Alkaline Hydrolysis Products Research Articles

Biochemical changes in Bifidobacterium bifidum var. Pennsylvanicus after cell wall inhibition VII. Structure of the phosphogalactolipids

The structures of two major phosphogalactolipids from Bifidobacterium bifidum var. pennsylvanicus have been established by chemical analysis and chemical and enzymatical degradation procedures. The compounds were identified as 3-O-(6'-sn- glycero-1- phosphoryl)-β- d- galactofuranosyl)-sn-1, 2- diglyceride and its lysoderivative. A third minor phosphogalactolipid was a diacyl derivative of the former compound. About 10–20% of these compounds appeared to be galactopyranosyl derivatives. Phosphorylgalactosylglycerol and galactose phosphate were identified as one of the products of alkaline and acid hydrolysis, respectively. Marked differences were present in the fatty acid composition of monogalactosyldiglyceride, phosphatidylglycerol and the two main phosphogalactolipids.

Structure of Alkaline Hydrolysis Products of Neostigmine Methylsulfate and Neostigmine Bromide

Abstract The nuclear magnetic resonance spectra of the alkaline hydrolysis products of neostigmine bromide and neostigmine methylsulfate confirm that the products are m-hydroxyphenyltrimethylammonium salts and not 3-dimethylaminophenol as mentioned in early literature. Ultraviolet, infrared, and elemental analysis data are also presented in the quaternary structure confirmation of the alkaline hydrolysis product of neostigmine bromide.

28‐S RNA from Xenopus laevis Contains a Sequence of Three Adjacent 2′‐O‐Methylations

Evidence is presented to show that an alkaline hydrolysis product from 40‐S and 28‐S RNA of Xenopus laevis is a tetranucleotide containing three adjacent 2′‐O‐methylations.This is the longest such sequence yet reported and is believed to be Gm‐Am‐Am‐Ap.

The chemistry of heteroarylphosphorus compounds. Part VI. Alkaline hydrolysis of 1-methylpyrrol-2-yl- and 1-methylpyrrol-2-yl-methyl-phosphonium salts. A comparison with 2-furyl, 2-thienyl, phenyl, and related heteroarylmethyl and benzyl derivatives. Relative stabilities of forming carbanions

Studies of the products of alkaline hydrolysis of phenyl- and benzyl-phosphonium salts bearing 1-methylpyrrol-2-yl substituents show that while the forming 1-methylpyrrol-2-yl carbanion is more stable than the forming phenyl carbanion, in contrast to the 2-furyl and 2-thienyl analogues it is less stable than the forming benzyl carbanion. The order of cleavage of heteroaryl substituents from phosphorus is established as 2-thienyl > 2-furyl > benzyl > 1-methylpyrrol-2-yl > phenyl. Kinetic studies show that methyltris-1-methylpyrrol-2-ylphosphonium iodide (VII) undergoes hydrolysis considerably more slowly than the 2-furyl- and 2-thienyl analogues, but slightly faster than methyltriphenylphosphonium iodide. The ability of the 1-methylpyrrol-2-yl substituent to stabilise a forming negative charge on an adjacent carbon has been investigated by studies of the kinetics of hydrolysis of (1-methylpyrrol-2-ylmethyl)triphenylphosphonium iodide (XI). Comparison of the rate data with those for the 2-furylmethyl-, 2-thenyl-, and benzyl analogues indicates that the relative order of stability of the forming 2-heteroarylmethyl carbanions is 2-furylmethyl > 2-thenyl > benzyl > 1-methylpyrrol-2-ylmethyl.

ChemInform Abstract: RESONANCE RAMAN SPECTRA OF VITAMIN B12 AND SOME COBALT CORRINOID DERIVATIVES

Resonance Raman spectra in the frequency region 200–3200 cm–1 are reported for very dilute aqueous solutions of the following compounds: cyanocobalamin (vitamin B12), aquocobalamin (B12a), hydroxocobalamin (B12b), dicyanocobinamide, the alkaline hydrolysis products of B12(penta- and hexa-carboxylate derivatives), aquocobalamin (B12r), and {cobalamin}–cobalt(I)(B12s). The spectra were excited by lines from an argon laser, selected so as to coincide with bands in the visible absorption spectra of the compounds, and to satisfy the conditions for rigorous resonance enhancement of selected vibrational band intensities. The CoIII compounds all gave closely similar spectra, with no major changes being induced by coordination displacement even of the large 5,6-dimethylbenzimidazole base group from the metal. However, large changes in the structure of the spectra resulted from reduction of B12 to B12r and B12s; these changes appear to be related to conformational changes in the corrin ring chromophor.

