CN110803980B - Method for preparing 4-n-butylresorcinol by one-pot method - Google Patents
Method for preparing 4-n-butylresorcinol by one-pot method Download PDFInfo
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- CN110803980B CN110803980B CN201911168209.8A CN201911168209A CN110803980B CN 110803980 B CN110803980 B CN 110803980B CN 201911168209 A CN201911168209 A CN 201911168209A CN 110803980 B CN110803980 B CN 110803980B
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- butylresorcinol
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/11—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/64—Preparation of O-metal compounds with O-metal group bound to a carbon atom belonging to a six-membered aromatic ring
- C07C37/66—Preparation of O-metal compounds with O-metal group bound to a carbon atom belonging to a six-membered aromatic ring by conversion of hydroxy groups to O-metal groups
Abstract
The invention discloses a method for preparing 4-n-butylresorcinol by a one-pot method, belonging to the field of synthesis of cosmetic intermediates. The method comprises the steps of taking resorcinol as a raw material, reacting with alkali in n-butyl alcohol to obtain monophenolate, then reacting with Lewis acid in a one-pot dehydration method to obtain a crude product after acidolysis, and then recrystallizing to obtain 4-n-butylresorcinol. The method has the advantages of simple operation, mild conditions, low cost and high yield, and the obtained product has the purity of more than 99.0 percent and has potential amplification prospect.
Description
Technical Field
The invention relates to a method for preparing 4-n-butylresorcinol by a one-pot method, belonging to the technical field of chemical intermediate synthesis.
Background
4-n-butylresorcinol, alias 4-butylresorcinol, Invitrogen name 4-butyl-resorcinol, and molecular formula C10H14O2The molecular weight is 166.22, CAS is 18979-61-8, is commonly used as a whitening additive of a skin care product, can be used for synthesizing FXR agonist intermediates, treating diseases such as cholestasis, hypercholesterolemia, heart disease and the like, and is mainly used in the fields of spices, medicines, dyes and the like.
At present, the synthesis method of the product literature is mainly to synthesize resorcinol and n-butyric acid in AlCl3The Friedel-crafts acylation reaction is carried out under catalysis, and then the carbonyl is reduced into methylene by utilizing Wolff-Kishner-Huang Minlon or Clemmen sen reduction reaction to obtain the 4-butyl resorcinol with the total yield of 44%. Reference: bioorg.med.chem.2014,22, 1596-.
However, the carbonyl group is reduced to methylene group by Wolff-Kishner-yellow dragon reaction or Clemmensen reduction reaction, a large amount of hydrazine or zinc amalgam is used, the production safety is reduced, the environment is polluted, a mercury reagent with high toxicity is used, and the purchase is limited during the amplification.
Aiming at the defects of the method, the method is improved in process route so as to be suitable for an industrial scale-up method.
Disclosure of Invention
In order to overcome the technical defects, the invention discloses a method for preparing 4-butyl resorcinol by a one-pot method, which comprises the steps of taking resorcinol as a raw material, reacting with alkali in n-butyl alcohol to obtain monophenolate, then reacting with Lewis acid by a one-pot dehydration method, carrying out acidolysis to obtain a crude product, and then recrystallizing to obtain the 4-n-butyl resorcinol. The method has the advantages of simple operation, mild conditions, low cost and high yield, and the obtained product has the purity of more than 99.0 percent and has potential amplification prospect.
The method for preparing 4-n-butylresorcinol by the one-pot method comprises the following steps:
the preparation method comprises the steps of obtaining resorcinol mono-lithium/sodium/potassium salt by using resorcinol and alkali, then carrying out dehydration friedel-crafts reaction on resorcinol and n-butanol and a Lewis acid catalyst in an organic solvent, obtaining a crude product of 4-n-butyl resorcinol after the reaction is finished and carrying out acidolysis, and recrystallizing to obtain a pure product of 4-butyl resorcinol.
Further, in the above technical solution, the base is selected from sodium hydroxide, potassium hydroxide, sodium hydride, n-butyl lithium, sodium n-butoxide or potassium n-butoxide.
