CN115304569A - Method for protecting alcohol-terminated hydroxyl group by using 4-pyridinium methyl benzenesulfonate as catalyst - Google Patents
Method for protecting alcohol-terminated hydroxyl group by using 4-pyridinium methyl benzenesulfonate as catalyst Download PDFInfo
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- CN115304569A CN115304569A CN202211114524.4A CN202211114524A CN115304569A CN 115304569 A CN115304569 A CN 115304569A CN 202211114524 A CN202211114524 A CN 202211114524A CN 115304569 A CN115304569 A CN 115304569A
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- C07D309/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
- C07D309/08—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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Abstract
The invention discloses a method for protecting a terminal alcoholic hydroxyl group by taking 4-pyridinium methyl benzenesulfonate as a catalyst, which comprises the following steps: (1) Adding raw material alcohol and 4-methyl pyridinium benzenesulfonate into a reactor, and then adding a solvent; (2) dripping a protective reagent, and separating an oil phase; (3) Extracting the water phase with dichloromethane, and mixing the water phase and the oil phase; (4) Washing the oil phase, drying the oil phase by using a drying agent, and performing rotary evaporation to obtain a hydroxyl protection product. Compared with the existing catalytic reaction taking p-toluenesulfonic acid monohydrate as a catalyst, the method has the advantages of mild reaction conditions, high yield, few byproducts, simple post-treatment and the like.
Description
Technical Field
The invention relates to the technical field of organic synthesis, in particular to a method for protecting a terminal alcoholic hydroxyl group by using 4-pyridinium methyl benzenesulfonate as a catalyst.
Background
The long straight-chain halogen alkanol is an important chemical raw material and a medical intermediate, is mainly used for manufacturing medicines and materials, such as medical intermediates for producing decyl oxybenzoic acid, decyl allyl ester, hydroxyundecanoic acid, 11-hexadecene-1-ol and the like, can also be used for preparing functional materials, adhesives, polymer materials and the like, and has wide application.
At present, the long straight-chain halogen alkanol mainly comprises the following synthesis methods:
(1) In the literature (Journal of Chemical Ecology,2007, 33.
(2) The literature (chemical reagent, 2013,35 (07): 659-661) reports that 13-octadecen-1-ol is produced by protecting hydroxyl group with glacial acetic acid and concentrated sulfuric acid through unilateral esterification using toluene as solvent, with a yield of 84%, and has the disadvantages of complicated operation, dangerous use of raw materials and low yield.
(3) The literature (synthetic chemistry, 2020,28 (09): 791-795.) reports that 2- (12-bromo-dodecyloxy) -tetrahydropyran is produced by protecting the starting material 12-bromo-1-dodecanol with p-toluenesulfonic acid (pTSA) as a catalyst and dichloromethane as a solvent in 92% yield, which has the disadvantage that the starting material is not reacted completely and the starting material alcohol remains.
The synthesis method has the problems of incomplete reaction, low product purity and the like, and the problems restrict the experimental stability of the protection of the long-linear-chain halogen alkanol and the proceeding of subsequent reactions.
Disclosure of Invention
In order to overcome the defects of low yield and high byproduct of the existing catalyst, the invention adopts 4-pyridinium methyl benzene sulfonate as the catalyst, and provides the method for protecting the terminal alcohol by using the 4-pyridinium methyl benzene sulfonate as the catalyst.
The invention provides the following scheme:
a method for protecting a terminal alcoholic hydroxyl group by using pyridinium 4-methylbenzenesulfonate as a catalyst, comprising the following steps of:
(1) Adding raw material alcohol and 4-methyl pyridinium benzenesulfonate into a reactor, and then adding a solvent;
(2) Then dropping a protective reagent, and separating an oil phase;
(3) Extracting the water phase with nonpolar solvent such as dichloromethane, etc., and mixing the water phase and the oil phase;
(4) Washing the oil phase, drying the oil phase by using a drying agent, and performing rotary evaporation to obtain a hydroxyl protection product.
Preferably, the protection reaction route of the protection method of the terminal alcoholic hydroxyl group is as follows:
wherein the content of the first and second substances,
is a structure of a terminal alcohol;
PPTS stands for pyridinium 4-methylbenzenesulfonate. DHP represents dihydropyran. DCM stands for dichloromethane. reflux stands for reflux.
Preferably, the molar ratio of the starting alcohol to pyridinium 4-methylbenzenesulfonate is 1.