Chromatographic separation of the alkaline hydrolysis products of shellac

the methyl ester-trimethylsilyl ethers of the alkaline hydrolysis products of Super Blonde Shellac were analysed by gas-liquid chromatography. The results were compared with the thin-layer chromatographic and column chromatographic patterns of different fractions, analysed as the methyl esters. The main hydroxy fatty acid of shellac, viz., threo-aleuritic acid, was completely separated from the terpene acids and a separation of some of the terpene components was achieved on a 3% SE-30 column. The terpene acids were also analysed on a column of 15% EGSS-X and 1% HI-EFF-8 BP with essentially similar results. The hydrolyzate is complex and a number of components are yet to be identified in the pure state, accounting for the numerous gummy fractions obtained in column chromatography.

The structure of ferutinin

FromFerula tenuisecta Eug. Kor. a new substance with the composition C19H24O4 (mp 121–122°C) has been isolated, and it has been named ferutinin. On the basis of UV, IR, mass, and NMR spectra and the products of alkaline hydrolysis it has been established that ferutinin is an ester of p-hydroxybenzoic acid and ferutinol.

Determination of Neostigmine Bromide by Ion-Pairing Column Chromatography

Abstract A rapid and sensitive method for the assay of neostigmine bromide (NBr) in tablets and ophthalmic solutions has been developed. NBr is isolated from its pharmaceutical excipients by the ion-pairing partition column chromatographic principles of Levine and Doyle followed by ultraviolet determination of its alkaline hydrolysis product. Standard recoveries of NBr from simulated tablet mixtures and ophthalmic solutions averaged 99.8%. The standard deviation of repeated analyses of commercial products was less than±1%. The results of the proposed method for commercial products are in good agreement with the USP XVIII procedure. The procedure is applicable to individual tablet assay.

The chemistry of heteroarylphosphorus compounds. Part V. The alkaline hydrolysis of 2-furyldiphenyl-(2-thienyl)phosphonium bromide, and some mixed heteroarylmethylphosphonium salts. Relative stabilities of the forming carbanions

Alkaline hydrolysis of 2-furyl(diphenyl)-2-thienyl-phosphonium bromide (V) gives both furan and thiophen in a 1 : 3 molar ratio, indicating that the forming 2-thienyl carbanion is more stable than the 2-furyl analogue, and implying stabilisation of the forming negative charge in the former by sulphur 3d orbital participation. A kinetic isotope effect, kH/kD≈ 1·2 is observed for the formation of both furan and thiophen in this reaction. The previously reported greater rate of alkaline hydrolysis of alkyltri-(2-furyl)phosphonium salts compared to the 2-thienyl analogues is now attributable to the greater electron-withdrawing effect of the 2-furyl substituent on the magnitude of the equilibrium constants of the pre-equilibria involved in the reactions. The products of alkaline hydrolysis of the mixed arylmethyldiphenylphosphonium salts (X)–(XII) indicate the relative stabilities of the forming carboanions to be in the order 2-furylmethyl > 2-thenyl > benzyl. The implications of this order are discussed in relation to earlier kinetic studies.

Resonance Raman spectra of vitamin B12 and some cobalt corrinoid derivatives

Resonance Raman spectra in the frequency region 200–3200 cm–1 are reported for very dilute aqueous solutions of the following compounds: cyanocobalamin (vitamin B12), aquocobalamin (B12a), hydroxocobalamin (B12b), dicyanocobinamide, the alkaline hydrolysis products of B12(penta- and hexa-carboxylate derivatives), aquocobalamin (B12r), and {cobalamin}–cobalt(I)(B12s). The spectra were excited by lines from an argon laser, selected so as to coincide with bands in the visible absorption spectra of the compounds, and to satisfy the conditions for rigorous resonance enhancement of selected vibrational band intensities. The CoIII compounds all gave closely similar spectra, with no major changes being induced by coordination displacement even of the large 5,6-dimethylbenzimidazole base group from the metal. However, large changes in the structure of the spectra resulted from reduction of B12 to B12r and B12s; these changes appear to be related to conformational changes in the corrin ring chromophor.