Further, in the above technical solution, the solvent is selected from toluene, dioxane, heptane, cyclohexane, NMP, chlorobenzene, or xylene.
Further, in the above technical solution, the Lewis acid catalyst is selected from zinc chloride, ferric chloride, triphenylborane or (C)6F5)3B。
Further, in the above technical scheme, in the dehydration friedel-crafts reaction, an initiator is added to facilitate the start of the reaction, and the initiator is concentrated sulfuric acid, anhydrous calcium chloride or anhydrous copper sulfate.
Further, in the technical scheme, the molar ratio of the resorcinol to the alkali to the Lewis acid catalyst is 1:1-1.03: 0.1-0.6.
Further, in the above technical scheme, the recrystallization conditions are 6 times volume of water, 5% of activated carbon and 2% of sodium thiosulfate are refluxed, and the mixture is subjected to heat filtration, cooling and crystallization.
Further, in the above technical scheme, the initiator is added in the dehydration reaction to facilitate the start of the reaction, and the initiator is concentrated sulfuric acid, anhydrous calcium chloride or anhydrous copper sulfate. The initiator is added in an amount of 0.05 to 0.1 eq.
Advantageous effects of the invention
According to the invention, the 4-n-butylresorcinol is prepared by adopting a one-pot method, one hydroxyl group is changed into a stronger electron-donating positioning group, and then the appropriate catalyst and n-butyl alcohol are adopted for dehydration and selective positioning, so that the 4-n-butylresorcinol is obtained, and the method has the advantages of simple operation, high atom utilization rate, mild conditions, low cost and high yield, and has the prospect of industrial amplification production through process verification.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
Example 1
Under the protection of nitrogen, adding 110g (1mol) of resorcinol and 350g of toluene into a reaction bottle, mixing and dissolving, cooling to 10 ℃, adding 98g (1.02mol) of n-butyl sodium alkoxide in batches, controlling the temperature to be 10-15 ℃, adding 2.2mol of n-butyl alcohol, 27.2g (0.2mol) of zinc chloride and 1.1g of calcium chloride after TLC (EA developing agent) detects that raw materials are almost not left, heating to 40-45 ℃, reacting for 1 hour, heating to 102 ℃, refluxing and dividing water, sampling and quenching GC to detect that resorcinol is less than 1 percent after dividing water for 6 hours, cooling to room temperature, filtering out a catalyst by diatomite, adding dilute sulfuric acid to adjust the pH to be 1-2, concentrating an organic phase to a non-flowing liquid, adding water for replacement, adding 660g of water, 2.2g of sodium thiosulfate and 5.5g of activated carbon, heating to reflux for 1 hour, carrying out heat filtration to obtain a light yellow solution, cooling to separate out a light yellow flaky crystal, filtration gave 134.1g of 4-n-butylresorcinol, GC: 99.3%, yield: 80.7 percent.1HNMR(400MHz,CDCl3):0.96(t,3H),1.35-1.62(m,4H),2.55(m,2H),6.15-6.24(m,2H),6.75(s,1H),8.46(s,1H),12.83(s,1H).
Example 2
Under the protection of nitrogen, 110g (1mol) of resorcinol and 350g of xylene are put into a reaction bottle, mixed and dissolved, cooled to 10 ℃, added with 113.3g (1.01mol) of potassium n-butoxide in batches, the temperature is controlled to be 10-15 ℃, TLC (EA developing agent) detects that almost no raw materials remain, added with 2.2mol of n-butanol, 27.2g (0.2mol) of zinc chloride and 2.2g of concentrated sulfuric acid, heated to 40-45 ℃ for reaction for 1 hour, heated to 112 ℃ for reflux water diversion, sampled and quenched by GC to detect that resorcinol is less than 1 percent after 4 hours of water diversion, cooled to room temperature, introduced with gas, and cooled to room temperature, and subjected to Gas Chromatography (GC) detectionFiltering solid catalyst with diatomite, adding dilute sulfuric acid to adjust the pH value to be 1-2, concentrating an organic phase to obtain a non-flowing liquid, adding water for replacement, adding 660g of water, 2.2g of sodium thiosulfate and 5.5g of activated carbon, heating to reflux for 1 hour, carrying out hot filtration to obtain a light yellow solution, cooling to separate out a flaky crystal, and filtering to obtain 130.2g of 4-n-butylresorcinol, wherein GC: 99.1%, yield: 78.3 percent.1HNMR(400MHz,CDCl3):0.96(t,3H),1.35-1.62(m,4H),2.55(m,2H),6.15-6.24(m,2H),6.75(s,1H),8.46(s,1H),12.83(s,1H).
