CN101367713A - Method for synthesis of p-[1-(4-hydroxyl phenyl)-1-methyl ethyl] calix[8]arene - Google Patents
Method for synthesis of p-[1-(4-hydroxyl phenyl)-1-methyl ethyl] calix[8]arene Download PDFInfo
- Publication number
- CN101367713A CN101367713A CNA2008101432897A CN200810143289A CN101367713A CN 101367713 A CN101367713 A CN 101367713A CN A2008101432897 A CNA2008101432897 A CN A2008101432897A CN 200810143289 A CN200810143289 A CN 200810143289A CN 101367713 A CN101367713 A CN 101367713A
- Authority
- CN
- China
- Prior art keywords
- methylethyl
- cup
- aromatic hydrocarbons
- hydroxy phenyl
- temperature
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a process method for synthesizing p-[1-(4-hydroxy phenyl)-1-methyl ethyl]calix[8] arene. P-[1-(4-methoxy phenyl)-1-methyl ethyl]calix [8] arene is added into methylene chloride solvent which is cooled in low temperature and stirred to be dissolved; and under the protection of the insert gas and the stirring, the methylene chloride solvent of boron bromide is added in drops; and then the temperature is increased the room temperature, and the mixture is continuously stirred, at last the reacted mixture is mixed with water, and then acutely stirred, filtered, washed and precipitated with water, dried and precipitated, and then recrystallized with absolute alcohol to obtain light brown powder solid. Compared with the prior method, the reaction process is easy to be controlled, the process is more reasonable and the yield is improved.
Description
Technical field
The present invention relates to a kind of processing method of synthetic preparation cup [8] arene derivatives, particularly relate to the synthetic processing method for preparing right-[1-(4-hydroxy phenyl)-1-methylethyl] cup [8] aromatic hydrocarbons of a kind of selectivity.
Background technology
Calixarene is that a class is by para-orientation phenol and the formaldehyde oligomerization macrocylc compound with unique cavity structure that condensation forms under alkaline condition.Calixarene can form inclusion compound, thereby be widely used in host-guest coordination and bionics in conjunction with neutral organic molecule, polymer molecule, metal ion and negatively charged ion.In order to make the calixarene can be in conjunction with big organic guest molecule, the size that just needs expansion calixarene cavity, this respect has been done a lot of effort, there is several dark chambeies calixarene to synthesize out (as A.Arduini by derivatize at the calixarene upper limb, et al., Extension of the hydrophobic cavity ofcalix[4] arene by " upper rim " functionalization.Tetrahedron, 1992,48:905-912; R.K.Juneja, etal., Synthesis and characterization of rigid, deep-cavity calix[4] arenes.J.Am.Chem.Soc., 1993,115:3818-3819; I.E.Lubitov, et al., New class of host molecules.p-1-Adamantylcalix[8] arenes.Synlett, 1993,647-648 etc.).Yet the chemistry and the applied research slower development thereof of dark chamber calixarene are because these compounds lack the synthetic method of high yield.Therefore, the new Calixarene Derivatives synthetic method of research and development is significant.People such as Tung (A novel host molecule p-[1-(4-hydroxyphenyl)-1-methylethyl]-calix[8] arene.Synthesis and complexation properties in non-aqueous polar solution; J.Chem.Soc.; PerkinTrans.; 1997; 2:185-188) once reported a kind of processing method for preparing right-[1-(4-hydroxy phenyl)-1-methylethyl] cup [8] aromatic hydrocarbons; promptly under nitrogen protection; the dichloromethane solution of boron bromide is added drop-wise to refrigerative is dissolved with in the methylene dichloride of right-[1-(4-p-methoxy-phenyl)-1-methylethyl] cup [8] aromatic hydrocarbons in ice-water bath; stir under the room temperature then and spend the night; again reaction mixture is mixed with water; filter; dry thick product; recrystallization from alcohol-water at last; obtain light brown powder shape product, productive rate 79%.We experimental studies have found that, there are serious problems in this method: this method does not point out that control drips boron bromide--the speed of dichloromethane solution.In fact, rate of addition is one of crux factor that influences reaction result, as not controlling the dropping boron bromide--and the speed of dichloromethane solution will cause that reaction process is wayward, emulsion etc. can occur in the recrystallization, cause the target product productive rate to reduce, and unstable.In addition, proportioning between each reactant and concentration, the control that respectively goes on foot reaction conditions also are the important factors that influences reaction result.
