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Our objective was to determine the effect of ultrasonics on biodiesel production from soybean oil. In this study, ultrasonic energy was applied in two different modes: pulse and continuous sonication. Soybean oil was mixed with methanol and a catalytic amount of sodium hydroxide, and the mixture was sonicated at three levels of amplitude (60, 120, and 180 μm pp ) in pulse mode (5 s on/25 s off). In the continuous mode, the same reaction mixture was sonicated at 120 μm pp for 15 s. The reaction was monitored for biodiesel yield by stopping the reaction at selected time intervals and analyzing the biodiesel content by thermogravimetric analysis (TGA). The results were compared to a control group, in which the same reactant composition was allowed to react at 60 °C for intervals ranging from 5 min to 1 h without ultrasonic treatment. It was observed that ultrasonic treatment resulted in a 96% by weight isolated yield of biodiesel in less than 90 s using the pulse mode, compared to 30−45 min for the unsonicated control sample with comparable yields (83−86%). In the pulse mode, the highest yield (96%) was obtained by sonicating the mixture at 120 μm pp amplitude. In the continuous sonication mode, the highest biodiesel yield was 86% by weight, which was obtained in 15 s. Our objective was to determine the effect of ultrasonics on biodiesel production from soybean oil. In this study, ultrasonic energy was applied in two different modes: pulse and continuous sonication. Soybean oil was mixed with methanol and a catalytic amount of sodium hydroxide, and the mixture was sonicated at three levels of amplitude (60, 120, and 180 μm pp ) in pulse mode (5 s on/25 s off). In the continuous mode, the same reaction mixture was sonicated at 120 μm pp for 15 s. The reaction was monitored for biodiesel yield by stopping the reaction at selected time intervals and analyzing the biodiesel content by thermogravimetric analysis (TGA). The results were compared to a control group, in which the same reactant composition was allowed to react at 60°C for intervals ranging from 5 min to 1 h without ultrasonic treatment. It was observed that ultrasonic treatment resulted in a 96% by weight isolated yield of biodiesel in less than 90 s using the pulse mode, compared to 30-45 min for the unsonicated control sample with comparable yields (83-86%). In the pulse mode, the highest yield (96%) was obtained by sonicating the mixture at 120 μm pp amplitude. In the continuous sonication mode, the highest biodiesel yield was 86% by weight, which was obtained in 15 s.

The bicyclic triaminophosphine P(RNCH(2)CH(2))(3)N (R = i-Bu, 1c) serves as an effective promoter for the room-temperature stereoselective synthesis of α,β-unsaturated esters, fluorides, and nitriles from a wide array of aromatic, aliphatic, heterocyclic, and cyclic aldehydes and ketones, using a range of Wadsworth-Emmons (WE) phosphonates. Among the analogues of 1c [R = Me (1a), i-Pr (1b), Bn (1d)], 1a and 1b performed well, although longer reaction times were involved, and 1d led to poorer yields than 1c. Functionalities such as cyano, chloro, bromo, methoxy, amino, ester, and nitro were well tolerated. We were able to isolate and characterize (by X-ray means; see above) the reactive WE intermediate species formed from 2b and 1c.

Herein we find that proazaphosphatrane 1c is a very efficient catalyst for Mukaiyama aldol reactions of aldehydes with trimethylsilyl enolates in THF solvent. Only the activated ketone 2,2,2-trifluoroacetophenone underwent clean aldol product formation with a variety of trimethylsilyl enolates under similar conditions as the aldehydes. The reactions were carried out at room temperature using (1-methoxy-2-methyl-1-propenyloxy)trimethylsilane, whereas the temperature was -15 degrees C in the case of 1-phenyl-1-(trimethylsilyloxy)ethylene. The reaction conditions are mild and operationally simple, and a variety of aryl functional groups, such as nitro, amino, ester, chloro, trifluoromethyl, bromo, iodo, cyano, and fluoro groups, are tolerated. Product yields are generally better than or comparable to those in the literature. 1-Phenyl-1-(trimethylsilyloxy)ethylene, 1-(trimethylsilyloxy)cyclohexene, and 2-(trimethylsilyloxy)furan underwent clean conversion to beta-hydroxy carbonyl compounds under our reaction conditions. In the case of bulky (2,2-dimethyl-1-methylenepropoxy)trimethylsilane, only alpha,beta-unsaturated esters were isolated. Heterocyclic aldehydes, such as pyridine-2-carboxaldehyde, benzofuran-2-carboxaldehyde, benzothiophene-2-carboxaldehyde, and 1-methyl-2-imidazolecarboxaldehyde, gave good yields of Mukaiyama products. An optimized synthesis for the catalyst 1c is also reported herein.

Herein we report that tetrabutylammonium fluoride (TBAF) is a very efficient catalyst for the addition of trialkylsilylalkynes to aldehydes, ketones, and trifluoromethyl ketones in THF solvent at room temperature. The reaction conditions are mild and operationally simple, and a variety of aryl functional groups, such as chloro, trifluoromethyl, bromo, and fluoro groups, are tolerated. Impressively, using our protocol, useful CF(3)-bearing tertiary propargylic alcohols can be synthesized. Product yields are generally better than or comparable to those in the literature. 1-Phenyl-2-trimethylsilyl acetylene, trimethyl ((4-(trifluoromethyl)phenyl)ethynyl)silane, 1-trimethylsilyl-1-hexyne, and trimethyl(thiophen-3-ylethynyl)silane underwent clean conversion to their corresponding propargylic alcohols as products under our conditions. Heterocyclic carbonyl compounds, such as furan-3-carboxaldehyde, thiophene-3-carboxaldehyde, and 2-pyridyl ketone, gave good yields of propargylic alcohols.

Proazaphosphatrane P(PhCH(2)NCH(2)CH(2))(3)N (1a) is an efficient catalyst for the addition of aryl trimethylsilyl alkynes to a variety of aromatic, aliphatic, and heterocyclic aldehydes in THF at room temperature. The reaction conditions are mild and employ a low catalyst loading (ca. 5 mol %). Only propargylic alcohols were isolated in good to excellent isolated yields when electron-rich, electron-neutral, heterocyclic, and aliphatic aldehydes were employed, whereas beta-branched Morita-Baylis-Hillman (MBH) type adducts were isolated with electron-deficient aromatic aldehydes after conventional acid hydrolysis of the TMS ether products. Alkynes containing heterocyclic and aromatic groups bearing electron-withdrawing or -donating substituents underwent clean addition to cyclohexanecarboxaldehyde and to electron-rich aromatic aldehydes to give propargylic alcohols in excellent isolated yields. beta-Branched Morita-Baylis-Hillman (MBH) type adducts were isolated when electron-deficient aromatic aldehydes were employed. Reaction pathways to both types of products are proposed.

An efficient method for the synthesis of industrially important dibenzyls and alkyl phenyl esters via sequential Heck coupling and hydrogenation of the alkenyl double bond in one pot with a single recyclable catalyst under mild conditions has been realised. The catalyst was recovered by simple filteration and reused for several cycles with consistent activity.

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