CN106478617A - A kind of sulphur bridge is oxidized and lower edge contains thio cup [4] arene derivatives and its synthetic method and the application of picolyl amides - Google Patents

A kind of sulphur bridge is oxidized and lower edge contains thio cup [4] arene derivatives and its synthetic method and the application of picolyl amides Download PDF

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CN106478617A
CN106478617A CN201610734766.1A CN201610734766A CN106478617A CN 106478617 A CN106478617 A CN 106478617A CN 201610734766 A CN201610734766 A CN 201610734766A CN 106478617 A CN106478617 A CN 106478617A
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cup
lower edge
thio cup
arene derivatives
oxidized
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谢长江
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing three or more hetero rings
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
    • G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
    • G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry

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Abstract

The present invention relates to a kind of sulphur bridge is oxidized and lower edge contains thio cup [4] arene derivatives and its synthetic method and the application of picolyl amides.Introducing oxygen atom and thio cup [4] aromatic hydrocarbons lower edge on bridging sulphur atom are contained picolyl amides and combine by thio cup [4] arene derivatives first that provide, using its synergism with thio cup [4] aromatic hydrocarbons hole, increase the coordination to metal ion for gained thio cup [4] arene derivatives.It has preferable coordination function to metal ion is shown to the preliminary experimental results of such compound.

