CN109096137A - A kind of synthetic method of S-metolachlor - Google Patents
A kind of synthetic method of S-metolachlor Download PDFInfo
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- C07C249/00—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C249/02—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of compounds containing imino groups
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- C07C213/02—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups
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Abstract
The invention belongs to herbicide field more particularly to a kind of synthetic methods of S-metolachlor.The present invention is by providing a kind of synthetic method of S-metolachlor, using cheap and easily-available -6 ethyl aniline of compound 2- methyl as raw material, by condensation reaction, catalytic hydrogenating reduction reaction, chlorine acetylation, purification process finally obtains the herbicide products S-metolachlor of high-quality, the present invention is by establishing a kind of simple and easy water phase S-metolachlor synthetic method, in the experiment of kilogram magnitude, S-metolachlor product yield reaches 98.5% purity and reaches 98.2%, it is a kind of green synthesis method suitable for industrialized production, simultaneously, the logical conventional organic solvents synthetic method of this method is compared, avoid the use of organic base, post-processing step is few, production pollution is small, it is at low cost, required material variety is few, solvent usage is few, it is at low cost, it is suitble to large-scale promotion to use.
Description
Technical field
The invention belongs to herbicide field more particularly to a kind of synthetic methods of S-metolachlor.
Background technique
S-metolachlor is the chloroacetamide developed and promoted by i.e. present Syngenta Co., Ltd of vapour Ba-Jia Ji company
Class highy potent herbicide.It is organic heterocyclic class efficiently, low toxicity, highly selective internal-suction type herbicide.The product has excellent
Performance and outstanding drug effect, one of reason are exactly because its own chiral structure and the chiral structure isomers are showed
Ultra high efficiency activity.Since the chiral difficulty for synthesizing the product is larger, for a long time, the staple market of the product and production are supplied
It should exclusively be occupied by Syngenta.In order to enter and share the production and supply market of the product, the synthesis work of the herbicide
Skill route becomes the research hotspot of domestic enterprise and research institution.
Currently, the synthesis main method of S-metolachlor has following 3 kinds: 1, Split Method: the principle of fractionation is to N-
(2- methyl -6- ethylphenyl) alanine ester carries out chemistry or Enzymatic kinetic resolution, restores again, is acylated, methylates
Obtain S- isopropyl methoxalamine, products material and preparation process higher cost；2, it chiral raw material synthetic method: specifically utilizes
(D)-methyl lactate or (D)-ethyl lactate are that raw material first reacts generation (R) -2- (tolysulfonyl oxygen with paratoluensulfonyl chloride
Base propionic ester, then react to obtain S- (-)-N- (2- methyl -6- ethylphenyl) alanine ester with 2- methyl -6- ethyl aniline, so
React to obtain S- (-)-N- (1 '-methyl -2 '-ethoxy) -2- methyl -6- ethyl aniline with reducing agent C afterwards, further with chlorine
Chloroacetic chloride is acylated, and finally methylation obtains (S)-isopropyl methoxalamine.Whole process is not necessarily to split, but due to the selection of acylation
The problems such as property, keeps total recovery unsatisfactory, and the cost of industrialized production is still higher；3, the asymmetric hydrogenation synthesis of imines
Method, this method is current research and uses more synthetic route, mainly with 2,6- Methylethyl aniline and methoxy acetone
For raw material, asymmetric hydrogenation is carried out under the action of chiral catalyst after synthesizing imine, then smart isopropyl is obtained by acylation reaction
Alachlor, technological difficulties are the synthesis or selection of chiral catalyst, and the selection of suitable chiral catalyst is the guarantor of product yield
Card, but, there is situations such as chiral content is low, whole yield is not high at present, is unfavorable for realizing that industrialization promotion utilizes.
Summary of the invention
Technical problem present in synthesis technology of the present invention for above-mentioned S-metolachlor, proposes a kind of design
Rationally, the synthetic method of a kind of S-metolachlor of simple process and low in cost, whole high income.
