CN1821203A - Synthetic method for preparing 2-acyl 4-allcyl phenol - Google Patents
Synthetic method for preparing 2-acyl 4-allcyl phenol Download PDFInfo
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Abstract
The present invention relates to the synthesis process of different kinds of 2-acyl-4-alkyl phenol, which is the important intermediate of metal extractant 5-alkyl-2-hydroxyalkyl benzopheonone oxime. Through a two-step reaction under relatively mild condition, the present invention can obtain the target product in high yield and high selectivity, and the solvent, the reaction produced halohydrocarbon and the catalyst aqua may be reused without exhaust. The synthesis process has industrial production foreground obviously.
Description
Technical field
The invention belongs to chemical material field, relate to a kind of synthetic method for preparing metal extraction agent important as precursors 2-acyl group-4-alkylphenol.
Background technology
2-acyl group-4-alkylphenol (I) is metal extraction agent 5-alkyl-2-hydroxyalkyl benzophenone oxime (II) important intermediate, the 5-alkyl that itself and azanol reaction can obtain-2-hydroxyalkyl benzophenone oxime (II).Such ketoxime is used extremely wide in the metal extraction field.As: 2-ethanoyl-4-nonylphenol is that purification of metals such as copper, nickel (are seen: U.S.Pat.No.5,300,689 with the important as precursors of extraction agent; U.S.Pat.No.5,969,185; U.S.Pat.No.5,488,161; WO.95/01957; J.Prakt.Chem.1989,331 (4), 617-630).Its structural formula is as follows:
U.S.Pat.No.5; described in 300,689 and a kind ofly reset the method prepare 2-acyl group-4-alkylphenol with Fries, this method exists yield low; temperature of reaction is higher, and product is difficult for purifying, product purity not high (its purity is generally 80-85%) and produces problems such as " three wastes " more.Have bibliographical information directly to carry out the Friedel-Crafts reaction with acetyl chloride with to alkylphenol in addition, this method exists needs pressurization, temperature of reaction is higher, by product is many, yield is lower, problem (J.Prakt.Chem such as product purification difficulty; EN; 1989,331 (4), 617-630).U.S.Pat.No.5,969,185 described be the acetaldehyde of catalyzer with the aluminum isopropylate with to the reaction of alkylphenol, also can obtain the 4-alkylphenol that 2 alkyloyls or aroyl replace.But its yield is lower than 20%, and reaction needed is carried out under certain pressure simultaneously.
Summary of the invention
The synthetic method that the purpose of this invention is to provide a kind of novel 2-acyl group-4-alkylphenol.Problems such as the total recovery that exists in the prior art is low, equipment requirements is harsh, reaction conditions is violent to overcome, operational path is unstable, and product separation and purification difficulty and product purity are not high.
Advantage of the present invention and novelty have been 1. to avoid using high temperature and comparatively expensive reagent; 2. problems such as complicated operation, severe reaction conditions, product separation and purification difficulty have been overcome; 3. under the condition of gentleness high yield highly selective obtain target product; 4. the product purity height for preparing than other production methods of product purity, patent of the present invention provides method gained 2-acyl group-its purity of 4-alkylphenol generally can reach more than 90%, and uses 2-acyl group-its purity of 4-alkylphenol of traditional method preparation generally to have only 80-85%; 5. the by product hydrochloric ether major part of reaction generation can reclaim, the while catalyzer, also can well recycle as aluminum chloride aqueous solution etc., the colourless aluminum chloride aqueous solution that this reaction the produces purifying that need not further to decolour promptly can be used for preparing polymerize aluminum chloride (being called for short PAC), and PAC is a kind of novel inorganic polymer coagulant, it has replaced iron trichloride, Tai-Ace S 150, alum as a kind of novel water treatment agent, and be used widely (" commentary of polymerize aluminum chloride production method ", the Henan chemical industry, 1994,8)." three wastes " discharging reduces significantly in obvious its production technique.This is that additive method is beyond one's reach.
