Organic bismuth derivatives for X-ray imaging

A process of producing an organic bismuth derivative represented by formula (I-1) or its salt:

• ##STR22## wherein each of X.sup.2 and X.sup.3 is, independently of each other, a hydrogen atom, a C.sub.4 alkyl group, a C.sub.1-4 alkoxy group, a C.sub.1-4 alkylsulfonyl group, a C.sub.1-4 alkylcarbonyl group, a nitro group, a cyano group or YNR.sup.1 R.sup.2, wherein Y is --SO.sub.2 -- or --C(O)--, R.sup.1 is a C.sub.3-6 alkyl group which has from 2 to 5 hydroxyl groups optionally being protected, and R.sup.2 is a hydrogen atom, a C.sub.1-6 alkyl group or a C.sub.1-5 acyl group optionally having from 1 to 5 hydroxyl groups optionally being protected, or R.sup.1 or R.sup.2, together with each other, represent a C.sub.2-6 cyclic alkylene optionally having from 1 to 4 hydroxyl groups optionally being protected, and X.sup.5 is YNR.sup.1 R.sup.3, wherein Y and R.sup.1 are the same as defined above, and R.sup.3 is a C.sub.1-6 alkyl group or a C.sub.1-5 acyl group optionally having from 1 to 5 hydroxyl groups optionally being protected, which comprises treating an organic bismuth derivative represented by formula (I'-1):
• ##STR23## wherein X.sup.4 is YNR.sup.1 H, wherein Y and R.sup.1 are the same as defined above, and X.sup.2 and X.sup.3 are the same as defined above with a base, and then reacting it with a compound represented by formula (IV):
• R.sup.3 X (IV)
• wherein R.sup.3 is the same as defined above, and X is a halogen atom.

A process of producing an organic bismuth derivative represented by formula (I-2) or its salt:

• ##STR24## wherein each of X.sup.2 and X.sup.3 is, independently of each other, a hydrogen atom, a C.sub.1-4 alkyl group, a C.sub.1-4 alkoxy group, a C.sub.1-4 alkylsulfonyl group, a C.sub.1-4 alkylcarbonyl group, a nitro group, a cyano group or YNR.sup.1 R.sup.2, wherein Y is --SO.sub.2 -- or --C(O)--, R.sup.1 is a C.sub.3-6 alkyl group which has from 2 to 5 hydroxyl groups optionally being protected, and R.sup.2 is a hydrogen atom, a C.sub.1-6 alkyl group or a C.sub.1-5 acyl group optionally having from 1 to 5 hydroxyl groups optionally being protected, or R.sup.1 and R.sup.2, together with each other, represent a C.sub.2-6 cyclic alkylene optionally having from 1 to 4 hydroxyl groups optionally being protected, and X.sup.7 is YNR.sup.1 R.sup.2, wherein y, R.sup.1 and R.sup.2 are the same as defined above, which comprises treating an organic bismuth derivative represented by formula (I'-2):
• ##STR25## wherein X.sup.6 is YNHR.sup.2, wherein Y and R.sup.2 are the same as defined above, and X.sup.2 and X.sup.3 are the same as defined above with a base, and then reacting it with a compound represented by formula (V):
• R.sup.1 X (V)
• wherein R.sup.1 is C.sub.3-6 alkyl group which has from 2 to 5 hydroxyl groups optionally being protected, and X is a halogen atom.

A process of producing an organic bismuth derivative represented by formula (I-3):

• ##STR26## wherein X.sup.9 is YNR.sup.1 R.sup.2, wherein Y is --SO.sub.2 -- or --C(O)--, and R.sup.1 and R.sup.2, together with each other, represent a C.sub.2-6 cyclic alkylene optionally having from 1 to 4 hydroxyl groups optionally being protected, and each of X.sup.2 and X.sup.3 is, independently of each other, a hydrogen atom, a C.sub.1-4 alkyl group, a C.sub.1-4 alkoxy group, a C.sub.1-4 alkylsulfonyl group, a C.sub.1-4 alkylcarbonyl group, a nitro group, a cyano group or YNR.sup.1 R.sup.2, wherein Y is the same as defined above, R.sup.1 is a C.sub.3-6 alkyl group which has from 2 to 5 hydroxyl groups optionally being protected, and R.sup.2 is a hydrogen atom, a C.sub.1-6 alkyl group or a C.sub.1-5 acyl group optionally having from 1 to 5 hydroxyl groups optionally being protected, or and R.sup.2, together with each other, represent a C.sub.2-6 cyclic alkylene optionally having from 1 to 4 hydroxyl groups optionally being protected, which comprises treating an organic bismuth derivative represented by formula (I'-3):
• ##STR27## wherein X.sup.8 is YNH.sub.2, wherein Y is the same as defined above, and X.sup.2 and X.sup.3 are the same as defined above with a base, and then reacting it with a compound represented by formula (VI):
• X--R.sup.1 --R.sup.2 --X' (VI)
• wherein R.sup.1 and R.sup.2, together with each other, represent a C.sub.2-6 alkylene optionally having from 1 to 4 hydroxyl groups optionally being protected, and X and X' are halogen atoms.