Preferably, the solvent comprises one or more of dichloromethane, N-hexane, methanol, N-dimethylformamide, tetrahydrofuran.
Preferably, the mass ratio of the solvent to the raw material alcohol is 8: 1-20: 1.
preferably, the solvent is dichloromethane, and the mass of the added dichloromethane is 8-20 times of that of the raw material alcohol.
Preferably, the protecting reagent comprises one or more of 3, 4-dihydropyran, tert-butyldimethylchlorosilane, allyl chloroformate and oxygenated methyl ether.
Preferably, the molar ratio of the protecting agent to the starting alcohol is 1.2.
Preferably, the protective reagent is 3,4-dihydropyran, and the dosage of 3,4-dihydropyran is 1.2-2.0 mol equivalent of the raw material alcohol.
Preferably, the structure of the terminal alcohol is that X is fluorine (F), chlorine (Cl), bromine (Br), iodine (I).
Preferably, the desiccant is one or more of anhydrous sodium sulfate, anhydrous sodium carbonate, anhydrous magnesium sulfate and anhydrous calcium chloride.
Preferably, the terminal alcohols include 10-chloro-1-decanol, 10-bromo-1-decane, 8-chloro-1-octanol, 8-bromo-1-octanol, 12-chloro-1-dodecanol.
Preferably, the protection product is 2- (10-chloro-decyloxy) -tetrahydropyran, 2- (10-bromo-decyloxy) -tetrahydropyran, 2- (8-chloro-octyloxy) -tetrahydropyran, 2- (8-bromo-octyloxy) -tetrahydropyran, 2- (12-chloro-dodecyloxy) -tetrahydropyran.
Preferably, the starting alcohols include 10-bromo-1-decanol, 8-bromo-1-octanol, 12-chloro-1-dodecanol.
Preferably, the step (2) specifically comprises the following steps: preserving the temperature for 10-30min at-10 ℃, and dropwise adding a protective reagent with 1.2-2.0 equivalent of raw material alcohol.
Preferably, the step (2) specifically comprises the following operations: after the protective agent is added dropwise, the temperature is returned to the room temperature, the mixture is stirred for 5-10h, and after the GC detection is qualified, the mixture is quenched by ice water, stirred uniformly, and the oil phase is separated.
Preferably, the step (3) specifically comprises the following steps: the aqueous phase was extracted 2-4 times with dichloromethane and the oil phases were combined.
Preferably, the step (4) specifically comprises the following steps: and washing the oil phase with saturated sodium bicarbonate solution and saturated brine, drying the oil phase with a drying agent, and performing rotary evaporation to obtain the protected product.
The invention provides another scheme that:
a method for protecting a terminal alcoholic hydroxyl group by using pyridinium 4-methylbenzenesulfonate as a catalyst, comprising the following steps of: adding raw material alcohol/4-pyridine methyl benzene sulfonate with a molar ratio of 1.02-1; after the dropwise addition, the temperature is returned to the room temperature, the stirring is carried out for 5-10h, after the GC detection is qualified, ice water is used for quenching, the stirring is carried out uniformly, the oil phase is separated, dichloromethane is used for extracting the water phase for 2-4 times, the oil phase is combined, the saturated sodium bicarbonate solution and the saturated salt water are used for washing the oil phase, the anhydrous sodium sulfate is used for drying the oil phase, and the rotary evaporation is carried out to obtain the protected product.
The invention has the beneficial effects that: a method for protecting terminal alcohol by using 4-pyridinium methyl benzene sulfonate as a catalyst comprises the steps of firstly adding raw material alcohol and 4-pyridinium methyl benzene sulfonate into a dichloromethane solution under the nitrogen atmosphere (firstly, vacuumizing a reaction bottle, and then inflating a nitrogen steel bottle to enable a reaction system to be in the nitrogen atmosphere), then dropwise adding 3,4-dihydropyran, stirring at normal temperature, pouring a reaction solution into an ice-water bath for extraction and layering, retaining an oil phase, respectively washing the oil phase by using a saturated sodium bicarbonate solution and a saturated sodium chloride solution, drying by using anhydrous sodium sulfate, and carrying out rotary evaporation to obtain a protected product. Compared with the existing catalytic reaction by using p-toluenesulfonic acid monohydrate, the method has the advantages of mild reaction conditions, high yield, few byproducts, simple post-treatment and the like.
