CN105273004A - Preparation method of pillar[n]arenes - Google Patents
Preparation method of pillar[n]arenes Download PDFInfo
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- CN105273004A CN105273004A CN201410358785.XA CN201410358785A CN105273004A CN 105273004 A CN105273004 A CN 105273004A CN 201410358785 A CN201410358785 A CN 201410358785A CN 105273004 A CN105273004 A CN 105273004A
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Abstract
The invention provides a preparation method of pillar[n]arenes, belongs to the field of a chemical industry, and especially relates to a preparation method of pillar[n]arenes. The invention provides a preparation method of pillar[n]arenes, and the method has the advantages of mild reaction, easy operation and low raw material price. The preparation method of pillar[n]arenes comprises the following steps: (1) 150ml of acetonitrile is added into a 250ml one-necked flask, 3.3g of hydroquinone and 9g of potash, that is 30mmol and 65mmol are separately added into the flask with stirring; (2) 160ml of dried dichloromethane is added into a 250ml two-necked flask, 3.8g and 0.9g of paraformaldehyde, that is 10mmol and 30mmol are added into the flask under nitrogen protection, the materials are stirred for thoroughly dissolving, the reaction bottle is placed in an ice-bath till the reaction system temperature drops to 0 DEG C; and (3) 0.5g of bromine derivatized pillar[n]arenes 2, that is 0.25mmol, is dissolved into 3ml of triethyl phosphate, the materials are heated to 150 DEG C with stirring, the reaction degree is monitored by TLC, after the reaction finishes, superfluous triethyl phosphite is removed by reduced pressure distillation; a silica gel column chromatography with ethyl acetate/methanol whose ratio is 15:1 is carried out for residues in the flask to obtain a colorless colloidal product.
Description
Technical field
the invention belongs to chemical field, especially relate to a kind of preparation method of post aromatic hydrocarbons.
Background technology
post aromatic hydrocarbons is after synthesis is reported first, and the morphological structure of its uniqueness has just attracted the attention of vast supramolecular chemistry investigator, and multiple seminars are successively studied its synthetic methodology.2 of phenyl ring with 5 relative calixarene of post aromatic hydrocarbons by methylene-bridged, structurally have more symmetry and rigidity, therefore, post aromatic hydrocarbons has advantageous advantage as neozoic host molecule in supramolecular chemistry research.Since 2010, successively successfully synthesized the water-soluble post aromatic hydrocarbons of functionalization, and to its Host-guest Recognition with should be used as certain research.2014, we were by Optimal reaction conditions, simplified under experimental implementation successful design has synthesized acidic conditions and had excellent water miscible amino functional post aromatic hydrocarbons.In order to the research making post aromatic hydrocarbons further can be applied to life system, the design and synthesis of new type water-solubility post aromatic hydrocarbons becomes particularly important.Phosphorus is indispensable element in human body, meanwhile, there is good consistency in vivo between phosphate group and different substances.Therefore, phosphoryl functionalization post aromatic hydrocarbons is that the research of post aromatic hydrocarbons in life system provides possibility.Although phosphorus carbonyl is successfully introduced in post aromatic hydrocarbons by Yuan etc., and be applied to the research to the metalloform-selective such as radioelement, rare earth bonding further, this post aromatic hydrocarbons limits its further application in life system owing to lacking water-soluble.We design and successfully synthesize water miscible phosphoryl functionalization post aromatic hydrocarbons herein.With Resorcinol and 1; 4-dibromobutane is that the intermediate 1 of starting raw material synthesis becomes ring to obtain bromine functionality post aromatic hydrocarbons 2 with paraformaldehyde under the catalysis of trifluoromethanesulfonic acid; phosphide base functionalization post aromatic hydrocarbons 3 is obtained by reacting again by Michaelis-Arbuzov; finally under the de-esterification of bromotrimethylsilane, obtain the phosphoryl functionalization post aromatic hydrocarbons 4 in alkaline aqueous solution with good solubility, product and intermediate product etc. are characterized by nuclear-magnetism, mass spectrum, the multiple method such as infrared.But common preparative column aromatic hydrocarbons method, reaction is violent, complicated operation and expensive starting materials.
