropanoates class herbicide sent out.Its chemical name is (R) -2- [4- (6- chloroquinoxalin-2-yloxy base)] propanoic acid second
Ester, its structural formula is as shown in (I)：
Quizalotop-ethyl is a kind of stem and leaf treating agent in dry farmland possessing high selectivity, is acetyl-CoA carboxylase
(ACCase) inhibitor, it has the selectivity of height between grassy weed and dicotyledonous crops, the grass to broad leaf crop field
Section weeds have good preventive effect.Quizalotop-ethyl is low toxicity herbicide, environmentally safe.
The preparation method of Quizalotop-ethyl is more, and production method general at present is：Paratoluensulfonyl chloride and Pfansteihl ethyl ester
Reaction obtain intermediate (II) S (-)-p-toluenesulfonyl ethyl lactate, intermediate (II) 2- chloro- with compound (III) 6- again
The reaction of (4- hydroxyphenoxy) quinoxaline obtains Quizalotop-ethyl.
Reaction equation is as follows：
It is easy to industrial operation, cost of material is relatively low for this two-step reaction route process is simple, but, in its reaction many with
The aromatic hydrocarbon solvents such as toluene, dimethylbenzene are solvent, the easy racemization of product of acquisition, and the response time is long, and the optical purity of product is relatively
Low (R/S～95/5 ,～90%e.e.).
International monopoly WO2004/002925 discloses the technical side making solvent using hexamethylene in above-mentioned second step reacts
Case, can obtain the Quizalotop-ethyl of high-optical-purity, but the low boiling point due to hexamethylene, cause the response time very long, need back
Stream 18h, is not suitable for large-scale industrial production.
Chinese patent CN101531640 discloses a kind of synthetic method of Quizalofop-p-ethyl with high optical content, above-mentioned second
In step reaction, make solvent using non-polar solven petroleum ether or Petroleum etc., the generation of racemization can be suppressed, obtain high optics and contain
The Quizalotop-ethyl (R/S ＞ 98.5/1.5) of amount, but, it obtains, and the yield of Quizalotop-ethyl is relatively low, and yield is 85～87%.
Chinese patent CN102584724 discloses a kind of preparation method of Quizalotop-ethyl：Including two step substitution reactions, first
Step substitution reaction synthetic intermediate (II) S (-)-p-toluenesulfonyl ethyl lactate, second step substitution reaction synthesis Quizalotop-ethyl,
It using substantial amounts of aromatic solvent and desiccant, makees solvent in second step substitution reaction using petroleum ether in first step reaction,
This synthetic method simple to operate it is easy to industrialization.But, it is in first step substitution reaction using sodium hydroxide, potassium hydroxide
Do acid binding agent Deng inorganic base, easily cause Pfansteihl second ester hydrolysis, the impurity of generation is difficult to remove, the content of intermediate (II) is subject to
To impact, this impurity generates corresponding by-product in second step reaction again, thus having influence on the chemistry of finished product Quizalotop-ethyl
Content, the Quizalotop-ethyl chemical content of acquisition 97% about, wherein has 0.7～0.8% impurity to hydrolyze because of Pfansteihl ethyl ester
Produce；Meanwhile, the aromatic solvent that it uses is unfriendly to environment, increases production cost, still not high in second step reaction yield
(about 92% about), and, it is used methanol, DMF etc. as recrystallisation solvent in post processing, reaction needs first precipitation, first after terminating
Alcohol also easily makes Quizalotop-ethyl that ester exchange reaction occurs, and DMF is too big to the dissolubility of Quizalotop-ethyl, makes crystallization yield substantially low.
Content of the invention
It is an object of the invention to provide a kind of preparation method of Quizalotop-ethyl, alkali is made with liquid trimethylamine, using no
Solvent and drier system reaction, reduce the content of the impurity (ethyl p-toluenesulfonate) in existing production technology, and then drop
The content of impurity (IV) 6- chloro- 2- (4- ethoxy phenoxy) quinoxaline in low Quizalotop-ethyl, improves Quizalotop-ethyl chemistry and contains
Measure to more than 98%, simplify rule of operation, reduce production cost.
