CN108373405A - A kind of 2-（4- ethoxyl phenenyls）The preparation method of -2.2- dimethyl ethanols - Google Patents
A kind of 2-（4- ethoxyl phenenyls）The preparation method of -2.2- dimethyl ethanols Download PDFInfo
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Abstract
The invention discloses a kind of preparation method of 2 (4 ethoxyl phenenyl) 2.2 dimethyl ethanols, preparation process is as follows：(1) 1 equimolar acid is taken, the in the mixed solvent that in alcoholic solvent or alcoholic solvent is formed with ether solvent is dissolved in；(2) mixed solvent in step (1) is heated up；Boron hydride and metal salt is added；(3) continue insulation reaction, alcoholic solvent or alcoholic solvent or ether solvent is recovered under reduced pressure；Organic solvent, the reaction of agitation and dropping hydrochloric acid is added, then adds, stands, be layered, extraction；Organic phase is dried using anhydrous sodium sulfate, product is obtained after reduced pressure；The method of the present invention is safe compared with prior art, and technique is more reasonable, easy；Raw material is easy to get.Low with product cost, quality is high, environmentally friendly, more suitable for industrialized production；Overall yield of reaction is with 2 (4 ethoxyl phenenyl) 2.2 dimethyl acetic acids up to 95% or more, and product content is up to 98%.
Description
Technical field
The present invention relates to technical field of insecticide, specially a kind of 2- (4- ethoxyl phenenyls) -2.2- dimethyl ethanols
Preparation method.
Background technology
2- (4- ethoxybenzenes) -2- methylpropanols are the synthesis material of ethofenprox, ethofenprox (common name:Etofenprox,
Trade name:Trebon) also known as trebon, benzyl oxide pyrethroids, Li Laiduo, according to phenin, be by Mitsui east press Chemical Co., Ltd.
The efficient pyrethrin pesticide that (Mitsui Toatsu Chemicals Inc.) has found the beginning of the eighties, has that insecticidal spectrum is wide, kills
Worm activity is high, knock down speed is fast, the lasting period is long, to crop safety the features such as, for prevent Lepidoptera, Semiptera, Diptera and
Isoptera pest, as brown paddy plant hopper, white backed planthopper, rice green leafhopper, bollworm, pink bollworm, black peach aphid, melon aphid, trialeurodes vaporariorum, cabbage caterpillar,
It is Euproctis pseudoconspersa, tea ruler pot, Iragoides fasciata, peach and oriental fruit months, citrus leaf-miner, cigarette beetle, diamondback moth, corn borer, pink rice borer, big
Beans heart-eating worm etc..Currently used pyrethroid, which generally has, tags and stomach poison function, and intramolecular is in addition to C, H, outside O elements,
Often there are nitrogen and halogen element.Ethofenprox has breakthrough in these areas, and intramolecular contains only C, tri- kinds of elements of H, O, to lactation
Animal, fish and shrimp low toxicity, such as:Decis rat acute oral toxicity LD50=128.5mg/kg, and ethofenprox rat is anxious
Property oral toxicity be LD50>107200mg/kg；Permethrin is to carp TLm48=0.005mg/m3, and ethofenprox is to carp
TLm48=5mg/m3, more than all low three orders of magnitude of toxicity.For environmental protection, to there is the organochlorine insecticide of high residue very
Multinational family has stopped producing, and non-harmful new pyrethroid insecticides are because insecticidal activity is high, dosage is few, toxicity is low, not dirty
Environment is contaminated, and causes the attention of people.
2- (4- ethoxyl phenenyls) -2.2- dimethyl ethanols are the key intermediates for synthesizing ethofenprox, and structural formula is as follows：
The preparation of 2- (4- ethoxyl phenenyls) -2.2- methyl ethanols mainly has following several process routes at present, is respectively：
1) go out 2- (4- ethoxyl phenenyls) -2.2- two by Material synthesis of 2- (4- ethoxyl phenenyls) 2.2- dimethyl acetic acids
Methyl ethanol.
