CN106366020B - A kind of method of synthesis of chiral fenoxanil - Google Patents
A kind of method of synthesis of chiral fenoxanil Download PDFInfo
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- CN106366020B CN106366020B CN201610781157.1A CN201610781157A CN106366020B CN 106366020 B CN106366020 B CN 106366020B CN 201610781157 A CN201610781157 A CN 201610781157A CN 106366020 B CN106366020 B CN 106366020B
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/26—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of esters of sulfonic acids
- C07C303/28—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of esters of sulfonic acids by reaction of hydroxy compounds with sulfonic acids or derivatives thereof
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- C07—ORGANIC CHEMISTRY
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- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/31—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by introduction of functional groups containing oxygen only in singly bound form
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- C07B2200/07—Optical isomers
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Abstract
The present invention relates to a kind of methods of synthesis of chiral fenoxanil; it is characterized in that chiral ethyl lactate passes through and obtains sulphonic acid ester with sulfonylation; sulphonic acid ester and 2; the reaction of 4- chlorophenesic acid generates 2- (2; 4- dichlorophenoxy) ethyl propionate; 2- (2; 4- dichlorophenoxy) ethyl propionate and 2- amino -2; 3- nitrile dimethyl carries out urethane exchange reaction and generates corresponding chiral fenoxanil; wherein molar ratio is 2- (2; 4- dichlorophenoxy) ethyl propionate: 2- amino -2,3- nitrile dimethyl=1:1, reaction temperature are 60-85 DEG C.This method synthetic route is simple, it is not required to by hydrolysis, chlorination reaction, waste water, the exhaust gas of generation are few, with very high environmental benefit, greatly reduce production cost, mild condition is of great significance to the light property for further probing into fenoxanil by selecting the ethyl lactate of various configuration that can have the fenoxanil of optics chirality with controlled syntheses.
Description
Technical field
The present invention relates to agricultural chemical compound synthesis technical fields, and in particular to a kind of method of synthesis of chiral fenoxanil.
Background technique
Fenoxanil also known as zarilamid, belong to benzene oxanamide class fungicide, and the mechanism of action is that black bio synthesis inhibits
Agent mainly inhibits the activity of pillar spore ketone dehydrogenase, so that Pyricularia oryzae melanin be inhibited to be formed.With good absorbability
With brilliant wholesomeness, also there is good effect to the blade being newly unfolded after application.
Currently, we are deep not enough to the optical Quality Research of fenoxanil, therefore controlled syntheses have chiral rice
Pest amide facilitates the further research to fenoxanil optical property.
The present invention is to provide one kind using (S)-ethyl lactate as Material synthesis (R)-N- (1- itrile group -1,2- dimethyl propylene
Base) -2- (2,4- dichlorophenoxy) propionamide, using (R)-ethyl lactate as Material synthesis (S)-N- (1- itrile group -1,2- dimethyl
Propyl) -2- (2,4 dichloro benzene oxygroup) propionamide method.
Chemical name: N- (1- itrile group -1,2- dimethyl propyl) -2- (2,4 dichloro benzene oxygroup) propionamide
Molecular formula: C15H18Cl2N2O2
Relative molecular weight 329
Structural formula:
,
。
Wo Fugangbuke in 1988, which are mentioned in the patent in the synthetic method of arylcarboxylic acid derivative, to react by 5 steps
Can just obtain product, at the same starting material be not it is naturally occurring, need through reaction preparation synthesis.It will be through in synthesis process
Hydrolysis, chlorinating step are crossed, waste water, the exhaust gas of generation are more, cause reaction cost higher, pollute more serious.
Summary of the invention
The purpose of the present invention is to provide a kind of methods of synthesis of chiral fenoxanil, and this method synthetic route is simple, no
Need to be by hydrolysis, chlorination reaction, waste water, the exhaust gas of generation are few, have very high environmental benefit, greatly reduce and be produced into
This, mild condition, by select various configuration ethyl lactate can with controlled syntheses have optics chirality fenoxanil, into
The light property that one step probes into fenoxanil is of great significance.