Example 3
Under the protection of nitrogen, putting 110g (1mol) of resorcinol and 350g of m-chlorobenzene in a reaction bottle, mixing and dissolving, cooling to 10 ℃, adding 81.7g (1.02mol) of lithium n-butoxide in batches, controlling the temperature to be 10-15 ℃, detecting that almost no raw materials remain by TLC (EA developing agent), adding 2.5mol of n-butanol, 272g (0.2mol) of zinc chloride and 1.5g of anhydrous copper sulfate, heating to 40-45 ℃, reacting for 1 hour, heating to 113 ℃ for refluxing and water diversion, sampling and quenching GC to detect that the resorcinol is less than 1 percent after 4 hours of water diversion, cooling to room temperature, filtering off a solid catalyst by diatomite, adding dilute sulfuric acid to adjust the pH value to be 1-2, concentrating an organic phase to a non-flowing liquid, adding water for replacement, adding 660g of water, 2.2g of sodium thiosulfate and 5.5g of active carbon, heating to reflux for 1 hour, thermally filtering to obtain a light yellow solution, then cooling to separate out flaky crystals, and filtering to obtain 135.8g of 4-n-butylresorcinol, wherein GC: 98.7%, yield: 81.7 percent.
Example 4
Under the protection of nitrogen, adding 110g (1mol) of resorcinol and 220g of n-heptane into a reaction bottle, mixing, heating and dissolving, cooling to 10 ℃, adding turbid solution of 40.8g (1.02mol) of sodium hydroxide and 100g of n-butanol in batches, controlling the temperature to be 10-15 ℃, adding 2.5mol of n-butanol, 17.5g (0.1mol) of tris (pentafluorobenzene) borane and 1.1g of calcium chloride after TLC (EA developing agent) detection raw materials are almost not left, heating to 40-45 ℃, reacting for 1 hour, heating to 98 ℃ for refluxing and water diversion, sampling and quenching GC to detect that the resorcinol is less than 1 percent after the water diversion is finished for 8 hours, cooling to room temperature, adding a small amount of water for quenching, adding dilute sulfuric acid to adjust the pH to be 1-2, filtering out insoluble solids by diatomite, concentrating an organic phase to a non-flowing liquid, adding water for replacement, adding 660g of water, 2.2g of sodium thiosulfate and 5.5g of activated carbon, heating to reflux for 1 hour, carrying out hot filtration to obtain a light yellow solution, cooling to precipitate a flaky crystal, and filtering to obtain 151g of 4-n-butylresorcinol, wherein GC: 99.3%, yield: 90.9 percent.
Example 5
Under the protection of nitrogen, adding 110g (1mol) of resorcinol and 220g of n-butyl alcohol into a reaction bottle, mixing and dissolving, cooling to 10 ℃, adding 98g (1.02mol) of n-butyl sodium alkoxide in batches, controlling the temperature to be 10-15 ℃, adding 2.2mol of n-butyl alcohol, 48.7g (0.3mol) of ferric trichloride and 2.2g of concentrated sulfuric acid after TLC (EA developing agent) detects that almost no raw materials remain, heating to 40-45 ℃, reacting for 1 hour, heating to 98 ℃ for refluxing and water distribution, sampling, quenching, detecting resorcinol by GC, cooling to room temperature after 8 hours of water distribution, filtering out a solid catalyst by diatomite, adding dilute sulfuric acid to adjust the pH to be 1-2, concentrating an organic phase to a non-flowing liquid, adding water for replacement, adding 660g of water, 2.2g of sodium thiosulfate and 5.5g of activated carbon, heating to reflux for 1 hour, performing heat filtration to obtain a light yellow solution, then cooling to separate out flaky crystals, and filtering to obtain 128g of 4-n-butylresorcinol, wherein GC: 99.3%, yield: 77.1 percent.