Summary of the invention
the present invention is exactly for the problems referred to above, provide a kind of reaction temperature and, the simple to operate and preparation method of the post aromatic hydrocarbons of low in raw material price.
for achieving the above object, the present invention adopts following technical scheme, and the preparation method of post aromatic hydrocarbons comprises step:
(1) in 250mL single port flask, acetonitrile 150mL is added, add Resorcinol 3.3g respectively more under agitation, 30mmol and salt of wormwood 9g, 65mmol, the potassiumiodide and 1 of catalytic amount is added after stir-activating 30min more respectively under normal temperature, 4-dibromobutane 17.8g, 82mmol, is heated with stirring to backflow; After question response completes, suction filtration, removing salt of wormwood, filter residue methylene dichloride 50mL × 2 washing, merging filtrate; Concentrating under reduced pressure, gained crude by column chromatography is separated petrol ether/ethyl acetate=5:1 and obtains intermediate;
(2) in 250mL two-mouth bottle, the methylene dichloride of 160mL through drying treatment is added, then 3.8g is added respectively under nitrogen protection, 10mmol and paraformaldehyde 0.9g, 30mmol, reaction flask is placed in ice bath, until temperature of reaction system drops to 0 ° of C after making 1 thoroughly to dissolve by stirring; Add catalyzer trifluoromethanesulfonic acid 5%mmol fast, 0.11mL; Continue stirring reaction under nitrogen protection, TLC monitors reaction process; After question response completes, add a small amount of sodium hydrogen carbonate solution cancellation reaction; Reaction solution uses 10% sodium hydrogen carbonate solution 50mL × 3, saturated aqueous common salt 50mL × 3 and the washing of water 50mL × 3 successively; Collect and merge organic layer, concentrated, crude on silica gel column chromatography for separation, petrol ether/ethyl acetate=5:1 obtain white product;
(3) get the post aromatic hydrocarbons 2 of bromine derivatize, 0.5g, 0.25mmol be dissolved in 3mL triethyl-phosphite, the degree of carrying out is reacted in heated and stirred to 150 ° C, a TLC monitoring, and after question response completes, underpressure distillation is except unnecessary triethyl-phosphite; In bottle, residue obtains colourless glutinous product after silica gel column chromatography, ethyl acetate/methanol 15:1.
further, bromotrimethylsilane 2mL is diluted in after in 10mL methylene dichloride, under condition of ice bath, solution is slowly added drop-wise in the dichloromethane solution being dissolved with phosphide base functionalization post aromatic hydrocarbons 2,0.5g, after being added dropwise to complete, mixed solution is stirring reaction 10h at room temperature, adds a small amount of shrend and to go out reaction, then steam altogether with the ether of H2O and the 5mL of 5mL and obtain muddy solid, add water to obtain white solid again, with 20mL washing after suction filtration, then washes away organic solvent with the cold pentane of 50mL; Now, white product can be obtained.
beneficial effect of the present invention:
raw material Resorcinol of the present invention and 1,4-dibromobutane reacts, first the monomer synthesized, then under the catalysis of trifluoromethanesulfonic acid, pass through the post aromatic hydrocarbons of methylene-bridged and synthetic bromide alkyl functional, and then reacted by Michaelis-Arbuzov, the steps such as de-ester group have synthesized post arene derivatives, and this post aromatic hydrocarbons not only has good solubility in organic solvent DMSO, and it also has good solvability in the aqueous solution of alkalescence.This synthetic method has reaction conditions gentleness, simple to operation, the advantage of cheaper starting materials.