In order to achieve the above object, the technical solution adopted by the present invention is, the present invention provides a kind of S-metolachlor
Synthetic method, comprising the following steps:
A, it is analytically pure toluene solvant that purity is added first into reaction kettle, then, addition and toluene into reaction kettle
The methoxy acetone of solvent equal volume amounts and and double of volume 2,6- Methylethyl aniline and a small amount of catalyst,
Imines synthetic reaction is carried out, raw material finishes, and opens stirring, is warming up to 88 DEG C, controls and keep reacting liquid temperature at 88 DEG C, instead
The time answered is 10h, wherein the catalyst is p-methyl benzenesulfonic acid, and the volume ratio of the p-methyl benzenesulfonic acid and toluene solvant is
1:15；
B, vacuum decompression distillation after reaction, is carried out, excess of solvent is boiled off, vacuum concentration organic layer is oilyly final
Shape product-imines；
C, the imines for obtaining b step is added in autoclave, and be added catalyst 1-S- diphenylphosphine -2-R- two (3,
5- 3,5-dimethylphenyl) phosphine ferrocene-iridium and iridium catalyst metal complex mixture, charging finishes, autoclave tightened so
It is replaced in turn each 2 times, after replacement completion with nitrogen and hydrogen afterwards, opens stirring, reaction is at 50 DEG C, the reaction item of 7.5MPa
It is reacted 4.5 hours under part, obtains amidogen ether；
D, the amidogen ether for obtaining step c is added in stirred autoclave, at the same be added toluene solvant and water effect solvent,
Then sodium carbonate is slowly added dropwise material chloracetyl chloride, 25 DEG C of temperature or so, continues to stir after dripping off as alkali, high-speed stirred
0.5h stands liquid separation, arrives S-metolachlor product after organic phase concentration.
Preferably, in the step c, catalyst 1-S- diphenylphosphine -2-R- two (3, the 5- 3,5-dimethylphenyl) phosphine
The volume ratio of ferrocene-iridium and iridium catalyst metal complex is 1~2:1~2.
Preferably, in the step c, catalyst 1-S- diphenylphosphine -2-R- two (3, the 5- 3,5-dimethylphenyl) phosphine
The additive amount of the mixture of ferrocene-iridium and iridium catalyst metal complex is 1st/20th to 35 of imines quality
Between/mono-.
Preferably, toluene solvant and water are added according to the ratio that volume ratio is 1:1 in the Step d.With existing skill
Art is compared, and the advantages and positive effects of the present invention are:
The present invention is by providing a kind of synthetic method of S-metolachlor, with cheap and easily-available compound 2- methyl -6
Ethyl aniline is raw material, finally obtains height by condensation reaction, catalytic hydrogenating reduction reaction, chlorine acetylation, purification process
The herbicide products S-metolachlor of quality, the present invention is by establishing a kind of simple and easy water phase S-metolachlor
Synthetic method, in the experiment of kilogram magnitude, S-metolachlor product yield reaches 98.5% purity and reaches 98.2%, is
A kind of green synthesis method suitable for industrialized production, meanwhile, the logical conventional organic solvents synthetic method of this method is compared, and is kept away
Exempt from the use of organic base, post-processing step is few, and small, at low cost, the required material variety of production pollution is few, and solvent usage is few, at
This is low, and large-scale promotion is suitble to use.
Specific embodiment
To better understand the objects, features and advantages of the present invention, below with reference to embodiment to this hair
It is bright to be described further.It should be noted that in the absence of conflict, the feature in embodiments herein and embodiment
It can be combined with each other.
In the following description, numerous specific details are set forth in order to facilitate a full understanding of the present invention, still, the present invention may be used also
To be implemented using other modes described herein are different from, therefore, the present invention is not limited to the specific of specification is described below
The limitation of embodiment.
