Patent ID: 6372903
Filing Date: 2002-04-16
Classification: B01J,C07F

Abstract:
A process for the preparation of a polyazacycloalkane, immobilized on a silica gel, from a polyazacycloalkane of formula (A): in whichR1 and R2, which are identical or different, each represent, independently of one another, a hydrogen atom, a linear or branched alkyl radical having from 1 to 15 carbon atoms, W1, W2 and W3, which are identical or different, represent, independently of one another, a divalent radical chosen from those represented by the general formula (B1): â€”(CH2)nâ€”(NH)pâ€”(CH2)mâ€”â€ƒâ€ƒ(B1) â€ƒin which:n and m are, independently of one another, equal to 2 or to 3 and p is equal to 0 or to 1, it being understood that the polyazacycloalkane nucleus of the compound of formula (A) has at most 30 cyclic carbon atoms and at most 6 cyclic nitrogen atoms, â€ƒwhich comprises: a) the reaction of the compound of formula (A) with a compound of formula (C1) Zâ€³â€”(CH2)oâ€”(Q)qâ€”(CH2)râ€”(Ar)sâ€”(CH2)tâ€”(U)uâ€”(CH2)vâ€”Si(X1)(X2)(X3)â€ƒâ€ƒ(C1) â€ƒin whichZâ€² represents either a halo radical or an R7Oâ€”C(&boxH;O)â€” group, in which R7 represents a hydrogen atom, a sodium atom, a potassium atom or a radical chosen from alkyl radicals having from 1 to 4 carbon atoms or the tosyl, mesyl or trifluoromethylsulfonyl radicals, or an oxiran-2-yl group or an ethenyl group, o, r, t and v, which are identical or different, represent, independently of one another, an integer greater than or equal to 0 and less than or equal to 6, Q and U, which are identical or different, represent, independently of one another, an oxygen atom, a sulfur atom or one of the â€”Oâ€”COâ€”, â€”COâ€”Oâ€”, â€”NHâ€”COâ€”, â€”COâ€”NHâ€” or â€”NHâ€” groups, q, s and u, which are identical or different, represent, independently of one another, an integer greater than or equal to 0 and less than or equal to 1, Ar represents a phenylene radical, it being understood that: â€ƒwhen q is equal to 1, o is other that 0, â€ƒwhen q is equal to 1 and when u is equal to 0, the sum r+s+t+v is other than 0, â€ƒwhen u is equal to 1, v is other than 0, â€ƒwhen u is equal to 1 and when q is equal to 0, the sum o+r+s+t is other than 0, â€ƒwhen s is equal to 0 and when q and u are equal to 1, the sum r+t is other than 0, â€ƒthe sum o+r+t+v is less than or equal to 12, and X1, X2 and X3, which are identical or different, each represent, independently of one another, a hydrogen atom, a halogen atom or an OR5 radical, in which R5 represents a hydrogen atom or an alkyl radical having from 1 to 4 carbon atoms, to form a compound of formula (D), â€ƒin which Râ€²4 represents either R4 wherein R4 represents a divalent radical derived from a chain having from 1 to 10 carbon atoms, in which chain are optionally inserted one or more structural links chosen from the arylene group or the â€”Oâ€”, â€”Sâ€”, â€”Oâ€”C(&boxH;O)â€”, â€”N(R6)â€”C(&boxH;O)â€” or â€”N(R6)â€” fragments, in which fragments R6 represents a hydrogen atom, an aliphatic hydrocarbonaceous radical comprising from 1 to 6 carbon atoms, a benzyl radical or a phenethyl radical, the said chain being unsubstituted or substituted by one or more radicals chosen from halogen atoms, the hydroxyl group, alkyl radicals comprising from 1 to 4 carbon atoms or the benzyl or phenethyl radicals, or R4 substituted by a radical originating from the reaction of Zâ€³ with the secondary amine group &boxH;Nâ€”H, b) the condensation of said compound of formula (D) with silanol sites of a silica gel, to form the immobilized polyazacycloalkane of formula (E): â€ƒin which: Xâ€²2 represents X2 as defined above or O-(silica gel), and Xâ€²3 represents X3 as defined above or O-(silica gel); c) and the protection, if desired of some of the unreacted silanol sites with Zâ€², a protective group for the hydroxyl functional group, to form the immobilized polyazacycloalkane of formula (Eâ€²), corresponding to the formula (E) in which all or a portion of the free â€”OH sites of the silica gel are blocked in the form of OZâ€² sites and in particular in the form of (trialykl) silyloxy sites.