Studies in sesquiterpenes-XIX. Action of perbenzoic acid on longifolene

Oxidation of longifolene, a mono-olefinic sesquiterpene, with a chloroform solution of perbenzoic acid proceeded to almost two mole consumption of the peracid to furnish a number of products, important ones being an α-ketol, a norketone (longicamphenilone) and the corresponding C14-alcohols. Under certain conditions it has been possible to arrest the reaction at one mole consumption and to isolate longifolene-α-epoxide, which is the major product; some amounts of epimeric longifolaldehydes and longicamphenilone were also formed. Further action of perbenzoic acid on longifolene oxide and longifolaldehydes has been investigated and the results used to interpret the mechanism of abnormal peracid oxidation of longifolene.

Biosynthesis of β-N-oxalyl-l-α,β-diaminopropionic acid, the lathyrus sativus neurotoxin

The biosynthesis of β-N-oxalyl-l-α,β-diaminopropionic acid (ODAP) the Lathyrus sativus neurotoxin has been found to follow the scheme depicted below: {A figure is presented}. The first reaction is catalysed by oxalyl-CoA synthetase which has properties similar to that of the enzyme in peas. The second reaction is catalysed by another enzyme which is specific to L. sativus and is designated as oxalyl-CoA-α,β-diaminopropionic acid oxalyl transferase. The enzymes have been purified by about 60-fold and their properties studied. A partial resolution of the two enzyme activities has been achieved using CM-sephadex columns.

Cerimetry in non-aqueous media - Oxidation of oxalic acid through the intermediate formation of ceric oxalate

It was found that ceric oxalate is an intermediate product in the oxidation of oxalic acid by ammonium hexanitrato cerate in solvents such as acetonitrile, and a mixture of acetonitrile and glacial acetic acid. Conditions for the formation of ceric oxalate and its decomposition into carbon dioxide and cerous oxalate have been studied. An analytical method for the estimation of oxalic acid in non-aqueous media has been evolved based on this reaction.

Alkaline and acid phosphatases of the silkworm, Bombyx mori L.

The variations in the activities of the alkaline and acid phosphatases of the silkworm, Bombyx mori, were studied in all stages of the life cycle. From hatching until the spinning stage a steady increase was recorded in the activity of both the enzymes followed with a conspicuous decrease at each moult. During the pupal stage the alkaline phosphatase was almost absent, whereas the acid phosphatase maintained a high and constant value. Increase or decrease of the activity of the enzymes during larval development was reflected in a decrease or increase in the acid-soluble phosphorus content. Acid phosphatase activity slowly increased from laying of the eggs to hatching of the larvae with a concomitant decrease in the acid-soluble phosphorus. Tissue analysis showed a high concentration of the alkaline enzyme in the intestines, but the haemolymph was almost free of both enzymes. Feeding of inorganic phosphate increased the alkaline enzyme in the intestines, whereas glucose had no effect on either of the enzymes in the intestines.

Urey-Bradley potential function for the in-plane vibrations of boric acid

The Urey-Bradley force constants for the in-plane vibrations of the boric acid molecule are calculated using the Wilson's F-G matrix method. They are as follows: KO-H=5·23, KB-O=4·94, HBOH=0·36, {Mathematical expression}, F00=0·68 and FBH=0·98 in units of 105 dynes/cm. Using the force constants, the frequencies are recalculated and the calculated values agree with the observed values satisfactorily. The in-plane vibrational frequencies of deuterated boric acid are also calculated and again satisfactory agreement with the observed values is found.

The Raman spectrum of boric acid

The Raman spectrum of crystalline boric acid is recorded using mercuryλ2537 excitation. Fifteen Raman lines, three of them belonging to the lattice spectrum, are reported. Satisfactory assignments of all the observed Raman frequencies are made using the available X-ray crystal structure data. From the presence of a new high frequency Raman band at about 3420 cm.−1 it is suggested that there might be a small number of long, weak O-H....O hydrogen bonds in the crystal, in addition to the hydrogen bonds of moderate strength reported from X-ray diffraction data.

Electron spin resonance in cupric acid fluoride

The electron spin resonance in undiluted single crystals of cupric acid fluoride has been investigated at room temperature with microwaves of frequency 9625 Mc/s. The anisotropy in the g value has been measured in three orthogonal planes. The principal g values gave gshort parallel = 2.410 ± 0.010, gperpendicular = 2.090 ± 0.010. The linewidth shows anisotropy with orientation. The exchange frequency has been estimated to be approximately 0.08 cm-1.The powdered specimen shows asymmetry in the line shape.

Hydrogen bonding in thiolbenzoic acid. Infra-red, ultra-violet, n.m.r. and cryoscopic studies

Dimerization of thiolbenzoic acid has been studied by infra-red, ultra-violet and n.m.r. spectroscopy and cryoscopy. The results indicate that the tendency to form S - H. O hydrogen bonds is not appreciable.

