CN105820059B - A kind of synthetic method of cup [4] aromatic hydrocarbons containing amino acid structure - Google Patents
A kind of synthetic method of cup [4] aromatic hydrocarbons containing amino acid structure Download PDFInfo
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- CN105820059B CN105820059B CN201610185170.0A CN201610185170A CN105820059B CN 105820059 B CN105820059 B CN 105820059B CN 201610185170 A CN201610185170 A CN 201610185170A CN 105820059 B CN105820059 B CN 105820059B
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- aromatic hydrocarbons
- cup
- amino acid
- synthetic method
- containing amino
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C227/14—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton from compounds containing already amino and carboxyl groups or derivatives thereof
- C07C227/18—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton from compounds containing already amino and carboxyl groups or derivatives thereof by reactions involving amino or carboxyl groups, e.g. hydrolysis of esters or amides, by formation of halides, salts or esters
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C227/14—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton from compounds containing already amino and carboxyl groups or derivatives thereof
- C07C227/18—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton from compounds containing already amino and carboxyl groups or derivatives thereof by reactions involving amino or carboxyl groups, e.g. hydrolysis of esters or amides, by formation of halides, salts or esters
- C07C227/20—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton from compounds containing already amino and carboxyl groups or derivatives thereof by reactions involving amino or carboxyl groups, e.g. hydrolysis of esters or amides, by formation of halides, salts or esters by hydrolysis of N-acylated amino-acids or derivatives thereof, e.g. hydrolysis of carbamates
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C227/38—Separation; Purification; Stabilisation; Use of additives
- C07C227/40—Separation; Purification
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C227/38—Separation; Purification; Stabilisation; Use of additives
- C07C227/40—Separation; Purification
- C07C227/42—Crystallisation
Abstract
A kind of synthetic method of cup [4] aromatic hydrocarbons containing amino acid structure, belong to chemosynthesis technical field, reaction temperature of the present invention is room temperature, absolute ethyl alcohol is used as solvent in reaction and recrystallization, anhydrous sodium sulfate is co-catalyst, and raw material is cheap and easy to get, realizes one pot of two-step reaction, it is easy to operate, mild condition.
Description
Technical field
The invention belongs to chemosynthesis technical field, more particularly to 4,6,10,12,16,18,22,24- eight hydroxyl of compound
Four n-pentyl -5,11,17,23- four of base -2,8,14,20-（3- azepine n-butyric acies -4-）The technology of preparing of base cup [4] aromatic hydrocarbons.
Background technology
Calixarenes is a kind of organic compound with preferable biology and catalytic activity, and amino acid is because of its unique parent's acid
Be widely used in life chemistry and materials chemistry with the structure of close alkali, all the time, by amino acid scion grafting on calixarenes with
Physicochemical property after both research collective effect is the pursuit of chemists, regrettably, by amino acid scion grafting on calixarenes
There is not yet document report has preferable method.
Eight hydroxyl -2,8,14,20- of 4,6,10,12,16,18,22,24-, four n-pentyl -5,11,17,23- four（3- azepines
N-butyric acie -4-）Base cup [4] aromatic hydrocarbons is the calixarene kind organic compound containing amino acid functional group artificial synthesized for the first time, should
Compound has eight hydroxyls and four carboxyls, and Polarity comparision is strong, while the compound has calixarenes precursor skeleton and four
N-pentyl non-polar functional group, therefore the compound is with the application value in terms of potential drug and material.
Invention content
A kind of eight hydroxyl -2,8,14,20- of synthesis 4,6,10,12,16,18,22,24- of offer, four n-pentyls of the present invention -
5,11,17,23- tetra-（3- azepine n-butyric acies -4-）The method of base cup [4] aromatic hydrocarbons.