Fungitoxicity of acid and alkaline hydrolysis products of drazoxolon and related arylhydrazonoisoxazolones

AbstractDrazoxolon and related 3‐methyl‐4‐arylhydrazono‐5‐isoxazolones are hydrolysed by acid to 2‐arylhydrazono‐3‐oxobutyric acids and by alkali to 1‐arylhydrazono‐2‐hydroxyiminopropanes and 2‐arylhydrazono‐3‐hydroxyiminobutyric acids. Although many of the hydrolysis products show good antifungal activity in spore germination tests they are inferior to drazoxolon as protectants for the control of Uromyces fabae on broad bean and as protectants and eradicants against Erysiphe graminis on wheat. Neither drazoxolon nor its hydrolysis products show much activity as therapeutants.

The physiological disposition of 14 C-methsuximide in the rat.

1. (14)C-Methsuximide (N-methyl-(14)C-2-methyl-2-phenylsuccinimide) was rapidly absorbed from the small intestine of the rat (t(1/2) 17.4 min).2. The drug was rapidly and fairly evenly distributed throughout the body with peak blood and tissue levels occurring 1 h after oral administration. At all times, adrenals, body fat, kidneys and liver had higher levels of (14)C-methsuximide than other tissues and the drug freely traversed the blood-brain barrier. However, radioactivity disappeared rapidly from most tissues after the initial phase of the distribution.3. During 24 h, 26% of the orally administered radioactivity was recovered in urine and 29% appeared in expired air as (14)CO(2). The excretion of (14)CO(2) indicated N-demethylation of (14)C-methsuximide to 2-methyl-2-phenylsuccinimide. 2.7% of an administered dose of methsuximide was excreted unchanged in 24 h urine and 2.7% appeared as 2-methyl-2-phenylsuccinimide. 2-Methyl-2-phenylsuccinimide was also detected as a urinary metabolite of methsuximide in man.4. 2-Methyl-2-phenylsuccinimide possesses anticonvulsant activity and it is suggested that this metabolite contributes to the overall anticonvulsant activity and toxicity of methsuximide.5. Rat urine also contained a radioactive substance with similar chromatographic properties to one of the products of alkaline hydrolysis of methsuximide. This compound may arise from the spontaneous decomposition of the parent drug in vivo.

The structures of chimganin and chimgin

The roots ofFerula tschimganica Lipsky have yielded two new compounds with the compositions C18H24O4 (mp 85°C) and C17H22O3 (mp 155°C), which have been calledchimganin andchimgin. On the basis of their UV, IR, and NMR spectra and the products of alkaline hydrolysis, it has been shown that chimganin is the ester of 4-hydroxy-3-methoxybenzoic acid and chimgin that of 4-hydroxybenzoic acid with (+)-borneol.

Benzo [1] thiéno (2,3- d) pyridazines—I : Etude des conditions d'accès aux benzothiénopyridazines

The synthesis of carbonyled benzothiophenic derivatives at C-2 and C-3 has been developed through intermediate organolithium compounds with a view to subsequent cyclization as in benzothienopyridazines: benzothiophene-dialdehyde-2,3 ketone-aldehydes, acid-aldehydes and aldehyde-ketoneamides. The condensation with hydrazine gave benzothienopyridazine, 1-methyl derivative, and N,N-diethylcarboxamides at C-1 and C-4. The heterocycle was obtained by mild degradation reactions. The study of the alkaline hydrolysis product of the 1-N,N-diethylcarboxamidopyridazine by RMN and mass spectrometry lead to proposed bridged cyclic structure.

UV Spectrophotometric Assay of Neostigmine Methylsulfate as the Alkaline Hydrolysis Product, 3-Dimethylaminophenol

Abstract A rapid and sensitive method for the assay of neostigmine methylsulfate (NMS) in injectables has been developed. Following extraction of phenol and paraben preservatives, NMS is hydrolyzed to 3-dimethylaminophenol, which is determined by ultraviolet spectrophotometry. Standard recoveries of NMS from simulated injection solutions containing either (1) no preservatives, (2) phenol, or (3) parabens averaged 99.8%. A collaborative study was conducted using 2 simulated injection solutions (one without preservatives, one containing parabens) and 2 commercial injectables (one containing phenol, one containing parabens). Results of 9 collaborators averaged 100.6±1.4 and 102.1±1.5% for the simulated solutions. Results for the 2 commercial preparations averaged 103.0±1.2 and 101.8±1.6% of the respective label declarations. The results of the proposed method are in good agreement with the USP XVII and the new USP XVIII methods. The method is recommended for adoption as official first action.

