44982-72-1

A palladium-catalyzed C-H arylation of aliphatic amines with arylboronic esters is described, proceeding through a four-membered-ring cyclopalladation pathway. Crucial to the successful outcome of this reaction is the action of an amino-acid-derived ligand. A range of hindered secondary amines and arylboronic esters are compatible with this process and the products of the arylation can be advanced to complex polycyclic molecules by sequential C-H activation reactions. Four corners: A palladium-catalyzed C-H arylation of aliphatic amines with arylboronic esters is described to proceed by a four-membered-ring cyclopalladation pathway. Crucial to the successful outcome of this reaction is the action of an amino-acid-derived ligand. A range of hindered secondary amines and arylboronic esters are compatible with this process and the products of the arylation can be advanced to complex polycyclic molecules by sequential C-H activation reactions.

An essentially single stage reaction has been discovered in which a disubstituted ethanolamine, that is, a 2,2'-substituted-2-aminoethanol, may be reacted with a haloform and a carbonyl containing compound selected from the group consisting of monoketones and benzaldehyde, in the presence of an alkali metal hydroxide, and optionally in the presence of a phase transfer catalyst, to produce an alkali metal hydroxyethylaminoacetate ("HEAA") which has N-adjacent C atoms on which there are a total of at least three substituents (hence "polysubstituted"), and one or both pairs of substituents on each N-adjacent C atom may be cyclized. The HEAA may be cyclized by the action of a mineral acid to produce a 2-morpholone hydrochloride which is characterized by having a total of at least three substituents on the N-adjacent C atoms of the ring. The 2-morpholone so produced may be reduced to a polysubstituted aminodiol. The aminodiol so produced may be cyclized with an alkane sulfonic acid to yield a polysubstituted morpholine which could not otherwise have been made. The aminodiol may also be alkylated to produce diethers with polysubstituted N-adjacent C atoms. If the aminodiol is tosylated, a polysubstituted crown ether is produced with plural polyalkylene groups. The foregoing HEAA and related compounds are used as u-v light stabilizers in novel compositions in which a small but effective amount of one or more of the HEAA and related compounds is incorporated, in an amount sufficient to produce desirable stabilization against degradation by u-v light in a wide variety of organic materials.

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