Method of the present invention comprises following two steps:
1. to the etherification reaction of alkylphenol:
In the presence of the organic solvent neutralization bases, industry was reacted 0.2～24 hour in-20～170 ℃ alkylphenol and etherifying reagent, boil off solvent (its by product and solvent are recyclable to be utilized again) after conventional processing such as extraction, washing, drying, carrying out underpressure distillation again must be to alkyl phenyl ether.Yield is 60～100%.Reaction equation is as follows:
Described R is C
4～C
20Alkyl;
Described R
1Be C
1～C
20Alkyl, allyl group, propargyl, various benzyl;
Described etherifying reagent is for containing C
1～C
20The halohydrocarbon of alkyl, allyl group, propargyl or benzyl, wherein halogen atom can be chlorine, bromine, iodine; Contain C
1～C
20The carbonic ether and the sulfuric ester of alkyl, allyl group, propargyl or benzyl; Contain C
1～C
20The sulphonate of alkyl, allyl group, propargyl or benzyl, and triflate is as p-toluenesulfonic esters; Methanesulfonates etc.;
Described alkali is the oxyhydroxide or the carbonate of basic metal or alkaline-earth metal, perhaps is organic bases, as: compounds such as potassium hydroxide, salt of wormwood, hydrated barta, trialkylamine, pyridines.
In this step along with employed etherifying reagent difference, need to select also to have corresponding variation with respect to feed ratio to alkylphenol, in etherification reaction, etherifying reagent be 1～5: 1 to the mole ratio of alkylphenol, the usage quantity of alkali and the mole ratio of etherifying reagent are 1～4: 1.Temperature of reaction is generally-20 ℃～170 ℃, and the reaction times was generally 0.2～24 hour.
2. to the acylation reaction of alkyl aryl ether:
In organic solvent and in the presence of Louis (Lewis) acid; to alkyl aryl ether and acylating reagent in-20～80 ℃ of reactions after 0.5～12 hour; after conventional processing such as extraction, washing, drying, boil off solvent; its by product and solvent are recyclable to be utilized again; carry out underpressure distillation and get 2-acyl group-4-alkylphenol; yield is 60～98%, and product purity is not less than 90%.Reaction equation is as follows:
Described R is C
4～C
20Alkyl;
Described R
1Be C
1～C
20Alkyl, allyl group, propargyl or various benzyl;
Described R
2Be C
1～C
20Alkyl, aryl or allyl group;
Described acylating reagent is for containing C
1～C
20The carboxylic acid halides of alkyl, allyl group or aryl; Contain C
1～C
20The carboxylic acid anhydride of alkyl, allyl group or aryl or their mixed acid anhydride; Contain C
1～C
20The carboxylic acid of alkyl, allyl group or aryl;
Described Lewis acid is the mixture of aluminum trihalide, three iron halide, boron trihalides, titanium tetrahalide, the inferior tin of halogenation, zinc chloride etc. or above-mentioned Lewis acid.
In this step along with use acylating reagent difference; need to select also to have corresponding variation with respect to feed ratio to alkyl aromatic ether; acylating reagent be 1～3: 1 to the mole ratio of alkyl aromatic ether, Lewis its usage quantity of acid and etherifying reagent mole ratio are 2～6: 1.Temperature of reaction is generally-20 ℃～80 ℃, and the reaction times was generally 0.5～12 hour.
In above-mentioned two step reaction, described organic solvent can be ethanol, methyl alcohol, Virahol, ethylene glycol, nitro benzene,toluene,xylene, two diethyl acetal dme, N, N '-dimethyl formamide, dimethyl sulfoxide (DMSO), glycol dimethyl ether, acetone, methylene dichloride, ethylene dichloride, trichloromethane, tetracol phenixin, 6-methyl phosphonic triamide, dithiocarbonic anhydride, chlorobenzene, dichlorobenzene or sherwood oil or their mixture.