Summary of the invention
In right-synthetic preparation of [1-(4-hydroxy phenyl)-1-methylethyl] cup [8] aromatic hydrocarbons that the present invention is intended to solve, problems such as reaction process operation is wayward, the target product productive rate is lower, the method for the synthetic target product of selectivity that provide that a kind of technical process is more reasonable, reaction process is easy to control, the target product productive rate is higher.
Technical scheme of the present invention is achieved in that
A. right-[1-(4-p-methoxy-phenyl)-1-methylethyl] cup [8] aromatic hydrocarbons is joined in subcooled dichloromethane solvent, stirs and make its dissolving;
B. under protection of inert gas and stirring, in above-mentioned system, drip the dichloromethane solution of boron bromide, make temperature rise to room temperature after dripping, at room temperature continue to stir 12-18h; What drip is that the boron bromide strength of solution of solvent is 0.05-0.10g/mL with the methylene dichloride, the ratio of the quality of the boron bromide that adds and right-[1-(4-p-methoxy-phenyl)-1-methylethyl] cup [8] aromatic hydrocarbons is 1.2:1-1.5:1, and rate of addition is controlled to be 5-60 and drips/min;
C. the gained mixture of reaction products is poured in the distilled water, and vigorous stirring 35-50min, filter, wash precipitation with water, drying precipitated, get thick product;
D. with dehydrated alcohol thick product is carried out recrystallization, and drying precipitated, and getting target product is the light brown powder solid.
The favor speed that described B dripped in the step is that 5-15 drips/min.
Low temperature referred to that temperature is 0-10 ℃ during described A went on foot, and preferred temperature range is 0-5 ℃.
Rare gas element can be a high pure nitrogen during described B went on foot, or helium, or argon gas.
After described C is poured into distilled water with the gained mixture of reaction products in the step, the cumulative volume of gained be gained mixture of reaction products volume 6-7 doubly.
The drying temperature of described C in the step is 50-100 ℃, and be 1.5-3h time of drying.
The drying temperature of described D in the step is 50-100 ℃, and be 1.5-3h time of drying.
Described A right-[1-(4-p-methoxy-phenyl)-1-methylethyl] cup [8] aromatic hydrocarbons in the step can adopt the contriver makes by oneself or other can be bought approach or other people to prepare the chamber by experiment, wherein homemade synthetic method has been applied for Chinese invention patent, patent (application) number 200810031422.X, its homemade preparation process is: add (the self-control of 17.0g (0.070mol) 2-(4-hydroxy phenyl)-2-(4-p-methoxy-phenyl) propane successively in the 250mL four-hole boiling flask, its synthetic method has been applied for Chinese invention patent, number of patent application 200710035967.3), 3.95g Paraformaldehyde 96,0.6mL10mol/L sodium hydroxide and 78mL dimethylbenzene; Structure has the chemical synthesizer system of nitrogen protection, stirring, oil bath heating, backflow and oil-water separating function, and reactor is a part wherein; Under high pure nitrogen protection and vigorous stirring, reaction-ure mixture is heated to backflow from room temperature, the control temperature-rise period time is 2.5h, and keeps backflow 4.5h; After stopping to reflux, be cooled to room temperature gradually; The suction filtration mixture of reaction products leaches precipitation and uses toluene, sherwood oil, acetone and water washing successively, and in baking oven 105 ℃ of following dry 2h; Use the chloroform recrystallization then, and at 80 ℃ of following dry 2h, making target product at last is the white powder solid, heavy 9.9g, productive rate 55.5%.The analysis and characterization data acknowledgement structure of target product.Fusing point (Mp)〉300 ℃.The target product molecular formula is C
136H
144O
16, the constituent content calculated value is: C, 80.31%; H, 7.09%; Measured value is: C, 79.92%; H, 7.18%.
