CN105601529A - Pretilachlor synthesis method - Google Patents
Pretilachlor synthesis method Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/02—Preparation of carboxylic acid amides from carboxylic acids or from esters, anhydrides, or halides thereof by reaction with ammonia or amines
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- 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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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/48—Preparation of compounds having groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
- C07C45/511—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition involving transformation of singly bound oxygen functional groups to >C = O groups
- C07C45/513—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition involving transformation of singly bound oxygen functional groups to >C = O groups the singly bound functional group being an etherified hydroxyl group
Abstract
The invention discloses a pretilachlor synthesis method. The pretilachlor synthesis method comprises steps as follows: sodium propanolate is dissolved in an organic solvent I, 2-chloroacetaldehyde dimethyl acetal is added dropwise, and heat is preserved until the reaction is performed completely; propoxy acetaldehyde dimethyl acetal and tetrahydrofuran are mixed, aqueous acid is added, and heat is preserved until the reaction is performed completely; 3-propoxy propionaldehyde, 2,6-diethyl aniline and an organic solvent II are mixed, a catalyst is added, hydrogen is introduced until certain pressure is obtained, and heat is preserved until the reaction is performed completely; amidogen ether, a sodium hydroxide solution and methylbenzene are mixed, chloroacetyl chloride is added dropwise at certain temperature, heat is preserved until the reaction is performed completely, and pretilachlor is prepared. With the adoption of the method, high-quality pretilachlor can be obtained.
Description
Technical field
The invention belongs to chemical field, is particularly a kind of synthetic method of the third careless amine.
Background technology
The third careless amine (English name: Pretilachlor) is a kind of efficient, low toxicity, selective bud phase herbicide, belongs to transportingType herbicide, global marketing at present exceedes 200,000,000 U.S. dollars, and wherein 80% market supply is from Chinese Enterprise. Its structure is formula oneShown in:
The third careless amine production technology that Present Domestic is conventional is: first the hydroxyl in ethylene glycol ether (1) is transformed into easily fromGo base (LeavingGroup=LG) to generate intermediate (2). Then, intermediate (2) and 2, the reaction of 6-diethylaniline obtains listAlkylation intermediate (3). Finally, intermediate (3) obtains the third careless amine (4) with chloracetyl chloride generation acylation reaction.
Reagent＝SOCl2,MeSO2Cl,4-CH3C6H4SO2Cl,etc；
LG(LeavingGroup)＝Cl,MeSO3,4-CH3C6H4SO3,etc.
There is following shortcoming in this technique:
In the time that the hydroxyl in ethylene glycol ether (1) is transformed into easy leaving group by the first step, need to use sulfonic acid chloride reaction reagent(Reagent), this class acid reagent is large to equipment corrosion, some sulfonic acid chloride reaction reagent price, some accessory substance of leaving awayDifficult recovery, causes waste and pollutes.
While carrying out above-mentioned second step alkylated reaction, have unavoidably dialkyl accessory substance, increased the pollution of environment andTo the consumption of raw material, and, need rectifying to isolate monoalkylation intermediate (3).
Separately have bibliographical information, by excessive ethylene glycol ether and 2,6-diethylaniline in homemade platinum catalyst catalysisUnder, be heated to 200 DEG C, under the existence of hydrogen, after completion of the reaction, recovered under reduced pressure ethylene glycol ether, synthetic key intermediateMonoalkylation intermediate (3). Finally, intermediate (3) obtains the third careless amine (4) with chloracetyl chloride generation acylation reaction.(US4168965)
The method has been avoided the use of sulfonic acid chloride reaction reagent, but need to use expensive platinum catalyst, and existence is urgedAgent can not repeat to apply mechanically and reclaim the problems such as difficult, especially need under the high temperature of 200 DEG C, lead to hydrogen reaction, exists safety hiddenSuffer from.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of synthetic method of the third careless amine, and the method has successfully overcome at presentThe defect that the third careless amine production technology exists, adopts raw material inexpensive, that be easy to get, with easy, gentle condition, and the synthetic height of high yieldThe third careless amine of quality (, purity >=95%).
