Patent ID: 8895730

Claim:
A method of synthesizing a two-photon active tris(diphenylamino-9,9-di(R)fluorenyl)-1,3,5-triazine compound having the structure: wherein the R′—(OY) x groups are attached to the phenyl rings of the triarylamine moiety in either a para position or a meta position, R′ of the R′—(OY) x group is a linear or branched oxyalkylene group, —(OY) x of the R′—(OY) x group is a ketal moiety or a diol, and the subscript x of the —(OY) x group is 2; and R is an alkyl group of the formula —C m H 2m+1 , wherein the subscript m ranges from 1 to 6, or an alkylether group of the formula —(CH 2 CH 2 O) p Me, wherein the subscript p ranges from 1 to 5, the method comprising: (a) synthesizing a diphenylamine intermediate by: (1) protecting each diol group of tris-1,1,1-(hydroxymethyl)ethane, via a ketal formation with acetone, as an acetonide derivative; (2) generating bromophenoxy-methyltrimethyl-1,3-dioxane from the acetonide derivative and a hydroxl- or iodo-substituted bromobenzene reagent; and (3) N-arylating aniline (C 6 H 5 NH 2 ) with the bromophenoxy-methyltrimethyl-1,3-dioxane by a palladium-catalyzed, N-aryl coupling reaction; (b) synthesizing a tris(bromo-9,9-dialkylfluorenyl)-1,3,5-triazine intermediate by: (1) monoformylating 2,7-dibromo-9,9-di(R)fluorene to an aldehyde product; (2) converting the aldehyde product to a nitrile product; and (3) trimerizing the nitrile product in trifluoromethanesulfonic acid to the tris(bromo-9,9-dialkylfluorenyl)-1,3,5-triazine intermediate having a three-arm core; and (c) forming the two-photon active tris(diphenylamino-9,9-di(R)fluorenyl)-1,3,5-triazine polyhydroxy compound by: (1) N-arylating the diphenylamine intermediate to each arm of the three-arm core at the bromide position via a palladium-catalyzed, N-Aryl coupling reaction; and (2) removing acetone from each ketal moiety via acid hydrolysis to expose each diol group.