Description

A kind of sulphur bridge is oxidized and lower edge contains thio cup [4] virtue of picolyl amides Hydrocarbon derivative and its synthetic method and application
Technical field
The present invention relates to a kind of sulphur bridge is oxidized and lower edge contains thio cup [4] arene derivatives of picolyl amides And its synthetic method and application.
Background technology
The Thiacalixarenes occurring in recent years are the newcomers of calixarenes family, because it instead of traditional cup with sulphur atom The methylene bridge of aromatic hydrocarbons, makes rigid, the polarity of fragrant macrocyclic structure all there occurs larger change, has larger cave to tie Structure, conformation more flexible, significant complexing power and sulphur bridge is oxidizable etc., and the flexible of especially conformation causes people Very keen interest.
All kinds of Thiacalixarenes derivants of report, the typically lower edge in parent aromatic hydrocarbons introduce carboxyl, amido, fat Base, carbonyl etc. also have the group of lone pair electrons as chelate, coordination of metal ion.But for the bridging sulfur to Thiacalixarenes The report that atom is modified is less, introduces oxygen atom, not only can fix the structure of Thiacalixarenes derivant on bridging sulphur atom As, and the lone pair electrons due to oxygen atom, the coordination ability of Thiacalixarenes derivant can be further enhanced.
Picolyl amides are the compounds that a class has biological activity mostly, are widely used in pharmaceutical research, anti- Funguses, are used for preventing the aspects such as pellagra, stomatitis from having good effect.Moreover, picolyl amides analog derivative is also easy In forming stable coordination compound with metal ion, also there is important application in Coordinative Chemistry research field.
At present, thio cup [4] arene derivatives that sulphur bridge is oxidized and lower edge contains picolyl amides yet there are no report Road.
Content of the invention
The problem that present aspect solves is that on bridging sulphur atom, introducing oxygen atom and lower edge contain picolyl amides.Using The complexing power of oxygen atom and metal ion on picolyl amides and bridging sulfur, and combine the distinctive hole of Thiacalixarenes with Increase ability and the selectivity of coordination.
The technical solution used in the present invention is：Synthesize the sulfur that a kind of sulphur bridge is oxidized and lower edge contains picolyl amides For cup [4] arene derivatives it is characterised in that structural formula is as follows：
Wherein N is nitrogen.
Above-mentioned sulphur bridge is oxidized and lower edge contain picolyl amides thio cup [4] arene derivatives preparation side Method is：Four oxoacetic acid methyl ester thio cup [4] arene derivatives and glacial acetic acid and 30% hydrogen peroxide mixed solution, in organic solvent Middle back flow reaction, stops after 24-36 hour, adds distilled water and chloroform, separate organic layer, organic layer saturation in flask NaHSO3Solution washs, vacuum distillation major part solvent, adds petroleum ether to obtain white solid, crude product, after recrystallization, obtains To intermediate；Intermediate is reacted with aminomethyl-pyridine, under nitrogen protection, oil bath, and stop, after cooling after reaction 12-24 hour Add water, have dark thick shape solid to generate, separate out to a large amount of solids with Sal, leach solid, filter cake washes with water for several times, dries in the air Dry, recrystallization, obtain target product.
Described four oxoacetic acid methyl ester thio cup [4] arene derivatives are 25,26,27,28- tetra- [Oxoacetic Acid first Ester] tetra-tert thio cup [4] aromatic hydrocarbons, structural formula is as follows:
.
Described organic solvent is acetonitrile, dichloromethane, chloroform or one or more the mixing of oxolane volume.
Described aminomethyl-pyridine is 2- aminomethyl-pyridine, 3- aminomethyl-pyridine, 4- aminomethyl-pyridine, and structural formula is as follows：
OrOr.
The compound synthesis route of the present invention is simple, and reaction condition is gentle, and easily, easy to operate, yield is higher for post processing.
The present invention will introduce oxygen atom on sulphur bridge, and picolyl amides be introduced the lower edge of thio cup [4] aromatic hydrocarbons, profit With its synergism with calixarenes hole, increase the selective coordination ability to metal ion for the gained derivant.By to change Compound property carries out Preliminary Determination, it is found that compound has preferable coordination function to metal ion, potentially should have Use prospect.
Specific embodiment
Below by specific embodiment, the synthetic method of the present invention is further illustrated.
Embodiment：Thio cup [4] arene derivatives（Compound 1-3）
（One）Prepare compound 1
Four oxoacetic acid methyl ester thio cup [4] arene derivatives (1.0g, 0.94mmol) and glacial acetic acid（20 mL) and 30% dioxygen The mixed solution of water (10mL), back flow reaction in chloroform (10mL), stop after 24-36 hour, add distillation in flask Water (100mL) and chloroform (15mL), separate organic layer, organic layer saturation NaHSO3Solution washs, and vacuum distillation major part is molten Agent, adds petroleum ether to obtain white solid, (volume ratio is 3 to crude product chloroform/ethanol:1), after recrystallization, obtain colourless crystalline substance Body, yield 71%.Take this clear crystal (3.0g, 2.0mol) and 2- aminomethyl-pyridine (1.4g, 13.0mol) reaction, nitrogen is protected Under shield, oil bath, stop after reaction 12-24 hour, add water after the cooling of question response liquid, have dark thick shape solid to generate, with Sal Separate out to a large amount of solids, leach solid, filter cake washes with water for several times, dries, (volume ratio is 3 with chloroform/ethanol:1) recrystallization, Obtain target product compound 1, yield 88%.
m.p. 219-2210C.
. IR(KBr) v:3632 (w), 3315 (s), 3060 (w), 2965 (vs), 2870 (w), 1669 (vs), 1586 (w), 1536 (s), 1470 (w), 1434 (s), 1387 (w), 1266 (s), 1149 (w), 1091 (s), 1040 (s), 1006 (s), 884 (w), 824 (w), 756 (s) cm-1;
1H NMR (DMSO-d 6, 600MHz): δ = 8.51-8.50 (t,J=6Hz, 4H, NH), 8.39-8.37 (t,J=12Hz, 4H, ArH), 7.78-7.76 (t,J=12Hz, 4H, ArH), 7.56 (s, 8H, ArH), 7.31-7.28 (t,J=18Hz, 8H, ArH), 4.45-4.43 (d,J=12Hz, 8H, NCH2), 4.02 (s, 8H, OCH2), 1.06 (s, 36H, C(CH3)3).
（Two）Prepare compound 2-3
Method, with compound 1, the results are shown in Table 1
Sequence number Four oxoacetic acid methyl ester thio cup [4] aromatic hydrocarbons Acetic acid and 30% hydrogen peroxide Aminomethyl-pyridine Yield %
Compound 2 Four oxoacetic acid methyl ester thio cup [4] aromatic hydrocarbons Acetic acid and 30% hydrogen peroxide 3- aminomethyl-pyridine 83%
Compound 3 Four oxoacetic acid methyl ester thio cup [4] aromatic hydrocarbons Acetic acid and 30% hydrogen peroxide 4- aminomethyl-pyridine 81%
（Three）The structural formula of compound 1-3 is as follows：
Compound 1 compound 2
Compound 3.
(4) coordination to metal ion
Method：Compound concentration is 1 × 10 respectively-3The Ni of mol/L2+, Cu2+, Co2+, Pb2+, Hg2+, Pd2+, Zn2+, K+, In3+, Nd3+, La3+Nitrate aqueous solution and concentration be 1 × 10-3The DMF titer of the compound 1-3 of mol/L is as storage Liquid.Accurately measure the above-mentioned metal-nitrate solutions preparing of 0.25ml to be added separately in 25ml different capabilities bottle, more accurately The titer measuring 0.25ml compound 3 is added in above-mentioned each volumetric flask, uses THF constant volume, vibrates 15min.
Compound 3 is tested respectively to Ni for detection meanss with UV-vis2+, Cu2+, Co2+, Pb2+, Hg2+, Pd2+, Zn2+, K+, In3+, Nd3+, La3+Deng the recognition reaction of metal ion, it is found that when with THF for solvent, compound 1 can To be coordinated Co2+, Pb2+, Hg2+, Pd2+, Zn2+, compound 2 can be coordinated Co2+, Pb2+, Hg2+, Pd2+, Zn2+, K+, Compound 3 can be coordinated Ni2+, Pb2+, Hg2+, Pd2+, Zn2+, K+, La3+.

