Study of the microwave-assisted hydrolysis of nitriles and esters and the implementation of this system in rapid microwave-assisted Pd-catalyzed amination
Gitte Van Baelena and Bert U.W. Maes
Tetrahedron Volume 64, Issue 23, 2 June 2008, Pages 5604-5619


Abstract
Microwave-assisted hydrolysis of benzonitriles and methyl benzoates has been studied using a toluene/
concd aq KOH two phase system in the presence and absence of phase transfer catalyst. Conditions to
allow and avoid smooth hydrolysis could be identified. Based on the latter, the first microwave protocol
which allows the rapid Pd-catalyzed amination of aliphatic amines with chlorobenzenes containing
sensitive functional groups has been developed.

Thermolysis of Alkyl Sulfoxides and Derivatives:  A Comparison of Experiment and Theory 
Jerry W. Cubbage, Yushen Guo, Ryan D. McCulla, and William S. Jenks
J. Org. Chem. 2001, 66 (26), pp 8722–8736




Abstract
Gas-phase activation data were obtained for model sulfoxide elimination reactions. The activation enthalpy for methyl 3-phenylpropyl sulfoxide is 32.9 ± 0.9 kcal/mol. Elimination by methyl vinyl sulfoxide to form acetylene has an enthalpic barrier of 41.6 ± 0.8 kcal/mol and that of 3-phenylpropyl methanesulfinate to form hydrocinnamaldehyde is 34.6 ± 0.6 kcal/mol. Calculations at the MP2/6-311+G(3df,2p)//MP2/6-31G(d,p) level for simplified models of these reactions provide barriers of 32.3, 40.3, and 32.7 kcal/mol, respectively. A series of other compounds are examined computationally, and it is shown that the substituent effects on the sulfoxide elimination reaction are much more straightforward to interpret if ?H data are available in addition to the usually determined ?H. The activation enthalpy of the reverse addition reaction is also subject to structural variation and can usually be rationalized on the basis of nucleophilicity of the sulfur or polarity matching between the sulfenic acid and olefin derivative.

Sodium Cyanoborohydride - A Highly Selective Reducing Agent for Organic Functional Groups
Clinton F. LANE
Synthesis 1975, 135.


Abstract
The utility of sodium cyanoborohydride as a selective reducing agent for organic synthesis is reviewed. Firstly a summary of the preparation and properties of sodium cyanoborohydride is given. Then some examples of sodium cyanoborohydride reductions of various systems are given including some applications of sodium cyanoborodeuteride. 1. Preparation 2. Purification 3. Physical Properties 4. Chemical Properties 4.1. Hydrolysis 4.2. Exchange 5. Selective Reducing Properties 5.1. Reduction of Aldehydes and Ketones 5.2. Reduction of Oximes 5.3. Reduction of Enamines 5.4. Reductive Amination of Aldehydes and Ketones 5.5. Reductive Alkylation of Amines and Hydrazines 5.6. Reductive Displacement of Halides and Tosylates 5.7. Deoxygenation of Aldehydes and Ketones

High Temperature Proton Exchange Reactions by Hydroxide In Water 
Dean A. Smith a; Donald R. Dlmmel
Journal of Wood Chemistry and Technology Volume 4, Issue 1 March 1984 , pages 75 - 90


Abstract
The ability of hydroxide Ion to produce carbanlons at 170°C In water has been determined by measuring the extent of deuteratlon and reexchange of deuterium labels for several organic acids and phenols. The results of the exchange reactions provide a rough estimate of the types of reactions that are possible between hydroxide Ion and wood components during alkaline pulping. It has been estimated that NaOH/H20 at 170° can deprotonate organic acids having pKa values of about 35 and can produce polyanlon intermediates. Several experiments were directed toward understanding the effects of ct-hydroxyl groups and zinc ions on carbanion formation. Exchange reactions involving Na2S at 170° showed that this species is largely dissociated to NaOH and NaSH and that the latter does not contribute to the basicity of the solution.

ELECTROLYTIC CONDENSATION OF CARBOXYLIC ACIDS
G E Svadkovskaya et al
Russ. Chem. Rev. 29 161-180, 1960

doi: 10.1070/RC1960v029n03ABEH001225  
  

G E Svadkovskaya and S A VoitkevichCONTENTS
I. Introduction 161
II. Effect of experimental conditions on the course of the Kolbe synthesis 162
III. Electrolytic condensation in non-aqueous solvents 163
IV. Effect of the structure of acids on the course of the Kolbe synthesis 163
V. "Crossed" electrolytic condensation 171
VI. Mechanism of the Kolbe reaction 174

Electrochemical synthesis of L-histidinol using solvated electrons
BELTRA A. P. ; BONETE P. ; GONZALEZ-GARCIA J. ; GARCIA-GARCIA V. ; MONTIEL V. ;
Journal of the Electrochemical Society (2005), 152(4), pp.65-68



Abstract
The feasibility of the preparation of L-histidinol (I) by reduction of L-histidine methyl ester (II) using an electrogenerated solvated electrons solution has been studied in a laboratory scale reactor. The solvated electrons solution was obtained by electrolysis of a solution of LiCI in EtNH2 that permits an easier handling than NH3or MeNH3. All components of the electrochemical setup have been optimized for the reaction conditions used. The influence of some reaction variables on the yield of (I) has been studied. Thus, increasing current intensity and temperature enhances the yield of L-histidinol. Nevertheless, the volatility of ethylamine limits the increase of the intensity current and the temperature. A fractionated feeding procedure of (II) was shown to be desirable. The work-up and isolation procedure of (I) has also been described. It includes an electrodialysis process that makes easier the isolation of (I), as well as the recovered LiCl could be recycled as supporting electrolyte.