1H and
13C NMR data are: δ
H(CDCl
3) 9.56 (1H, OH, s), 7.06 (2H, ArH, d), 6.84 (2H, ArH, s), 6.76 (2H, ArH, d), 3.73 (3H, OCH
3, s), 4.27,3.35 (2H, CH
2, 2 * d), 1.48 (6H, CH
3-C-CH
3, s); δ
C(CDCl
3) 157.25,146.52,144.62,142.64,128.55,127.62,126.78,113.17 (ArC), 55.01 (OCH
3), 41.52 (C-), 32.07 (CH
2-), 31.22 and 30.70 (CH
3).It is 2032 that fast atom bombardment(FAB) MALDI-MS (FAB-MS) negative ion mode monitors the molecule formula weight.
Beneficial effect of the present invention is: owing to controlled the rate of addition of one of reactant, make the phenomenon that can not occur the local overrich of reactant in the reaction system, help under lower concentration, forming between the reactant stable title complex like this, reduced the side reaction odds, can improve productive rate, and the control of reaction process easy handling.Present method technical process is easy, and the target product productive rate is higher.Target productive rate by preparation method's gained of the present invention can be up to more than 88.9%, improved tens percent than original preparation method's 79% productive rate.Efficient also improves a lot.
Embodiment
Following examples are intended to illustrate the present invention rather than limitation of the invention further, and the present invention can implement by the described arbitrary mode of summary of the invention.
Embodiment 1
In the 250mL four-hole boiling flask, add 25mL exsiccant methylene dichloride, temperature is 3.5 ℃ in being cooled in the ice-water bath, add 1.0125g right-(self-control of [1-(4-p-methoxy-phenyl)-1-methylethyl] cup [8] aromatic hydrocarbons, its synthetic method has been applied for Chinese invention patent, number of patent application 200810031422.X), stirring makes its dissolving; Structure has the chemical synthesizer system of protection of inert gas, stirring, low temperature controlled function, and reactor is a part wherein; Under high pure nitrogen protection and vigorous stirring, by constant pressure funnel, the dichloromethane solution of dropping 25mL boron bromide in the reactor, concentration is 0.060g/mL, rate of addition is controlled to be 10/min; Drip recession deicing water-bath, at room temperature continue stirred reaction mixture 15h again; Remove nitrogen protection, impouring 200mL distilled water in the reaction mixture, and vigorous stirring 40min; The suction filtration mixture of reaction products washes precipitation with water, and filter cake is 80 ℃ of following dry 2.5h in baking oven, get thick product; Use the dehydrated alcohol recrystallization then, be deposited in 80 ℃ of dry 2h down, making target product at last is the light brown powder solid, heavy 0.8594g, productive rate 89.83%.The analysis and characterization data acknowledgement structure of target product.Fusing point (Mp)〉300 ℃.The target product molecular formula is C
128H
128O
16, the constituent content calculated value is: C, 80.00%; H, 6.67%; Measured value is: C, 80.10%; H, 6.66%.
1H and
13C NMR data are: δ
H[(CD
3)
2SO] 9.08 (1H, OH, s), 8.93 (1H, OH, s), 6.89 (2H, ArH, d), 6.69 (2H, ArH, s), 6.58 (2H, ArH, d), 3.70 (2H, CH
2, s), 1.38 (6H, CH
3, s); δ
C[(CD
3)
2SO] 154.82,148.37,142.42,140.68,127.10,126.98,126.16,114.45 (ArC), 40.80 (C-), 31.02 (CH
2) and 30.72 (CH
3).It is 1920 that fast atom bombardment(FAB) MALDI-MS (FAB-MS) negative ion mode monitors the molecule formula weight.
Embodiment 2
Add 25mL exsiccant methylene dichloride in the 250mL four-hole boiling flask, temperature is 3.5 ℃ in being cooled in the ice-water bath, add 1.0175g right-[1-(4-p-methoxy-phenyl)-1-methylethyl] cup [8] aromatic hydrocarbons, stir and make its dissolving; Structure has the chemical synthesizer system of protection of inert gas, stirring, low temperature controlled function, and reactor is a part wherein; Under high pure nitrogen protection and vigorous stirring, by constant pressure funnel, the dichloromethane solution of dropping 25mL boron bromide in the reactor, concentration is 0.060g/mL, rate of addition is controlled to be 6/min; Drip recession deicing water-bath, at room temperature continue stirred reaction mixture 15h again; Remove nitrogen protection, impouring 200mL distilled water in the reaction mixture, and vigorous stirring 40min; The suction filtration mixture of reaction products washes precipitation with water, and filter cake is 80 ℃ of following dry 2.5h in baking oven, get thick product; Use the dehydrated alcohol recrystallization then, be deposited in 80 ℃ of dry 2h down, making target product at last is the light brown powder solid, heavy 0.8812g, productive rate 91.66%.The analysis and characterization data acknowledgement structure of target product (concrete data with embodiment 1).
