Chemistry: natural resins or derivatives; peptides or proteins; – Proteins – i.e. – more than 100 amino acid residues
Patent
1983-12-07
1987-11-10
Kight, John
Chemistry: natural resins or derivatives; peptides or proteins;
Proteins, i.e., more than 100 amino acid residues
585352, 585 22, 568719, 570183, C07D 900, C07D32100, C07C 2338
Patent
active
047058471
DESCRIPTION:
BRIEF SUMMARY
BACKGROUND OF THE INVENTION
A process for preparing substituted polycyclo-alkylidene polycyclo-alkanes and the corresponding epidioxy compounds; as well as said substituted polycyclo-alkylidene polycyclo-alkanes and the corresponding epidioxy compounds.
The invention relates to a process for preparing substituted polycyclo-alkylidene polycyclo-alkanes and the corresponding epidioxy compounds, as well as to these substituted polycycloalkylidene polycyclo-alkanes and the corresponding epidioxy compounds.
The term "substituted polycyclo-alkylidene polycyclo-alkanes" as used herein comprises especially compounds of formula 44 of the formula sheet, in which A and B represent alkylene radicals, which alkylene radicals may be attached to each other via an alkylene radical C, and wherein R.sub.1 represents a substituent which, in the case of 4-equatorially R.sub.1 -substituted 2.2'-adamantylidene adamantanes, cannot be chloro, hydroxy, oxo, D or a radical of formula 1 of the formula sheet. In preferred compounds of formula 44, alkylene radical A contains 2 to 5 carbo atoms, alkylene radical B 2 to 5 carbon atoms, and alkylene radical C, if present, 1 to 4 carbon atoms. Examples of compounds of formula 44 are 4-eq-R.sub.1 -2,2'-adamantylidene adamantanes, 4-eq-R.sub.1 -9,9'-bicyclo [3,3,1]-nonylidene-bicyclo[3,3,1]-nonanes, 2- or 7-R.sub.1 -8,8'-bicyclo[3,2,1]-octylidene-bicyclo[3,2,1]-octanes and 2- or 7-R.sub.1 - 10,10'-bicyclo[4,3,1]-decylidene-bicyclo[4,3,1]-decanes, in which the two rings of each of the bicyclic radicals may be attached to each other via an alkylene bridge.
The corresponding epidioxy compounds--which contain a dioxetane ring--are especially compounds of formula 45, in which A, B and C, if present, have the above-mentioned meanings, and R.sub.2 represents a substituent which, in the case of 4-eq-R.sub.2 -2,2'-epidioxy-2,2'-adamantyl adamantane cannot be chloro or hydroxy.
The invention relates to these compounds and to processes for the preparation thereof. Especially, the invention relates to a process for preparing substituted polycyclo-alkylidene polycyclo-alkanes, in which a corresponding non-substituted compound is subjected to a halogenation reaction, using a halogenating agent in a solvent, and the halogenation product is recovered from the reaction mixture and/or, if desired, is subjected to a substitution reaction.
In Tetrahedron Letters 1970, 4579-82, J. H. Wieringa, J. Strating and H. Wynberg describe a process in which adamantylidene adamantane is reacted with chlorine is tetrachloromethane at a temperature of -20.degree. to +10.degree. C. to form 4-eq.-chloroadamantylidene adamantane in addition to polychlorinated products. The chloro-substituted adamantane compound is the starting point for further reaction in the presence of AgNO.sub.3 and THF/H.sub.2 O to form a mixture of the corresponding 4-hydroxy-adamantylidene adamantane compounds, which with the appropriate oxidant (Jones reagent: CrO.sub.3, H.sub.2 SO.sub.4, acetone) are finally converted into the corresponding ketone compound, in which the carbonyl group is in the 4-position.
SUMMARY OF THE INVENTION
It is an object of the invention to provide a process for preparing substituted polycyclo-alkylidene polycyclo-alkane compounds, in which these compounds are selectively produced in a high yield and in a simple manner and/or from which other substituted polycyclo-alkylidene polycyclo-alkane compounds can be selectively prepared in a high yield.
According to the invention, for this purpose, the process as defined above is carried out using as the halogenating agent N-halosuccinimide, tert-butylhypohalite, or sodium hypohalite/CH.sub.3 COOH.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 illustrates a dioxazole radical which can be a substituent in some of the compounds of this invention.
FIG. 2 illustrates the structural formula of 4-eq.-chloroadamantylideneadamantane.
FIG. 3 illustrates the structural formula of 4-eq.-hydroxyadamantylideneadamantane.
FIG. 4a illustrates the structural formula of a 4-eq.-4'-eq.-bisadamantyli
REFERENCES:
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Muller et al, Methoden der Organishen Chemie, Band V/4, 1960, Verlag Publishers, pp. 23, 24 & 30.
Muller et al, Methoden der Organishen Chemie, Band V/3, 1962, Verlag Publishers, pp. 765, 780, 800.
Wierenga et al, "Tetrahedron Letters", No. 52, pp. 4579-4582, 1980, Pergamon Press.
Wierenga et al, "Tetrahedron Letters", No. 2, pp. 169-172, 1972, Pergamon Press.
Hummelen Jan C.
Meijer Egbert W.
Wynberg Hans
Akzo N.V.
Blackstone William M.
Kight John
Nutter Nathan M.
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