In order to solve the problems of the technologies described above, the invention provides a kind of synthetic method of the third careless amine, synthesize as follows successivelyStep:
1), normal propyl alcohol sodium is dissolved in organic solvent I, add (dropping) 2-chloroacetaldehyde contracting as raw material in 0～150 DEG CDimethanol, in 0～150 DEG C to react completely (reaction time is 1～24 hour), described normal propyl alcohol sodium and the 2-chlorine as raw materialThe mol ratio of dimethylacetal is 2:1～1:10;
First the product air-distillation of gained is removed to organic solvent I, then decompression distillation, obtains propoxyl group acetaldehyde contracting twoMethyl alcohol;
2), propoxyl group dimethylacetal and oxolane are mixed, at-10 DEG C～50 DEG C, add aqueous acid straightTo pH be 0～3, insulation to react completely (reaction time is 1～24 hour),
The product of gained is through dichloromethane extraction, and de-carrene, obtains 3-propoxyl group propionic aldehyde;
Generally speaking, the amount ratio of described propoxyl group dimethylacetal and oxolane is 1g/1～5ml;
3), in autoclave, by 3-propoxyl group propionic aldehyde, 2,6-diethylaniline mixes with organic solvent II, adds catalysisAgent, passing into hydrogen to pressure is 1～10MPa, in 20～150 DEG C of insulations to react completely (reaction time is 1～24 hour); InstituteStating catalyst is palladium carbon; The mol ratio of 3-propoxyl group propionic aldehyde and 2,6-diethylaniline is 1～2:1 (preferably 1.1～1.45:1),Palladium in described palladium carbon is 0.1%～10% (preferably 0.5%～1%) of the mole of 2,6-diethylaniline;
By the product cooling release (to normal temperature and pressure) of gained, to filter, gained filtrate removes organic solvent II, obtains amineEther;
4), amidogen ether, sodium hydroxide solution and toluene are mixed, at the temperature of-10～20 DEG C (preferably 0～5 DEG C), add(in the mode dripping) chloracetyl chloride, then in 20～100 DEG C (preferably 30～80 DEG C, more preferably 40～50 DEG C) insulation to reaction(reaction time is 1～24 hour) completely, the mol ratio of described amidogen ether and chloracetyl chloride is 1:1～2 (preferably 1:1.1～1.5),Sodium hydroxide solution is 1～2 quality times of chloracetyl chloride;
Generally speaking, the amount ratio of toluene and chloracetyl chloride is 3～10ml/g;
The product separatory of gained, decompression distillation after the organic layer washing of separatory gained, collect 100～105 DEG C/1mmHg cut, obtains the third careless amine.
Improvement as the synthetic method of the third careless amine of the present invention:
When described step 1) in organic solvent I while being toluene, cyclohexane, normal propyl alcohol (preferably normal propyl alcohol), described positive thirdSodium alkoxide is 1:1～2 with the mol ratio of the 2-chloroacetaldehyde dimethyl acetal as raw material; Generally speaking, organic solvent I and normal propyl alcohol sodiumAmount ratio be 3～10ml/g;
When described step 1) in organic solvent I while being 2-chloroacetaldehyde dimethyl acetal, described normal propyl alcohol sodium is with all (,Comprise as raw material with as organic solvent I) the mol ratio of 2-chloroacetaldehyde dimethyl acetal be 1:3～10 (preferably 1:4～6).
Further improvement as the synthetic method of the third careless amine of the present invention: described step 2) in, acid in aqueous acidConcentration be 1～10mol/L; Described acid is hydrochloric acid, sulfuric acid, phosphonic acids, acetic acid, p-methyl benzenesulfonic acid, methanesulfonic acid or trifluoroacetic acid.
Further improvement as the synthetic method of the third careless amine of the present invention: described step 3) in organic solvent II be firstAlcohol, ethanol, toluene, benzene, DMF (preferably toluene).
Further improvement as the synthetic method of the third careless amine of the present invention: described step 3) in palladium carbon be 5% palladium carbonOr 10% palladium carbon (, in palladium carbon, the mass content of active ingredient palladium is 5% or 10%).
Further improvement as the synthetic method of the third careless amine of the present invention: described step 4) hydrogen-oxygen in sodium hydroxide solutionThe mass concentration of changing sodium is 10～30%.