The method that reaches described in this patent is not appeared in the newspapers in relevant document and patent, and this method can obtain the higher product of purity with higher yields and highly selective.Problems such as the product purification difficulty, the yield that are run in this compounds traditional synthesis be low have been avoided simultaneously; 2-acyl group-its purity of 4-alkylphenol for preparing with traditional technology is generally 80～85% purity, with containing the disadvantageous unreacted alkylphenol of metal extraction and other isomerization products often.And with of the present invention and 2-acyl group-4-alkylphenol of preparing of method because its reaction conditions gentleness reacts more complete, its purity can reach more than 90%.Employed reagent all comparatively is easy to get in entire reaction, while reaction yield height, the reaction conditions gentleness, solvent and byproduct of reaction halohydrocarbon can be recycled, the resulting aqueous catalyst solution in reaction back also can directly be recycled, as reclaim the aluminum chloride aqueous solution and can be directly used in preparation inorganic polymer flocculation agent PAC, do not have obviously " three wastes " discharging, thereby be convenient to industrializing implementation.
Specific implementation method
To help to understand the present invention by following specific implementation method, but not limit content of the present invention.
The preparation of embodiment 1:4-hexyl benzene ether
In the there-necked flask of 250mL, add 4-hexylphenol 17.8 grams, Anhydrous potassium carbonate 16.6 grams, DMF100mL successively.Subsequently 25.1 gram iodoethane are slowly dropped in the reaction system, vigorous stirring, temperature of reaction is controlled at room temperature in the dropping process.After dropwising, system is warming up to 60～70 ℃, continues to stir 3 hours, be cooled to room temperature, reaction solution is poured onto in the 400mL water, re-use the ethyl acetate extraction water, merge organic phase, use anhydrous magnesium sulfate drying, get weak yellow liquid after the filtration, boil off solvent, carry out underpressure distillation get product 19.6 gram (b.p.85-90 ℃/1mmHg)
1H NMR (CDCl
3, 300MHz) δ 7.10-7.03 (m, 2H), 6.99-6.89 (m, 2H), 3.82 (q, J=1.1Hz, 2H), 2.11-0.76 (m, 16H) ppm; Yield is 95%.
Embodiment 2:(4-nonyl phenyl) preparation of benzylic ether
In the there-necked flask of 250mL, add 4-nonylphenol 26.2 grams, pyridine 11.9 grams, ethylene dichloride 100mL successively.Subsequently 16.4 gram benzyl chlorine are slowly dropped in the reaction system, vigorous stirring, temperature of reaction is controlled at room temperature in the dropping process.After dropwising, system is warming up to backflow, continues to stir 3 hours, be cooled to room temperature, reaction solution is poured onto in the 400mL water, re-use the ethyl acetate extraction water, merge organic phase, use anhydrous magnesium sulfate drying, get weak yellow liquid after the filtration, boil off solvent, carry out underpressure distillation get product 28.5 gram (b.p.150-153 ℃/1mmHg)
1H NMR (CDCl
3, 300MHz) δ 7.43-6.87 (m, 9H), 4.45 (s, 2H), 2.03-0.61 (m, 19H) ppm; Yield is 92%.
Embodiment 3:(4-nonyl phenyl) preparation of allyl ethers
In the there-necked flask of 250mL, add 4-nonylphenol 22.0 grams, Anhydrous potassium carbonate 20.7 grams, methyl alcohol 100mL successively.Subsequently 15.7 gram allyl bromide 98s are slowly dropped in the reaction system, vigorous stirring, temperature of reaction is controlled at room temperature in the dropping process, after dropwising in about 20 minutes, system is warming up to 100 ℃, continues to stir 3 hours, be cooled to room temperature, reaction solution is poured onto in the 600mL water, re-use the ethyl acetate extraction water, merge organic phase, use anhydrous magnesium sulfate drying, get weak yellow liquid after the filtration, boil off solvent, carry out underpressure distillation get product 24.2 gram (b.p.115-118 ℃/1mmHg)
1H NMR (CDCl
3, 300MHz) δ 7.20-7.14 (m, 2H), 7.05-6.97 (m, 2H), 5.64-5.52 (m, 1H); 5.33-5.03 (m, 2H), 4.35-4.25 (d * t, 2H), 2.06-0.57 (m, 19H) ppm; Yield is 93%.