Example 6
Under the protection of nitrogen, adding 110g (1mol) of resorcinol and 220g of toluene into a reaction bottle, mixing, heating and dissolving, cooling to 10 ℃, adding a solution of 57.2g (1.02mol) of potassium hydroxide and 100g of n-butyl alcohol in batches, controlling the temperature to be 10-15 ℃, adding 11.1g of n-butyl alcohol, 48.4g (0.2mol) of triphenylborane and 11.1g of calcium chloride after TLC (EA developing agent) detection raw materials are almost not left, heating to 40-45 ℃, reacting for 1 hour, heating to 98 ℃ for refluxing and water distribution, sampling and quenching to detect that resorcinol is less than 1 percent after water distribution is finished for 8 hours, cooling to room temperature, adding a small amount of water for quenching, adding dilute sulfuric acid for adjusting pH to be 1-2, filtering out insoluble solids by diatomite, concentrating an organic phase to be a non-flowing liquid, adding water for replacement, adding 660g of water, 2.2g of sodium thiosulfate and 5.5g of activated carbon, heating to reflux for 1 hour, hot filtering to obtain a light yellow solution, cooling to precipitate a flaky crystal, and filtering to obtain 133g of 4-n-butylresorcinol, wherein GC: 99.3%, yield: 80.1 percent.
Example 7
Under the protection of nitrogen, putting 110g (1mol) of resorcinol, 100g of n-butanol and 200g of dioxane into a reaction bottle, mixing and dissolving, cooling to 10 ℃, adding 35g (1.02mol) of 70% sodium hydride in batches, controlling the temperature to be 10-15 ℃, detecting that almost no raw materials are left by TLC (EA developing agent), adding 1.5mol of n-butanol, 8.75g (0.05mol) of tris (pentafluorobenzene) borane and 1.5g of anhydrous copper sulfate, heating to 40-45 ℃, reacting for 1 hour, heating to 98 ℃ for refluxing and water distribution, after 2.5 hours of water distribution, sampling and detecting that the resorcinol is less than 1% by GC, cooling to room temperature, adding a small amount of water for quenching, adding dilute sulfuric acid for adjusting the pH to be 2-3, filtering out insoluble solids by diatomite, concentrating an organic phase to be a non-flowing liquid, adding water for replacement, adding 660g of water, 2.2g of sodium thiosulfate and 5.5g of activated carbon, heating to reflux for 1 hour, carrying out hot filtration to obtain a light yellow solution, cooling to precipitate a flaky crystal, and filtering to obtain 137g of 4-n-butylresorcinol, wherein GC: 99.3%, yield: 82.5 percent.
Example 8:
under the protection of nitrogen, 6.6kg (60mol,1eq) of resorcinol and 19.8kg of toluene are put into a 100L reaction bottle, mixed and dissolved, the temperature is reduced to 10 ℃, 4.9kg (61.2mol,1.02eq) of lithium n-butoxide is added in batches, the temperature is controlled to be 10-15 ℃, TLC (EA developing agent) detection raw materials are almost not left, n-butanol (130mol), zinc chloride (36mol,0.6eq), calcium chloride (69 g) and triphenylborane (47.8 g) are added, the temperature is increased to 40-45 ℃ for reaction for 1 hour, the temperature is increased to 115 ℃ for reflux water diversion, after 4 hours of water diversion, sampling and quenching GC detection resorcinol is less than 1%, the temperature is reduced to room temperature, and the solid catalyst is removed by diatomite assisted filtration. Quench with dilute sulfuric acid and adjust pH 2-3. Concentrating the organic phase to obtain a non-flowing liquid, adding water for replacement, adding 39kg of water, 0.132kg of sodium thiosulfate and 0.33kg of activated carbon, heating to reflux for 1 hour, carrying out hot filtration to obtain a light yellow solution, cooling to separate out a flaky crystal, and filtering to obtain 8.5kg of 4-n-butylresorcinol, wherein GC: 99.2%, yield: 85.2 percent.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be able to cover the technical solutions and the inventive concepts of the present invention within the technical scope of the present invention.