The synthetic route of the third careless amine provided by the invention is as follows:
In the present invention,
1, step 1) " reacting completely " refer to that detecting 2-chloroacetaldehyde dimethyl acetal through GC method is less than 1%;
2, step 2) " reacting completely " refer to that detecting propoxyl group dimethylacetal through GC method is less than 1%;
3, step 3) " reacting completely " refer to that detecting 2,6-diethylaniline through GC method is less than 1%;
4, step 4) " reacting completely " refer to through GC method detect amidogen ether be less than 1%.
Preferred concrete operation step is as follows:
Step 1): be, under the condition of 0～150 DEG C, in normal propyl alcohol sodium, to drip 2-chloroacetaldehyde dimethyl acetal in temperature, dripAfter, in 0～150 DEG C of reaction 6 hours, normal pressure steamed solvent (for example normal propyl alcohol); Then, water pump decompression distillation obtains the third oxygenEthylhexanal dimethyl acetal.
Step 1 of the present invention) in, while adding solvent, considering raw materials used is normal propyl alcohol sodium, therefore, solvent is selectedThe material not reacting with it, this material comprises: toluene, cyclohexane, normal propyl alcohol etc., wherein with normal propyl alcohol the best; Also optionalSelect taking another raw material 2-chloroacetaldehyde dimethyl acetal as solvent.
Step 1 of the present invention) in, if select non-raw material solvent, normal propyl alcohol sodium is suitably excessive to be conducive to reaction and to carry outCompletely, rate of charge, it is 1:1～2:1 that normal propyl alcohol sodium/2-chloroacetaldehyde dimethyl acetal can be selected interval, wherein with rate of charge 1.1:1～1.2:1 is best. Be solvent if select raw material 2-chloroacetaldehyde dimethyl acetal, 2-chloroacetaldehyde dimethyl acetal inventory is with canGuarantee that reaction stirring is as the criterion smoothly, it is 1:3～1:10 that normal propyl alcohol sodium/2-chloroacetaldehyde dimethyl acetal can be selected interval, wherein to throwMaterial is best than 1:4～1:6.
Step 1 of the present invention) in, reaction is preferably carried out in the temperature range of 0～150 DEG C, and especially 20～80 DEG C,Particularly 50～60 DEG C.
Step 1 of the present invention) in, while dripping as the 2-chloroacetaldehyde dimethyl acetal of raw material, time for adding control is 5～60 minutes.
Step 2): propoxyl group dimethylacetal is dissolved in a certain amount of oxolane, at a certain temperature, adds acidThe aqueous solution, then insulation to reacting completely, dichloromethane extraction, desolventizing obtains 3-propoxyl group propionic aldehyde.
Step 2 of the present invention) in, oxolane amount may be selected to be 1～5 times of propoxyl group dimethylacetal, whereinTaking 2～3 times as best.
Step 2 of the present invention) in, acid can be selected inorganic acid, such as: hydrochloric acid, sulfuric acid, phosphonic acids etc., wherein preferred hydrochloric acidAnd sulfuric acid; Acid also can be selected organic acid, such as: acetic acid, p-methyl benzenesulfonic acid, methanesulfonic acid, trifluoroacetic acids etc., wherein preferably to tolueneSulfonic acid.
Step 2 of the present invention) in, reaction is preferably carried out in the temperature range of-10～50 DEG C, and especially 0～30 DEG C,Particularly 0～10 DEG C.
Described step 2) in, the product of gained, through dichloromethane extraction, extracts the organic layer (being positioned at lower floor) of gained,With anhydrous sodium sulfate drying after clear water washing, to filter, filtrate is concentrated, obtains 3-propoxyl group propionic aldehyde.
Step 3): in autoclave, by 3-propoxyl group propionic aldehyde, 2,6-diethylaniline and solvent, add catalyst,Pass into hydrogen to certain pressure, insulation is at a certain temperature to reacting completely, and cooling release, filters, and desolventizing obtains amidogen ether.
In step 3) in add appropriate acid and accelerate catalytic reaction, described acid is for example acetic acid, described acetic acid is 3-the third oxygen10%～15% of base propionic aldehyde mole.
Step 3 of the present invention) in, solvent can be selected methyl alcohol, ethanol, toluene, benzene, DMF etc., wherein preferred toluene.