Compressibility of dilute solutions of sulphuric acid

By employing Carstensen's phase-comparison pulse method for measuring ultrasonic velocity-differences, the compressibility of sulphuric acid has been studied anew, the special interest being in the low concentration region. Sulphuric acid is found to show at first a decrease in velocity with increasing concentration and then an increase. The curve representing the apparent molal compressibility Φ(κ̄2) against the square root of the molar concentration c, shows a maximum and a minimum. This anomalous behaviour is interesting in view of the extreme anomalies in other colligative properties of sulphuric acid. A qualitative explanation of the observed maximum and minimum has been suggested.

Studies in the sandalwood-oil series. I. The structure, synthesis, and configuration of the lactone of tricycloekasantalic acid

The structure, synthesis, and configuration of the lactone of tricycloekasantalic acid have been described. It has been shown that in the formation of this lactone (XII) from the acids (I) or (II) a rearrangement is involved.

Stimulation by thyrotropin, long-acting thyroid stimulator, and dibutyryl 3′, 5′-adenosine monophosphate of protein and ribonucleic acid synthesis and ribonucleic acid polymerase activities in porcine thyroid in Vitro

The in vitro incorporation of [3H]uridine into RNA and [3H]leucine into protein in slices of porcine thyroid was studied. Thyrotropin (10-500 mU/ml of medium), when added with [3H]uridine, inhibited incorporation into RNA, but as little as 10 mU of thyrotropin per ml stimulated incorporation of [3H]orotic acid into RNA. Uridine kinase (EC 2.7.1.48) was found to be inhibited in slices incubated with thyrotropin whereas UMP 5′ nucleotidase (EC 2.1.3.5) was not. Preincubation of slices with thyrotropin (5-50 mU/ml) led to enhanced incorporation of subsequently added [3H]uridine and [3H]leucine. When slices were preincubated with long-acting thyroid stimulator-IgG (2.5 or 5 mg per ml of medium) incorporation of [3H]uridine and [3H]leucine was similarly enhanced, with the smaller concentration being more effective. Without preincubation these stimulatory effects were mimicked by 1 mM dibutyryl 3′,5′-AMP and, to a lesser extent, 1 mM 3′,5′-AMP. AMP and ATP also stimulated [3H]uridine incorporation in this system but only after more prolonged periods of incubation than were required for the other nucleotides. RNA polymerase (EC 2.7.7.6) activity measured in isolated thyroid nuclei had two components, one Mg2+-stimulated and the other requ ring Mn2+ and high salt content [0.4 M (NH4)2SO4]. These activities, and particularly the former, were enhanced if thyroid slices were incubated with thyrotropin (5-100 mU/ml of medium), 2.5 mg or 5.0 mg of long-acting thyroid stimulator-IgG per ml, or 1 mM dibutyryl 3′,5′-AMP, before isolatior of the nuclei and measurement of enzyme activities; 1 mM AMP, ADP, or 2′,3′-GMP had no influence. Added directly to the nuclei, thyrotropin, long-acting thyroid stimulator-IgG, and dibutyryl 3′,5′-AMP had no effect on RNA polymerase activities. These data are seen as affording evidence for mediation by 3′,5′-AMP of effects of thyrotropin and long-acting thyroid stimulator on thyroid RNA and protein synthesis, at least in part through an indirect stimulation of nuclear RNA polymerase activities.

Aspects of tautomerism. Part II. Reactions of the pseudo-acid chloride of o-benzoylbenzoic acid with nucleophiles

Reactions of fourteen nucleophiles with the pseudo-acid chloride of o-benzoylbenzoic acid in two solvents have been studied. The nucleophiles that react primarily at the tetrahedral carbon atom to give pseudo derivatives, are weaker than those that react at the carbonyl carbon atom causing opening of the lactone ring. An explanation for this phenomenon is advanced.

Aspects of tautomerism. Part III. A new dimerisation reaction of pseudo-acid chlorides

Pseudo-acid chlorides of five 4′-substituted o-benzoylbenzoic acids are converted into a mixture of dilactones with sodium iodide in acetone. The meso-isomer is always formed to a larger extent than the (±)-mixture. These results imply that the radicals involved are not planar.

Hydrolytic reactions of esters and amides of thiosulphurous acid in a homogeneous medium

The hydrolytic reactions of esters and amides of thiosulphurous acid are investigated in a homogeneous medium. The esters are hydrolysed by alkali to give sulphide, sulphite and thiosulphate whereas the amides are resistant towards alkali. Both the esters and amides are hydrolysed by acids giving hydrogen sulphide, sulphur dioxide, polythionates and elemental sulphur. The hydrolysis of these esters and amides in presence of sulphurous acid and thiosulphuric acid gives tetrathionate and hexathionate, respectively.

Cerimetry in nonaqueous media - Oxidation of ascorbic acid

The reaction between ascorbic acid and ammonium hexa nitrato cerate was studied potentiometrically in the mixed solvent glacial acetic acid acetonitrile medium. It was found that one mole of ascorbic acid consumes four equivalents of cerate in non-aqueous medium. This reaction can be made use of to estimate potentiometrically ascorbic acid with ammonium nitrato cerate in non-aqueous media, using either glass or antimony as reference electrode and platinum as indicator electrode.