Bisulfite Addition Compounds Research Articles

Bisulfite Addition Compounds as Substrates for Reductive Aminations in Water.

Highly valued products resulting from reductive aminations utilizing shelf-stable bisulfite addition compounds of aldehydes can be made under aqueous micellar catalysis conditions. Readily available α-picolineborane serves as the stoichiometric hydride source. Recycling of the aqueous reaction medium is easily accomplished, and several applications to targets in the pharmaceutical industry are documented.

Rate constants for formation of bisulfite addition compounds: an examination in terms of No Barrier Theory

We report a study of the rates of sulfite addition to carbonyl compounds. This reaction is useful in separating compounds (aldehydes react more extensively than ketones, thus becoming water soluble) because the reaction is readily reversible. Although the reaction is mainly by addition of sulfite dianion, the equilibrium is much more favorable for the addition of bisulfite to give a monoanionic adduct. It is also of interest because bisulfite addition is very favorable; thus, we are dealing with a very strong nucleophile. This work demonstrates that No Barrier Theory can calculate rates for good nucleophiles (cyanide and now sulfite) as well as poor nucleophiles such as water. It has been necessary to develop good ways to handle the anionic tetrahedral adducts (in the case of sulfite as nucleophile, dianionic), which tend to break down in the gas phase unless explicitly solvated, and modified procedures for crowded transition states to allow for some relief of steric congestion while maintaining the essential definition of the distorted species resulting from bond formation without geometry change.

Substituted 1-(2-Thienyl)cyclohexylamines and Related Compounds as Potential NMDA Antagonists

Reactions of bisulfite addition compounds prepared in situ from cyclohexanone or 3,4,5,6-tetrahydro-2H-thiopyran-3-one with potassium cyanide and corresponding amines resulted with high yields in amino nitriles type of V and VI. These compounds were subjected to reactions with 2-thienylmagnesium bromide and in the case of the amino nitriles Vc and Vf with 5-bromo-2-thienylmagnesium bromide. Only in the case of compound Vf, a by-product X was isolated in addition to the desired 1-[1-(5-bromo-2-thienyl)-1-cyclohexyl]piperidine (VIIf). Compound VIIf was used for the synthesis of the carboxylic acid XI. The compounds prepared were tested by some methods of biochemical and behavioural pharmacology.

An unusual bisulfite addition compound from 3,5-dipyrrolidinophenol

Etude de la conversion du compose du titre en dipyrrolidino-3,5 cyclohexadienones et de son comportement dans SO 2 +H 2 O

Réactions d'addition nucleophiles sur les cétones. Une méthode directe, simple, rapide et précise de mesure de vitesse de formation et de décomposition des combinaisons bisulfitiques

A method is described which allows, with a single experiment, the determination of the rate constants of formation and decomposition of bisulfite addition compounds.

Determining Free Sulfur Dioxide in Red Wine

Apparent equilibrium constants were determined for dissociation of the bisulfite addition compounds of malvidin-3-glucoside and of an extract of anthocyanins from a red wine. Normal methods of determining the free SO₂ content of wines, which require acidification of the sample, give high results because anthocyanin bisulfites are unstable. The true free SO₂ content of red wines can be calculated from the extent to which the natural anthocyanins are decolorized by SO₂.

Determining Free Sulfur Dioxide in Red Wine

Apparent equilibrium constants were determined for dissociation of the bisulfite addition compounds of malvidin-3-glucoside and of an extract of anthocyanins from a red wine. Normal methods of determining the free SO₂ content of wines, which require acidification of the sample, give high results because anthocyanin bisulfites are unstable. The true free SO₂ content of red wines can be calculated from the extent to which the natural anthocyanins are decolorized by SO₂.

PH Independent equilibrium constants and rate constants for formation of the bisulfite addition compound of isobutyraldehyde in water

pH Independent equilibrium constants and rate constants for formation of the bisulfite addition compound of isobutyraldehyde in water

Recherche d'effets stériques dans la réactivité de la norbornanone‐2 par la mesure des effets isotopiques secondaires du deuterium

AbstractThe following compounds have been prepared: 2‐norbornanone‐3d1 exo, ‐3‐d1 endo, ‐ 3,3‐d2 and 5,6‐d2 endo; the rates of borohydride ion addition and of decomposition of bisulfite addition compounds have been measured in order to explain the high exo side reactivity of norbormyl systems. In both reactions, there is no significant isotope effect due to deuteration at the 5,6 endo positions. This observation can result either from an absence of any steric interaction or from a non‐bonded interaction potential much smaller than usually admitted. The protons in 3‐endo and 3‐exo positions are not equivalent towards the nucleophile approach.