Embodiment 4:(4-butyl phenyl) preparation of allyl ethers
In the there-necked flask of 250mL, add 4-butylphenol 15.0 grams, Anhydrous potassium carbonate 20.7 grams, glycol dimethyl ether 100mL successively.Subsequently 15.7 gram 3-bromopropylenes are slowly dropped in the reaction system, vigorous stirring, temperature of reaction is controlled at room temperature in the dropping process, after dropwising in about 40 minutes, system is warming up to 100 ℃, continues to stir 3 hours, be cooled to room temperature, reaction solution is poured onto in the 600mL water, re-use the ethyl acetate extraction water, merge organic phase, use anhydrous magnesium sulfate drying, get weak yellow liquid after the filtration, boil off solvent, carry out underpressure distillation get product 18.4 gram (b.p.84-86 ℃/1mmHg)
1H NMR (CDCl
3, 300MHz) δ 7.19-7.12 (m, 2H), 7.06-6.94 (m, 2H), 5.66-5.51 (m, 1H); 5.28-5.07 (m, 2H), 4.28-4.19 (d * t, 2H), 1.80-0.92 (m, 9H) ppm; Yield is 97%.
Embodiment 5:(4-dodecylphenyl) preparation of propargyl ether
In the there-necked flask of 250mL, add 4-dodecyl base phenol 26.2 grams, pyridine 11.9 grams, toluene 100mL successively.Subsequently 13.0 gram propargyl bromides are slowly dropped in the reaction system, vigorous stirring, temperature of reaction is controlled at room temperature in the dropping process.After dropwising, system is warming up to backflow, continues to stir 3 hours, be cooled to room temperature, reaction solution is poured onto in the 400mL water, re-use the ethyl acetate extraction water, merge organic phase, use anhydrous magnesium sulfate drying, get weak yellow liquid after the filtration, boil off solvent, carry out underpressure distillation get product 26.1 gram (b.p.182-185 ℃/1mmHg)
1H NMR (CDCl
3, 300MHz) δ 7.30-7.19 (m, 2H), 7.00-6.84 (m, 2H), 4.50-4.45 (d, J=2.3Hz, 2H), 2.42 (t, J=2.1Hz, 2.11-0.65 (m, 25H) ppm; Yield is 87%.
The preparation of embodiment 6:2-ethanoyl-4-hexylphenol
In being full of the there-necked flask of 250mL of nitrogen, a drying adds aluminum chloride 16.7 gram and 80mL dithiocarbonic anhydride, system is cooled to-10 ℃, 10.3 gram 4-hexyl benzene ether were added dropwise to system in 20～30 minutes, temperature is controlled at-10～-5 ℃, then 4.3 gram acetyl chlorides are diluted in the 30mL dithiocarbonic anhydride, slowly drop to system, dripped off in 1.5～2 hours, temperature of reaction is controlled at-10～-5 ℃.Be warming up to backflow after dropwising, continue to stir 3 hours, the monochloroethane gas that produces in the reaction can be by freezing recycling.After reaction finishes, system is cooled to room temperature, reaction solution slowly is poured onto in 40 gram trash ices and the 10mL concentrated hydrochloric acids, leaves standstill, layering, tell organic phase, water extracts with dithiocarbonic anhydride, merge organic phase, use anhydrous magnesium sulfate drying, get weak yellow liquid after the filtration, boil off solvent (recyclable utilization again), residuum carry out underpressure distillation get product 9.9 gram (b.p.100-103 ℃/1mmHg)
1H NMR (CDCl
3, 300MHz) δ 11.51 (s, 1H), 7.45-7.01 (m, 3H), 2.53 (s, 3H), 2.21-0.73 (m, 13H) ppm; Yield is 90%, and its purity is analyzed through HPLC can reach 94.7%.
