Examinations of the effects of (a.) alkyl carbon chain length and (b.) perfluorination of acyl chlorides; propionyl chloride, butyryl chloride, valeroyl chloride, and perfluorinated acyl chlorides; perfluoropropionyl chloride and perfluorobutyryl chloride, are reported and compared using CP-FTMW spectroscopy. All of these molecules are already published in various journals except for valeroyl chloride. The chapters are organized by molecule alkyl chain length and include some background theory. Conformational stability, internal rotation, helicity, and ionic character of the C-Cl bond via the nuclear electric quadrupole coupling constant (χzz) are analyzed. Results show syn, syn-anti/syn-gauche, and syn-anti-anti/syn-gauche-anti stable conformations. Internal rotation was only seen in propionyl chloride. Helicity was not observed. (χzz) was observed to be inert to alkyl chain length, ~ 60 MHz and ~ 65 MHz for the nonfluorinated and fluorinated acyl chlorides. Partial fluorination and varying functional groups are recommended.

This work reports a effective method for the preparation of a series of the new 3-alkoxy acrylamides of general formula R3HNC(O)CR1=CR2(OR), where R/ R1/ R2 = Et/H/H, Me/H/Me, -(CH2)2-/H, -(CH2)3-/H; R3 = Allyl, n-Pr, Bn, Phenetyl. However, the 3-alkoxy acrylamides where R/ R1/ R2 = Et/H/H/, Me/H/Me, R3 = Bn, have already been described in the literature. The 3-alkoxy acrylamides were obtained through three reaction steps. The first step, β-alkoxyvinyl trichloroacetyl ketones were synthesized through the acylation of enolethers using trichloroacetyl chloride as the acylating agent. In the second step, β-alkoxyvinyl trichloroacetyl ketones were converted to the corresponding β-alkoxyvinyl carboxylic acids from a basic hydrolysis using a 1 M sodium hydroxide solution. In the third step, β-alkoxyvinyl carboxylic acids were treated with thionyl chloride, using toluene as solvent, leading to the corresponding acyl chlorides intermediaries, which were not isolated. The acyl chlorides were reacted with primary amines such as allylamine, propylamine, benzylamine, and phenethylamine under basic catalysis of triethylamine, furnishing a new series of 3-alkoxy acrylamides in good yields of 48-90%. The 3-alkoxy acrylamides obtained in this study were identified by 1H and 13C Nuclear Magnetic Resonance spectroscopy, Mass spectroscopy and Elemental analysis. Keywords: 3-alkoxy acrylamides, β-alkoxyvinyl carboxylic acids, β-alkoxyvinyl trichloroacetyl ketones, acyl chlorides, amines / Este trabalho apresenta um método eficiente para preparação de uma série inédita de 3-alcoxiacrilamidas de fórmula geral R3HNC(O)CR1=CR2(OR), onde R/ R1/R2 = Et/H/H, Me/H/Me, -(CH2)2-/H, -(CH2)3-/H; R3 = Alil, n-Pr, Bn, Fenetil. Sendo que as 3-alcoxiacrilamidas onde R/ R1/ R2 = Et/H/H, Me/H/Me, R3 = Bn, já foram descritas anteriormente na literatura. As 3-alcoxiacrilamidas foram obtidas através de três etapas reacionais, sendo que a primeira etapa constitui-se da acilação dos enol éteres, utilizando cloreto de tricloroacetila como agente acilante. Na segunda etapa as β-alcoxivinil tricloroacetil cetonas sintetizadas anteriormente, foram convertidas aos respectivos ácidos β-alcoxivinil carboxílicos a partir da hidrólise básica (utilizando solução de NaOH 1 M). Na terceira etapa, os ácidos β-alcoxivinil carboxílicos foram submetidos à reação com cloreto de tionila, utilizando tolueno como solvente, formando como intermediários os cloretos ácidos, os quais não foram isolados. Posteriormente, esses cloretos ácidos foram submetidos á reação de substituição nucleofílica, utilizando diferentes aminas alquílicas primárias (alilamina, propilamina, benzilamina, fenetilamina) como nucleófilo, sob catálise básica de trietilamina, promovendo assim, a síntese da série inédita das 3-alcoxiacrilamidas com bons rendimentos de 48-90%. As 3-alcoxiacrilamidas obtidas neste trabalho foram identificadas através de técnicas de Ressonância Magnética Nuclear de Hidrogênio, Ressonância Magnética Nuclear de Carbono-13, Espectrometria de Massas e Análise elementar.