The gas chromatography conditions in the present invention are as follows:
the purity of the product was characterized by Agilent-7890B Gas Chromatography (GC) from Agilent, inc., i.e., GC assay.
A detector: a hydrogen Flame Ionization Detector (FID); a chromatographic column: HP-5 (30 m.times.0.320 mm.times.0.25 μm); injector and detector temperatures: 280 ℃; the split ratio is as follows: 3:1.
four stages of temperature programming were used as shown in the table below:
temperature program
In chromatography, it is desirable to know the concentration of the sample being measured. An external standard method can be used for firstly drawing a working curve by using a standard sample of the component to be measured, measuring the peak height of each peak or the sample concentration corresponding to the peak area, and drawing a standard curve. In actual application, the sample concentration can be obtained by measuring the peak height or the peak area corresponding to the standard curve.
The purity is measured by an external standard method.
Yield calculation formula:
Y＝m 1 *M 0 *c/(m 0 *M 1 )
wherein:
y-represents the yield,%, of the reaction;
m 0 -represents the mass of the raw material, g:
M 0 -represents the molar mass of the starting material, g/mol;
m 1 -representing the mass of the product obtained from the reaction, g;
M 1 -represents the molar mass of the product, g/mol;
c-represents the product GC apparent purity,%.
The foregoing description is only an overview of the technical solutions of the embodiments of the present invention, and the embodiments of the present invention can be implemented according to the content of the description in order to make the technical means of the embodiments of the present invention more clearly understood, and the detailed description of the present invention is provided below in order to make the foregoing and other objects, features, and advantages of the embodiments of the present invention more clearly understandable.
Detailed Description
The technical solutions in the embodiments will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments, and not all of the embodiments.
Example 1:
in a 500mL three-necked flask, 10-bromo-1-decanol 50.04g (0.2108 mol), 4-methylbenzenesulfonic acid pyridinium 0.53g (2.108 mmol), 400mL CH 2 Cl 2 Keeping the temperature of the solution at-15 ℃ for 15min, and keeping the temperature constant at about-5 ℃ of the internal temperatureWen Dijia allyl chloroformate 50.80g (0.4216 mol), after the addition, the reaction mixture was stirred at room temperature for 8h to stop the reaction. Pouring the reaction solution into ice water, stirring for 10-20min, standing for layering, and using CH as upper water 2 Cl 2 Extracting for 2-4 times until the lower layer is colorless, mixing the lower layers, and extracting the lower layer with saturated NaHCO solution 3 The solution was washed with saturated NaCl solution, the lower layer was dried over anhydrous sodium sulfate and rotary evaporated to give a pale yellow oily liquid, i.e., product 2- (10-bromo-decyloxy) -tetrahydropyran 69.60g, purity protection 91% by GC external standard, 93.6% yield.
Example 2:
in a 1000mL three-necked flask, 50.08g (0.2395 mol) of 8-bromo-1-octanol, 0.60g (2.395 mmol) of pyridinium 4-methylbenzenesulfonate, and 500mL of CH were charged 2 Cl 2 The solution is kept at the temperature of minus 12 ℃ for 15min, 3,4-dihydropyran 32.23g (0.3832 mol) is dripped at the constant temperature of about minus 2 ℃ at the internal temperature, and after the dripping is finished, the solution is transferred to the room temperature to be stirred for 5h, and then the reaction is stopped. Pouring the reaction solution into ice water, stirring for 10-20min, standing for layering, and using CH as upper water 2 Cl 2 Extracting for 2-4 times until the lower layer is colorless, mixing the lower layers, and adding saturated NaHCO into the lower layer solution 3 The solution is washed, then washed by saturated NaCl solution, the lower layer is dried by anhydrous sodium sulfate and is evaporated in a rotary way to obtain light yellow oily liquid, namely 68.56g of the product 2- (8-bromine-octyloxy) -tetrahydropyran, the purity of the product is 94 percent of the protected product by GC external standard detection, and the yield is 91.8 percent.