Embodiment
the preparation method of post aromatic hydrocarbons comprises step:
(1) in 250mL single port flask, acetonitrile 150mL is added, add Resorcinol 3.3g respectively more under agitation, 30mmol and salt of wormwood 9g, 65mmol, the potassiumiodide and 1 of catalytic amount is added after stir-activating 30min more respectively under normal temperature, 4-dibromobutane 17.8g, 82mmol, is heated with stirring to backflow; After question response completes, suction filtration, removing salt of wormwood, filter residue methylene dichloride 50mL × 2 washing, merging filtrate; Concentrating under reduced pressure, gained crude by column chromatography is separated petrol ether/ethyl acetate=5:1 and obtains intermediate;
(2) in 250mL two-mouth bottle, the methylene dichloride of 160mL through drying treatment is added, then 3.8g is added respectively under nitrogen protection, 10mmol and paraformaldehyde 0.9g, 30mmol, reaction flask is placed in ice bath, until temperature of reaction system drops to 0 ° of C after making 1 thoroughly to dissolve by stirring; Add catalyzer trifluoromethanesulfonic acid 5%mmol fast, 0.11mL.Continue stirring reaction under nitrogen protection, TLC monitors reaction process.After question response completes, add a small amount of sodium hydrogen carbonate solution cancellation reaction; Reaction solution uses 10% sodium hydrogen carbonate solution 50mL × 3, saturated aqueous common salt 50mL × 3 and the washing of water 50mL × 3 successively; Collect and merge organic layer, concentrated, crude on silica gel column chromatography for separation, petrol ether/ethyl acetate=5:1 obtain white product;
(3) get the post aromatic hydrocarbons 2 of bromine derivatize, 0.5g, 0.25mmol be dissolved in 3mL triethyl-phosphite, the degree of carrying out is reacted in heated and stirred to 150 ° C, a TLC monitoring, and after question response completes, underpressure distillation is except unnecessary triethyl-phosphite; In bottle, residue obtains colourless glutinous product after silica gel column chromatography, ethyl acetate/methanol 15:1.
bromotrimethylsilane 2mL is diluted in after in 10mL methylene dichloride, under condition of ice bath, solution is slowly added drop-wise in the dichloromethane solution being dissolved with phosphide base functionalization post aromatic hydrocarbons 2,0.5g, after being added dropwise to complete, mixed solution is stirring reaction 10h at room temperature, add a small amount of shrend to go out reaction, then steam altogether with the ether of H2O and the 5mL of 5mL and obtain muddy solid, then the white solid that adds water to obtain, with 20mL washing after suction filtration, then wash away organic solvent with the cold pentane of 50mL.Now, white product can be obtained.
with Resorcinol and 1,4-dibromobutane is initial feed synthetic intermediate 1, then under the catalysis of trifluoromethanesulfonic acid, obtain the post aromatic hydrocarbons 2 of key compound bromine functionality with polyformaldehyde reaction smoothly, then reacted by Michaelis-Arbuzov and obtain the post aromatic hydrocarbons 3 of phosphide base functionalization.Finally after the effect of grease-removing agent, obtain target product 4 by the process of alcohol and ether.Compound 4 produces the precipitation of solvability extreme difference in acid condition, only can be dissolved in DMSO in organic solvent.But in the basic conditions, can salt be formed, therefore have good water-soluble.Compound 3 is due to containing multiple phosphate-based and exist in fluid form.In Michaelis-Arbuzov reaction, carry out control experiment, 1) using dimethylbenzene as solvent, experimental result finds can not once replace completely, could well replace completely after only having repeatedly reaction repeated; 2) directly with triethyl-phosphite directly as while reaction raw materials also as solvent, result can be good at replacing completely, also substantially reduces the time of reaction simultaneously.Simultaneously; also grope by changing the synthesis of route of synthesis to phosphinylidyne pilum aromatic hydrocarbons; directly synthesized by triflic acid catalyzes with relatively easy phosphate-based functionalization monomer or phosphoryl functionalization monomer; the results show this kind of approach successfully can not synthesize phosphoryl functionalization post aromatic hydrocarbons, has the effect of cancellation thus make catalyst failure due to the existence of P=O to catalyzer.
be understandable that, above about specific descriptions of the present invention, the technical scheme described by the embodiment of the present invention is only not limited to for illustration of the present invention, those of ordinary skill in the art is to be understood that, still can modify to the present invention or equivalent replacement, to reach identical technique effect; Needs are used, all within protection scope of the present invention as long as meet.