Technical solution of the present invention includes the following steps：
1）By eight hydroxyl -2,8,14,20- of 4,6,10,12,16,18,22,24-, four n-pentyl -5,11,17,23-, four formyls
Base cup [4] aromatic hydrocarbons, glycine ethyl ester hydrochloride, triethylamine and absolute ethyl alcohol are placed in reactor, and stirring at normal temperature to reaction terminates；
2）Anhydrous sodium sulfate is added in into above-mentioned reactor, solid is filtered out after stirring, solid is transferred to containing boron hydrogen
In the ethanol solution for changing sodium, stirring at normal temperature to reaction terminates；
3）It filters out solid and is transferred in sodium hydrate aqueous solution, insoluble impurity is filtered out after being sufficiently stirred, mother liquor is used
Hydrochloric acid tune pH to 7.0, filters out solid, with ethyl alcohol recrystallization, obtains 4,6,10,12,16,18,22,24- eight hydroxyl -2 of product,
Tetra- n-pentyl -5,11,17,23- four of 8,14,20-（3- azepine n-butyric acies -4-）Base cup [4] aromatic hydrocarbons.
The present invention reaction equation be：
Reaction temperature of the present invention is room temperature, uses absolute ethyl alcohol as solvent in reaction and recrystallization, anhydrous sodium sulfate is helps
Catalyst, raw material is cheap and easy to get, realizes one pot of two-step reaction, easy to operate, mild condition.
Further, step 1 of the present invention）The middle reaction time is 2~3 hours.During time deficiency, reaction is not thorough,
It tests and shows within the time, products collection efficiency highest.
The step 2）The middle reaction time is 3~5 hours.During time deficiency, reaction is not thorough, and experiment showed in the time
It is interior, products collection efficiency highest.
Eight hydroxyl-the 2,8,14,20- of 4,6,10,12,16,18,22,24-, four n-pentyl -5,11,17,23-, four formyls
Base cup [4] aromatic hydrocarbons, glycine ethyl ester hydrochloride, triethylamine, sodium borohydride and anhydrous sodium sulfate molar ratio be 1: 4: 4:
16.4∶2.The yield highest that this proportional quantity obtains.
The mass percent of the sodium hydrate aqueous solution is 10%.
The mass percent of the hydrochloric acid is 10%.
Description of the drawings
Eight hydroxyl -2,8,14,20- of 4,6,10,12,16,18,22,24-, four n-pentyls that Fig. 1 is prepared for the method for the present invention -
5,11,17,23- tetra-（3- azepine n-butyric acies -4-）The hydrogen spectrogram of base cup [4] aromatic hydrocarbons.
Specific embodiment
2nd, synthetic method：
Eight hydroxyls of 4,6,10,12,16,18,22,24- of 1mmo are added in into the 100mL round-bottomed flasks containing 20mL ethyl alcohol
Base -2,8,14,20- tetra- n-pentyls -5,11,17,23- tetra- formoxyl cup [4] aromatic hydrocarbons, 4mmol glycine ethyl ester hydrochlorides,
4mmol triethylamines, stirring at normal temperature 3h.The anhydrous sodium sulfate of 2mmol is added in into reactor, solid is filtered out after stirring, it will be solid
Body is transferred in the 50mL ethanol solutions of the sodium borohydride containing 16.4mmol.Stirring at normal temperature 4h.It filters out solid and is transferred to
30 mL mass percents are in 10% sodium hydrate aqueous solution, and insoluble impurity, mother liquor quality are filtered out after being sufficiently stirred
Percentage is 10% hydrochloric acid tune pH to 7.0, filters out solid, with ethyl alcohol recrystallization, obtains product 4,6,10,12,16,18,
Eight hydroxyl -2,8,14,20- of 22,24-, four n-pentyl -5,11,17,23- four（3- azepine n-butyric acies -4-）Base cup [4] aromatic hydrocarbons.
The present invention reaction equation be：
2nd, product is identified：
Product hydrogen spectrogram is shown in Fig. 1, as seen from Figure 1：Eight groups of hydrogen being connected with nitrogen-atoms all occur, and illustrate using the present invention
Method has successfully synthesized eight hydroxyl -2,8,14,20- of 4,6,10,12,16,18,22,24-, four n-pentyl -5,11,17,23- four
（3- azepine n-butyric acies -4-）Base cup [4] aromatic hydrocarbons.