The preparation of embodiment 7:2-propionyl-4-nonylphenol
In being full of the there-necked flask of 250mL of nitrogen, a drying adds boron tribromide 31.3 gram and 100mL orthodichlorobenzenes, 15.5 gram (4-nonyl phenyl) benzylic ethers are added dropwise to system, then 5.5 gram chlorination propionyl are diluted in the 10mL orthodichlorobenzene, slowly drop to system, dripped off in 0.5～1 hour, temperature of reaction is controlled at room temperature.Be warming up to 80 ℃ after dropwising, continue to stir 5 hours.After reaction finishes, system is cooled to room temperature, reaction solution slowly is poured onto in 40 gram trash ices and the 10mL concentrated hydrochloric acids, leaves standstill, layering, tell organic phase, the water dichloromethane extraction, merge organic phase, use anhydrous magnesium sulfate drying, get yellow liquid after the filtration, boil off solvent and by product Benzyl Chloride (solvent and Benzyl Chloride are recyclable to be utilized) again, residuum carry out underpressure distillation get product 11.7 gram (b.p.110-115 ℃/1mmHg)
1H NMR (CDCl
3, 300MHz) δ 12.02 (s, 1H), 7.35-6.93 (m, 3H), 2.83 (q, J=1.2Hz, 2H), 2.31-0.62 (m, 22H) ppm; Yield is 85%, and its purity is analyzed through HPLC can reach 93.2%.
The preparation of embodiment 8:2-butyryl radicals-4-nonylphenol
In being full of the there-necked flask of 250mL of nitrogen, a drying adds aluminum trichloride (anhydrous) 16.7 gram and 100mL toluene, system is cooled to-10 ℃, 13.0 gram (4-nonyl phenyl) allyl etherss are added dropwise to system, temperature is controlled at-10～-5 ℃, then 6.4 gram chlorination butyryl are diluted in the 40mL toluene, slowly drop to system, dripped off in 0.5～1 hour, temperature of reaction is controlled at room temperature.Be warming up to 50 ℃ after dropwising, continue to stir 3 hours.After reaction finishes, system is cooled to room temperature, reaction solution slowly is poured onto in 40 gram trash ices and the 10mL concentrated hydrochloric acids, leaves standstill, layering, tell organic phase, the water dichloromethane extraction, merge organic phase, use anhydrous magnesium sulfate drying, get deep yellow liquid after the filtration, boil off the by product chlorallylene (solvent and chlorallylene are recyclable to be utilized again) that produces in solvent and the reaction, residuum carry out underpressure distillation get product 11.7 gram (b.p.120-124 ℃/1mmHg)
1H NMR (CDCl
3, 300MHz) δ 11.97 (s, 1H), 7.45-7.02 (m, 3H), 2.76 (t, J=2.7Hz, 2H), 2.51-0.72 (m, 24H) ppm; Yield is 81%, and its purity is analyzed through HPLC, can reach 90.5%.
The preparation of embodiment 9:2-benzoyl group-4-butylphenol
In being full of the there-necked flask of 250mL of nitrogen, a drying adds aluminum trichloride (anhydrous) 16.7 gram and 100mL chlorobenzenes, system is cooled to-10 ℃, 9.5 gram (4-butyl phenyl) allyl etherss are added dropwise to system, temperature is controlled at-10～-5 ℃, then 8.4 gram Benzoyl chlorides are diluted in the 40mL chlorobenzene, slowly drop to system, dripped off in 0.5 hour, temperature of reaction is controlled at room temperature.Be warming up to 70 ℃ after dropwising, continue to stir 3 hours.After reaction finishes, system is cooled to room temperature, reaction solution slowly is poured onto in 40 gram trash ices and the 10mL concentrated hydrochloric acids, leaves standstill, layering, tell organic phase, the water dichloromethane extraction, merge organic phase, use anhydrous magnesium sulfate drying, get deep yellow liquid after the filtration, boil off the by product chlorallylene (solvent and chlorallylene are recyclable to be utilized again) that produces in solvent and the reaction, residuum carry out underpressure distillation get product 10.8 gram (b.p.163-165 ℃/1mmHg)
1H NMR (CDCl
3, 300MHz) δ 11.67 (s, 1H), 7.53-6.70 (m, 8H), 2.01-1.04 (m, 9H) ppm; Yield is 85%, and its purity is analyzed through HPLC, can reach 92.5%.
