The action of acid halides of carboxylic acids on some tertiary amines

Elucidating Colorization in the Functionalization of Hydroxyl-Containing Polymers Using Unsaturated Anhydrides/Acyl Chlorides in the Presence of Triethylamine

“…The supposed reaction between AC and ROH (R ) H, CH 3 , C 2 H 5 , or polymer backbone) in the presence of TEA via the bottom two-step route is parallel to the formation of complex or acylammonium salt (CH 2 dCH-CONEt 3 + Cl -) between AC and TEA, although the final products are theoretically identical (CH 2 dCH-COOR and Et 3 N • HCl). Suggested by earlier investigations, [17][18][19][20][21][22][23][24][25][26][27] a ketene intermediate (CH 2 dCdCdO) formed in situ is in equilibrium with the complex, although we and some other researchers 20,23 were not able to detect. Unlike R,β-unsaturated acid chlorides such as crotonoyl chloride, [17][18][19][20][21][22][23][24][25][26][27] no double bond shift can be proposed for AC and FC.…”

“…Suggested by earlier investigations, [17][18][19][20][21][22][23][24][25][26][27] a ketene intermediate (CH 2 dCdCdO) formed in situ is in equilibrium with the complex, although we and some other researchers 20,23 were not able to detect. Unlike R,β-unsaturated acid chlorides such as crotonoyl chloride, [17][18][19][20][21][22][23][24][25][26][27] no double bond shift can be proposed for AC and FC. The salt Et 3 N • HCl in Figure 2 itself was also prepared by directly reacting TEA with hydrochloride and it was white.…”

“…As an electron donor, TEA or pyridine forms n −π type complexes with electron acceptors such as alkyl halides, sulfonyl chlorides, and acyl chlorides, involving proton/charge transfer. − Under photoirradiation, TEA can also react with methylene chloride and C 60 . , Known as the Einhorn reaction, much attention was paid in the past to the formation of intermediate ketenes and the double bond shift from the α,β- to the β,γ-position in the alcoholysis of α,β-unsaturated acyl chlorides such as crotonoyl chloride with tertiary amines, such as TEA and pyridine. − The reaction of TEA with maleic anhydride (MA) was first reported by Mayahi and El-Bermani to yield a yellow solution first and then a dark brown solid in a few minutes . Such reaction between tertiary and primary amines with cyclic anhydrides was further investigated in terms of kinetics. , Though extensive, the above studies were not performed on the esterification of hydroxyl-containing polymers, and therefore, little attention was paid to how such complexation would affect the properties and biological performance of the polymers resulted.…”

“…14,15 Known as the Einhorn reaction, 16 much attention was paid in the past to the formation of intermediate ketenes and the double bond shift from the R,βto the β,γ-position in the alcoholysis of R,β-unsaturated acyl chlorides such as crotonoyl chloride with tertiary amines, such as TEA and pyridine. [17][18][19][20][21][22][23][24][25][26][27] The reaction of TEA with maleic anhydride (MA) was first reported by Mayahi and El-Bermani to yield a yellow solution first and then a dark brown solid in a few minutes. 28 Such reaction between tertiary and primary amines with cyclic anhydrides was further investigated in terms of kinetics.…”