2) to go out 2- (4- ethoxyl phenenyls) -2.2- dimethyl ethanols as Material synthesis to Bromoethyl phenyl ether
The synthetic method reported at present finds that route (1) uses lithium aluminium hydride reduction by Literature Consult and experiment route verification
(LiAlH4) it restores, lithium aluminium hydride reduction (LiAlH4) is expensive and cannot be used for industrialized production；Route (2) raw material 2.2- diformazans
Hexadecyl ethylene oxide synthesis is difficult, is not easy to obtain, unfavorable to Product Cost Control.
Invention content
(1) the technical issues of solving
In view of the deficiencies of the prior art, the present invention provides a kind of 2- (4- ethoxyl phenenyls) -2.2- dimethyl ethanols
Preparation method, this method is safe, and technique is more reasonable, easy.Raw material is easy to get.Low with product cost, quality is high, to ring
Border is friendly, more suitable for industrialized production, solves prior art complexity, expensive, the big problem of toxicity.
(2) technical solution
For the purpose for realizing above-mentioned, the present invention provides the following technical solutions：A kind of 2- (4- ethoxyl phenenyls) -2.2- diformazans
The preparation method of base ethyl alcohol, preparation process are as follows：
(1) 1 equimolar acid is taken, the mixed solvent that in the alcoholic solvent of 300-600ml or alcoholic solvent is formed with ether solvent is dissolved in
In；
(2) mixed solvent in step (1) is warming up to 30-85 DEG C；Boron hydride and metal salt is added；
(3) continue insulation reaction 3-8 hours；Alcoholic solvent or alcoholic solvent or ether solvent is recovered under reduced pressure；300-600ml is added
Organic solvent, the pH value of agitation and dropping hydrochloric acid to reaction mass is 3-4, adds 200-500ml water, stand, layering, extraction
It takes；Organic phase is dried using anhydrous sodium sulfate, product is obtained after reduced pressure.
Preferably, the alcoholic solvent in the step (1) is methanol or ethyl alcohol, and ether solvent is selected from tetrahydrofuran, 2- methyl
Tetrahydrofuran, dioxane, ether, isopropyl ether or methyl tertiary butyl ether(MTBE), acid are 2- (4- ethoxyl phenenyls) -2.2- dimethyl second
Acid.
Preferably, reaction temperature is preferably 60-70 DEG C in the step (1).
Preferably, the molar ratio of boron hydride, metal salt and substrate is 1.0-2.0 in the step (2)：0.5-1.0：
1.0。
Preferably, organic solvent is selected from ethyl acetate, dichloromethane, chloroform or dichloroethanes in the step (3),
Toluene.
(3) advantageous effect
Compared with prior art, the present invention is using boron hydride metal salt mixed system as reducing agent, reductase 12-(4- ethoxies
Base phenyl) -2.2- dimethyl acetic acids obtain 2- (4- ethoxyl phenenyls) -2.2- dimethyl ethanols, by can be with after reduced pressure
Obtain the product of 95%-97% yields.
Boron hydride is a kind of effective reducing agent, and common sodium borohydride (potassium) is the carbonyl for restoring aldehyde, ketone and carboxylic acid halides,
Other carboxylic acids, the compounds such as carboxylic acid derivates, nitro cannot be restored.But sodium borohydride (potassium) and some metal salts, it is such as anhydrous
The system of alchlor, anhydrous lithium halide, anhydrous zinc halide or anhydrous calcium chloride etc., can improve its reducing power so that
Also carboxylic acid and carboxylic acid derivates original is at corresponding alcohol.With sodium borohydride (potassium)/zinc halide reductase 12-(4- ethoxyl phenenyls)-2.2-
Dimethyl acetic acid advantage is：1) economy of reducing agent and safety；2) when sodium borohydride (potassium)/zinc halide reduction, first is used
The alcohol such as alcohol or ethyl alcohol make solvent, and solvent is without doing special processing, and recovery is convenient, at low cost, and pollution is small；3) item is reacted
Part is safe to use without particular/special requirement, easy to operate, is easy to industrialization and uses.
