Polyiodinated compounds, process of preparation and contrast age

Organic compounds -- part of the class 532-570 series – Organic compounds – Amino nitrogen containing

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Details

564139, 424 9451, 424 9452, C07C23746, C07C23742, C07C23516, A61K 4904

Patent

active

056189770

DESCRIPTION:

BRIEF SUMMARY
The present invention relates to new polyiodinated compounds which can be used in contrast agents for radiography.
The invention also relates to a process for the preparation of these compounds and to the contrast agents containing them.
The subject matter of the invention is thus polyiodinated compounds of formula: ##STR4## in which R.sub.1 and R.sub.2, which are identical to or different from each other, represent a group of formula: ##STR5## and R.sub.3 and R.sub.4, which are identical to or different from each other, represent a group of formula ##STR6## in which R.sub.5 and R.sub.6, and R.sub.7 and R.sub.8, which are identical to or different from each other, represent a hydrogen atom, a linear or branched C.sub.1 -C.sub.6 alkyl, a linear or branched C.sub.1 -C.sub.6 hydroxy- or polyhydroxyalkyl, optionally additionally containing one or more C.sub.1 -C.sub.6 alkoxys, especially methoxy or ethoxy, a linear or branched (C.sub.1 -C.sub.6) alkoxy(C.sub.1 -C.sub.6)alkyl or a linear or branched (C.sub.1 -C.sub.6) hydroxy- or polyhydroxyalkoxy (C.sub.1 -C.sub.6) alkyl, said substituents R.sub.1, R.sub.2 , R.sub.3 and R.sub.4 comprising in total at least ten hydroxyls.
The preferred compounds are those of general formula (I) in which: --CH.sub.2 --CH.sub.2 OH, ##STR7## R.sub.7 being as defined above. ##STR8## are those in which: R.sub.5 represents the ##STR9## and R.sub.6 is selected from --CH.sub.3, --CH.sub.2 --CH.sub.2 OH and ##STR10##
Preferred groups ##STR11## are those in which: R.sub.7 is a defined above, ##STR12## --CHOH--CH.sub.2 OH and R.sub.8 is selected from ##STR13##
The preferred compounds of the present invention are those in which: ##STR14## and R.sub.3 and R.sub.4 represent ; ##STR15## and R.sub.3 and R.sub.4 represent ##STR16## R.sub.1 and R.sub.2 represent ##STR17## and R.sub.3 and R.sub.4 represent ; ##STR18## and R.sub.3 and R.sub.4 represent ##STR19## R.sub.1 and R.sub.2 represent ##STR20## and R.sub.3 and R.sub.4 represent ##STR21## R.sub.1 and R.sub.2 represent ##STR22## and R.sub.3 and R.sub.4 represent ##STR23## R.sub.1 and R.sub.2 represent ##STR24## and R.sub.3 and R.sub.4 represent ##STR25## R.sub.1 and R.sub.2 represent ##STR26## and R.sub.3 and R.sub.4 represent ; ##STR27## and R.sub.3 and R.sub.4 represent ; ##STR28## and R.sub.3 and R.sub.4 represent 10); ##STR29## and R.sub.3 and R.sub.4 represent ) ##STR30## and R.sub.3 and R.sub.4 represent 12).
The compounds of formula (I) of the present invention can be prepared by alkylation and/or acylation reactions.
The compounds of formula (I) of the present invention can especially be prepared by a process comprising the following stages: ##STR31## X being selected from chlorine, bromine and iodine and R'.sub.1 and R'.sub.2 represent --CO.sub.2 R with R representing C.sub.1 -C.sub.6 alkyl, and R'.sub.3 and R'.sub.4 represent --NO.sub.2, so as to produce a compound of formula (IV): ##STR32## in which R'.sub.1, R'.sub.2, R'.sub.3 and R'.sub.4 are as defined above; b) amidation of --CO.sub.2 R with an amine ##STR33## R.sub.5 and R.sub.6 being as defined above; c) reduction of nitro groups to amino groups; R'.sub.8 --COCl, R'.sub.8 representing a group R.sub.8 as defined above in which hydroxyls are protected using a conventional protective group; and, either Z--R.sub.7, Z being a labile group such as Cl, Br or I and R.sub.7 being as defined above, and deprotection of protected hydroxyls; or groups with a reagent of formula Z--R.sub.7, Z being a labile group such as Cl, Br or I and R.sub.7 being as defined above.
The reaction of stage a) preferably takes place in a suitable solvent such as xylene, nitrobenzene, nitrotoluene, DMF or pyridine, in the presence of a metal catalyst such as copper according to the Ullman method (E. Fanta, Chem. Rev., 64, 613, 1964).
The reaction of stage c) is a catalytic reduction by hydrogen on palladium charcoal or on Ranney nickel or a chemical reduction.
The iodination reaction of stage d) takes place under usual conditions, such as with aqueous ICl or I.sub.2, in the presence of KI/ethylalnine at tempe

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