Introduction of functional groups

Polymer Modification. The introduction of functional groups on polysdanes using the alkah metal coupling of dichlorosilanes is extremely difficult to achieve. Some polymers and copolymers with 2-(3-cyclohexenyl)ethyl substituents on siUcon have been made, and these undergo hydrogen hahde addition to the carbon—carbon double bond (94,98). 

Multistage emulsion polymerization techniques are usually applied for (1) the synthesis of large uniform latex particles, (2) the introduction of functional groups into the uniform latex particles, or (3) the synthesis of macroporous uniform latex particles. 

The pharmaceutical interest in the tricyclic structure of dibenz[6,/]oxepins with various side chains in position 10(11) stimulated a search for a convenient method for the introduction of functional groups into this position. It has been shown that nucleophilic attack at the carbonyl group in the 10-position of the dibenzoxepin structure renders the system susceptible to water elimination. Formally, the hydroxy group in the enol form is replaced by nucleophiles such as amines or thiols. The Lewis acids boron trifluoride-diethyl ether complex and titanium(IV) chloride have been used as catalysts. 

Introduction of Functional Groups by Nucleophilic Substitution at Saturated Carbon... 

Inman, J.K., and Dintzis, H.M. (1969) The derivatization of cross-linked polyacrylamide beads. Controlled introduction of functional groups for the preparation of special-purpose, biochemical adsorbents. Biochemistry 8, 4074-4082. 

Bicyclic-monocyclic ion-complex tautomerism The introduction of functional groups onto the substituent at carbon, nitrogen, or phosphorus atoms increases the number of possible types of ion-complex tautomerism. For example, the presence of one more hydroxyalkyl group at the phosphorus atom results in bicyclic-monocyclic tautomerism [Eq. (91)] (85IZV469, 85IZV1102 89IZV946). 

Some transition metal catalysts induce the living polymerization of various acetylenic compounds.68,69 Such polymerizations of phenylacetylene catalyzed by rhodium complexes are used in conjunction with a quantitative initiation and introduction of functional groups at the initiating chain end (Scheme 16).70 The catalyst is prepared from an [RhCl(nbd)]2/Ph2C=C(Ph)Li/PPh3 mixture and proceeds smoothly to give quantitatively the polymer 54 with a low polydispersity ratio. 

C-C bond formation using the Heck reaction allows the introduction of functional groups to obtain new organic structures on solid supports. This reaction between an alkene with an alkenyl or an aryl halide has been widely employed in various in-tra- and inter-molecular versions on solid-phase because of the readily accessibility of starting materials. The Heck reaction was performed on immobilized aryl or alkenyl halides with soluble alkenes and vice versa (Scheme 3.11). 

SECTION 3.2. INTRODUCTION OF FUNCTIONAL GROUPS BY NUCLEOPHILIC SUBSTITUTION AT SATURATED CARBON... 

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