The method of the present invention is safe, and technique is more reasonable, easy；Raw material is easy to get.Low with product cost, quality is high,
It is environmentally friendly, more suitable for industrialized production；Overall yield of reaction is reachable with 2- (4- ethoxyl phenenyls) -2.2- dimethyl acetic acids
95% or more, product content is up to 98%.
Specific implementation mode
Below in conjunction with the embodiment of the present invention, technical solution in the embodiment of the present invention is clearly and completely retouched
It states, it is clear that described embodiment is only a part of the embodiment of the present invention, instead of all the embodiments.Based in the present invention
Embodiment, every other embodiment obtained by those of ordinary skill in the art without making creative efforts,
It shall fall within the protection scope of the present invention.
A kind of preparation method of 2- (4- ethoxyl phenenyls) -2.2- dimethyl ethanols, preparation process are as follows：
1 equimolar acid is taken, the in the mixed solvent that in the alcoholic solvent of 300-600ml or alcoholic solvent is formed with ether solvent is dissolved in,
The alcoholic solvent is methanol or ethyl alcohol, and ether solvent is selected from tetrahydrofuran, 2- methyltetrahydrofurans, dioxane, ether, different
Propyl ether or methyl tertiary butyl ether(MTBE)；Its acid is：
It is warming up to 30-85 DEG C；Boron hydride and metal salt, the molar ratio of boron hydride, metal salt and substrate, which is added, is
1.1-2.0：0.55-1.0：1.0；Continue insulation reaction 3-8 hours；Alcoholic solvent or alcoholic solvent is recovered under reduced pressure to form with ether solvent
Mixed solvent；The organic solvent of 300-600ml is added, the pH value of agitation and dropping hydrochloric acid to reaction mass is 3-4, is added
200-500ml water, stands, layering extraction, and the organic solvent is selected from ethyl acetate, dichloromethane, chloroform or dichloro
Ethane, toluene；Anhydrous sodium sulfate dries organic phase, and product is obtained after reduced pressure.
The process route of the present invention is as follows：
Embodiment one
Embodiment 1
1 equimolar acid is taken, the in the mixed solvent that in the alcoholic solvent of 300-600ml or alcoholic solvent is formed with ether solvent is dissolved in,
The alcoholic solvent is methanol or ethyl alcohol, and ether solvent is selected from tetrahydrofuran, 2- methyltetrahydrofurans, dioxane, ether, different
Propyl ether or methyl tertiary butyl ether(MTBE)；The acid is：
It is warming up to 30 DEG C；Boron hydride and metal salt is added, the molar ratio of boron hydride, metal salt and substrate is 1.5：
0.5：1；Continue insulation reaction 3 hours；Alcoholic solvent or the molten mixed solvent with ether solvent composition of alcohol is recovered under reduced pressure；300- is added
The pH value of the organic solvent of 600ml, agitation and dropping hydrochloric acid to reaction mass is 3-4, adds 200-500ml water, described has
Solvent is selected from ethyl acetate, dichloromethane, chloroform or dichloroethanes, toluene；Anhydrous sodium sulfate dries organic phase, decompression
Product is obtained after concentration.
Embodiment 2
1 equimolar acid is taken, the in the mixed solvent that in the alcoholic solvent of 300-600ml or alcoholic solvent is formed with ether solvent is dissolved in,
The alcoholic solvent is methanol or ethyl alcohol, and ether solvent is selected from tetrahydrofuran, 2- methyltetrahydrofurans, dioxane, ether, different
Propyl ether or methyl tertiary butyl ether(MTBE)；The acid is：
It is warming up to 85 DEG C；Boron hydride and metal salt is added, the molar ratio of boron hydride, metal salt and substrate is 2.0：
1.5：1；Continue insulation reaction 8 hours；The mixed solvent of alcoholic solvent or alcoholic solvent and ether solvent composition is recovered under reduced pressure；It is added
The pH value of the organic solvent of 300-600ml, agitation and dropping hydrochloric acid to reaction mass is 3-4, adds 200-500ml water, described
Organic solvent be selected from ethyl acetate, dichloromethane, chloroform or dichloroethanes, toluene；Anhydrous sodium sulfate dries organic phase,
Product is obtained after reduced pressure.