Specific step is as follows for a kind of method of synthesis of chiral fenoxanil of the application:
A chirality ethyl lactate, which is passed through, obtains sulphonic acid ester with sulfonylation,
；
B sulphonic acid ester and 2, the reaction of 4- chlorophenesic acid generate 2- (2,4- dichlorophenoxy) ethyl propionate,
；
It is raw that c 2- (2,4 dichloro benzene oxygroup) ethyl propionate and 2- amino -2,3- nitrile dimethyl carry out urethane exchange reaction
At corresponding chiral fenoxanil, wherein molar ratio is 2- (2,4- dichlorophenoxy) ethyl propionate: 2- amino -2,3- dimethyl
Butyronitrile=1:1, reaction temperature are 60-85 DEG C,
。
Further, chiral ethyl lactate described above is (S)-ethyl lactate or (R)-ethyl lactate, respectively for conjunction
At (R)-N- (1- itrile group -1,2- dimethyl propyl) -2- (2,4 dichloro benzene oxygroup) propionamide and (S)-N- (1- itrile group -1,2-
Dimethyl propyl) -2- (2,4- dichlorophenoxy) propionamide, structural formula is as follows:
,
。
Further, to be chiral ethyl lactate react above-described sulfonylation with sulfonylation agent, and solvent is
Toluene, wherein the molar ratio of chiral ethyl lactate and sulfonylation agent is 1:1.1~1.5, sulfonylation temperature is 15~30
℃。
Further, above-described sulfonylation agent is or mixtures thereof paratoluensulfonyl chloride or mesyl chloride.
Further, it because sulfonylation can generate HCl, also needs to add after sulfonylation and ties up acid
Agent, wherein the molar ratio of chiral ethyl lactate and acid binding agent is 1:1.2~2.
Further, above-described acid binding agent is at least one of triethylamine, potassium carbonate, sodium hydroxide, pyridine.
Further, sulphonic acid ester and 2 in above step b, the molar ratio of 4- chlorophenesic acid are 1:0.1-1.
Further, above step b will be carried out under alkaline condition, and solvent is toluene, and the molar ratio of sulphonic acid ester and alkali is
1:1.1~2, reaction temperature are 90~120 DEG C.
Further, above-described alkali is at least one of sodium hydroxide, sodium carbonate, potassium carbonate, triethylamine.
Further, reaction dissolvent is ethyl alcohol in above step c.
The present processes synthetic route is simple, it is only necessary to which 3 steps, first two steps reaction dissolvent are toluene, it can be achieved that the first step
It does not discharge and directly carries out second step reaction；First step sulfonylation can generate HCl, therefore select suitable acid binding agent, tie up
Sour agent can be at least one of triethylamine, potassium carbonate, sodium hydroxide, pyridine；Third step reaction selects ethyl alcohol as solvent,
It is generated in reaction process without other by-products, post-processing can be crystallized directly with water composition mixed solvent, be more energy-saving and environmentally friendly.
Raw material (S)-ethyl lactate is naturally occurring simultaneously, is easily obtained, has in synthesis cost and have great advantage；Synthesize road
Sulphonic acid ester directly generates corresponding ester with the reaction of 2,4- chlorophenesic acid in line, then passes through 1 step with 2- amino -2,3- nitrile dimethyl
Urethane exchange reaction can obtain product, be not required to by hydrolysis, chlorination reaction, and waste water, the exhaust gas of generation are few, have very high ring
Protect benefit；Mild condition, various configuration fenoxanil drug effect is different, if the fenoxanil of the configuration of controlled syntheses good drug efficacy,
Optics is higher, more has advantage, by selecting the ethyl lactate of various configuration that can have the rice blast of optics chirality with controlled syntheses
Amide is of great significance to the light property for further probing into fenoxanil.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, present invention following specific embodiments
It is illustrated, but the present invention is by no means limited to these examples.
By taking the synthesis of (R)-N- (1- itrile group -1,2- dimethyl propyl) -2- (2,4 dichloro benzene oxygroup) propionamide as an example.
Embodiment 1:
(S) preparation (compound I) of-p-methyl benzenesulfonic acid ethyl lactate:
(S)-ethyl lactate (optics 98%) 12g (0.1mol), paratoluensulfonyl chloride 19g (0.1mol) are thrown into four-hole bottle,
Toluene 60g, stirs 12h at room temperature, and triethylamine 15g (0.15mol) is added into system, washes twice after being stirred to react 2h
It is directly used in and reacts in next step.
(R) preparation (compound II) of 2- (2,4 dichloro benzene oxygroup) ethyl propionate:
It is added 2,4- chlorophenesic acid 16.3g (0.1mol) into four-hole bottle, 70g toluene, sodium hydroxide 4.8g (1.2mol),
80 DEG C step gained compound I (0.95mol) is added into system, and heat up 110 DEG C of back flow reaction 2h, washes twice, organic phase
(R) -2- (2,4- dichlorophenoxy) ethyl propionate of normalizing content 95%, optics 97% are obtained after negative pressure abjection toluene.
(R) preparation of-N- (1- itrile group -1,2- dimethyl propyl) -2- (2,4 dichloro benzene oxygroup) propionamide:
Compound II28g (0.1mol) is added into four-hole bottle, ethyl alcohol 100g, 2- amino -2,3- nitrile dimethyl 15g
(0.1mol) is warming up to back flow reaction 2h.The water of 60-70 DEG C of dropwise addition 100g of post-processing, slow cooling is to 20 DEG C hereinafter, filtering
To white solid (R)-fenoxanil, content 96.8%, optics 95.5%, total recovery 69.5%.