Step 3 of the present invention) in, 3-propoxyl group propionic aldehyde is suitably excessive to be conducive to reaction and to carry out completely, rate of charge, 3-thirdOxygen base propionic aldehyde/2, it is 1:1～2:1 that 6-diethylaniline can be selected interval, wherein taking rate of charge 1.1:1～1.45:1 as best.
Step 3 of the present invention) in, catalyst is selected 5% palladium carbon and 10% palladium carbon the best.
Step 3 of the present invention) in, it is raw material 2,6-diethylaniline mole that catalyst amount can be selected interval0.1%～10%, preferably 0.5%～1%.
Step 3 of the present invention) in, reaction is preferably carried out in the temperature range of 20～150 DEG C, and especially 50～100DEG C, particularly 60～70 DEG C.
Step 3 of the present invention) in, Hydrogen Vapor Pressure is preferably at 1MPa～10MPa, especially 2MPa～5MPa, particularly2MPa～3MPa。
Step 4): amidogen ether, sodium hydroxide solution and toluene are mixed, at a certain temperature, drip chloracetyl chloride, dripBi Hou, insulation is at a certain temperature to reacting completely, and separatory, washes, and decompression distillation is collected 100～105 DEG C/1mmHg and is heated up in a steamerPoint, obtain product.
Step 4 of the present invention) in, chloracetyl chloride is suitably excessive to be conducive to reaction and to carry out completely, rate of charge, amidogen ether/chlorineIt is 1:1～1:2 that chloroacetic chloride can be selected interval, wherein taking rate of charge 1:1.1～1:1.5 as best.
Step 4 of the present invention) in, dropping temperature preferably carries out in the temperature range of-10～20 DEG C, and especially 0～5℃。
Step 4 of the present invention) in, holding temperature is preferably carried out in the temperature range of 20～100 DEG C, especially 30～80 DEG C, particularly 40～50 DEG C.
Step 4 of the present invention) in, while dripping chloracetyl chloride, time for adding control is 10～30 minutes.
The synthetic method of the third careless amine of the present invention, has successfully overcome the defect that current the third careless amine production technology exists, and adoptsInexpensive, to be easy to get raw material, with easy, gentle condition, the third careless amine of the synthetic high-quality of high yield. Institute is in steps without harsh barPart, simple to operate, environmentally friendly, solvent is easy to recovery of applied, is applicable to being applied to industrial production.
Detailed description of the invention
In following case, that does not clearly inform is room temperature, and room temperature generally refers to 10～25 DEG C.
Embodiment 1:
(1) in 500ml there-necked flask, add normal propyl alcohol 160mL and 30g (0.365mol) normal propyl alcohol sodium, stir, just treatAfter sodium propoxide dissolves completely, drip (dropwising for 30 minutes) 65mL (0.571mol) 2-chloroacetaldehyde dimethyl acetal, drip Bi ShengwenTo refluxing, stirring reaction 6h. Cooling, filtration, normal propyl alcohol is reclaimed in the first air-distillation of filtrate, rear water pump decompression distillation, collection 70～80 DEG C of (0.098MPa) cuts, obtain product--propoxyl group dimethylacetal (colourless liquid) 60.6g, productive rate 81.9%, GC inspectionSurvey, content is 95%.
(2) in 1000ml there-necked flask, add 10g propoxyl group dimethylacetal (0.0641mol) and THF40mL,Cryosel is bathed and is cooled to below 0 DEG C, drips the about 25mL of hydrochloric acid solution (thereby regulating pH to be less than 1) of (dropwising for 10 minutes) 5M,After dropwising, stirring at room temperature reaction 2 hours. Then use dichloromethane extraction, clear water washing one time for lower floor's organic layer, separatesOrganic layer, with anhydrous sodium sulfate drying, filters, and filtrate concentrates to obtain 3-propoxyl group propionic aldehyde 6.8g, and GC detects, and content is 90%, foldingHundred yields 88.7%, purifying is not directly used in the next step.
(3) the 3-propoxyl group propionic aldehyde 7.9g (0.0612mol), the toluene that in autoclave, add above-mentioned steps (2) to obtain200mL, 2,6-diethylaniline 6.5g (0.0435mol), acetic acid 0.5g (0.0083mol), 5% palladium carbon 0.5g, nitrogen replacement 3Inferior, stir 30 minutes, hydrogen exchange 3 times, is forced into 2MPa, is heated to 60～70 DEG C of reactions 3 hours, and process keeps pressure2MPa, cooling release, filters, and filtrate concentrates to obtain weak yellow liquid 10.6g, and GC detects, and content is 85.3%, folding hundred yields88.2%, purifying is not directly used in the next step.