Embodiment 3,
1 equimolar acid is taken, the in the mixed solvent that in the alcoholic solvent of 300-600ml or alcoholic solvent is formed with ether solvent is dissolved in,
The alcoholic solvent is methanol or ethyl alcohol, and ether solvent is selected from tetrahydrofuran, 2- methyltetrahydrofurans, dioxane, ether, different
Propyl ether or methyl tertiary butyl ether(MTBE)；The acid is：
It is warming up to 60-70 DEG C；Boron hydride and metal salt, the molar ratio of boron hydride, metal salt and substrate, which is added, is
2.5：1.2：1；Continue insulation reaction 5-6 hours；The mixed solvent of alcoholic solvent or alcoholic solvent and ether solvent composition is recovered under reduced pressure；
The organic solvent of 300-600ml is added, the pH value of agitation and dropping hydrochloric acid to reaction mass is 3-4, adds 200-500ml water,
The organic solvent is selected from ethyl acetate, dichloromethane, chloroform or dichloroethanes, toluene；Anhydrous sodium sulfate drying has
Machine phase obtains product after reduced pressure.
Embodiment 4
In preparation method described in embodiment 1 or 2 or 3：The boron hydride is potassium borohydride or sodium borohydride, metal
Salt is selected from aluminum trichloride (anhydrous), anhydrous lithium halide, zinc halide or anhydrous calcium chloride.
Embodiment 5
In preparation method described in embodiment 1 or 2 or 3：The reducing agent is potassium borohydride/zinc chloride system, or
Sodium borohydride/zinc chloride system.
Embodiment 6
In preparation method described in embodiment 1 or 2 or 3：The molar ratio of the boron hydride, metal salt and hydrochloric acid is
1.1：0.55:1.0.
Embodiment 7
2- (4- ethoxyl phenenyls) -2.2- dimethyl acetic acids (208.3g, 1mol) are dissolved in 500g ethyl alcohol, anhydrous chlorine is added
Change zinc (75g 0.55mol) and potassium borohydride (59.4g1.1mol), be first warming up to 30-35 DEG C, reacts 2-3 hours, gradually heat up
To back flow reaction, it is complete to track to raw material fundamental reaction with GC, ethyl alcohol is recovered under reduced pressure.Recycling is finished, and room temperature is down to, and dichloroethanes is added
500ml, agitation and dropping 3mol/L hydrochloric acid adjust pH value 3-4, add 200ml water, stratification, and water layer extracts 3 (100ml
+ 50ml+50ml), merge dichloroethanes and dried with anhydrous sodium sulfate, after removed under reduced pressure dichloroethanes, obtains 2- (4- ethoxybenzenes
Base) -2.2- dimethyl ethanol 185.5g, yield 95.5%, content 98.2%.
Embodiment 8
2- (4- ethoxyl phenenyls) -2.2- dimethyl acetic acids 236.3g (1mol) are dissolved in 500g ethyl alcohol, are added anhydrous
Zinc chloride 75g (0.55mol) and potassium borohydride 14.85g (0.275mol) is first warming up to 30-35 DEG C, reacts 1 hour, gradually rises
Temperature is to 60 DEG C of reactions, and every 30 minutes plus a potassium borohydride 27g, totally 4 1.1mol, raw material fundamental reaction was tracked to GC
It is complete, ethyl alcohol is recovered under reduced pressure.Recycling is finished, and room temperature is down to, and dichloroethanes 500ml is added, and agitation and dropping 3mol/L hydrochloric acid adjusts pH value
3-4 adds 200ml water, stratification, and water layer extracts 3 times (100ml+50ml+50ml), merges the anhydrous sulphur of dichloroethanes
Sour sodium is dried, and after removed under reduced pressure dichloroethanes, obtains 2- (4- ethoxyl phenenyls) -2.2- dimethyl ethanol 186.9g, yield
96.2%, content 98.5%.
