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Cucurbiturils and method for synthesis

A cucurbit-shaped, glycoluril technology, used in organic chemistry and other directions

Inactive Publication Date: 2007-09-26
NEWSOUTH INNOVATIONS PTY LTD
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Although the patent states that the degree of polymerization n of the circular oligomer is from about 3 to about 8, its examples give a degree of polymerization n of the circular oligomer of only 6

Method used

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  • Cucurbiturils and method for synthesis
  • Cucurbiturils and method for synthesis
  • Cucurbiturils and method for synthesis

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0078] Synthesis of Cucurbituride[n]

[0079] 1.5g-glycoluril

[0080] 6.9ml - Inorganic acid (36% hydrochloric acid, 48% hydrobromic acid, 47% hydroiodic acid or 98% or 50% sulfuric acid) or organic acid (p-toluenesulfonic acid)

[0081] 1.5ml-30% aqueous formaldehyde

[0082] 5 mmol - the corresponding alkali metal halide, ammonium halide or in the case of sulfuric acid the corresponding sulfate or alkali metal tosylate.

[0083] 600 mg - red phosphorus (this red phosphorus is added to the reaction mixture when using hydriodic acid)

[0084] Glycoluril (1.5 gm, 10.6 mmol) was dissolved or suspended in the appropriate acid (6.9 ml). The alkali metal or ammonium salt (5 mmol) of the corresponding anion belonging to the acid is then added in the case of salts to control the reaction product. Formaldehyde (1.5 ml) was added to the mixture at room temperature over a period of 5-10 minutes, and the mixture coagulated into a gel (Note 1). After standing still for 3 hours (Note...

Embodiment 2

[0101] Synthesis of Cucurbituride [s, u]

[0102] The same pattern control was applied to the substituted cucurbituril[n] by the method described above in which the glycoluril used was a substituted glycoluril or the method described below.

[0103] A mixture of tetracyclic ether B (2.5 mol) and glycoluril (0.355 gm, 2.5 mmol) was dissolved or suspended in the appropriate acid (6.9 ml) (Note 1). The alkali metal or ammonium salt (5 mmol) of the corresponding anion belonging to the acid is then added in the case of salts to control the reaction product. The reaction mixture was heated and kept at 100°C for 3 hours (Note 2). The reaction mixture was cooled to room temperature, the product was isolated by the addition of methanol (10 ml), and the resulting precipitate was collected by filtration. The solid material was washed with methanol and acetone and air dried. Further purification is carried out by recrystallization from aqueous hydrochloric or hydrobromic acid, or by di...

Embodiment 3

[0109] Analysis of Cucurbituril Mixture

[0110] The analysis of cucurbit uril reaction mixture was routinely used 13 C NMR method. The present invention has been able to obtain the X-ray crystal structures of cucurbit biurea [5], cucurbit biurea [8] and cucurbit biurea [10]. These structures are shown in Figure 9a, where formula 12 is cucurbit biurea [5], formula 13 is cucurbit biurea [8], and formula 14 is cucurbit biurea [10]. Crystallized water and salt etc. are not shown.

[0111] Cucurbituril

[n]

n =

Methine C

Observations *

(ppm)

Methine C

Calculated

(ppm)

Methylene C

Observations *

(ppm)

Methylene C

Calculated

(ppm)

4

-

68.54

-

48.75

5

69.84

69.87

50.58

50.68

6

70.98

70.96

52.29

52.17

7

71.90

71.88

53.48

53.43

8

72.70

72.68

54.49 ...

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Abstract

A method for producing cucurbit[n]urils, comprising mixing substituted and / or unsubstituted glycoluril with an acid and a compound that can form methylene bridges between glycoluril units, and heating the mixture to a temperature of from 20 DEG to 120 DEG to thereby form cucurbit[n]. Novel cucurbit[n]urils, where n = 4, 5, 7, 8, 9, 10, 11 and 12 and substituted cucurbit[s,u]urils, where s is number of substituted glycoluril units, u is number of unsubstituted units and s + u is 4 - 12 are also described.

Description

technical field [0001] The present invention relates to a process for the preparation of cucurbit biuret [n] and cucurbit biurea [s,u]. The present invention also relates to cucurbit urea [n], to cucurbit urea [s, u], and to a process for isolating cucurbit urea [n] and / or cucurbit urea [s, u]. The present invention also relates to novel compounds useful for the preparation of cucurbiturils [n] and cucurbiturils [s,u]. Background technique [0002] Cucurbituril is the name given to a circular oligomer, which is formed by linking six glycoluril units through methylene bridges. Cucurbituril was first described in the literature in 1905 in a paper by R. Behrend, E. Meyer and F. Rusche, Leibigs Ann. Chem., 339, 1, 1905. The macrocyclic structure of cucurbituril was first described in 1981 by W.A. Freeman et al., "Cucurbituril", J. Am. Chem. Soc., 103 (1981), 7367-7368. The chemical formula of cucurbituril is C 36 h 36 N 24 o 12 , and are macrocyclic compounds with a centr...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07D487/22C07D487/04C07D471/22C08G61/12
CPCC07D487/04C07D487/22
Inventor 安东尼·I·戴艾伦·P·阿诺德罗德尼·J·布兰奇
Owner NEWSOUTH INNOVATIONS PTY LTD
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