Process for producing radiolabelled benzodiazepine receptor agen

Drug – bio-affecting and body treating compositions – Radionuclide or intended radionuclide containing; adjuvant... – In an organic compound

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424 111, 424 165, 424 181, 540450, 548100, A61K 5100, A61M 3614

Patent

active

060155442

DESCRIPTION:

BRIEF SUMMARY
TECHNICAL FIELD

The present invention relates to a process for producing radioactive substituted benzodiazepines and to pharmaceutical compositions containing said benzodiazepines.


BACKGROUND ART

Radiolabelled compounds which are subject to localization in particular organs or tumors therein are of great value for the diagnosis of diseases of the human body. For example, iodine-123 labelled fatty acids and thallium-201 have been utilized as heart imaging agents. Various isonitrile ligands labelled with technetium-99m have been used to image infarcted regions on the heart.
Substituted benzodiazepines, which are labelled with iodine-123, iodine-125 or iodine-131 have been used for studies of benzodiazepine receptors in the brain.
A new benzodiazepine receptor ligand [radioiodine]3-(5-cyclopropyl-1,2,4-oxadiazol-3-yl)-7-iodo-5,6-dihydro-5-m ethyl-6-oxo-4H-imidazo[1,5-a][1,4]-benzodiazepine was introduced recently (C. Foged et al., J. Nucl Med. 1993: 34, p89).
The common preparation scheme for radioiodined carrier free neuroreceptor ligands employs a trialkyltin precursor and radioactive iodine by the chloramin-T method in strongly acidic conditions. However the labelling reaction is associated with a large and consistent formation of a radioactive volatile reaction product: methyliodine (Y. Zea-Ponce et al., J. Lab. Comp. Rad. 1994: 36, 331-337).
The side reaction products may contain up to 60% of the activity that is added into the reaction mixture. The loss of that amount of the activity increases production costs tremendously.
An another disadvantage, which results from the formation of methyliodine, is radio protection costs and problems. The high increase of the required radioactivity increases the need for radioprotection of persons in the very early moments during upscaling the process. Another radioprotection problem resides in the need to catch up methyliodine. Active charcoal filters, which are used to capture radioiodine from the air, do not hold methyliodine. It requires special reactor grade active charcoal filters that are another source of extra expenses.


DISCLOSURE OF THE INVENTION

To avoid the radioactive volatile by-product of the prior art we found an alternative route to produce [radiohalogenated]3-(5-cyclopropyl-1,2,4-oxadiazol-3-yl)-5,6-dihydro-5-met hyl-6-oxo-4H-imidazo[1,5-a][1,4]-benzodiazepine (II). ##STR1## wherein R' is a radioactive halogen at position 7, 8, 9 or 10. Said radioactive halogen is preferably 123.sub.I, 124.sub.I, 125.sub.I, 131.sub.I. Other suitable radioactive halogens are F.sup.18, Br.sup.75, Br.sup.76, Br.sup.77.
The present invention is directed to a process for producing carrier free [radiohalogen]3-(5-cyclopropyl-1,2,4-oxadiazol-3-yl)-5,6-dihydro-5-methyl- 6-oxo-4H-imidazo[1,5-a][1,4]-benzodiazepine using a halogenated precursor and HPLC purification with a high yield.
The present invention is also directed to a pharmaceutical composition containing said radiohalogenated benzodiazepine.
The process according to the present invention is defined in the appended claims. As described below, radioiodine is used as a non limiting example of radiohalogens.
According to the present invention formation of the radioactive methyliodine is avoided and the yield of the labelled benzodiazepine increases.
It is known that one can easily exchange a halogen on the benzene ring into another one having a lower atom number. In the opposite direction the reaction is rather slow and normally yields a poor result. Neuroreceptor imaging agents are required to be carrier free. The above mentioned exchange process results in a product having a carrier, where precursor and radiolabelled product are difficult to separate from each other.
The pharmaceutical composition according to the invention contains an effective amount of the compound (II) and a pharmaceutically acceptable liquid carrier material and optionally one or more pharmaceutically acceptable adjuvants. It is suitable for use as a benzodiazepine receptor imaging agent. In such medical use the radiohalogenated benzodiaze

REFERENCES:
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patent: 4727153 (1988-02-01), Watjen et al.
patent: 4745112 (1988-05-01), Watjen et al.
patent: 5096695 (1992-03-01), Carmann et al.
Foger et al., "Development of 123 I-labelled NNC 13-8241 as a Radioligand for SPECT, Visualization of Benzodiazepine Receptor Binding", Nuclear Medicine & Biology, vol. 23, No. 3, p. 202-209, (1996).
Kuikka et al., "Initial human studies with single-photon emission tomography using iodine-123 labelled 3-(5-cyclopropyl-1,2,4-oxadiazo-3-yl) 7-iodo-5,6-dihydro-5-methyl-6-0x0-4H-imidazo[1,5-a][1,4]-benzodiazepine (NNC 13-8241)", European Journal of Nuclear Medicine, vol. 23, No. 7, p. 798-803, (1996).
Kuikka et al., "Initial Human Studies with Spect Using [I-123] NNC 13-8241 for Visualization of Benzodiazepine Receptors.", The Journal of Nuclear Medicine, vol. 37, No. 5, p. 76-77, (1996).
Foged et al., "New Selective Radioligands for Examination of Benzodiazepine Receptors", Journal of Nuclear Medicine, vol. 34, No. 5, p. 89, (1993).

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