Embodiment 3
Add 20mL exsiccant methylene dichloride in the 250mL four-hole boiling flask, temperature is 3.5 ℃ in being cooled in the ice-water bath, add 1.0026g right-[1-(4-p-methoxy-phenyl)-1-methylethyl] cup [8] aromatic hydrocarbons, stir and make its dissolving; Device is with embodiment 1; Drip the dichloromethane solution of 20mL boron bromide in the reactor, concentration is 0.06g/mL, and rate of addition is controlled to be 6/min.Other process flow steps is with embodiment 1.Making target product is light brown powder 0.8423g, productive rate 88.91%.The analysis and characterization data acknowledgement structure of target product (concrete data with embodiment 1).
Claims (7)
- One kind synthetic right-method of [1-(4-hydroxy phenyl)-1-methylethyl] cup [8] aromatic hydrocarbons, it is characterized in that:A. right-[1-(4-p-methoxy-phenyl)-1-methylethyl] cup [8] aromatic hydrocarbons is joined in subcooled dichloromethane solvent, stirs and make its dissolving;B. under protection of inert gas and stirring, in above-mentioned system, drip the dichloromethane solution of boron bromide, make temperature rise to room temperature after dripping, at room temperature continue to stir 12-18h; What drip is that the boron bromide strength of solution of solvent is 0.05-0.10g/mL with the methylene dichloride, the ratio of the quality of the boron bromide that adds and right-[1-(4-p-methoxy-phenyl)-1-methylethyl] cup [8] aromatic hydrocarbons is 1.2:1-1.5:1, and rate of addition is controlled to be 5-60 and drips/min.C. the gained mixture of reaction products is poured in the distilled water, and vigorous stirring 35-50min, filter, wash precipitation with water, drying precipitated, get thick product;D. with dehydrated alcohol thick product is carried out recrystallization, and drying precipitated, and getting target product is the light brown powder solid.
- 2. a kind of method of synthesizing right-[1-(4-hydroxy phenyl)-1-methylethyl] cup [8] aromatic hydrocarbons according to claim 1 is characterized in that low temperature referred to that temperature is 0-10 ℃ during described A went on foot.
- 3. a kind of method of synthesizing right-[1-(4-hydroxy phenyl)-1-methylethyl] cup [8] aromatic hydrocarbons according to claim 1 is characterized in that rare gas element was a high pure nitrogen during described B went on foot, or helium, or argon gas.
- 4. a kind of method of synthesizing right-[1-(4-hydroxy phenyl)-1-methylethyl] cup [8] aromatic hydrocarbons according to claim 1 is characterized in that the speed that described B dripped in the step is that 5-15 drips/min.
- 5. a kind of method of synthesizing right-[1-(4-hydroxy phenyl)-1-methylethyl] cup [8] aromatic hydrocarbons according to claim 1, it is characterized in that, after described C is poured into distilled water with the gained mixture of reaction products in the step, the cumulative volume of gained be gained mixture of reaction products volume 6-7 doubly.
- 6. a kind of method of synthesizing right-[1-(4-hydroxy phenyl)-1-methylethyl] cup [8] aromatic hydrocarbons according to claim 1 is characterized in that the drying temperature of described C in the step is 50-100 ℃, and be 1.5-3h time of drying.