The preparation of embodiment 10:2-ethanoyl-4-dodecyl phenol
In being full of the there-necked flask of 250mL of nitrogen, a drying adds Zinc Chloride Anhydrous 8.7 grams, aluminum trichloride (anhydrous) 8.5 gram and 100mL toluene, system is cooled to-10 ℃, 15.1 gram (4-dodecylphenyl) propargyl ethers are added dropwise to system, temperature is controlled at about-10 ℃, then 4.3 gram acetyl chlorides are diluted in the 40mL toluene, slowly drop to system, dripped off in 2 hours, temperature of reaction is controlled at-10 ℃.Be warming up to 40 ℃ after dropwising, continue to stir 1 hour.After reaction finishes, system is cooled to room temperature, reaction solution slowly is poured onto in 40 gram trash ices and the 10mL concentrated hydrochloric acids, leaves standstill, layering, tell organic phase, the water dichloromethane extraction, merge organic phase, use anhydrous magnesium sulfate drying, get deep yellow liquid after the filtration, boil off the by product propargyl chloride (solvent and propargyl chloride are recyclable to be utilized again) that produces in solvent and the reaction, residuum carry out underpressure distillation get product 13.5 gram (b.p.85-86 ℃/1mmHg)
1H NMR (CDCl
3, 300MHz) δ 11.47 (s, 1H), 7.47-6.96 (m, 3H), 2.59 (s, 3H), 2.21-0.69 (m, 25H) ppm; Yield is 89%, and its purity is analyzed through 1HNMR and HPLC, can reach 91.7%.
Example 11: aluminum chloride aqueous solution recycling
The aluminum chloride aqueous solution through reclaiming the wherein content of aluminum chloride is between the 25-30% substantially, and aqueous solution water white transparency does not have organic impurity after testing, can directly utilize.As find to contain in the aqueous solution organic impurity, can adopt the method for solvent extraction, the bright steam distillation of high temperature to remove organic impurity.Under special catalyst (as: KF etc.) and special reaction condition, prepare polymerize aluminum chloride (" commentary of polymerize aluminum chloride production method ", Henan chemical industry, 1994,8) through two-step reaction.
Claims (4)
1. the synthetic method of 2-acyl group-4-alkylphenol is characterized in that by following two steps
In the presence of the organic solvent neutralization bases, industry was obtained alkyl aryl ether in-20～170 ℃ of reactions alkylphenol and etherifying reagent in 0.2～24 hour; Described etherifying reagent be 1～5: 1 to the mole ratio of alkylphenol, the mole ratio of alkali and etherifying reagent is 1～4: 1;
In organic solvent and in the presence of the Lewis acid, above-mentioned after 0.5～12 hour, obtains 2-acyl group-4-alkylphenol in-20～80 ℃ of reactions to alkyl aryl ether and acylating reagent; Described acylating reagent be 1～3: 1 to the mole ratio of alkyl aromatic ether, Lewis acid and etherifying reagent mole ratio are 2～6: 1;
It is described to alkylphenol, the structural formula of alkyl aryl ether and 2-acyl group-4-alkylphenol is followed successively by
With
Wherein, R is for being C
4～C
20Alkyl;
R
1Be C
1～C
20Alkyl, allyl group, propargyl or various? benzyl;
R
2Be C
1～C
20Alkyl, aryl or allyl group;
Described etherifying reagent is C
1～C
20Alkyl, allyl group, propargyl or benzyl halogenide; Contain C
1～C
20Alkyl, allyl group, propargyl, the carbonic ether or the sulfuric ester of benzyl; Contain C
1～C
20Alkyl, allyl group, propargyl, the sulphonate or the triflate of benzyl;
Described acylating reagent is for containing C
1～C
20Alkyl, allyl group or aryl carboxylic acid halides; Contain C
1～C
20The carboxylic acid anhydride of alkyl, allyl group or aryl or their mixed acid anhydride; Contain C
1～C
20The carboxylic acid of alkyl, allyl group or aryl;
Described alkali is oxyhydroxide or the carbonate and the organic bases of basic metal or alkaline-earth metal;
Described Lewis acid is aluminum trihalide, three iron halide, boron trihalides, titanium tetrahalide, the inferior tin of halogenation, tin chloride, zinc chloride or their mixture.