Example 3:
in a 1000mL three-necked flask, 50.02g (0.2266 mol) of 12-chloro-1-dodecanol, 0.57g (2.266 mmol) of pyridinium 4-methylbenzenesulfonate, and 600mL of CH were charged 2 Cl 2 61.47g (0.4078 mol) of tert-butyldimethylsilyl chloride is dropwise added into the solution at a constant temperature of about 0 ℃ at the internal temperature, and after the dropwise addition is finished, the solution is transferred to the room temperature and stirred for 10 hours, and then the reaction is stopped. Pouring the reaction solution into ice water, stirring for 10-20min, standing for layering, and using CH as upper water 2 Cl 2 Extracting for 2-4 times until the lower layer is colorless, mixing the lower layers, and extracting the lower layer with saturated NaHCO solution 3 The solution was washed with saturated NaCl solution, the lower layer was dried over anhydrous sodium sulfate and rotary evaporated to give the product 2- (12-chloro-dodecyloxy) -tetrahydropyran 68 as a pale yellow oily liquid.01g, GC external standard detection purity protects 92% of the product, and the yield is 90.56%.
Through three examples, the yield of the reaction scheme is stabilized to be more than 90%, and the purity is also more than 90%, so that the reaction scheme is feasible, and the subsequent production of other products is guaranteed.
Comparative example 1:
in a 500mL three-necked flask, 10-bromo-1-decanol 50.04g (0.2108 mol), p-toluenesulfonic acid monohydrate 0.40g (2.108 mmol), 400mL of CH 2 Cl 2 Keeping the temperature of the solution at-15 ℃ for 15min, dropwise adding allyl chloroformate 50.80g (0.4216 mol) at the constant temperature of about-5 ℃ at the internal temperature, keeping the temperature after dropwise adding, continuously stirring for 8h, and stopping reaction. Pouring the reaction solution into water, stirring for 10-20min, standing for layering, and using CH as upper layer water 2 Cl 2 Extracting for 2-4 times until the lower layer is colorless, mixing the lower layers, and adding saturated NaHCO into the lower layer solution 3 The solution is washed, then washed by saturated NaCl solution, the lower layer is dried by anhydrous sodium sulfate and is evaporated in a rotary way to obtain light yellow oily liquid, namely a product 2- (10-bromine-decyloxy) -tetrahydropyrane 67.03g, a purity protection product 86.16 percent by GC external standard detection, and the yield is 85.23 percent.
Comparative example 2:
in a 1000mL three-necked flask, 50.08g (0.2395 mol) of 8-bromo-1-octanol, 0.46g (2.395 mmol) of p-toluenesulfonic acid monohydrate, 500mL of CH were added 2 Cl 2 The solution is kept at the temperature of minus 12 ℃ for 15min, 3,4-dihydropyran 32.23g (0.3832 mol) is dripped at the constant temperature of about minus 2 ℃ at the internal temperature, the temperature is maintained after the dripping is finished, the stirring is continued for 5h, and the reaction is stopped. Pouring the reaction solution into water, stirring for 10-20min, standing for layering, and using CH as upper layer water 2 Cl 2 Extracting for 2-4 times until the lower layer is colorless, mixing the lower layers, and adding saturated NaHCO into the lower layer solution 3 The solution was washed with saturated NaCl solution, the lower layer was dried over anhydrous sodium sulfate and rotary evaporated to give a pale yellow oily liquid, product 2- (8-bromo-octyloxy) -tetrahydropyran 64.50g, product 87.59% purity by GC external standard assay, 80.45% yield.
Comparative example 3:
in a 1000mL three-necked flask, 50.02g (0.2266 mol) of 12-chloro-1-dodecanol was added,p-toluenesulfonic acid monohydrate 0.43g (2.266 mmol), 600mL CH 2 Cl 2 61.47g (0.4078 mol) of tert-butyldimethylsilyl chloride is dropwise added into the solution at a constant temperature of about 0 ℃ at the internal temperature, and the reaction is stopped after the dropwise addition is finished and the temperature is maintained and the stirring is continued for 10 hours. Pouring the reaction solution into water, stirring for 10-20min, standing for layering, and using CH as upper layer water 2 Cl 2 Extracting for 2-4 times until the lower layer is colorless, mixing the lower layers, and adding saturated NaHCO into the lower layer solution 3 The solution was washed with saturated NaCl solution, the lower layer was dried over anhydrous sodium sulfate and rotary evaporated to give a pale yellow oily liquid, product 2- (12-chloro-dodecyloxy) -tetrahydropyran 62.97g, purity protection 89.25% by GC external standard assay, yield 81.36%.
The comparative experiment shows that the yield of the original experimental method is 80.45-85.23%, the purity of the product is 86.16-89.25%, and compared with the purity and the yield obtained in the current embodiment which are both more than 90%, the yield and the purity of the current embodiment are obviously improved, so that the feasibility of the reaction is shown.