In order to achieve the above object, the technical scheme that the present invention provides is as follows：
A kind of preparation method of Quizalotop-ethyl, comprises the following steps：
1) preparation S (-)-p-toluenesulfonyl ethyl lactate
, in the presence of liquid trimethylamine, controlling reaction temperature does not surpass for paratoluensulfonyl chloride and excessive Pfansteihl ethyl ester
Cross 60 DEG C, insulation reaction 3～4 hours, reaction terminate rear pickling, washing, be dehydrated obtain S (-)-p-toluenesulfonyl lactic acid second
Ester；
2) synthesize Quizalotop-ethyl
Solvent is done with hexahydrotoluene, carbonate does alkali, the chloro- 2- of compound 6- (4- hydroxyphenoxy) quinoxaline and excess
S (-)-p-toluenesulfonyl ethyl lactate back flow reaction 2～6 hours, through washing, crystallizing, filter, be dried to obtain target product
Quizalotop-ethyl.
Preferably, described step 1) in, described liquid trimethylamine is triethylamine, tetramethylethylenediamine or pyridine.
Further, described step 1) in, the mol ratio of paratoluensulfonyl chloride, Pfansteihl ethyl ester and liquid trimethylamine is 1：
1.0～1.5：1.0～2.0.
Preferably, step 1) reaction temperature be 40～60 DEG C.
Preferably, step 2) described carbonate be alkali carbonate or bicarbonate, preferably potassium carbonate, sodium carbonate, carbon
Potassium hydrogen phthalate or sodium bicarbonate.
Further, described step 2) in, the chloro- 2- of 6- (4- hydroxyphenoxy) quinoxaline, S (-)-p-toluenesulfonyl lactic acid
The mol ratio of ethyl ester and carbonate is 1:1.0～1.5：1.0～3.0.
Preferably, step 2) in recrystallisation solvent be hexahydrotoluene or ethanol, the water content of described ethanol 0～
20%.
The present inventor pass through experimental studies have found that, prepare S (-)-p-toluenesulfonyl ethyl lactate when, using hydroxide
The inorganic bases such as sodium, potassium hydroxide do acid binding agent, cause Pfansteihl ethyl ester to hydrolyze, produce impurity, its reaction mechanism is：Pfansteihl second
Ester hydrolyzes generation ethanol in sodium hydroxide or potassium hydroxide, and ethanol reacts in the middle of generation in alkalescence condition and paratoluensulfonyl chloride
Impurity ethyl p-toluenesulfonate, ethyl p-toluenesulfonate is reacted with intermediate III in the preparation of Quizalotop-ethyl and generates impurity IV,
Reaction equation is as follows：
On the basis of the studies above, the present invention prepare S (-)-p-toluenesulfonyl ethyl lactate when, with the organic uncle of liquid
Amine is as acid binding agent, it is to avoid Pfansteihl ethyl ester hydrolyzes, and greatly reduces the content of impurity in Quizalotop-ethyl (IV), by its from
Original 0.7～0.8% is reduced to less than 0.1%, and Quizalotop-ethyl chemical content improves to more than 98%, is had with liquid meanwhile
When machine tertiary amine (as triethylamine, pyridine etc.) makees acid binding agent, not only reduce and cause brine waste using inorganic base and desiccant
Process operation, trimethylamine can effectively reduce production cost with recycling.
The present invention prepare S (-)-p-toluenesulfonyl ethyl lactate when, using solvent-free system, reaction raw materials Pfansteihl
Ethyl ester and tertiary amine are liquid, and reaction can be smoothed out, and due to the diluting effect of solvents no a large amount of in reaction system, reactant is dense
Degree becomes big, and reaction is easy to occur, and then shortens the response time；Without adding desiccant in reaction, further simplify behaviour
Make, saved solvent cost, improve and produce production capacity.
The present invention is in step 2) in using hexahydrotoluene be solvent, hexahydrotoluene simultaneously as reaction and crystallization molten
Agent, direct decrease temperature crystalline after can washing reacting end, it is to avoid using two kinds of solvents in same reaction with last handling process, can
Quizalotop-ethyl reaction yield is made to improve to more than 95%, streamline operation, it is more suitable for industrialized production.