Embodiment 2:
(S) preparation (compound I) of-p-methyl benzenesulfonic acid ethyl lactate:
(S)-ethyl lactate (optics 98%) 12g (0.1mol), paratoluensulfonyl chloride 19g (0.1mol) are thrown into four-hole bottle,
Toluene 60g, stirs 12h at room temperature, and pyridine 11.9g (0.15mol) is added into system, washes twice after being stirred to react 2h
It is directly used in and reacts in next step.
(R) preparation (compound II) of 2- (2,4 dichloro benzene oxygroup) ethyl propionate:
It is added 2,4- chlorophenesic acid 16.3g (0.1mol) into four-hole bottle, 70g toluene, potassium carbonate 16.8g (1.2mol),
80 DEG C step gained compound I (0.95mol) is added into system, is warming up to 110 DEG C of back flow reaction 2h, and washing is twice, organic
(R) -2- (2,4- dichlorophenoxy) ethyl propionate of normalizing content 96%, optics 96% are obtained after phase negative pressure abjection toluene.
(R) preparation of-N- (1- itrile group -1,2- dimethyl propyl) -2- (2,4 dichloro benzene oxygroup) propionamide:
Compound II28g (0.1mol) is added into four-hole bottle, ethyl alcohol 100g, 2- amino -2,3- nitrile dimethyl 15g
(0.1mol) is warming up to back flow reaction 2h.The water of 60-70 DEG C of dropwise addition 100g of post-processing, slow cooling is to 20 DEG C hereinafter, filtering
To white solid (R)-fenoxanil, content 97%, optics 96%, total recovery 70.5%.
Embodiment 3:
(S) preparation (compound I) of-methanesulfonic acid ethyl lactate:
(S)-ethyl lactate (optics 98%) 12g (0.1mol), mesyl chloride 11.5g (0.1mol), first are thrown into four-hole bottle
Benzene 60g, stirs 8h at room temperature, and triethylamine 15g (0.15mol) is added into system, is stirred to react after 2h that wash twice can be straight
It connects for reacting in next step.
(R) preparation (compound II) of -2- (2,4 dichloro benzene oxygroup) ethyl propionate:
It is added 2,4- chlorophenesic acid 16.3g (0.1mol) into four-hole bottle, 70g toluene, potassium carbonate 16.8g (1.2mol),
Compound I (0.95mol), is warming up to 110 DEG C of back flow reaction 2h, and washing twice, is returned after organic phase negative pressure abjection toluene
(R) -2- (2,4- dichlorophenoxy) ethyl propionate of one content 95%, optics 96.5%.
(R) preparation of-N- (1- itrile group -1,2- dimethyl propyl) -2- (2,4 dichloro benzene oxygroup) propionamide:
Compound II28g (0.1mol) is added into four-hole bottle, ethyl alcohol 100g, 2- amino -2,3- nitrile dimethyl 15g
(0.1mol) is warming up to 65 DEG C of reaction 2h.The water of 60-70 DEG C of dropwise addition 100g of post-processing, slow cooling is to 20 DEG C hereinafter, filtering
To white solid (R)-fenoxanil, content 96.6%, optics 97%, total recovery 70.4%.
Embodiment 4:
(R) preparation (compound I) of-methanesulfonic acid ethyl lactate:
Throw (R)-ethyl lactate (optics 98%) 0.1mol, mesyl chloride 0.15mol, toluene 60g into four-hole bottle, 30 DEG C
Triethylamine 0.2mol is added into system by lower stirring 8h, and being stirred to react after 2h to wash can be directly used for next step twice and react.
(S) preparation (compound II) of -2- (2,4 dichloro benzene oxygroup) ethyl propionate:
It is added 2,4- chlorophenesic acid 0.1mol, 70g toluene into four-hole bottle, potassium carbonate 0.2mol, compound I 0.1mol,
120 DEG C of back flow reaction 2h are warming up to, washing twice, obtains (S) -2- of normalizing content 95% after organic phase negative pressure abjection toluene
(2,4- dichlorophenoxy) ethyl propionate, optics 96.5%.
(S) preparation of-N- (1- itrile group -1,2- dimethyl propyl) -2- (2,4 dichloro benzene oxygroup) propionamide:
Compound II 0.1mol, ethyl alcohol 100g, 2- amino -2,3- nitrile dimethyl 0.1mol are added into four-hole bottle, rises
Temperature is to 70 DEG C of reaction 2h.The water of 60-70 DEG C of dropwise addition 100g of post-processing, slow cooling obtain white solid hereinafter, filtering to 20 DEG C
(S)-fenoxanil, content 96.3%, optics 96.1%, total recovery 72.1%.