It should be noted that, in this document, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising a … …" does not exclude the presence of another identical element in a process, method, article, or apparatus that comprises the element.
The above description is only for the preferred embodiment of the present invention, and is not intended to limit the scope of the present invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention shall fall within the protection scope of the present invention.
Claims (10)
1. A method for protecting a hydroxyl group of a terminal alcohol by using pyridinium 4-methylbenzenesulfonate as a catalyst is characterized by comprising the following steps:
(1) Adding raw material alcohol and 4-methyl pyridinium benzenesulfonate into a reactor, and then adding a solvent;
(2) Then dropping a protective reagent, and separating an oil phase;
(3) Extracting the water phase with nonpolar solvent, and mixing the water phase and the oil phase;
(4) Washing the oil phase, drying the oil phase by using a drying agent, and performing rotary evaporation to obtain a hydroxyl protection product.
2. The method for protecting terminal alcoholic hydroxyl group by using pyridinium 4-methylbenzenesulfonate as a catalyst according to claim 1, wherein the protection reaction route of the method for protecting terminal alcoholic hydroxyl group is as follows:
wherein the content of the first and second substances,
is a structure of a terminal alcohol;
3. The method for protecting hydroxyl groups on terminal alcohols using pyridinium 4-methylbenzenesulfonate as a catalyst according to claim 1, wherein the molar ratio of the starting alcohol to pyridinium 4-methylbenzenesulfonate is 1.
4. The method for protecting hydroxyl end group of alcohol with pyridinium 4-methylbenzenesulfonate as the catalyst according to claim 1, wherein the nonpolar solvent comprises one or more of dichloromethane, N-hexane, methanol, N-dimethylformamide and tetrahydrofuran.
5. The method for protecting hydroxyl groups of terminal alcohols by using pyridinium 4-methylbenzenesulfonate as a catalyst according to claim 1, wherein the mass ratio of the nonpolar solvent to the raw material alcohol is 8: 1-20: 1.
6. the method for protecting hydroxyl end groups of alcohols by using pyridinium 4-methylbenzenesulfonate as a catalyst according to claim 1, wherein the protecting reagent comprises one or more of 3, 4-dihydropyran, tert-butyldimethylchlorosilane, allyl chloroformate and oxymethyl ether.
7. The method for protecting hydroxyl groups of terminal alcohols using pyridinium 4-methylbenzenesulfonate as a catalyst according to claim 1, wherein the molar ratio of the protecting agent to the starting alcohol is 1.2.
8. The method for protecting hydroxyl group of terminal alcohol using pyridinium 4-methylbenzenesulfonate as a catalyst according to claim 2, wherein X in the structure of the terminal alcohol is F, cl, br or I.
9. The method for protecting hydroxyl end groups of alcohols by using pyridinium 4-methylbenzenesulfonate as a catalyst according to claim 1, wherein the drying agent is one or more of anhydrous sodium sulfate, anhydrous sodium carbonate, anhydrous magnesium sulfate and anhydrous calcium chloride.
10. The method for protecting hydroxyl groups of terminal alcohols using pyridinium 4-methylbenzenesulfonate as a catalyst according to claim 1, wherein the terminal alcohols include 10-chloro-1-decanol, 10-bromo-1-decane, 8-chloro-1-octanol, 8-bromo-1-octanol, and 12-chloro-1-dodecanol.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101952243A (en) * | 2008-04-29 | 2011-01-19 | 霍夫曼-拉罗奇有限公司 | 4-dimethylaminobutyric acid derivatives |
| CN104974027A (en) * | 2015-07-30 | 2015-10-14 | 黑龙江省科学院微生物研究所 | Synthesis method of Chilosuppressalis (Walker) pheromone cis-11-hexedecanal |
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- 2022-09-14 CN CN202211114524.4A patent/CN115304569A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101952243A (en) * | 2008-04-29 | 2011-01-19 | 霍夫曼-拉罗奇有限公司 | 4-dimethylaminobutyric acid derivatives |
| CN104974027A (en) * | 2015-07-30 | 2015-10-14 | 黑龙江省科学院微生物研究所 | Synthesis method of Chilosuppressalis (Walker) pheromone cis-11-hexedecanal |
| CN110143856A (en) * | 2019-06-12 | 2019-08-20 | 山东省农药科学研究院 | A kind of synthetic method of dichocrocis punctiferalis sex pheromone (Z, E) -10- hexadecene aldehyde compound |
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