- 7. a kind of method of synthesizing right-[1-(4-hydroxy phenyl)-1-methylethyl] cup [8] aromatic hydrocarbons according to claim 1 is characterized in that the drying temperature of described D in the step is 50-100 ℃, and be 1.5-3h time of drying.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008101432897A CN101367713B (en) | 2008-09-25 | 2008-09-25 | Method for synthesis of p-[1-(4-hydroxyl phenyl)-1-methyl ethyl] sulfonatocalyx [8]arene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008101432897A CN101367713B (en) | 2008-09-25 | 2008-09-25 | Method for synthesis of p-[1-(4-hydroxyl phenyl)-1-methyl ethyl] sulfonatocalyx [8]arene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101367713A true CN101367713A (en) | 2009-02-18 |
| CN101367713B CN101367713B (en) | 2011-05-04 |
Family
ID=40411743
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2008101432897A Active CN101367713B (en) | 2008-09-25 | 2008-09-25 | Method for synthesis of p-[1-(4-hydroxyl phenyl)-1-methyl ethyl] sulfonatocalyx [8]arene |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101367713B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101822426B (en) * | 2010-02-05 | 2011-08-03 | 湖南中烟工业有限责任公司 | Application method of para-[1-(4-methoxyphenyl)-1-methylethyl] calix [8] arene |
-
2008
- 2008-09-25 CN CN2008101432897A patent/CN101367713B/en active Active
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101822426B (en) * | 2010-02-05 | 2011-08-03 | 湖南中烟工业有限责任公司 | Application method of para-[1-(4-methoxyphenyl)-1-methylethyl] calix [8] arene |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101367713B (en) | 2011-05-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103265420B (en) | A kind of preparation method of aromatic diketone compound | |
| CN112544621A (en) | Method for preparing 2- (4-chlorophenoxy) -propoxyamine | |
| CN110627693A (en) | Allyl sulfone compound and preparation method and application thereof | |
| CN110483267B (en) | Method for synthesizing asymmetric diarylmethane derivative | |
| CN101367713B (en) | Method for synthesis of p-[1-(4-hydroxyl phenyl)-1-methyl ethyl] sulfonatocalyx [8]arene | |
| TW202108551A (en) | A method for producing 9,9-bis(3-phenyl-4-(2-hydroxyethoxy)phenyl)fluorene | |
| CN103450005B (en) | A kind of preparation method of clopidogrel and the alpha-brominated (2-Chlorophenyl)acetic acid of intermediate and α-thiophene ethamine base substituted acetic acid hydrochlorate | |
| CN107056792A (en) | A kind of novel porphyrin class compound and its preparation method and application | |
| CN110483387A (en) | A kind of method of one pot process nicotimine amide derivatives | |
| CN110372653A (en) | A kind of selenizing benzofuran compound and its synthetic method | |
| CN101279898B (en) | Synthetic method of p-[1-(4-methoxyphenyl)-1- methyl ethyl] calyx[8] arene | |
| CN101362691B (en) | Functional acrylic esters monomers containing perfluorocyclobutane aryl-ether unit, preparation method and application | |
| CN106831862B (en) | Chiral bridged axial chiral monophosphine ligand and preparation method thereof | |
| CN109180473A (en) | A method of synthesis alkynes bromoacetic acid ester type compound | |
| JP2010254693A (en) | Method for producing substituted 1,4-quinone methide | |
| WO2006062477A1 (en) | Chemical process | |
| CN110590621B (en) | Method for synthesizing 1, 2-bis (arylsulfonyl) ethylene derivative by copper-catalyzed terminal alkyne | |
| CN106573867B (en) | The method for preparing phenyl indan compound | |
| CN110357880B (en) | Folded body-based chiral fluorescent compound with circular polarization luminescence property and preparation method and application thereof | |
| CN113372219B (en) | Method for preparing ethynylnaphthalene derivative by [4+2] cyclization reaction with water as solvent | |
| CN100537577C (en) | Preparation process of 6'-nitroindolyline benzspriothiane | |
| CN105175359A (en) | Lomerizine Hydrochloride isomeride and preparation method therefor | |
| CN109912661A (en) | Pyrimidine with catalytic performance-pyrazoles ruthenium complex and preparation method thereof | |
| CN109942553A (en) | A kind of synthesis of tri- substituted-tetrahydro 2H- pyran-2-one compound of chirality 3,4,6- and its method for transformation | |
| CN108997297A (en) | A kind of preparation method of Nebivolol Intermediates, the intermediate for being used to prepare the Nebivolol Intermediates and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |