CN101440084B - Sulfonylcalix [4] aromatic compounds and microwave assisted synthesizing method thereof - Google Patents
Sulfonylcalix [4] aromatic compounds and microwave assisted synthesizing method thereof Download PDFInfo
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- CN101440084B CN101440084B CN200810249836A CN200810249836A CN101440084B CN 101440084 B CN101440084 B CN 101440084B CN 200810249836 A CN200810249836 A CN 200810249836A CN 200810249836 A CN200810249836 A CN 200810249836A CN 101440084 B CN101440084 B CN 101440084B
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- aromatic hydroxy
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Abstract
The invention discloses a sulfonylcalix[4]arene compound and a microwave-assisted synthesis method thereof. The concrete synthetic route comprises the following steps: with the assistance of microwave, hydrogen peroxide and acetic acid are used to react for 5 to 50 minutes at a temperature of between 20 and 50 DEG C, and sulfonylcalix[4]arene is quantificationally oxidized into the corresponding sulfonylcalix[4]arene compound. The method does not need poisonous chloroform solvents and expensive trifluoroacetic acid, has short reaction time, high yield and single product, and has the advantages of low cost and small environmental pollution.
Description
Technical field
The present invention relates to a kind of sulfone assorted cup [4] aromatic hydroxy compound and microwave assisted synthesizing method thereof.
Background technology
Calixarene is the most deep third generation supramolecule acceptor of research after crown ether, Schardinger dextrins; Have unique topological framework and abundant chemical reaction site; Many ions and neutral molecule are had excellent molecular recognition and selectivity inclusion function, are the outstanding structure platforms of constructing the new function acceptor molecule.Thiacalixarene is with the methylene bridge (CH in the calixarene structure
2-) change sulphur bridge (the one type of novel macrocycle molecule that S-) obtains into.The Thiacalixarene compound is compared with calixarene, because sulphur bridge (S-) has substituted the methylene bridge (CH that connects phenol units in the calixarene structure
2-), not only enlarge the cup chamber of calixarene, and increased extra combination and chemically modified site, have abundant more chemical research content and application prospect.Therefore, receive much attention based on the Supramolecular Recognition of Thiacalixarene and assembling research in recent years.Particularly the sulphur bridge of Thiacalixarene is (S-) than the methylene bridge (CH of calixarene
2-) be easier to chemically modified, can be oxidized to corresponding sulfoxide bridge (SO-) or sulfone bridge (SO
2-), construct various novel Thiacalixarene acceptor molecules.
At present, (S-) be oxidized to sulfone bridge (SO to the sulphur bridge of Thiacalixarene
2-) method mainly contain 3 kinds:
(1) with NaBO
3/ AcOH makes oxygenant, the chloroform give solvent;
(2) make oxygenant with mCPBA, the chloroform give solvent;
(3) with H
2O
2/ TFA makes oxygenant, the chloroform give solvent.
Utilize above-mentioned three kinds of method oxidation Thiacalixarenes to prepare the assorted calixarene compound of sulfone, long reaction time not only, and also oxidation is incomplete sometimes, and product is complicated especially, is difficult to separate; Especially generally adopted the bigger chloroform give solvent of toxicity, environment has been polluted easily.Therefore, invent a kind of fast, the method for the oxidation Thiacalixarene of efficient, green, environmental protection, to the assorted calixarene compound of synthetic sulfone, construct novel supramolecule acceptor and have crucial meaning.Because method (1) and (2) employed Sodium peroxoborate (NaBO
3) and metachloroperbenzoic acid (mCPBA) all need use hydrogen peroxide (H
2O
2) prepare, therefore, comparatively speaking method (3) has certain advantage, but used trifluoroacetic acid (TFA) costs an arm and a leg.
Constantly perfect along with microwave technology and equipment thereof, microwave-assisted organic synthesis has in recent years obtained significant progress.Research shows that microwave is used for organic synthesis, can shorten the reaction times greatly, effectively improve reaction yield.We find, under the microwave-assisted condition, are oxidized to the assorted calixarene compound of sulfone to Thiacalixarene, only need ydrogen peroxide 50 (H
2O
2) and acetate (AcOH), do not need expensive trifluoroacetic acid and chloroform give solvent.
Summary of the invention
To the deficiency of prior art, the present invention aims to provide a kind of sulfone assorted cup [4] aromatic hydroxy compound and microwave assisted synthesizing method thereof, and purpose is to utilize the microwave-assisted condition to shorten the reaction times; Improve combined coefficient; Simplify synthetic operation, reduce environmental pollution, reduce energy consumption.
Synthetic compound structure of the present invention is suc as formula shown in (I):
R in the formula
1Be hydrogen, the tertiary butyl both any one; R
2For in ethyl, 2-chloroethyl, 2-bromotrifluoromethane, 2-methoxy ethyl, phenyl, p-nitrophenyl, m-nitro base, 2-p-nitrophenyl oxygen base ethyl, the 2-m-nitro oxygen base ethyl any one.
The concrete reaction process of the present invention is following:
Under microwave condition with thia cup [4] aromatic hydroxy compound and ydrogen peroxide 50 and acetate in 20 ℃ to 50 ℃ reactions 5-50 minute.Thia cup [4] aromatic hydroxy compound: ydrogen peroxide 50: the equivalence ratio of acetate is 1.0: 5.0: 2.0 ~ 1.0: 15.0: 9.0, and the concentration of ydrogen peroxide 50 is 10% ~ 35%; The gained reaction mixture is added water earlier stir, filter then, solid is used water washing, and vacuum-drying gets product.
Thia cup [4] aromatic hydroxy compound structure is suc as formula shown in (II):
R in the formula
1Be hydrogen, the tertiary butyl both any one; R
2For in ethyl, 2-chloroethyl, 2-bromotrifluoromethane, 2-methoxy ethyl, phenyl, p-nitrophenyl, m-nitro base, 2-p-nitrophenyl oxygen base ethyl, the 2-m-nitro oxygen base ethyl any one.R
1, R
2Difference can show different reactive behavioies.
The inventive method can be represented with following reaction formula:
Ydrogen peroxide 50 and acetate used among the present invention are commercially available general chemistry article, and the concentration of ydrogen peroxide 50 has significant effects to reaction times, yield and product purity.General concentration increases, corresponding shortening of reaction times, and preferred concentrations is 20%-30%.
Preferred thia cup [4] aromatic hydroxy compound among the present invention: ydrogen peroxide 50: the equivalence ratio of acetate is 1.0: 8.0: 4.0-1.0: 15.0: 8.0.
The temperature of reaction that adopts among the present invention is 20 ℃ to 50 ℃, and the reaction times is 5-50 minute.
The microwave power that adopts among the present invention is 400-800 watt.
Beneficial effect of the present invention is:
The present invention adopts the microwave-assisted technology, with the assorted cup of the synthetic corresponding sulfone of hydrogen peroxide oxidation thia cup [4] aromatic hydrocarbons [4] aromatic hydroxy compound.This compound method does not need deleterious chloroform give solvent, need not expensive trifluoroacetic acid, only need ydrogen peroxide 50 and a spot of acetate.The inventive method have the reaction times short, yield is high, product is single, cost is low, the advantage that environmental pollution is little.
Embodiment
Through embodiment the present invention is specifically described below, it is to be noted here: present embodiment only is used for the present invention is further specified, but does not limit to its scope.This area professional is conspicuous in the various improvement of having done without prejudice to essence of the present invention after reading the present invention, all belongs to requirement protection domain of the present invention.
Embodiment 1:
With 25,26,27,28-four [2-(2-p-nitrophenyl oxygen base oxethyl) oxyethyl group]-to tertiary butyl thia cup [4] aromatic hydrocarbons (0.100g, 0.064mmol), H
2O
2(0.33mL, 2.9mmol) and the mixture of AcOH (0.10mL), in microwave reactor, temperature is 30 ℃, power is 600W, reacts 15 minutes.Reaction mixture adds water and stirs, suction filtration, and washing, vacuum-drying gets yellow solid (mp.206-207 ℃), and 25,26,27,28-four [2-(2-p-nitrophenyl oxygen base oxethyl) oxyethyl group]-to the assorted cup of tertiary butyl sulfone [4] aromatic hydrocarbons, productive rate 95%.
1H?NMR(300MHz，CDCl
3)：δ8.37(s，8H)，8.24(d，8H，J＝9.20Hz)，7.03(d，8H，J＝9.20Hz)，4.60(t，8H，J＝5.30Hz)，4.30(t，8H，，J＝4.60Hz)，3.95(t，8H，J＝4.60Hz)，3.89(t，8H，J＝5.30Hz)，1.32(s，36H)。
Embodiment 2:
25,26,27,28-four [2-(2-chloroethoxy) oxyethyl group]-to tertiary butyl thia cup [4] aromatic hydrocarbons (0.200g, 0.174mmol), H
2O
2(0.90mL, 7.840mmol) and the mixture of AcOH (0.20mL), in microwave reactor, temperature is a room temperature, power is 500W, reacts 10 minutes.Reaction mixture adds water and stirs, suction filtration, and washing, vacuum-drying get white solid (mp.＞300 ℃), and 25,26,27,28-four [2-(2-chloroethoxy) oxyethyl group]-to the assorted cup of tertiary butyl sulfone [a 4] aromatic hydrocarbons, productive rate is 98%.
1H?NMR(300MHz，CDCl
3)：δ8.38(s，8H)，4.58(t，8H，J＝5.67Hz)，3.84(t，16H，J＝5.98Hz)，3.71(t，8H，J＝5.83Hz)，1.40(s，36H)。
Claims (4)
1. the assorted cup of a sulfone [a 4] aromatic hydroxy compound microwave assisted synthesizing method is characterized in that reaction process is following:
A. according to proper ratio thia cup [4] aromatic hydroxy compound is mixed with oxygenant, and under certain temperature and microwave-assisted condition, react;
B. after reacting for some time, the gained reaction mixture is added water earlier stir, filter then, solid is used water washing, and vacuum-drying gets product;
Wherein, thia cup [4] the aromatic hydroxy compound structure of participation reaction is following:
R in the formula
1Be hydrogen, the tertiary butyl both any one; R
2For in ethyl, 2-chloroethyl, 2-bromotrifluoromethane, 2-methoxy ethyl, phenyl, p-nitrophenyl, m-nitro base, 2-p-nitrophenyl oxygen base ethyl, the 2-m-nitro oxygen base ethyl any one; Oxygenant is ydrogen peroxide 50 and acetate;
The compound that synthesizes that obtains has following structure:
R in the formula
1Be hydrogen, the tertiary butyl both any one; R
2For in ethyl, 2-chloroethyl, 2-bromotrifluoromethane, 2-methoxy ethyl, phenyl, p-nitrophenyl, m-nitro base, 2-p-nitrophenyl oxygen base ethyl, the 2-m-nitro oxygen base ethyl any one;
Said thia cup [4] aromatic hydroxy compound: ydrogen peroxide 50: the equivalence ratio of acetate is 1.0:5.0:2.0---1.0:15.0:9.0; The concentration of said ydrogen peroxide 50 is 10%-35%; Said temperature of reaction is 20 ℃ to 50 ℃, and the reaction times is 5-50 minute.
2. the assorted cup of a kind of sulfone according to claim 1 [4] aromatic hydroxy compound microwave assisted synthesizing method is characterized in that microwave-assisted is synthetic, and microwave power is 400-800 watt.
3. the assorted cup of the described a kind of sulfone of claim 1 [4] aromatic hydroxy compound microwave assisted synthesizing method is characterized in that dioxygen wet concentration concentration is 20%-30%.
4. the assorted cup of a kind of sulfone according to claim 1 [4] aromatic hydroxy compound microwave assisted synthesizing method is characterized in that thia cup [4] aromatic hydroxy compound: ydrogen peroxide 50: the equivalence ratio 1.0:8.0:4.0 of acetate---1.0:15.0:8.0.
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| CN101440084B true CN101440084B (en) | 2012-10-03 |
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| CN106905308B (en) * | 2017-03-03 | 2019-09-10 | 福建中烟工业有限责任公司 | A kind of thia cup [4] arene derivatives and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1998009959A1 (en) * | 1996-09-06 | 1998-03-12 | Cosmo Research Institute | Cyclic phenol sulfide containing sulfinyl or sulfonyl group and process for preparing the same |
| WO2008087967A1 (en) * | 2007-01-16 | 2008-07-24 | Hodogaya Chemical Co., Ltd. | Process for production of oxidized cyclic phenol sulfide |
| WO2008139638A1 (en) * | 2007-05-07 | 2008-11-20 | National University Corporation Akita University | Extractant for rare metal or platinum-group metal and method of extracting rare metal or platinum-group metal |
-
2008
- 2008-12-29 CN CN200810249836A patent/CN101440084B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1998009959A1 (en) * | 1996-09-06 | 1998-03-12 | Cosmo Research Institute | Cyclic phenol sulfide containing sulfinyl or sulfonyl group and process for preparing the same |
| WO2008087967A1 (en) * | 2007-01-16 | 2008-07-24 | Hodogaya Chemical Co., Ltd. | Process for production of oxidized cyclic phenol sulfide |
| WO2008139638A1 (en) * | 2007-05-07 | 2008-11-20 | National University Corporation Akita University | Extractant for rare metal or platinum-group metal and method of extracting rare metal or platinum-group metal |
Non-Patent Citations (1)
| Title |
|---|
| 刘志鹏.新型电化学活性硫杂杯[4]芳烃多位点受体的合成、表征及超分子识别研究.《中国优秀硕士学位论文全文数据库 工程科技I辑》.2007,第50-51页. * |
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