2; the synthetic method of a kind of 2-acyl group as claimed in claim 1-4-alkylphenol; it is characterized in that described solvent is ethanol, methyl alcohol, Virahol, ethylene glycol, nitro benzene,toluene,xylene, glycol dimethyl ether, N, N '-dimethyl formamide, dimethyl sulfoxide (DMSO), glycol dimethyl ether, acetone, methylene dichloride, ethylene dichloride, trichloromethane, tetracol phenixin, 6-methyl phosphonic triamide, dithiocarbonic anhydride, chlorobenzene, dichlorobenzene or sherwood oil or their mixture.
3, the synthetic method of a kind of 2-acyl group as claimed in claim 1-4-alkylphenol is characterized in that described sulphonate is p-toluenesulfonic esters or methanesulfonates.
4, the synthetic method of a kind of 2-acyl group as claimed in claim 1-4-alkylphenol is characterized in that described organic bases is trialkylamine or pyridine.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102617301A (en) * | 2012-03-02 | 2012-08-01 | 浙江工业大学 | Synthesizing process for low rim tetra-benzyl substituted p-tert-butylcalix (4) arene derivative |
| CN103265458A (en) * | 2013-06-14 | 2013-08-28 | 杨锌荣 | Alkoxy aryl sulfonate and preparation method thereof |
| CN103265462A (en) * | 2013-06-14 | 2013-08-28 | 杨锌荣 | Alkoxy alkybenzene sulfonate and preparation method therof |
| CN113683492A (en) * | 2021-08-25 | 2021-11-23 | 常熟理工学院 | Preparation method of 3-phenoxybromopropane or analogue thereof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5300689A (en) * | 1992-03-20 | 1994-04-05 | Henkel Corporation | Oximation process |
| FR2759697B1 (en) * | 1997-02-18 | 1999-04-16 | Expansia Sa | PREPARATION OF 4-CYANO-4'-HYDROXY BIPHENYLE |
| US5956185A (en) * | 1997-11-14 | 1999-09-21 | Samsung Aerospace Industries, Ltd. | Compact camera zoom lens system |
| CN1207274C (en) * | 2003-06-28 | 2005-06-22 | 浙江大学 | Preparation method of 2-alkyl acyl-4-alkylamio phenol |
-
2006
- 2006-03-24 CN CNB2006100250483A patent/CN100384802C/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102617301A (en) * | 2012-03-02 | 2012-08-01 | 浙江工业大学 | Synthesizing process for low rim tetra-benzyl substituted p-tert-butylcalix (4) arene derivative |
| CN103265458A (en) * | 2013-06-14 | 2013-08-28 | 杨锌荣 | Alkoxy aryl sulfonate and preparation method thereof |
| CN103265462A (en) * | 2013-06-14 | 2013-08-28 | 杨锌荣 | Alkoxy alkybenzene sulfonate and preparation method therof |
| CN113683492A (en) * | 2021-08-25 | 2021-11-23 | 常熟理工学院 | Preparation method of 3-phenoxybromopropane or analogue thereof |
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| CN100384802C (en) | 2008-04-30 |
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