Embodiment 9
Ethyl alcohol 300g, anhydrous zinc chloride 75g (0.55mol) and potassium borohydride 59.4g (1.1mol) are added in reaction bulb,
It is first warming up to 30-35 DEG C, 2- (4- ethoxyl phenenyls) -2.2- dimethyl acetic acids 236.3g (1mol) are dissolved in 200g methanol,
Be slowly added dropwise 2- (4- ethoxyl phenenyls) -2.2- dimethyl acetic acid ethanol solutions, drop, which finishes, is gradually warming up to 60 DEG C of reactions, with GC with
Track is complete to raw material fundamental reaction, and ethyl alcohol is recovered under reduced pressure.Recycling is finished, and room temperature is down to, and dichloroethanes 500ml, agitation and dropping is added
3mol/L hydrochloric acid adjusts pH value 3-4, adds 200ml water, stratification, and water layer extracts 3 times (100ml+50ml+50ml), closes
And dichloroethanes is dried with anhydrous sodium sulfate, after removed under reduced pressure dichloroethanes, obtains 2- (4- ethoxyl phenenyls) -2.2- dimethyl second
Alcohol 186.1g, yield 95.8%, content 98.4%.
It although an embodiment of the present invention has been shown and described, for the ordinary skill in the art, can be with
Understanding without departing from the principles and spirit of the present invention can carry out these embodiments a variety of variations, modification, replace
And modification, the scope of the present invention is defined by the appended.
Claims (5)
1. a kind of preparation method of 2- (4- ethoxyl phenenyls) -2.2- dimethyl ethanols, it is characterised in that：Preparation process is as follows：
(1) 1 equimolar acid is taken, the in the mixed solvent that in the alcoholic solvent of 300-600ml or alcoholic solvent is formed with ether solvent is dissolved in；
(2) mixed solvent in step (1) is warming up to 30-85 DEG C；Boron hydride and metal salt is added；
(3) continue insulation reaction 3-8 hours；Alcoholic solvent or alcoholic solvent or ether solvent is recovered under reduced pressure；Having for 300-600ml is added
The pH value of solvent, agitation and dropping hydrochloric acid to reaction mass is 3-4, adds 200-500ml water, stands, layering, extracts；It adopts
Organic phase is dried with anhydrous sodium sulfate, product is obtained after reduced pressure.
2. a kind of preparation method of 2- (4- ethoxyl phenenyls) -2.2- dimethyl ethanols according to claim 1, feature
It is：Alcoholic solvent in the step (1) is methanol or ethyl alcohol, and ether solvent is selected from tetrahydrofuran, 2- methyltetrahydrofurans, two
Six ring of oxygen, ether, isopropyl ether or methyl tertiary butyl ether(MTBE), acid are 2- (4- ethoxyl phenenyls) -2.2- dimethyl acetic acids.
3. a kind of preparation method of 2- (4- ethoxyl phenenyls) -2.2- dimethyl ethanols according to claim 1, feature
It is：Reaction temperature is preferably 60-70 DEG C in the step (1).
4. a kind of preparation method of 2- (4- ethoxyl phenenyls) -2.2- dimethyl ethanols according to claim 1, feature
It is：The molar ratio of boron hydride, metal salt and substrate is 1.0-2.0 in the step (2)：0.5-1.0：1.0.
5. a kind of preparation method of 2- (4- ethoxyl phenenyls) -2.2- dimethyl ethanols according to claim 1, feature
It is：Organic solvent is selected from ethyl acetate, dichloromethane, chloroform or dichloroethanes, toluene in the step (3).
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2018
- 2018-02-09 CN CN201810132810.0A patent/CN108373405A/en active Pending
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| JPS58131931A (en) * | 1982-11-19 | 1983-08-06 | Mitsui Toatsu Chem Inc | 2-(4-ethoxyphenyl)-2-methylpropyl alcohol and its preparation |
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| CN101643385A (en) * | 2008-08-08 | 2010-02-10 | 夏恩将 | Method for preparing 3,5-dichlorobenzyl chloride |
| CN103467254A (en) * | 2013-09-13 | 2013-12-25 | 连云港市国盛化工有限公司 | Preparation method of 2-(4-oxethyl phenyl)-2-methyl propanol |
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Application publication date: 20180807 |