Claims (2)
1. the preparation method of post aromatic hydrocarbons, is characterized in that, comprises step:
(1) in 250mL single port flask, acetonitrile 150mL is added, add Resorcinol 3.3g respectively more under agitation, 30mmol and salt of wormwood 9g, 65mmol, the potassiumiodide and 1 of catalytic amount is added after stir-activating 30min more respectively under normal temperature, 4-dibromobutane 17.8g, 82mmol, is heated with stirring to backflow; After question response completes, suction filtration, removing salt of wormwood, filter residue methylene dichloride 50mL × 2 washing, merging filtrate; Concentrating under reduced pressure, gained crude by column chromatography is separated petrol ether/ethyl acetate=5:1 and obtains intermediate;
(2) in 250mL two-mouth bottle, the methylene dichloride of 160mL through drying treatment is added, then 3.8g is added respectively under nitrogen protection, 10mmol and paraformaldehyde 0.9g, 30mmol, reaction flask is placed in ice bath, until temperature of reaction system drops to 0 ° of C after making 1 thoroughly to dissolve by stirring; Add catalyzer trifluoromethanesulfonic acid 5%mmol fast, 0.11mL; Continue stirring reaction under nitrogen protection, TLC monitors reaction process; After question response completes, add a small amount of sodium hydrogen carbonate solution cancellation reaction; Reaction solution uses 10% sodium hydrogen carbonate solution 50mL × 3, saturated aqueous common salt 50mL × 3 and the washing of water 50mL × 3 successively; Collect and merge organic layer, concentrated, crude on silica gel column chromatography for separation, petrol ether/ethyl acetate=5:1 obtain white product;
(3) get the post aromatic hydrocarbons 2 of bromine derivatize, 0.5g, 0.25mmol be dissolved in 3mL triethyl-phosphite, the degree of carrying out is reacted in heated and stirred to 150 ° C, a TLC monitoring, and after question response completes, underpressure distillation is except unnecessary triethyl-phosphite; In bottle, residue obtains colourless glutinous product after silica gel column chromatography, ethyl acetate/methanol 15:1.
2. the preparation method of post aromatic hydrocarbons according to claim 1, it is characterized in that: bromotrimethylsilane 2mL is diluted in after in 10mL methylene dichloride, under condition of ice bath, solution is slowly added drop-wise in the dichloromethane solution being dissolved with phosphide base functionalization post aromatic hydrocarbons 2,0.5g, after being added dropwise to complete, mixed solution is stirring reaction 10h at room temperature, add a small amount of shrend to go out reaction, then steam altogether with the ether of H2O and the 5mL of 5mL and obtain muddy solid, add water to obtain white solid again, with 20mL washing after suction filtration, then wash away organic solvent with the cold pentane of 50mL; Now, white product can be obtained.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105622406A (en) * | 2016-02-04 | 2016-06-01 | 广西大学 | Preparation method and application of functionalized column [5] arene trimer |
| CN106349027A (en) * | 2016-07-29 | 2017-01-25 | 浙江大学 | Preparation method of high-order column aromatic hydrocarbon |
| CN113072709A (en) * | 2021-03-22 | 2021-07-06 | 贵州大学 | Supermolecule assembly based on ten-element cucurbituril and columnar arene, and preparation method and application thereof |
-
2014
- 2014-07-27 CN CN201410358785.XA patent/CN105273004A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105622406A (en) * | 2016-02-04 | 2016-06-01 | 广西大学 | Preparation method and application of functionalized column [5] arene trimer |
| CN106349027A (en) * | 2016-07-29 | 2017-01-25 | 浙江大学 | Preparation method of high-order column aromatic hydrocarbon |
| CN106349027B (en) * | 2016-07-29 | 2019-03-26 | 浙江大学 | A kind of preparation method of high-order column aromatic hydrocarbons |
| CN113072709A (en) * | 2021-03-22 | 2021-07-06 | 贵州大学 | Supermolecule assembly based on ten-element cucurbituril and columnar arene, and preparation method and application thereof |
| CN113072709B (en) * | 2021-03-22 | 2022-07-22 | 贵州大学 | Supramolecular assembly based on ten-membered cucurbituril and pillararene, preparation method and application |
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Application publication date: 20160127 |