Bromoacetic Acid → HCID 67960759, compound

HRID 217579Notes

Reaction equation

CC1C=CC(S(O[N:12]2[CH:23]([CH2:24][C:25]3[CH:30]=[CH:29][C:28]([N+:31]([O-:33])=[O:32])=[CH:27][CH:26]=3)[CH2:22][N:21](OS(C3C=CC(C)=CC=3)(=O)=O)[CH2:20][CH2:19][N:18](OS(C3C=CC(C)=CC=3)(=O)=O)[CH2:17][CH2:16][O:15][CH2:14][CH2:13]2)(=O)=O)=CC=1.Br[CH2:57][C:58]([OH:60])=[O:59]>>[N+:31]([C:28]1[CH:27]=[CH:26][C:25]([CH2:24][CH:23]2[CH2:22][N:21]([CH2:57][C:58]([OH:60])=[O:59])[CH2:20][CH2:19][N:18]([CH2:57][C:58]([OH:60])=[O:59])[CH2:17][CH2:16][O:15][CH2:14][CH2:13][N:12]2[CH2:57][C:58]([OH:60])=[O:59])=[CH:30][CH:29]=1)([O-:33])=[O:32]

Participants

Reactant 2

HCID 6227Bromoacetic Acid

HCID 86633204HCID 86633204, compound

Product 1

HCID 67960759HCID 67960759, compound

Procedure

Scheme 3 illustrates an example of a method that can be used to produce a compound of formula (XVIb). This method involves cyclizing 2,2′-oxybis(ethane-2,1-diyl) bis(4-methylbenzenesulfonate) (XXVIII) with (XXII) in DMF to produce 5-(4-nitrobenzyl)-1-oxa-4,7,10-triazacyclododecane-4,7,10-triyl tris(4-methylbenzenesulfonate) (XXIX), followed by deprotection and alkylation of (XXIX) using bromoacetic acid to yield 2,2′,2″-(5-(4-nitrobenzyl)-1-oxa-4,7,10-triazacyclododecane-4,7,10-triyl)triacetic acid (XXX). Hydrogenation of the nitro group of (XXX) is then achieved using 10% palladium on carbon catalyst at ambient pressure to give aniline intermediate 2,2′,2″-(5-(4-aminobenzyl)-1-oxa-4,7,10-triazacyclododecane-4,7,10-triyl)triacetic acid (XXXI). Conversion of (XXXI) to the reactive electrophilic isothiocyanate 2,2′,2″-(5-(4-isothiocyanatobenzyl)-1-oxa-4,7,10-triazacyclododecane-4,7,10-triyl)triacetic acid (XXXII) is carried out using a 2-phase reaction medium with chloroform/water and thiophosgene.

Sources & evidence

ORD record: ord-48d8483d4ae342d4b1441283757e0abb
Source dataset: uspto-grants-2012_06
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08198101B2

Reaction notes

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