Claims (6)

1. a kind of sulphur bridge is oxidized and lower edge contain picolyl amides thio cup [4] arene derivatives it is characterised in that Structural formula is as follows：
Wherein N is nitrogen.
2. the sulphur bridge described in claim 1 is oxidized and lower edge contains thio cup [4] arene derivatives of picolyl amides Preparation method it is characterised in that preparation method is：Four oxoacetic acid methyl ester thio cup [4] arene derivatives and glacial acetic acid and 30% hydrogen peroxide mixed solution, back flow reaction in organic solvent, stop after 24-36 hour, add distilled water and chlorine in flask Imitative, separate organic layer, organic layer saturation NaHSO3Solution washs, vacuum distillation major part solvent, adds petroleum ether to obtain white Color solid, crude product, after recrystallization, obtains intermediate；Intermediate is reacted with aminomethyl-pyridine, under nitrogen protection, oil bath, instead Stop after answering 12-24 hour, add water after cooling, have dark thick shape solid to generate, separate out to a large amount of solids with Sal, leach Solid, filter cake washes with water for several times, dries, and recrystallization obtains target product.
3. preparation method as claimed in claim 2 it is characterised in that：Described four oxoacetic acid methyl ester thio cup [4] aromatic hydrocarbons spreads out Biological is 25,26,27,28- tetra- [oxoacetic acid methyl ester] tetra-tert thio cup [4] aromatic hydrocarbons.
4. preparation method as claimed in claim 2 it is characterised in that：Described organic solvent is acetonitrile, dichloromethane, chloroform Or the mixing of one or more of oxolane.
5. preparation method as claimed in claim 2 it is characterised in that：Described aminomethyl-pyridine is 2- aminomethyl-pyridine, 3- Aminomethyl-pyridine, 4- aminomethyl-pyridine.
6. the sulphur bridge described in claim 1 is oxidized and lower edge contains thio cup [4] arene derivatives of picolyl amides Application in coordination of metal ion.
CN201610734766.1A 2016-08-28 2016-08-28 A kind of sulphur bridge is oxidized and lower edge contains thio cup [4] arene derivatives and its synthetic method and the application of picolyl amides Pending CN106478617A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113072487A (en) * 2021-03-26 2021-07-06 中南大学 Pyridyl-containing calix [4] arene derivative, preparation method thereof and application of derivative as manganese ion extracting agent

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101337918A (en) * 2008-08-11 2009-01-07 同济大学 Method for preparing 25,26,27,28-tetramercapto ethoxy-calix[4]arene
CN102140089A (en) * 2011-02-23 2011-08-03 大连民族学院 Thiacalix [8] arene diethyl acetamide as well as synthesis method and application thereof
CN102936237A (en) * 2012-11-13 2013-02-20 中国科学院长春应用化学研究所 Calixarene and method for separating and purifying thorium by calizarene
CN104193724A (en) * 2014-07-09 2014-12-10 北京理工大学 P-tert-butyl sulfone bridge thiacalixarene [4] and method for separating and purifying caesium of p-tert-butyl sulfone bridge thiacalixarene [4]

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101337918A (en) * 2008-08-11 2009-01-07 同济大学 Method for preparing 25,26,27,28-tetramercapto ethoxy-calix[4]arene
CN102140089A (en) * 2011-02-23 2011-08-03 大连民族学院 Thiacalix [8] arene diethyl acetamide as well as synthesis method and application thereof
CN102936237A (en) * 2012-11-13 2013-02-20 中国科学院长春应用化学研究所 Calixarene and method for separating and purifying thorium by calizarene
CN104193724A (en) * 2014-07-09 2014-12-10 北京理工大学 P-tert-butyl sulfone bridge thiacalixarene [4] and method for separating and purifying caesium of p-tert-butyl sulfone bridge thiacalixarene [4]

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Title
IVAN I. STOIKOV: "《p-tert-Butyl thiacalix[4]arenes functionalized at the lower rim by o-, m-, p-amido and o-, m-, p-(amidomethyl)pyridine fragments as receptors for a-hydroxy- and dicarboxylic acids》", 《TETRAHEDRON》 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113072487A (en) * 2021-03-26 2021-07-06 中南大学 Pyridyl-containing calix [4] arene derivative, preparation method thereof and application of derivative as manganese ion extracting agent
CN113072487B (en) * 2021-03-26 2022-09-06 中南大学 Pyridyl-containing calix [4] arene derivative, preparation method thereof and application of derivative as manganese ion extracting agent

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Application publication date: 20170308