The effect of thiols on the dehalogenation of 5-iodo and 5-bromouracil

The 5-iodo- and 5-bromo- analogs of uracil are dehalogenated in the presence of both cysteine and 2-mercaptoethanol to yield uracil. Presumably, the reaction involves the initial addition of the thiol group across the 5,6 double bond of the halopyrimidine to yield the corresponding 5-halo, 5,6-dihydrouracil-6-thioether which then dehalogenates to yield uracil. Under comparable conditions, cysteine causes more rapid dehalogenation of both halouracils than does 2-mercaptoethanol.Thiol containing compounds catalyze hydrogen-deuterium exchange at carbon five of uracil (1–3) and have been implicated as having a catalytic effect in the deamination of cytosine (4,5). Presumably, these reactions involve the reversible nucleophilic addition of the thiol group across the 5,6 double bond of the pyrimidine to yield the corresponding 5,6 dihydropyrimidine with a substituted thioether group on carbon six. This pathway is supported by comparable reactions involving the addition of bisulfite to the pyrimidine ring system (6–10). Different from the bisulfite addition compounds, the thioether containing dihydropyrimidine adducts have not been isolated and characterized; however, 5′-deoxy-5′,6-epithio-5,6-dihydro-2′,3′-0-isopropylideneuridine resulting from the intramolecular attack of the 5′ thiol group on carbon six of the uracil ring system of 5′-deoxy-5′-thio-2′,3′-0-isopropylideneuridine has been isolated and characterized (11).In a recent communication, we reported that bisulfite buffer systems catalyze the dehalogenation of 5-iodo-, 5-bromo-, and 5-chlorouracil (12). The object of this work is to demonstrate that cysteine and 2-mercaptoethanol, sulfur nucleophiles with more physiological importance than bisulfite, also cause halopyrimidine dehalogenation under nearly physiological conditions of temperature and pH.

GLC Analysis of Menadione Bisulfite Addition Compounds by On-Column Pyrolysis to Menadione

The GC determination of the on-column pyrolysis product of menadione bisulfite addition compounds as menadione is described. Differential thermal analysis, mass spectroscopy, and GC retention times conclusively prove the feasibility of on-column pyrolysis of menadione bisulfite addition compounds to menadione. Recovery values of menadione content of powdered and liquid injectable menadione bisufite compounds were the following: menadione sodium bisulfite (trihydrate) powder, 98.59 ± 3.4%, 5 mg./ml. liquid injectable, 97.04 ± 1.46%, and 10 mg./ml. liquid injectable, 100.40 ± 0.50%.

Reactions d'addition nucléophile sur les cétones : Addition de l'ion sulfite: mise en évidence de l'hyperconjugaison Par la mésure de l'éffet isotopique sécondaire du deutérium

Resume The rates of addition, at 25° in water, of the SO3−− ion to nine saturated ketones and their ga-deuterated homologs have been measured. The secondary kinetic isotope effects, expressed by the ratios (kH/kD)f, have been determined. We have also measured the isotope effect during the hydrolysis of bisulfite addition compounds of twelve ketones: (kH/kD. These isotope effects are discussed in terms of electronic and steric factors. The transition state has been shown to be ”reactant-like” for the addition reaction: the inductive and steric factors are of little importance, if any. The main factor, responsible for the isotope effects, seems to have a hyperconjugative origin: the deuterated ketone is less stabilized by σ-π8 overlap than the normal one. The variations of the isotope effect from one compound to another are easily interpreted by the consideration of the stable conformations of the ketone and the change of hyperconjugative stabilisation from one ketone to another.

Metachromatic staining of sodium bisulfite addition derivatives of glycogen.

In fixed tissues and cell cultures glycogen readily formed sodium bisulfite addition compounds following oxidation with 0.5% aqueous periodic acid. Sodium bisulfite derivatives of oxidized glycogen developed intense metachromasia if stained with 0.5% toluidine blue at the 1.0-5.0 pH range. Induced metachromasia of tissue glycogen was dehydration-labile if the oxidation with periodic acid was carried out for less than 15 min. Oxidation in excess of 15 min resulted in formation of dehydration-resistant metachromasia. The induction of the two types of metachromasia was determined primarily by the duration of oxidation and only secondarily by the duration of addition reaction and sodium bisulfite concentration. The origin of the dehydration-labile metachromasia probably resides with the external glucose units of glycogen depositions, whereas the induction of dehydration-resistant metachromasia may be attributed to the sodium bisulfite derivatives of the internally located glucosyl groups of glycogen.