Compared with prior art, beneficial effects of the present invention are as follows：
1) present invention prepare S (-)-p-toluenesulfonyl ethyl lactate when, alkali is made with tertiary amine, effectively reduces single miscellaneous
The content of matter, improves the chemical content of Quizalotop-ethyl, meanwhile, the recyclable recycling of tertiary amine.
2) present invention prepare S (-)-p-toluenesulfonyl ethyl lactate when, be not required to add aromatic hydrocarbon solvent, using no molten
Agent no drier system, shortened the response time to 3～4 hours, cost-effective.
3) present invention makees solvent when synthesizing Quizalotop-ethyl with hexahydrotoluene, improves reaction temperature, accelerate to react into
Journey, improves reaction yield (more than 95%), and reaction can use hexahydrotoluene to do recrystallisation solvent after terminating, and need not secondary take off
Molten, simplify operating process, recyclable recycling.
Brief description
Fig. 1 is the LC-MS spectrogram of the chloro- 2- of impurity 6- (4- ethoxy phenoxy) quinoxaline (IV) in comparative example.
Fig. 2 is the chloro- 2- of impurity 6- (4- ethoxy phenoxy) quinoxaline (IV) in comparative example1H-NMR spectrum.
Specific embodiment
The present invention will be further described with reference to embodiments.
Embodiment 1
1) preparation S (-)-p-toluenesulfonyl ethyl lactate
Paratoluensulfonyl chloride 192.6g (99.0%, 1.0mol), Pfansteihl is sequentially added in four mouthfuls of reaction bulbs of 1000ml
Ethyl ester 121.7g (99.0%, 1.02mol), after stirring, Deca triethylamine 112.4g (99.0%, 1.1mol), control
Dropping temperature processed<60 DEG C, 40～60 DEG C of reaction 3h of insulation after completion of dropwise addition, sampling in course of reaction carries out control, reactant liquor in GC
In paratoluensulfonyl chloride<When 0.1%, reaction terminates.
Reaction adds 200g water after terminating, and Deca 31% technical hydrochloric acid adjusts pH value to 1～2, stirs, standing separates lower floor has
Machine phase, organic faciess add 200g to wash twice to aqueous phase in neutrality again, a standing point water, organic faciess decompression dehydration, control vacuum
Degree<- 0.095MPa, temperature<100 DEG C, after organic faciess clear dehydration terminate, obtain S (-)-p-toluenesulfonyl lactic acid second
Ester product 265.5g, content 99.5%, molar yield 97% (in terms of paratoluensulfonyl chloride), impurity ethyl p-toluenesulfonate content
For 0.03%.
2) synthesize Quizalotop-ethyl
In the environment of being passed through nitrogen, sequentially add hexahydrotoluene 500ml, 6- in four mouthfuls of reaction bulbs of 1000ml chloro-
2- (4- hydroxyphenoxy) quinoxaline (III) 139.1g (98.0%, 0.5mol), S (-)-p-toluenesulfonyl ethyl lactate
139.6g, potassium carbonate 108g (96.0%, 0.75mol), temperature rising reflux reacts 3h, and HPLC detects (III) content<When 0.1%, instead
Should terminate.
It is cooled to 60～70 DEG C, washes three times, add water 100g every time, washing end is cooled to 0～5 DEG C of crystallization, filter, dry
Do to obtain product Quizalotop-ethyl 180.9g, chemical content 98.2%, optics content 99.3%, R body burden 97.5%, molar yield
95.3% (in terms of III), the chloro- 2- of 6- (4- ethoxy phenoxy) quinoxaline (IV) content is 0.03%.
Embodiment 2
1) preparation S (-)-p-toluenesulfonyl ethyl lactate
Paratoluensulfonyl chloride 192.6g (99.0%, 1.0mol), Pfansteihl is sequentially added in four mouthfuls of reaction bulbs of 1000ml
Ethyl ester 121.7g (99.0%, 1.02mol), after stirring, Deca pyridine 95.9g (99.0%, 1.2mol), control and drip
Degree of heating<60 DEG C, 40～60 DEG C of reaction 3h of insulation after completion of dropwise addition, sampling in course of reaction carries out control in GC, in reactant liquor
Paratoluensulfonyl chloride<When 0.1%, reaction terminates.
