Transmission of dipolar substituent effects: ionization of a series 3-(7-substituted-1-naphthyl) propynoic acid (E)-3-(7-substituted-1-naphthyl) propenoic acids and their Esterification with Diazodiphenylmethane

Alkaline hydrolysis rates coefficients for the series of methyl 3-(7-substituted-1-naphthyl) propynoate was calculated in 70%v/v dimethylsulphoxide-water at various temperatures (25,30,40, and 50̊ C). The pKa values of 3-(7-substituted-1-naphthyl) propynoic acid and (E)- 3-(7-substituted-1-naphthyl) propenoic acid calculated in 80%w/w 2-methoxyethanol-water at room temperature (25.0̊ C). logk2 of esterification rate coefficients for 3-(7-substituted-1-naphthyl) propynioc acid and (E)-3(7-substituted-1-naphthyl) propenioc acid with DDM have been measured at 30.0̊ C. Reversed substituent dipolar effects were found in the ionization reaction. In the esterification reaction with DDM the result show similar but reduced substituted effects. Rate retardations was found in the alkaline hydrolysis. It could be result from steric effect or reversal of substituent dipolar effect with a combination of steric effect.

In Vitro Evaluation of Different Dietary Methane Mitigation Strategies

We assessed and ranked different dietary strategies for mitigating methane (CH4) emissions and other fermentation parameters, using an automated gas system in two in vitro experiments. In experiment 1, a wide range of dietary CH4 mitigation strategies was tested. In experiment 2, the two most promising CH4 inhibitory compounds from experiment 1 were tested in a dose-response study. In experiment 1, the chemical compounds 2-nitroethanol, nitrate, propynoic acid, p-coumaric acid, bromoform, and Asparagopsis taxiformis (AT) decreased predicted in vivo CH4 production (1.30, 21.3, 13.9, 24.2, 2.00, and 0.20 mL/g DM, respectively) compared with the control diet (38.7 mL/g DM). The 2-nitroethanol and AT treatments had lower molar proportions of acetate and higher molar proportions of propionate and butyrate compared with the control diet. In experiment 2, predicted in vivo CH4 production decreased curvilinearly, molar proportions of acetate decreased, and propionate and butyrate proportions increased curvilinearly with increased levels of AT and 2-nitroethanol. Thus 2-nitroethanol and AT were the most efficient strategies to reduce CH4 emissions in vitro, and AT inclusion additionally showed a strong dose-dependent CH4 mitigating effect, with the least impact on rumen fermentation parameters.

Regioselective radical arylation: silver-mediated synthesis of 3-phosphorylated coumarins, quinolin-2(1H)-one and benzophosphole oxides

A silver-mediated domino radical addition/cyclization reaction of diaryl- or dialkyl-phosphine oxides with propynoic acid derivatives delivering 3-phosphorylated coumarins, quinolin-2(1H)-one and benzophosphole oxides is presented.