Embodiment 5:
(R) preparation (compound I) of-methanesulfonic acid ethyl lactate:
Throw (R)-ethyl lactate (optics 98%) 0.1mol, mesyl chloride 0.12mol, toluene 60g into four-hole bottle, 15 DEG C
Triethylamine 0.15mol is added into system by lower stirring 8h, and be stirred to react after 2h to wash can be directly used in next step instead twice
It answers.
(S) preparation (compound II) of -2- (2,4 dichloro benzene oxygroup) ethyl propionate:
2,4- chlorophenesic acid 0.1mol, 70g toluene, potassium carbonate 0.15mol, compound I are added into four-hole bottle
0.5mol, is warming up to 120 DEG C of back flow reaction 2h, and washing twice, obtains normalizing content 96% after organic phase negative pressure abjection toluene
(S) -2- (2,4- dichlorophenoxy) ethyl propionate, optics 96.5%.
(S) preparation of-N- (1- itrile group -1,2- dimethyl propyl) -2- (2,4 dichloro benzene oxygroup) propionamide:
Compound II 0.1mol, ethyl alcohol 100g, 2- amino -2,3- nitrile dimethyl 0.1mol are added into four-hole bottle, rises
Temperature is to 80 DEG C of reaction 2h.The water of 60-85 DEG C of dropwise addition 100g of post-processing, slow cooling obtain white solid hereinafter, filtering to 20 DEG C
(S)-fenoxanil, content 97.1%, optics 97.5%, total recovery 72.8%.
(the R)-fenoxanil or (S)-fenoxanil synthesized in above embodiments, 95% or more content, purity is higher, light
95% or more is learned, optics degree is higher, there is the fenoxanil of optics chirality to be of great significance controlled syntheses.
Claims (3)
1. a kind of method of synthesis of chiral fenoxanil, it is characterised in that synthetic method are as follows:
A chirality ethyl lactate, which is passed through, obtains sulphonic acid ester with sulfonylation；
B sulphonic acid ester is reacted with 2,4 dichloro phenol generates 2- (2,4 dichloro benzene oxygroup) ethyl propionate；
C 2- (2,4 dichloro benzene oxygroup) ethyl propionate and 2- amino -2,3- nitrile dimethyl carry out the generation pair of urethane exchange reaction
Chiral fenoxanil is answered, wherein molar ratio is 2- (2,4- dichlorophenoxy) ethyl propionate: 2- amino -2,3- nitrile dimethyl
=1:1, reaction temperature are 60-85 DEG C；
The above technology path and each component configuration are as follows:
The chiral ethyl lactate be (S)-ethyl lactate, synthesis (R)-N- (1- itrile group -1,2- dimethyl propyl) -2- (2,
4- dichlorophenoxy) propionamide, structural formula is as follows:
(R)-N- (1- itrile group -1,2- dimethyl propyl) -2- (2,4- dichlorophenoxy) propionamide
Step a, reaction dissolvent is toluene in step b, and step c reaction dissolvent is ethyl alcohol, and the sulfonylation agent is to toluene
Sulfonic acid chloride；
Sulfonylation described above is that chiral ethyl lactate is reacted with sulfonylation agent, wherein chiral ethyl lactate and sulfonylation
The molar ratio of reagent is 1:1.1~1.5, and sulfonylation temperature is 15~30 DEG C；
It also needs to add acid binding agent after sulfonylation, wherein the molar ratio of chiral ethyl lactate and acid binding agent is 1:1.2
~2；
The molar ratio of sulphonic acid ester and 2 in step b described above, 4- chlorophenesic acid is 1:0.1-1, and step b will be under alkaline condition
It carries out, the molar ratio of sulphonic acid ester and alkali is 1:1.1~2, and reaction temperature is 90~120 DEG C.
2. a kind of method of synthesis of chiral fenoxanil as described in claim 1, which is characterized in that the acid binding agent is three
At least one of ethamine, potassium carbonate, sodium hydroxide, pyridine.
3. a kind of method of synthesis of chiral fenoxanil as described in claim 1, which is characterized in that the alkali is hydroxide
At least one of sodium, sodium carbonate, potassium carbonate, triethylamine.
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| GB1586462A (en) * | 1976-08-02 | 1981-03-18 | Shell Int Research | Phenonyalkanoic acids and derivatives thereof useful as herbicides |
| US5942640A (en) * | 1998-04-20 | 1999-08-24 | American Cyanamid Company | Process for the manufacture of N-(1-cyanoalkyl)-2-phenoxypropionamide derivatives |
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