Raw material: toluene, rank: analysis is pure；2- methyl -6- ethyl aniline, rank: technical grade；Methoxy acetone, rank:
Technical grade；Chloracetyl chloride, rank, technical grade；Sodium carbonate, rank, technical grade；Two (3,5- diformazan of 1-S- diphenylphosphine -2-R-
Base phenyl) phosphine ferrocene-iridium, rank, technical grade；Iridium metal complex (chiral hydride H 8-BINOL diphosphine compound and iridium-
The iridium metal complex that cyclo-octadiene complex compound is formed by 0.5~5: 1 molar ratio), Yangnong Chemical Co., Ltd., Jiangsu
Production.
Embodiment 1, the present embodiment 1 provide a kind of synthetic method of S-metolachlor
First to reaction kettle (reaction kettle is that four-hole boiling flask is replaced with reaction kettle in the industrial production herein)
It is middle that the toluene solvant that purity is analytically pure 300ml is added, then, it is added into reaction kettle and toluene solvant equal volume amounts
Methoxy acetone and and to 2, the 6- Methylethyl aniline (equivalent 0.104mol) of 150ml and the p-methyl benzenesulfonic acid of 20mg,
Imines synthetic reaction is carried out, raw material finishes, and opens stirring, is warming up to 88 DEG C, controls and keep reacting liquid temperature at 88 DEG C, instead
The time answered is 10h, this step is condensation reaction, and condensation reaction (Condensation) refers to two or more organic compounds
Object interacts, and the reaction of a new bigger molecule is finally formed with Covalent bonding together.In the process that reaction carries out
In, it will usually slough the water or some small substances of one or more molecules, common hydrogen chloride, alcohols speciality etc..
Condensation reaction can both occur portion in the molecule can also occur, the condensation reaction yet having does not slough any small point intermolecular
Son, as common nucleophilic addition, after level-one amine and carbonyls generation condensation reaction, due to amine and carbonyls
Condensation reaction be reversible reaction, so hydrolysis can occur for imines under acid condition, can decompose to obtain original carbonylation
Object and amine are closed, meanwhile, there are one hydrogen atoms for the nitrogen-atoms of condensation product, so the water of a molecule can be lost, therefore how to protect
The water that card reaction generates ceaselessly is removed from reaction system in time, is the key that reaction forward is promoted to carry out.By select with
Water is insoluble and the toluene of azeotropic is as solvent, is ceaselessly separated reaction water from reaction system by reflux water-dividing in reaction.
After reaction, vacuum decompression distillation is carried out, excess of solvent is boiled off, vacuum concentration organic layer is final to obtain oily
Product-imines, vacuum concentration organic layer is final to obtain oil product 187.2g, reaction yield 88.2%.
Obtained imines is added in autoclave, in the present embodiment, catalyst is added for convenience, joined altogether
200g imines, and be added 10ml two (3,5- 3,5-dimethylphenyl) phosphine ferrocene of catalyst 1-S- diphenylphosphine -2-R--iridium and
The mixture of iridium catalyst metal complex, charging finish, and autoclave is tightened and is then replaced in turn respectively with nitrogen and hydrogen
2 times, after replacement completion, stirring is opened using the purpose replaced in turn, reaction is reacted under 50 DEG C, the reaction condition of 7.5MPa
4.5 hours, amidogen ether is obtained, the reaction of imines catalytic hydrogenation is relatively conventional, but directional catalyzing adds selective catalytic hydrogenation in other words
Hydrogen generates stereomeric target product, is especially pursuing highly selective, high yield, very challenging property today of high-quality.