Add 200g water, Deca 31% technical hydrochloric acid adjusts pH value to 1～2, stirs, standing separates lower floor's organic faciess, organic
200g is mutually added to wash twice to aqueous phase in neutrality again, standing point water, organic faciess decompression dehydration, control vacuum<-
0.095MPa, temperature<100 DEG C, after organic faciess clear dehydration terminate, obtain S (-)-p-toluenesulfonyl ethyl lactate produce
Product 264.9g, content 99.3%, molar yield 96.6% (in terms of paratoluensulfonyl chloride), impurity ethyl p-toluenesulfonate content is
0.05%.
2) synthesize Quizalotop-ethyl
In the environment of being passed through nitrogen, sequentially add hexahydrotoluene 500ml, 6- in four mouthfuls of reaction bulbs of 1000ml chloro-
2- (4- hydroxyphenoxy) quinoxaline (III) 139.1g (98.0%, 0.5mol), S (-)-p-toluenesulfonyl ethyl lactate
139.6g (embodiment 1), potassium carbonate 108g (96.0%, 0.75mol), temperature rising reflux reacts 3h, and HPLC detects (III) content<
When 0.1%, reaction terminates.
It is cooled to 60～70 DEG C, washes three times, add water 100g every time, washing terminates rear vacuum distillation recycling design methyl ring
Hexane, is cooled to 50-60 DEG C, will enter the ethanol of 300ml aqueous 10%, insulated and stirred fully dissolves, slow cooling is to 0～5 DEG C
Crystallization, filters, dries to obtain product Quizalotop-ethyl 181.3g, chemical content 98.5%, optics content 99.4%, R body burden
97.9%, molar yield 95.9% (in terms of III), the chloro- 2- of 6- (4- ethoxy phenoxy) quinoxaline (IV) content is 0.01%.
Comparative example
1) preparation S (-)-p-toluenesulfonyl ethyl lactate (II)
Toluene 400ml, anhydrous magnesium sulfate 20g, sodium hydroxide 30.6g is sequentially added in four mouthfuls of reaction bulbs of 1000ml
(98%, 0.75mol), mix and blend is cooled to 0 DEG C, adds paratoluensulfonyl chloride 96.3g (99%, 0.5mol), controls temperature
Between 0-5 DEG C, Deca Pfansteihl ethyl ester 71.5g (99%, 0.6mol), control temperature 0-5 DEG C insulation reaction after completion of dropwise addition
3h, detects tolysulfonyl chlorinity<0.1% reaction terminates, and in course of reaction, GC-MS follows the tracks of impurity ethyl p-toluenesulfonate
Generate.Reaction terminate after through pickling, washing, precipitation obtain S (-)-p-toluenesulfonyl ethyl lactate (II) product 131.6g, content
98.1%, molar yield 94.8% (being calculated with paratoluensulfonyl chloride), impurity ethyl p-toluenesulfonate 0.8%.
2) synthesize Quizalotop-ethyl
In the environment of being passed through nitrogen, in four mouthfuls of reaction bulbs of 1000ml, sequentially add petroleum ether 500ml, 6- chloro- 2- (4-
Hydroxyphenoxy) quinoxaline (III) 139.1g (98.0%, 0.5mol), S (-)-p-toluenesulfonyl ethyl lactate (II)
145.7g (comparative example 1), potassium carbonate 108g (96.0%, 0.75mol), temperature rising reflux reacts 3h, and HPLC detects (III) content<
0.1% reaction terminates, and is cooled to 60～70 DEG C, washes three times, add water 100g every time, and washing terminates rear vacuum distillation recycling design
Petroleum ether, precipitation terminates to be cooled to 50-60 DEG C, adds 300ml ethanol, and insulated and stirred fully dissolves, and slow cooling is to 0～5 DEG C
Crystallization, filters, dries to obtain product Quizalotop-ethyl 173.2g, chemical content 97.3%, optics content 99.2%, R body burden
96.5%, molar yield 90.5% (in terms of III), the chloro- 2- of 6- (4- ethoxy phenoxy) quinoxaline (IV) content is 0.76%,
Referring to Fig. 1-Fig. 2, Fig. 1 is the LC- of the chloro- 2- of impurity 6- (4- ethoxy phenoxy) quinoxaline (IV) to the structural confirmation spectrogram of impurity
MS spectrogram, Fig. 2 is the chloro- 2-'s of impurity 6- (4- ethoxy phenoxy) quinoxaline (IV)1H-NMR spectrum.
