Use Of Acid Chlorides Research Articles

Redox-Neutral Decarbonylative Cross-Couplings Coming of Age.

Major progress has recently been made in the challenging redox-neutral decarbonylative cross-coupling of carboxylic acids. For example, the use of acid fluorides as effective cross-coupling partners has been found to enable control of the decarbonylation selectivity and facilitates challenging Pd0 -catalyzed nucleophilic trifluoromethylation and exogenous base-free Suzuki cross-coupling reactions. In another recent advance, the use of acid chlorides in room temperature difluoromethylation and direct decarbonylative cross-coupling of carboxylic acids allows these classical substrates to be used as aryl electrophiles in cross-coupling reactions. Further challenges that are yet to be addressed in redox-neutral decarbonylative cross-couplings are also briefly summarized.

Modified synthesis scheme for N,N´-dimethyl-N,N´-dioctyl-2,(2´-hexyloxyethyl) malonamide (DMDOHEMA) and its comparison with proposed solvents for actinide partitioning

Abstract N,N´-dimethyl-N,N´-dioctyl-2,(2´-hexyloxyethyl) malonamide (DMDOHEMA) has been synthesized by a relatively simpler route with a better yield than the conventional procedures for the synthesis of pentaalkyl substituted diamides. The proposed route replaces the use of acid chlorides and brominating agents (corrosive in nature) by acid diester and p-toluene sulphonyl (tosyl) chloride, respectively. The later easily replaces hydrogen from primary OH group of the 3-oxanonyl side chain and relatively less corrosive. The synthesized product has been tested for the extraction behavior of 241Am, Np, Pu as pure tracers as well as under Pressurized Heavy Water Reactor (PHWR) Simulated High-Level Waste (SHLW) conditions. The stoichiometries of extracted species of Np(IV), Pu(IV), and Am(III) from 3 M HNO3 using varying concentrations of DMDOHEMA in n-dodecane has been determined. The effect of the nature of mineral acid (viz. HCl, HNO3, and HClO4) on the extraction of Am(III) has also been investigated employing DMDOHEMA and N,N´-dimethyl-N,N´-dibutyl-tetradecyl malonamide (DMDBTDMA) as extractants and explained in terms of the aggregation behavior of diamides. The performance of DMDOHEMA has been evaluated vis-à-vis other proposed extractants for actinide partitioning under PHWR-SHLW conditions.

Base-Catalyzed Direct Conversion of Dipyrromethanes to 1,9-Dicarbinols: A [2 + 2] Approach for Porphyrins

A variant of the MacDonald approach was devised for the synthesis of porphyrins. A new base-catalyzed one-step synthesis of 1,9-dipyrromethane-dicarbinols was achieved by Friedel-Crafts alkylation of dipyrromethanes using commercially available ethyl glyoxylate solution in toluene. This method avoids the use of acid chlorides, Grignard reagents, borohydride reductions, and acidic conditions. The [2 + 2] condensation of dipyrromethanedicarbinols and dipyrromethanes yielded 5,15-di(ethoxycarbonyl)porphyrins.

Controlled stereochemistry of polyamides derived fromcis/trans-1,4-cyclohexanedicarboxylic acid

A series of copolyamides 12.y was synthesized either with y = 6, or 1,4-cyclohexanedicarboxylic acid (1,4-CHDA) residue, or a mixture of both. The influence of the synthetic route of 1,4-CHDA containing polyamides on the obtained cis-trans ratio of the incorporated 1,4-CHDA was investigated. The use of acid chlorides provided a synthetic route with full control of the cis-trans ratio of the 1,4-CHDA residue during synthesis, whereas synthesis at elevated pressure and temperature caused isomerization. The content and cis-trans ratio of 1,4-CHDA in the copolyamides were determined by solution 13 C NMR spectroscopy. Increasing the degree of partial substitution of the adipic acid by 1,4-CHDA resulted in an increase in T m , even for low molar precentages of 1,4-CHDA. This phenomenon points to isomorphous crystallization of both the 12.6 and 12.CHDA repeating units. The mps of the synthesized polyamides were independent of the initial cis-trans ratio of 1,4-CHDA, provided that the samples were annealed at 300 °C before DSC analysis. The polyamides exhibited a different melting pattern depending on the 1,4-CHDA content. At a low a 1,4-CHDA content a net exothermic recrystallization occurred during melting, whereas at higher contents of 1,4-CHDA this recrystallization occurs to a lesser extent, and two separate melting areas are observed.

ChemInform Abstract: Reissert Compound Studies. Part 55. Studies with Reissert Compounds. Part 17. Mono‐Reissert Compound Formation at the 1,2‐Position of the Quinazoline System.

AbstractThe quinazolines (I) are selectively converted to the mono‐Reissert compounds (IV) by use of acid chlorides (III) and the cyanide (II).

Studies with Reissert compounds. Part 17. Mono-Reissert compound formation at the 1,2-position of the quinazoline system

4-Substituted quinazolines have been selectively converted into mono-Reissert compounds at the 1,2-position by use of acid chlorides and trimethylsilyl cyanide. Various reactions of the quinazoline Reissert compounds are reported. For example, conjugate base generation at the 2-position leads to a 1,2-rearrangement, whereas substitution occurs in the presence of an alkyl halide, providing, after hydrolysis, 2-alkyl-4-phenylquinazolines in good yield. Ring annellation by intramolecular alkylation is also reported. The quinazoline Reissert compound conjugate base reacts with aldehydes to give alcohol esters which can further be converted, via the alcohol and use of phosgene, to novel oxazolo[4,3-a]quinazoline derivatives.

N,N-Dimethylchlorosulfitemethaniminium chloride (SOCl 2-DMF) a versatile dehydrating reagent.

N,N-dimethylchlorosulfitemethaniminium chloride formed from thionyl chloride and dimethylformamide was found and efficient reagent for the synthesis of acyl azides from carboxylic acids and nitriles from oximes. It is also highly efficient for the direct synthesis of beta-lactams from carboxylic acids and imines avoiding the use of acid chlorides.

Polyesterification of halogen containing difunctional compounds

Abstract The increasing interest in halogen containing polymers has led us to re-evaluate the different methods for the polycondensation of fluorinated and chlorinated monomers to form polyesters. The use of acid chlorides easily gives polymers with relatively high molecular weights (above 3000). We also describe in this work a new method of polytransesterification from the bishydroxyethyl esters of fluorinated and chlorinated diacids at temperatures below 200°C.

ChemInform Abstract: ELECTROCHEMICAL REACTIONS OF ORGANIC COMPOUNDS IN LIQUID AMMONIA. III. REDUCTIVE ALKYLATION OF QUINOLINE

AbstractDie elektrochemische Reduktion von Chinolin in flüssigem Ammoniak verläuft in Abwesenheit eines Alkylierungsmittels in zwei Stufen über ein Radikal‐Anion und ein Dianion.

The preparation of some dipeptides containing asparagine, aspartic acid, and glutamine

Several methods have been used to synthesize dipeptides of asparagine, glutamine, and aspartic acid. Not all techniques were found to be equally applicable to the synthesis of a particular peptide. The methods examined involved the use of the chloracetyl-, phthalyl-, and carbobenzoxy- residues as protective groups and the use of acid chlorides, mixed carbonic anhydrides, phosphite amides, and isocyanate esters in the coupling reaction.