Polymers containing anthraquinone units: Polyimidazoles and polypyrrolones from 1,2,5,6‐tetraaminoanthraquinone

Abstract1,2,5,6‐Tetraaminoanthraquinone has been condensed with isophthalaldehyde and terephthalaldehyde and their bisulfite addition compounds to yield new heat‐stable polymers. It has also been condensed with pyromellitic anhydride to give the pyrrolone. The highest viscosities were obtained in polymers prepared with acid catalysts. The polymers were nearly all soluble in concentrated sulfuric acid but not in organic solvents. Those soluble in sulfuric acid could also be solubilized by reduction with sodium dithionite and potassium hydroxide in aqueous organic solutions. A few polymers were apparently crosslinked, since they would not dissolve in either sulfuric acid or in base on reduction. Weak fibers were obtained by spinning the reduced alkaline solutions of the polymers into aqueous acid.

Etude de l'effet isotopique secondaire du deuterium dans la décomposition de la combinaison bisulfitique de la tertiobutyl‐4 cyclohexanone. Énergie conformationnelle du groupe SO3−

AbstractThe rate constants for the hydrolysis of the bisulfite addition compounds of cyclohexanone, 4‐tert‐butylcyclohexanone and their α‐deuterated homologues have been measured.There is a large difference between the isotope effects observed for the cyclohexanone (kH/kD = 1.10) and the “slow” isomer from the 4‐tert‐butylcyclohexanone (‐ SO3− equatorial; kH/kD = 1.05). This result is discussed in terms of the existing difference between the geometries of the transition states.The conformational energy of the ‐ SO3− group has been determined and found to be equal to 2.25 kcal/mole.

Glycolic acid oxidase activity in crop plant leaves

Abstract Many workers have revealed the possible role of glycolic acid oxidase in the photosynthesis and the respiration of plant leaves (1, 5) and in the organic acid metabolism of rice plant roots (6). There is also abundant evidence that α-hydroxysulfonates, the bisulfite addition compounds of aldehydes and ketones, are the specific and competitive inhibitors of the enzyme (7, 8). The pevious works (9, 10) showed that a deficient application of potassium increased the content of amino-N and reducing sugars and concomitantly the respiratory activity in sweet potato roots. Such a derangement in the metabolic status of plant roots would be expected to be intimately connected with any changes in the photosynthesis and the respiration of the leaves. This paper, as a preliminary, describes some results from investigations into the glycolic acid oxidase activity in leaves of rice plant- and barley seedlings, sweet potato plants, and taro plants which were grown in solution culture at varying potassium applica...

The Bucherer Reaction and the Preparative Use of its Intermediate Products

AbstractThe study of purified intermediate products of the Bucherer reaction has shown that this reaction proceeds, not via bisulfite addition compounds of the keto form of the naphthols and the ketimine form of the naphthylamines, but via tetralonesulfonic acids and tetraloniminesulfonic acids. The intermediates lead to compounds that are otherwise difficult or impossible to obtain, and some of which are new. The mechanism of the Bucherer reaction is discussed in detail.

Differential estimation of adrenaline, noradrenaline, dopamine, metanephrine and normetanephrine in urine

A method is described for the determination of the individual levels of adrenaline, noradrenaline, dopamine, metanephrine and normetanephrine in urine. The amines present in the urine are adsorbed on a weak cation exchange resin (Amberlite IRC-50) and the catecholamines then eluted by a boric acid solution followed by metanephrine and normetanephrine with dilute sulfuric acid. The amines in each fraction are oxidised by iodine to the corresponding aminochromes which are then converted to their sodium bisulfite addition compounds. The levels of each of the five amines are calculated from measurements of the absorbances, at several wave-lengths, of the solutions of the bisulfite addition compounds. The average excretion rates of the free amines in urine, based on 41 determinations using this method are (in μg/h): A∗∗∗, 0.04; N.2.36; D.8.22; M, 1.25; NM, 8.55. The corresponding excretion rates (in μg/h) for the total amines ( i.e. free plus conjugated) are: A, 0.06; N, 4.69; D, 27.20; M, 3.65; N.M. 17.48.

Methyl azelaaldehydate purification via the bisulfite compound

AbstractMethyl azelaaldehydate was obtained at 99.8% purity with 82.5% recovery from the ozonolysis products of commercial methyl oleate by separations as the sodium bisulfite addition compound, regeneration with 10% NaOH, and distillation.

Adrenochrome bisulfite addition compound

1. (1) A method of preparing and purifying non-hygroscopic adrenochrome bisulfite, addition compound has been described. 2. (2) A new structure for adrenochrome bisulfite addition compound has been proposed. 3. (3) Evidence in support of this new structure is given.