Compositions – Miscellaneous
Reexamination Certificate
2002-01-07
2004-09-21
Thexton, Matthew A. (Department: 1714)
Compositions
Miscellaneous
C540S460000, C548S302100, C548S303400
Reexamination Certificate
active
06793839
ABSTRACT:
The present invention relates to a method for preparing cucurbit[n]urils and cucurbit[s,u]urils. The present invention also relates to cucurbit[n]urils, to cucurbit[s,u]urils, and to a method of separating cucurbit[n]urils and/or cucurbit[s,u]urils. The present invention also relates to novel compounds used in the preparation of cucurbit[n]urils and cucurbit[s,u]urils.
Cucurbituril is the name given to a cyclic oligomer formed by linking six (6) glycoluril units via 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. Cucurbituril has a chemical formula of C
36
H
36
N
24
O
12
and is a macrocyclic compound having a central cavity. An AM1 minimised structure of cucurbituril is shown in FIG.
1
.
The internal cavity of cucurbituril has a diameter of about 550 pm, a depth of 650 pm with portals at either end about 400 pm across. This rigid cavity has been shown to have high selectively in binding a variety of medium-small molecules and in this regard reference is made to Cintas. P. J. Inclusion Phenomena and Molecular Recognition in Chemistry; 17, 205, 1994.
The preparation of cucurbituril has generally followed the procedure first described in the article by R. Behrend et. al. published in 1905.
In German patent no. DE 196 03377. published 7 Aug. 1997, a process for synthesising cucurbituril is described. This process includes dissolving acetylene diurea (glycoluril) in an aqueous solution of a strong mineral acid in the presence of excess formaldehyde, with warming. The water is evaporated from the mixture to completely eliminate the water from the mixture. The remaining polymer mixture is then heated to a temperature up to 145° C. to complete the reaction. The applicants for this patent have stated that a yield of up to 82.4% of the theoretical yield can be obtained.
In German patent no. DE 4001139, the use of cucurbituril to remove organic compounds with hydrophobic groups, dyes, decomposition products from dyes and/or heavy metals from aqueous solutions is described. The patent actually states that a cyclic oligomer which is obtained by condensation of urea, thiourea, derivates of urea and/or derivatives of the thiourea with dialdehydes and formaldehyde is used. Although the patent states that the degree of polymerisation, n, of the cyclic oligomer varies between about 3 and about 8, the examples of the patent showing cyclic oligomers having a degree of polymerisation, n, only of 6. Example 1 shows the preparation of cucurbituril by heating glycoluril under reflux with formaldehyde.
Experiments conducted by the present inventors in following the procedure of Example 1 of DE 4001139 have shown that cucurbituril having 6 glycoluril units joined together is formed. In the words of DE 4001139, n=6 for this product. No evidence was found of any cyclic oligomer having a degree of polymerisation, n, other than 6. Indeed, a paper by Buschmann et. al., Inorgica Chimica Acta, 1992, 193.93 states that under the synthetic conditions as described in DE 400 1139, only cucurbituril having a degree of polymerisation, n, of 6 is formed.
The present inventors have now developed a method for producing cucurbiturils having a degree of polymerization of 4 to 12. To assist in differentiating such compounds, the present inventors have adopted the terminology “cucurbit[n]uril” where n is a number from 4 to 12, to denote the different compounds. For example, a cyclic oligomer having 4 basic glycoluril (substituted or unsubstituted) units joined together would be denoted as “cucurbit[4]uril”.
REFERENCES:
patent: 2654763 (1953-10-01), Adkins
patent: 3203960 (1965-08-01), Gandon et al.
patent: 3252901 (1966-05-01), Zettler
patent: 6365734 (2002-04-01), Kim et al.
patent: 6639069 (2003-10-01), Kim et al.
patent: 2002/0133003 (2002-09-01), Kim et al.
patent: 40 01 139 (1990-10-01), None
patent: 196 03 377 (1997-08-01), None
Translation of DE 4001139 (Jan. 25, 1999), Buschmann et al.*
Dantz, Dirk A. et al: “Complexation of volatile organic molecules from the gas phase with cucurbituril and beta—cyclodextrin”, Supramolecular Chemistry (1998), 9(2), 79-83, XP008016079, whole article.
A. Flinn et al., “Decamethylcucurbit[5]uril”, Angew. Chem. Int. Ed. Engl. 1992, 31, No. 11, pp. 1475-1477.
J.A.A.W. Elemans et al., “Bipyridine functionalized molecular chips. Self-assembly of their ruthenium complexes in water”, Chemical Abstracts, Abstract No. 129:183422, 1998.
J. Kim et al., New Cucurbituril Homologues: Synthesis, Isolation, Characterization, and X-ray Crystal Structures of Cucurbit[n]uril (n=5, 7 and 8), J. Am. Chem. Soc. 2000, 122, pp. 540-541, Jan. 8, 2000.
H.J. Buschmann et al., “Cucurbituril as a ligand for the complexation of cations in aqueous solutions”, Inorganica Chimica Acta, 193 (1992), pp. 93-97.
W.L. Mock in “Topics in Current Chemistry”, 1995, 175, 1-24.
Arnold Alan Peter
Blanch John Rodney
Day Anthony Ivan
Schulman B. Aaron
Stites & Harbison PLLC
Thexton Matthew A.
Unisearch Limited
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