Preparation of Optically Active Ketones

Rapoport, et al

United States Patent 4,618,710

Abstract

An optically active alpha-amino acid derivative having the formula (diagram omitted for clarity) wherein: X is OH, Cl, Br, I or OCOR3;
Y is a radical selected to stabilize the alpha carbon atom of the alpha-amino acid derivative sufficiently to prevent significant change in symmetry thereof during replacement of X with an alkyl, aryl, alkenyl, alkynyl, alkaryl, aralkyl, alkenaryl or alkynaryl radical, or such radical having one or more chemical substituents thereon; and
R1 and R2 are different from one another and are each hydrogen or an alkyl, aryl, alkenyl, alkynyl, alkaryl, aralkyl, alkenaryl or alkynaryl radical, or such radical having one or more non-protic chemical substituents thereon is conventionally synthesized from the corresponding alpha-amino acids. The portion (the diagram shows the carboxylic-X bond) is converted to a ketone functionality without racemization

THE PREPARATION OF ALIPHATIC AMIDES
James A. Mitchell, E. Emmet. Reid
J. Am. Chem. Soc., 1931, 53 (5), pp 1879–1883


Abstract
The most satisfactory methods of preparing amides have involved dehydration of the ammonium salt of the corresponding acid. Hofmann prepared various amides by heating ammonium salts of aliphatic acids for five or six hours at 230" under pressure. Kundig prepared acetamide by the rapid distillation of ammonium acetate and by heating an alcoholic solution of acetic acid and ammonia in a sealed tube for a long time at 100'C. He also obtained a yield of amide greater than 25% by passing dry ammonia through acetic acid and then heating to boiling. Grant and James have prepared amides by saturating the acid with dry ammonia and boiling. Dulap, Keller and Verley have modified the procedure by heating sodium acetate and ammonium chloride at 240'C.

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Stereospecific radioimmunoassays for d-pseudoephedrine in human plasma and their application to bioequivalency studies
John W. A. Findlay, James T. Warren, John A. Hill, Richard M. Welch
Journal of Pharmaceutical Sciences, Vol 70(6), pp.624-631



Abstract
Antiserum to d-pseudoephedrine was raised in New Zealand White rabbits in response to immunization with a conjugate of bovine serum albumin and d-pseudoephedrine-N-3-propionic acid. The hapten was prepared by reaction of methyl acrylate with d-pseudoephedrine, followed by ester hydrolysis. Sodium boro[3H]hydride reduction of dl-ephedrone gave [-3H]-dl-ephedrine, and a Welsh rearrangement with acetic anhydride followed by deacetylation gave [-3H]-dl-pseudoephedrine, which was used as a radioligand in radioimmunoassay procedures for direct plasma analyses. Three sensitive radioimmunoassay procedures were developed, two using [3H]pseudoephedrine as the radioligand and either adsorption on coated charcoal or polyethylene glycol precipitation for separation of antibody-bound from free radioligand. The third method used an [125I]tyrosine methyl ester analog of pseudo-ephedrine and charcoal separation, preceded by extraction and derivatization of pseudoephedrine with methyl acrylate. All three assays could detect 2.5 ng of pseudoephedrine/ml. The antiserum was stereospecific, showing low cross-reactivities with l-pseudoephedrine and d-and l-ephedrines. d-Norpseudoephedrine and some other related compounds also had low cross-reactivity in these radioimmunoassay procedures. Excellent agreement was found between pseudoephedrine concentrations in human plasma determined by radioimmunoassay and by a standard GLC method. The utility of radioimmunoassay was illustrated by application of one of these procedures to an assessment of the bioequivalence of immediate- and sustained-release pseudoephedrine formulations in normal volunteers. A sustained-release preparation containing 120 mg of pseudoephedrine hydrochloride given every 12 hr was shown by AUC comparisons to be bioequivalent to an immediate-release tablet (containing 60 mg of pseudoephedrine hydrochloride) given every 6 hr.



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alpha.-Amino acids as chiral educts for asymmetric products. Amino acylation with N-acylamino acids
Thomas F. Buckley III, Henry Rapoport
J. Am. Chem. Soc. 1981, 103 (20), pp 6157–6163


Abstract
a-N-Acylamino acids have been developed as useful reagents for the preparation of optically pure a-aminoalkyl aryl ketones. Protection of the amino group as either the ethoxycarbonyl or benzenesulfonyl derivative allows alanine to serve as an effective educt for the chirally specific synthesis of a variety of structures containing the phenylethylamine backbone. Benzene undergoes Friedel-Crafts acylation with the N-acylalanine acid chloride. Catalyst complexation with oxygenated aromatics, however, prohibits acylation of aryl ethers. An arylmetallo reaction scheme overcomes this problem and also affords regiospecificity not attainable in conventional acylations. As examples, optically pure ephedrines and amphetamines were directly synthesized without recourse to resolution since the chirality of the amino acid educt was entirely conserved throughout the process.

You can find articles on the Hofmann reaction by searching "Hofmann" here http://jchemed.chem.wisc.edu/