Claims (4)
1. The method for preparing 4-n-butylresorcinol by a one-pot method is characterized by comprising the following steps of: reacting resorcinol with alkali to obtain resorcinol monophenolate, adding a Lewis acid catalyst, n-butanol and an organic solvent for dehydration friedel-crafts reaction, and treating to obtain 4-n-butylresorcinol; the organic solvent is selected from toluene, dioxane, heptane, cyclohexane, NMP, chlorobenzene or xylene; the Lewis acid catalyst is selected from zinc chloride, ferric trichloride, triphenylboron or (C)6F5)3B。
2. The one-pot process for producing 4-n-butylresorcinol according to claim 1, wherein: the alkali is selected from sodium hydroxide, potassium hydroxide, sodium hydride, n-butyl lithium, n-butyl sodium alkoxide or n-butyl potassium alkoxide.
3. The one-pot process for producing 4-n-butylresorcinol according to claim 1, wherein: in the dehydration friedel-crafts reaction, initiator is added to facilitate the start of the reaction, and the initiator is concentrated sulfuric acid, anhydrous calcium chloride or anhydrous copper sulfate.
4. The one-pot process for producing 4-n-butylresorcinol according to claim 1, wherein: the mol ratio of the resorcinol to the alkali to the Lewis acid catalyst is 1:1-1.03: 0.1-0.6.
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Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6533967B1 (en) * | 1999-01-20 | 2003-03-18 | Orica Australia Pty Ltd | Initiating system for solid polyester granule manufacture |
CN1884244A (en) * | 2006-05-31 | 2006-12-27 | 天津大学 | Process for preparing 4,6-di-tert-butyl resorcin with resin as catalyst |
CN101591225A (en) * | 2009-06-05 | 2009-12-02 | 华东理工大学 | The synthetic method of 5-alkyl resorcinol |
CN103159596A (en) * | 2011-12-14 | 2013-06-19 | 南京华狮化工有限公司 | Preparation method for 4-butylresorcinol |
CN105016979A (en) * | 2015-08-07 | 2015-11-04 | 湖北荆洪生物科技股份有限公司 | Synthesis method of 4-n-alkyl substituted phenol |
CN107805186A (en) * | 2017-10-27 | 2018-03-16 | 南京斯拜科生化实业有限公司 | A kind of preparation method of 4 alkyl-resorcin |
-
2019
- 2019-11-25 CN CN201911168209.8A patent/CN110803980B/en active Active
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6533967B1 (en) * | 1999-01-20 | 2003-03-18 | Orica Australia Pty Ltd | Initiating system for solid polyester granule manufacture |
CN1884244A (en) * | 2006-05-31 | 2006-12-27 | 天津大学 | Process for preparing 4,6-di-tert-butyl resorcin with resin as catalyst |
CN101591225A (en) * | 2009-06-05 | 2009-12-02 | 华东理工大学 | The synthetic method of 5-alkyl resorcinol |
CN103159596A (en) * | 2011-12-14 | 2013-06-19 | 南京华狮化工有限公司 | Preparation method for 4-butylresorcinol |
CN105016979A (en) * | 2015-08-07 | 2015-11-04 | 湖北荆洪生物科技股份有限公司 | Synthesis method of 4-n-alkyl substituted phenol |
CN107805186A (en) * | 2017-10-27 | 2018-03-16 | 南京斯拜科生化实业有限公司 | A kind of preparation method of 4 alkyl-resorcin |
Non-Patent Citations (2)
Title |
---|
Investigation of butylphenols by chromatographic and spectral methods;Papazova,D.等;《Izvestiya po Khimiya (1990)》;19901231;第23卷(第1期);全文 * |
Noble synthesis of 1-Alkyl-2-naphthols;Kito,Taketoshi等;《Chemistry Letters (1975)》;19751231(第10期);全文 * |
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