The common reactant that imines participates in is more, has the hydrolysis of imines, generates corresponding amine and carbonyls, sub-
The most of chemical reactions similar to aldehyde and the compound of ketone of other reactions that amine participates in.Imines can also be raw with hydrogenating reduction
At amine.Step reaction is asymmetric hydro-reduction reaction and a kind of Stereoselective reaction.Prochirality base in reactant
Group's carbonyl, double bond etc. occur reduction reaction under the action of chiral factor and obtain the stereoisomeric products of correlative, these
Product both can be the isomers of mapping, it is also possible to diastereoisomer.For this purpose, the selection of chiral catalyst, is reaction product
A key factor, since the viscosity of imines is larger, for this purpose, in order to slacken the covalent bond between the two of hydrogen molecule hydrogen make
With in the present embodiment, iridium metal complex being selected to be acted on, in order to improve hydrogen source and be hydrogenated object in catalyst
Activated centre aggregation, to improve the e.e value of target amidogen ether, has selected the 1-S- diphenylphosphine -2-R- two (3,5- bis- of high activity
Aminomethyl phenyl) phosphine ferrocene-iridium is as catalyst, and by the cooperations of two kinds of catalyst, the yield of amidogen ether is in 305g, yield
95%, the volume ratio of two kinds of catalyst is 1:1, i.e., each 5ml herein.
45g amidogen ether is added to stirred autoclave (herein in the four-hole boiling flask with mechanical stirring and Dropping feeder)
In, while the toluene solvant of 100ml and the water effect solvent of 100ml, 34g sodium carbonate is added as alkali, high-speed stirred, then
18ml material chloracetyl chloride is slowly added dropwise, 25 DEG C of temperature or so, after completion of the reaction plus the water of 180ml stirs 30 minutes, then quiet
Set layering.Organic layer is dried, filtered with anhydrous magnesium sulfate.Concentration can obtain S-metolachlor raw medicine product about 69g.Sampling
HPLC analyzes ee value, is 82%.Yield is 98.50%, reaches 98.2% (quality after the calibration of purity liquid chromatogram external standard method
Score), it is poor in aqueous phase dispersibility since amidogen ether viscosity is larger, therefore, in the present embodiment, using toluene solvant as solvent, have
Conducive to the dispersion of reactant, to promote to react, and the effect of water is then the HCl generated in reaction to be extracted organic phase, and make
For the reaction medium of HCl and inorganic bases sodium carbonate, it is also beneficial to accelerate reaction.
Different catalyst is effectively selected in different phase by above-mentioned, and then the present embodiment is provided
The yield of synthetic method reach 98% or more, and then solve present in the asymmetric hydrogenation synthetic method of existing imines
The problem of low yield.In addition, it is necessary to illustrate, the reaction of composition principle provided by the present embodiment is existing imines
The common reaction of asymmetric hydrogenation synthetic method, the present embodiment emphasis improved place are the selection and temperature of catalyst
Control, to achieve the purpose that high yield.
2 the present embodiment 1 of embodiment provides a kind of synthetic method of S-metolachlor
First to reaction kettle (reaction kettle is that four-hole boiling flask is replaced with reaction kettle in the industrial production herein)
It is middle that the toluene solvant that purity is analytically pure 400ml is added, then, it is added into reaction kettle and toluene solvant equal volume amounts
Methoxy acetone and and to 2, the 6- Methylethyl aniline (equivalent 0.104mol) of 200ml and the p-methyl benzenesulfonic acid of 28mg,
Imines synthetic reaction is carried out, raw material finishes, and opens stirring, is warming up to 88 DEG C, controls and keep reacting liquid temperature at 88 DEG C, instead
The time answered is 10h, this step is condensation reaction, and condensation reaction (Condensation) refers to two or more organic compounds
Object interacts, and the reaction of a new bigger molecule is finally formed with Covalent bonding together.In the process that reaction carries out
In, it will usually slough the water or some small substances of one or more molecules, common hydrogen chloride, alcohols speciality etc..
Condensation reaction can both occur portion in the molecule can also occur, the condensation reaction yet having does not slough any small point intermolecular
Son, as common nucleophilic addition, after level-one amine and carbonyls generation condensation reaction, due to amine and carbonyls
Condensation reaction be reversible reaction, so hydrolysis can occur for imines under acid condition, can decompose to obtain original carbonylation
Object and amine are closed, meanwhile, there are one hydrogen atoms for the nitrogen-atoms of condensation product, so the water of a molecule can be lost, therefore how to protect
The water that card reaction generates ceaselessly is removed from reaction system in time, is the key that reaction forward is promoted to carry out.By select with
Water is insoluble and the toluene of azeotropic is as solvent, is ceaselessly separated reaction water from reaction system by reflux water-dividing in reaction.