Molecular ion peak M301=(M+1), M342=(M+MeCN+1) can be seen from LC-MS spectrogram；1H-NMR
(DMSO, 300MHz) δ (ppm) 1.36 (t, 3H), 4.06 (m, 2H), 7.01 (m, 1H), 7.03 (m, 1H), 7.22 (m, 1H),
7.24 (m, 1H), 7.70 (m, 1H), 7.74 (m, 1H), 8.14 (m, 1H), 8.87 (m, 1H).By1H-NMR and LC-MS spectrogram can
The structure of checking impurity (IV).
Claims (9)
1. a kind of preparation method of Quizalotop-ethyl, comprises the following steps：
1) preparation S (-)-p-toluenesulfonyl ethyl lactate
, in the presence of liquid trimethylamine, controlling reaction temperature is less than 60 for paratoluensulfonyl chloride and excessive Pfansteihl ethyl ester
DEG C, insulation reaction 3～4 hours, reaction terminate rear pickling, washing, be dehydrated obtain S (-)-p-toluenesulfonyl ethyl lactate；
2) synthesize Quizalotop-ethyl
Solvent is done with hexahydrotoluene, carbonate is alkali, the chloro- 2- of compound 6- (4- hydroxyphenoxy) quinoxaline and excessive S
(-)-p-toluenesulfonyl ethyl lactate back flow reaction 2～6 hours, through washing, crystallizing, filter, be dried to obtain target product essence
Quizalofop-ethyl.
2. according to claim 1 the preparation method of Quizalotop-ethyl it is characterised in that described step 1) in, described liquid
Trimethylamine is triethylamine, tetramethylethylenediamine or pyridine.
3. according to claim 1 the preparation method of Quizalotop-ethyl it is characterised in that described step 1) in, tolysulfonyl
The mol ratio of chlorine, Pfansteihl ethyl ester and liquid trimethylamine is 1：1.0～1.5：1.0～2.0.
4. according to claim 1 the preparation method of Quizalotop-ethyl it is characterised in that described step 1) reaction temperature be 40
～60 DEG C.
5. according to claim 1 the preparation method of Quizalotop-ethyl it is characterised in that step 2) described carbonate is alkali metal
Carbonate or bicarbonate.
6. according to claim 5 the preparation method of Quizalotop-ethyl it is characterised in that step 2) described alkali carbonate is
Potassium carbonate, sodium carbonate, described bicarbonate is potassium bicarbonate or sodium bicarbonate.
7. according to claim 1 the preparation method of Quizalotop-ethyl it is characterised in that described step 2) in, 6- chloro- 2- (4-
Hydroxyphenoxy) quinoxaline, S (-) mol ratio of-p-toluenesulfonyl ethyl lactate and carbonate is 1:1.0～1.5：1.0～
3.0.
8. according to any one of claim 1-7 the preparation method of Quizalotop-ethyl it is characterised in that step 2) in crystallization molten
Agent is hexahydrotoluene or ethanol.
9. according to claim 8 the preparation method of Quizalotop-ethyl it is characterised in that step 2) in recrystallisation solvent be ethanol
When, the water content of described ethanol is 0～20%.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108276313A (en) * | 2018-02-27 | 2018-07-13 | 东南大学 | A method of synthesizing (S) -2- p-toluenesulfonyl ethyl propionates using micro flow field technology continuous flow |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108276313A (en) * | 2018-02-27 | 2018-07-13 | 东南大学 | A method of synthesizing (S) -2- p-toluenesulfonyl ethyl propionates using micro flow field technology continuous flow |
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