Claims (5)
1. a kind of synthetic method of cup [4] aromatic hydrocarbons containing amino acid structure, it is characterised in that include the following steps：
1）By eight hydroxyl -2,8,14,20- of 4,6,10,12,16,18,22,24-, four n-pentyl -5,11,17,23-, four formoxyl cups
[4] aromatic hydrocarbons, glycine ethyl ester hydrochloride, triethylamine and absolute ethyl alcohol are placed in reactor, and stirring at normal temperature to reaction terminates；
2）Anhydrous sodium sulfate is added in into above-mentioned reactor, solid is filtered out after stirring, solid is transferred to containing sodium borohydride
Ethanol solution in, stirring at normal temperature to reaction terminates；
3）It filters out solid and is transferred in sodium hydrate aqueous solution, insoluble impurity, mother liquor hydrochloric acid are filtered out after being sufficiently stirred
PH to 7.0 is adjusted, solid is filtered out, with ethyl alcohol recrystallization, obtains 4,6,10,12,16,18,22,24- eight hydroxyl -2,8 of product,
Tetra- n-pentyl -5,11,17,23- four of 14,20-（3- azepine n-butyric acies -4-）Base cup [4] aromatic hydrocarbons；
Eight hydroxyl-the 2,8,14,20- of 4,6,10,12,16,18,22,24-, four n-pentyl -5,11,17,23-, four formoxyl cups
[4] molar ratio of aromatic hydrocarbons, glycine ethyl ester hydrochloride, triethylamine, sodium borohydride and anhydrous sodium sulfate is 1: 4: 4: 16.4:
2。
2. a kind of synthetic method of cup [4] aromatic hydrocarbons according to claim 1 containing amino acid structure, it is characterised in that：Institute
State step 1）The middle reaction time is 2~3 hours.
3. a kind of synthetic method of cup [4] aromatic hydrocarbons according to claim 1 containing amino acid structure, it is characterised in that：Institute
State step 2）The middle reaction time is 3~5 hours.
4. a kind of synthetic method of cup [4] aromatic hydrocarbons according to claim 1 containing amino acid structure, it is characterised in that：Institute
The mass percent for stating sodium hydrate aqueous solution is 10%.
5. a kind of synthetic method of cup [4] aromatic hydrocarbons according to claim 1 containing amino acid structure, it is characterised in that：Institute
The mass percent for stating hydrochloric acid is 10%.
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| CN201610185170.0A CN105820059B (en) | 2016-03-29 | 2016-03-29 | A kind of synthetic method of cup [4] aromatic hydrocarbons containing amino acid structure |
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| CN201610185170.0A CN105820059B (en) | 2016-03-29 | 2016-03-29 | A kind of synthetic method of cup [4] aromatic hydrocarbons containing amino acid structure |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103739464A (en) * | 2014-01-10 | 2014-04-23 | 扬州大学 | Method for producing tetra-formylated resorcinol calix [4] |
| WO2015123282A1 (en) * | 2014-02-12 | 2015-08-20 | Fotsing Joseph R | Improved process for the synthesis of substituted 1-benzyl-3-(1-(isoxazol-4-ylmethyl)-1h-pyrazol-4-yl)imidazolidine-2,4-diones |
-
2016
- 2016-03-29 CN CN201610185170.0A patent/CN105820059B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103739464A (en) * | 2014-01-10 | 2014-04-23 | 扬州大学 | Method for producing tetra-formylated resorcinol calix [4] |
| WO2015123282A1 (en) * | 2014-02-12 | 2015-08-20 | Fotsing Joseph R | Improved process for the synthesis of substituted 1-benzyl-3-(1-(isoxazol-4-ylmethyl)-1h-pyrazol-4-yl)imidazolidine-2,4-diones |
Non-Patent Citations (1)
| Title |
|---|
| N-Substituted 3-Acetyltetramic Acid Derivatives as Antibacterial Agents;Raghunandan Yendapally等;<J. Med. Chem.>;20080219;第51卷;1487–1491 * |
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