After reaction, vacuum decompression distillation is carried out, excess of solvent is boiled off, vacuum concentration organic layer is final to obtain oily
Product-imines, vacuum concentration organic layer is final to obtain oil product 250g, reaction yield 88.4%.
Obtained imines is added in autoclave, in the present embodiment, catalyst is added for convenience, joined altogether
300g imines, and be added 15ml two (3,5- 3,5-dimethylphenyl) phosphine ferrocene of catalyst 1-S- diphenylphosphine -2-R--iridium and
The mixture of iridium catalyst metal complex, charging finish, and autoclave is tightened and is then replaced in turn respectively with nitrogen and hydrogen
2 times, after replacement completion, stirring is opened using the purpose replaced in turn, reaction is reacted under 50 DEG C, the reaction condition of 7.5MPa
4.5 hours, amidogen ether is obtained, the reaction of imines catalytic hydrogenation is relatively conventional, but directional catalyzing adds selective catalytic hydrogenation in other words
Hydrogen generates stereomeric target product, is especially pursuing highly selective, high yield, very challenging property today of high-quality.
The common reactant that imines participates in is more, has the hydrolysis of imines, generates corresponding amine and carbonyls, sub-
The most of chemical reactions similar to aldehyde and the compound of ketone of other reactions that amine participates in.Imines can also be raw with hydrogenating reduction
At amine.Step reaction is asymmetric hydro-reduction reaction and a kind of Stereoselective reaction.Prochirality base in reactant
Group's carbonyl, double bond etc. occur reduction reaction under the action of chiral factor and obtain the stereoisomeric products of correlative, these
Product both can be the isomers of mapping, it is also possible to diastereoisomer.For this purpose, the selection of chiral catalyst, is reaction product
A key factor, since the viscosity of imines is larger, for this purpose, in order to slacken the covalent bond between the two of hydrogen molecule hydrogen make
With in the present embodiment, iridium metal complex being selected to be acted on, in order to improve hydrogen source and be hydrogenated object in catalyst
Activated centre aggregation, to improve the e.e value of target amidogen ether, has selected the 1-S- diphenylphosphine -2-R- two (3,5- bis- of high activity
Aminomethyl phenyl) phosphine ferrocene-iridium is as catalyst, and by the cooperations of two kinds of catalyst, the yield of amidogen ether is in 382g, yield
95%, the volume ratio of two kinds of catalyst is 2:1, i.e. 1-S- diphenylphosphine -2-R- two (3,5- 3,5-dimethylphenyl) phosphine herein
Ferrocene-iridium 10ml, iridium catalyst metal complex are 5ml.
100g amidogen ether is added to stirred autoclave (herein in the four-hole boiling flask with mechanical stirring and Dropping feeder)
In, while the toluene solvant of 220ml and the water effect solvent of 220ml, 75g sodium carbonate is added as alkali, high-speed stirred, then
40ml material chloracetyl chloride is slowly added dropwise, 25 DEG C of temperature or so, after completion of the reaction plus the water of 300ml stirs 30 minutes, then quiet
Set layering.Organic layer is dried, filtered with anhydrous magnesium sulfate.Concentration can obtain S-metolachlor raw medicine product about 152g.Sampling
HPLC analyzes ee value, is 82%.Yield is 98.60%, reaches 98.2% (quality after the calibration of purity liquid chromatogram external standard method
Score), it is poor in aqueous phase dispersibility since amidogen ether viscosity is larger, therefore, in the present embodiment, using toluene solvant as solvent, have
Conducive to the dispersion of reactant, to promote to react, and the effect of water is then the HCl generated in reaction to be extracted organic phase, and make
For the reaction medium of HCl and inorganic bases sodium carbonate, it is also beneficial to accelerate reaction.
