US 5,631,372 AGranted

Process for the manufacture of 1-substituted-4-fluoro-1,4-diazoniabicyclo[2.] octane salts

AssigneeAlliedSignal Inc.

InventorsAndrew J. Poss, George A. Shia, Dennis M. Lavery

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Abstract

A process for producing 1-substituted-4-fluoro-1,4-diazoniabicyclo[2.2.2]octane salts having the formula ##STR1## wherein the Z substituent is OH, OR, OC(O)R, SO.sub.3, SO.sub.2 R, NO.sub.2, NO, or PO(OR).sub.2, wherein R is an aryl or C.sub.1 -C.sub.8 alkyl group; n is 0, 1 or 2; each of R.sub.1, R.sub.2, R.sub.3, P.sub.4 and R.sub.5 independently represent hydrogen, C.sub.1 to C.sub.8 alkyl, or aryl 1-substituted-1,4-diazoniabicyclo[2.2.2]octane or 1,4-diazoniabicyclo[2.2.2]octane mono-N-oxide is reacted to attach the Z group and then the result is reacted with molecular fluorine in the presence of a solvent that substantially does not react with fluorine and a fluoride scavenger that results in an X counter ion. These compounds are useful as fluorinating agents for the introduction of fluorine into organic compounds.

Claims20

Dependent claims

A process for the preparation of 1-substituted-4-fluoro-1,4-diazoniabicyclo[2.2.2]octane salts having the formula ##STR4## wherein the Z substituent is OH, OR, OC(O)R, SO.sub.3, SO.sub.2 R, NO.sub.2, NO, or PO(OR).sub.2, wherein R is an aryl or C.sub.1 -C.sub.8 alkyl group;

n is 0, 1 or 2;
each of R.sub.1, R.sub.2, R.sub.3, R.sub.4 and R.sub.5 independently represent hydrogen, C.sub.1 to C.sub.8 alkyl, or aryl, which process comprises
(a) either (i) or (ii):
(i) reacting 1,4-diazoniabicyclo[2.2.2]octane with a reactant compound of the formula, L--SO.sub.2 R, HNO.sub.2, HNO.sub.3, or L--PO(OR).sub.2 ;
or
(ii) reacting 1,4-diazoniabicyclo[2.2.2]octane mono-N-oxide with a reactant compound of the formula L--H, L--R, R, L--C(O)R or SO.sub.3
to produce an intermediate having the formula ##STR5## wherein L is a leaving group;
(b) exchanging the leaving group L, from step (a) with an anion X which is selected from the group consisting of fluorosulfate (SO.sub.3 F.sup.-), alkyl sulfates, perfluoroalkylsulfonates, arenesulfonates, alkylcarboxylates, perfluoro-alkylcarboxylates, tetrafluoroborate (BF.sub.4.sup.-), tetraphenylborate (Ph.sub.4.sup.-), hexafluorophosphate (PF.sub.6.sup.-), hexafluoroantimonate (SbF.sub.6.sup.-), perchlorate (CIO.sub.4.sup.-) and sulfate SO.sub.4 =;
and
(c) reacting the result from step (b) with molecular fluorine in the presence of a solvent that does not react substantially with fluorine and a fluoride scavenger that results in an X counter ion.

7 more elements

Dependencies are inferred from the claim text.