(4) in 500ml there-necked flask, add amidogen ether 10.5g (0.0381mol), toluene 20mL that above-mentioned steps obtains,The sodium hydroxide solution 6.4g (0.048mol) of mass concentration 30%, stirs, and cryosel is bathed and is cooled to 0～5 DEG C, slowly drips chloroetheneToluene (10mL) solution of acyl chlorides 4.8g (0.0425mol), after dropwising, is incubated 0～5 DEG C of stirring reaction 30 minutes, thenSlowly be warming up to 40～50 DEG C, insulation reaction 1 hour, controls in thin layer silica gel chromatograph, and amidogen ether reacts completely. Add 20mL water, stirMix 5 minutes, stratification, organic layer (being positioned at upper strata) washes twice with water, and decompression distillation is collected 100～105 DEG C/1mmHg and is heated up in a steamerPoint, obtaining product 11.3g, GC detects, and normalizing content is 96%, folding hundred yields 91.3%.
Embodiment 2:
(1) in 500ml there-necked flask, add toluene 160mL and 30g (0.365mol) normal propyl alcohol sodium, stir, drip(dropwising for 30 minutes) 65mL (0.571mol) 2-chloroacetaldehyde dimethyl acetal, drips complete be warming up to backflow, stirring reaction 6h. ColdBut, filter, toluene is reclaimed in the first air-distillation of filtrate, rear water pump decompression distillation, collects 70～80 DEG C of (0.098MPa) cuts, mustProduct colourless liquid 56.8g, productive rate 76.7%, GC detects, and content is 94.3%.
(2) in 1000ml there-necked flask, add 15g (0.0954mol) propoxyl group dimethylacetal and THF60mL,Cryosel is bathed and is cooled to below 0 DEG C, drips the about 40mL of sulfuric acid solution (thereby regulating pH to be less than 1) of (dropwising for 20 minutes) 5M,After dropwising, stirring at room temperature reaction 2 hours. Then use dichloromethane extraction, clear water washing one time for lower floor's organic layer, separatesOrganic layer, with anhydrous sodium sulfate drying, filters, and filtrate concentrates to obtain 3-propoxyl group propionic aldehyde 10.3g, and GC detects, and content is 90.3%,Roll over hundred yields 89.5%, purifying is not directly used in the next step.
(3) the 3-propoxyl group propionic aldehyde 12.0g (0.0933mol), the toluene 300mL, 2 that in autoclave, add upper step to obtain,6-diethylaniline 9.8g (0.0657mol), acetic acid 0.8g (0.0133mol), 5% palladium carbon 0.8g, nitrogen replacement 3 times, stirs30 minutes, hydrogen exchange 3 times, was forced into 3MPa, was heated to 60～70 DEG C of reactions 2 hours, and process keeps pressure 3MPa, and cooling is unloadedPress, filter, filtrate concentrates to obtain weak yellow liquid 18.5g, and GC detects, and content is 86.1%, folding hundred yields 88.5%, and purifying is not straightConnect for the next step.
(4) in 500ml there-necked flask, the amidogen ether 10.5g (0.0384mol), the toluene 20mL, 30% that add step to obtainSodium hydroxide solution 6.4g (0.048mol), stir, cryosel bathe be cooled to-5～0 DEG C, slowly drip chloracetyl chloride 4.8g(0.0425mol) toluene (10mL) solution, after dropwising, is incubated-5～0 DEG C of stirring reaction 30 minutes, then slowly heats upTo 40～50 DEG C, insulation reaction 1 hour, controls in thin layer silica gel chromatograph, and amidogen ether reacts completely. Add 20mL water, stir 5 minutes,Stratification, organic layer (being positioned at upper strata) washes twice with water, and 100～105 DEG C/1mmHg cut is collected in decompression distillation, obtains productProduct 11.5g, GC detects, and content is 96.3%, folding hundred yields 91.6%.