Different catalyst is effectively selected in different phase by above-mentioned, and then the present embodiment is provided
The yield of synthetic method reach 98% or more, and then solve present in the asymmetric hydrogenation synthetic method of existing imines
The problem of low yield.In addition, it is necessary to illustrate, the reaction of composition principle provided by the present embodiment is existing imines
The common reaction of asymmetric hydrogenation synthetic method, the present embodiment emphasis improved place are the selection and temperature of catalyst
Control, to achieve the purpose that high yield.
The above described is only a preferred embodiment of the present invention, be not that the invention has other forms of limitations,
Any person skilled in the art is changed or is modified as equivalent variations possibly also with the technology contents of the disclosure above
Equivalent embodiment is applied to other fields, but without departing from the technical solutions of the present invention, technology according to the present invention is real
Matter any simple modification, equivalent variations and remodeling to the above embodiments, still fall within the protection model of technical solution of the present invention
It encloses.
Claims (4)
1. a kind of synthetic method of S-metolachlor, which comprises the following steps:
A, it is analytically pure toluene solvant that purity is added first into reaction kettle, then, addition and toluene solvant into reaction kettle
The methoxy acetone of equal volume amounts and and double of volume 2,6- Methylethyl aniline and a small amount of catalyst, carry out sub-
Amine synthetic reaction, raw material finish, and open stirring, are warming up to 88 DEG C, control and keep reacting liquid temperature at 88 DEG C, the time of reaction
For 10h, wherein the catalyst is p-methyl benzenesulfonic acid, and the volume ratio of the p-methyl benzenesulfonic acid and toluene solvant is 1:15；
B, vacuum decompression distillation after reaction, is carried out, excess of solvent is boiled off, vacuum concentration organic layer is final that oily produces
Object-imines；
C, the imines for obtaining b step is added in autoclave, and catalyst 1-S- diphenylphosphine -2-R- two (3,5- bis- is added
Aminomethyl phenyl) phosphine ferrocene-iridium and iridium catalyst metal complex mixture, charging finishes, and autoclave is tightened and is then used
It is replaced in turn each 2 times, after replacement completion with nitrogen and hydrogen,
Stirring is opened, reaction is reacted 4.5 hours under 50 DEG C, the reaction condition of 7.5MPa, obtains amidogen ether；
D, the amidogen ether for obtaining step c is added in stirred autoclave, while toluene solvant and water effect solvent, sodium carbonate is added
As alkali, then high-speed stirred is slowly added dropwise material chloracetyl chloride, 25 DEG C of temperature or so, continues to stir 0.5h standing after dripping off
Liquid separation arrives S-metolachlor product after organic phase concentration.
2. a kind of synthetic method of S-metolachlor according to claim 1, which is characterized in that in the step c, institute
State two (3,5- 3,5-dimethylphenyl) phosphine ferrocene of catalyst 1-S- diphenylphosphine -2-R--iridium and iridium catalyst metal complex
Volume ratio is 1~2:1~2.
3. a kind of synthetic method of S-metolachlor according to claim 2, which is characterized in that in the step c, institute
State two (3,5- 3,5-dimethylphenyl) phosphine ferrocene of catalyst 1-S- diphenylphosphine -2-R--iridium and iridium catalyst metal complex
The additive amount of mixture is between 1st/1st/20th to 35 of imines quality.
4. a kind of synthetic method of S-metolachlor according to claim 3, which is characterized in that in the Step d, first
Benzene solvent and water are added according to the ratio that volume ratio is 1:1.
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| CN109988080A (en) * | 2019-04-19 | 2019-07-09 | 武汉理工大学 | A method of using macropore strong acid cation exchanger resin as catalyst preparation imines |
| CN112209846A (en) * | 2020-11-02 | 2021-01-12 | 山东滨农科技有限公司 | Preparation method of s-metolachlor technical |
| CN112724028A (en) * | 2020-12-28 | 2021-04-30 | 山东滨农科技有限公司 | Interlocking control hydrogenation reaction method for agricultural herbicide technical production |
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