Single-stranded oligonucleotides from reovirus type III

Low molecular weight single-stranded RNA present in reovirus particles has been separated from the viral double-stranded RNA by zone sedimentation on SDS-sucrose gradients followed by chromatography on DEAE-cellulose-urea columns at pH 5.4. Oligonucleotides analyzed in this manner are heterogeneous in chain length and base composition and comprise one third of the amount of RNA present as double-stranded molecules, or 5 × 10 6 daltons. There are approximately 2000 lengths of oligonucleotide per virion. All are completely degradable by venom phosphodiesterase, indicating that they bear a terminal 3′OH. About 60% of the low molecular weight material consists of molecules rich in adenylate having chain lengths between 6 and 12 nucleotides. Oligonucleotides of chain lengths 3–6 are relatively richer in pyrimidines, principally U, and comprise 20% of the total material. Three other minor low molecular weight components chromatograph in positions indicating chain lengths of less than two nucleotides. A study of the charge properties and alkaline hydrolysis products of these molecules suggests that they bear an unusual positively charged group at the 5′ terminus.

An artificial top component of R17 bacteriophage

The RNA bacteriophage R17 when exposed to pH 10.5 is disrupted to yield a protein and products of alkaline hydrolysis of the viral RNA. The protein has an intrinsic sedimentation coefficient of 41.1 s and an intrinsic viscosity of 0.055 dl./g at 20 °C. It has a typical protein absorbancy spectrum and contains less than 1% RNA. These data, together with electron micrographs, indicate that the protein consists of a hollow protein shell similar in structure to the protein portion of R17.

Phospholipids from Bacillus stearothermophilus.

The lipids of Bacillus stearothermophilus strain 2184 were extracted with chloroform-methanol and separated into neutral lipid and three phospholipid fractions by chromatography on silicic acid columns. The phospholipids were identified by specific staining reactions on silicic acid-impregnated paper, by chromatography of alkaline and acid hydrolysis products, and by determination of acyl ester:glycerol:nitrogen:phosphorus molar ratios. The total extractable lipid was 8% of the dry weight of whole cells and consisted of 30 to 40% neutral lipid and 60 to 70% phospholipid. The phospholipid consisted of diphosphatidyl glycerol (23 to 42%), phosphatidyl glycerol (22 to 39%), and phosphatidyl ethanolamine (21 to 32%). The concentrations of diphosphatidyl glycerol and phosphatidyl glycerol were lower in 2-hr cells than in 4- and 8-hr cells. Whole cells were fractionated by sonic treatment and differential centrifugation. The total lipid content, expressed in per cent of dry weight of each fraction was: whole protoplasts, 10%; membrane fraction, 18%; 30,000 x g particulate fraction, 22%; and 105,000 x g particulate fraction, 26%. The relative phospholipid concentrations in each fraction were about the same. As had been previously reported, none of the phospholipid was stable to alkaline hydrolysis.

An artifact in the alkaline hydrolysis of RNA labeled with guanosine-8-T

RNA was prepared from sea urchin embryos exposed to guanosine-8-T. Analysis of the products of alkaline hydrolysis from crude or purified RNA showed an unknown radioactive substance in addition to the 2′(3′)-guanylate. This substance is probably H 3HO formed by an exchange reaction between guanosine monophosphate and water.

Isolation and analysis of two types of diester waxes from the skin surface lipids of the rat

Two types of aliphatic diester waxes have been isolated from the skin surface lipids of the rat using silicic acid chromatography. The isolated material and its alkaline hydrolysis products were characterized using infrared spectrometry, thin-layer and gas-liquid chromatography. One type of the isolated waxes appears to be a diester of a 2-hydroxy fatty acid (C 14−22) with 1 molecule of unsubstituted fatty acid (C 14−28) and 1 molecule of monohydric alcohol (C 14−32). The other type represents a diester of an alkane-1,2-diol (C 14−24) with 2 molecules of fatty acid (C 12−28). The molecular sizes of both types range from C 48 to C 68 with a maximum content at C 54−58.