A Theoretical Study on the Phosgenation of 2,4-Toluenediamine (2,4-TDA).

Industrially relevant phosgenation mechanisms of 2,4-toluenediamine (2,4-TDA) were investigated using G3MP2B3 model chemistry. Six reaction pathways had been explored, which resulted in the formation of toluene diisocyanate (2,4-TDI) including different scenarios of the 'phosgenations first' and 'consecutive phosgenations' mechanisms in both gas and condensed phases. Two possible 'phosgenations first' mechanisms show superior to the others in terms of energy, regardless of which phases are considered. Due to the o-dichlorobenzene (ODCB) solvation, the reaction barriers are dramatically reduced compared to the gas-phase reaction mechanism and the solvent effect can be described by linear relationship. Standard enthalpy of formation value was also recommended for 2,4-TDA (59.3 kJ/mol) and 2,4-TDI (-94.1 kJ/mol), as well as for the gas-phase intermediates (IM).

An Ab Initio Investigation of the 4,4'-Methlylene Diphenyl Diamine (4,4'-MDA) Formation from the Reaction of Aniline with Formaldehyde.

The most commonly applied industrial synthesis of 4,4'-methylene diphenyl diamine (4,4'-MDA), an important polyurethane intermediate, is the reaction of aniline and formaldehyde. Molecular understanding of the 4,4'-MDA formation can provide strategy to prevent from side reactions. In this work, a molecular mechanism consisted of eight consecutive, elementary reaction steps from anilines and formaldehyde to the formation of 4,4'-MDA in acidic media is proposed using accurate G3MP2B3 composite quantum chemical method. Then G3MP2B3-SMD results in aqueous and aniline solutions were compared to the gas phase mechanism. Based on the gas phase calculations standard enthalpy of formation, entropy and heat capacity values were evaluated using G3MP2B3 results for intermediates The proposed mechanism was critically evaluated and important side reactions are considered: the competition of formation of protonated p-aminobenzylaniline (PABAH⁺), protonated aminal (AMH⁺) and o-aminobenzylaniline (OABAH⁺). Competing reactions of the 4,4'-MDA formation is also thermodynamically analyzed such as the formation of 2,4-MDAH⁺, 3,4-MDAH⁺. AMH⁺ can be formed through loose transition state, but it becomes kinetic dead-end, while formation of significant amount of 2,4-MDA is plausible through low-lying transition state. The acid strength of the key intermediates such as N-methylenebenzeneanilium, PABAH⁺, 4-methylidenecyclohexa-2,5-diene-1-iminium, and AMH⁺ was estimated by relative pKa calculation.

Effects of in-season (5 weeks) creatine and pyruvate supplementation on anaerobic performance and body composition in American football players.

The purpose of this investigation was to study the efficacy of two dietary supplements on measures of body mass, body composition, and performance in 42 American football players. Group CM (n = 9) received creatine monohydrate, Group P (n = 11) received calcium pyruvate, Group COM (n = 11) received a combination of calcium pyruvate (60%) and creatine (40%), and Group PL received a placebo. Tests were performed before (T1) and after (T2) the 50 week supplementation period, during which the subjects continued their normal training schedules. Compared to P and PL, CM and COM showed significantly greater increases for body mass, lean body mass, 1 repetition maximum (RM) bench press, combined 1 RM squat and bench press, and static vertical jump (SVJ) power output. Peak rate of force development for SVJ was significantly greater for CM compared to P and PL. Creatine and the combination supplement enhanced training adaptations associated with body mass/composition, maximum strength, and SVJ; however, pyruvate supplementation alone was ineffective.