Embodiment 3:
(1) in 500ml there-necked flask, add 2-chloroacetaldehyde dimethyl acetal 250mL (2.2mol), slowly add (30 pointsClock adds) 30g (0.365mol) normal propyl alcohol sodium, stir, drip finish be warming up to 50～60 DEG C, stirring reaction 6h. Cooling, filtration, filterUnreacted 2-chloroacetaldehyde dimethyl acetal is reclaimed in the first air-distillation of liquid, rear water pump decompression distillation, collect 70～80 DEG C (0.098MPa) cut, obtains product colourless liquid 45g, productive rate 60.8%, and GC detects, and content is 96.0%.
(2) in 1000ml there-necked flask, add 15g (0.0972mol) propoxyl group dimethylacetal and THF60mL,Cryosel is bathed and is cooled to below 0 DEG C, drips the about 40mL of acetic acid solution (being 2～3 thereby regulate pH) of (dropwising for 20 minutes) 5M,After dropwising, stirring at room temperature reaction 2 hours. Then use dichloromethane extraction, clear water washing one time for lower floor's organic layer, separatesOrganic layer, with anhydrous sodium sulfate drying, filters, and filtrate concentrates to obtain 3-propoxyl group propionic aldehyde 9.2g, and GC detects, and content is 91%, foldingHundred yields 80.5%, purifying is not directly used in the next step.
(3) the 3-propoxyl group propionic aldehyde 12.0g (0.094mol), the toluene 300mL, 2 that in autoclave, add upper step to obtain, 6-Diethylaniline 9.8g (0.0657mol), acetic acid 0.8g (0.0133mol), 10% palladium carbon 0.5g, nitrogen replacement 3 times, stirs 30Minute, hydrogen exchange 3 times, is forced into 2MPa, is heated to 50～60 DEG C of reactions 2 hours, and process keeps pressure 2.0MPa, and cooling is unloadedPress, filter, filtrate concentrates to obtain weak yellow liquid 17.8g, and GC detects, and content is 87.0%, folding hundred yields 86.0%, and purifying is not straightConnect for the next step.
(4) in 500ml there-necked flask, the amidogen ether 10.5g (0.0388mol), the toluene 20mL, 30% that add step to obtainSodium hydroxide solution 6.4g (0.048mol), stir, cryosel bathe be cooled to 0～10 DEG C, slowly drip chloracetyl chloride 4.8g(0.0425mol) toluene (10mL) solution, after dropwising, is incubated 0～10 DEG C of stirring reaction 30 minutes, then slowly heats upTo 40～50 DEG C, insulation reaction 1 hour, controls in thin layer silica gel chromatograph, and amidogen ether reacts completely. Add 20mL water, stir 5 minutes,Stratification, organic layer (being positioned at upper strata) washes twice with water, and 100～105 DEG C/1mmHg cut is collected in decompression distillation, obtains productProduct 11.0g, GC detects, and content is 96.0%, folding hundred yields 87.3%.
Finally, it is also to be noted that, what more than enumerate is only several specific embodiments of the present invention. Obviously, thisBrightly be not limited to above embodiment, can also have many distortion. Those of ordinary skill in the art can be from content disclosed by the inventionAll distortion of directly deriving or associating, all should think protection scope of the present invention.
Claims (6)
1. the synthetic method of the third careless amine, is characterized in that carrying out successively following synthesis step:
1), normal propyl alcohol sodium is dissolved in organic solvent I, in 0～150 DEG C of 2-chloroacetaldehyde dimethyl acetal adding as raw material, in 0～150 DEG C to reacting completely, and described normal propyl alcohol sodium is 2:1～1 with the mol ratio of the 2-chloroacetaldehyde dimethyl acetal as raw material:10；
First the product air-distillation of gained is removed to organic solvent I, then decompression distillation, obtains propoxyl group acetaldehyde contracting diformazanAlcohol;
2), propoxyl group dimethylacetal and oxolane are mixed, at-10 DEG C～50 DEG C, add aqueous acid until pHBe 0～3, insulation is to reacting completely;
The product of gained is through dichloromethane extraction, and de-carrene, obtains 3-propoxyl group propionic aldehyde;
3), in autoclave, by 3-propoxyl group propionic aldehyde, 2,6-diethylaniline mixes with organic solvent II, adds catalyst, logicalEntering hydrogen to pressure is 1～10MPa, in 20～150 DEG C of insulations to reacting completely; Described catalyst is palladium carbon; 3-propoxyl group thirdThe mol ratio of aldehyde and 2,6-diethylaniline is 1～2:1, and palladium in described palladium carbon is the mole of 2,6-diethylaniline0.1％～10％；
By the product cooling release of gained, to filter, gained filtrate removes organic solvent II, obtains amidogen ether;
4), amidogen ether, sodium hydroxide solution and toluene are mixed, at the temperature of-10～20 DEG C, add chloracetyl chloride, then in 20～100 DEG C of insulations are to reacting completely, and the mol ratio of described amidogen ether and chloracetyl chloride is 1:1～2, and sodium hydroxide solution is chloracetyl1～2 quality of chlorine doubly;
The product separatory of gained, decompression distillation after the organic layer washing of separatory gained, collects 100～105 DEG C/1mmHg and heats up in a steamerPoint, obtain the third careless amine.
2. the synthetic method of the third careless amine according to claim 1, is characterized in that:
When described step 1) in organic solvent I while being toluene, cyclohexane, normal propyl alcohol, described normal propyl alcohol sodium with as raw materialThe mol ratio of 2-chloroacetaldehyde dimethyl acetal is 1:1～2;
When described step 1) in organic solvent I while being 2-chloroacetaldehyde dimethyl acetal, described normal propyl alcohol sodium and whole 2-chloroetheneThe mol ratio of methylal is 1:3～10.
3. the synthetic method of the third careless amine according to claim 1, is characterized in that:
Described step 2) in, in aqueous acid, the concentration of acid is 1～10mol/L;
Described acid is hydrochloric acid, sulfuric acid, phosphonic acids, acetic acid, p-methyl benzenesulfonic acid, methanesulfonic acid or trifluoroacetic acid.
4. the synthetic method of the third careless amine according to claim 1, is characterized in that:
Described step 3) in organic solvent II be methyl alcohol, ethanol, toluene, benzene, DMF.
5. the synthetic method of the third careless amine according to claim 1, is characterized in that: described step 3) in palladium carbon be 5% palladiumCarbon or 10% palladium carbon.
6. the synthetic method of the third careless amine according to claim 1, is characterized in that: described step 4) hydrogen in sodium hydroxide solutionThe mass concentration of sodium oxide molybdena is 10～30%.
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Cited By (3)
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| CN108271796A (en) * | 2018-03-27 | 2018-07-13 | 安徽圣丰生化有限公司 | A kind of herbicidal composition of penoxsuam and KIH 6127 |
| CN111100019A (en) * | 2020-01-08 | 2020-05-05 | 浙江工业大学 | N, N-di-N-propyl-2-propoxyethylamine and preparation method and application thereof |
| CN114249660A (en) * | 2021-12-10 | 2022-03-29 | 浙江工业大学 | Method for preparing ether-containing arylamine derivative by utilizing N-alkylation reaction of ether-bond-containing alcohol derivative |
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| CN102173998A (en) * | 2011-03-21 | 2011-09-07 | 南通大学 | Method for synthesizing herbicide pretilachlor by one-pot method |
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| CN102229542A (en) * | 2011-05-09 | 2011-11-02 | 南通维立科化工有限公司 | Method for synthesizing pretilachlor |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108271796A (en) * | 2018-03-27 | 2018-07-13 | 安徽圣丰生化有限公司 | A kind of herbicidal composition of penoxsuam and KIH 6127 |
| CN111100019A (en) * | 2020-01-08 | 2020-05-05 | 浙江工业大学 | N, N-di-N-propyl-2-propoxyethylamine and preparation method and application thereof |
| CN111100019B (en) * | 2020-01-08 | 2023-04-07 | 浙江工业大学 | N, N-di-N-propyl-2-propoxyethylamine and preparation method and application thereof |
| CN114249660A (en) * | 2021-12-10 | 2022-03-29 | 浙江工业大学 | Method for preparing ether-containing arylamine derivative by utilizing N-alkylation reaction of ether-bond-containing alcohol derivative |
| CN114249660B (en) * | 2021-12-10 | 2024-04-09 | 浙江工业大学 | Method for preparing ether-containing aromatic amine derivative by utilizing N-alkylation reaction of ether bond-containing alcohol derivative |
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| CN105601529B (en) | 2017-06-06 |
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