The High Temperature and Dilute Acid (HTDA) Procedure as a General Method of Replacing Aromatic Hydrogen by Deuterium. II

1974 ◽  
Vol 52 (11) ◽  
pp. 2169-2171 ◽  
Author(s):  
Nick H. Werstiuk ◽  
Tony Kadai

The preparation of aniline-d5, phenol-d5, and benzoic acid-d5 utilizing the conditions of high temperature and dilute acid (HTDA) is described.

The object of the inquiry detailed in the present paper is to determine at what degree of concentration the affinity of sulphuric acid for aqueous vapour is equal to that of anhydrous space for the same vapour at given temperatures. It has long been known that concentrated sulphuric acid abstracts moisture from the atmosphere, but the amount and the rate of this absorption have never been ascertained with accuracy; and consequently, in applying this acid to purposes of exsiccation, the experimenter has often been at a loss to know whether the acid was sufficiently strong to render the space in which it was confined perfectly anhydrous. By placing portions of the acid, previously weighed, and diluted with known quantities of water, under the receiver of an air-pump, with equal portions of concentrated acid, of the specific gravity 1·8428, in similar dishes, the author ascertained that the dilute acid could be concentrated to the specific gravity 1·814, at a temperature varying from 65° to 57°: whence he concludes that acid of such strength is capable of drying a vacuum when the temperature does not exceed 57°. By making similar experiments in air, the author compared together the weights lost by ten grains of dilute sulphuric acid of the specific gravity 1·135, at three different periods of the day for six days, taking note of the dew-point and the temperature; and infers that when the affinity of space for vapour, or the evaporating force, is equal to 0·15 of an inch of mercury, it is just able to balance the affinity for water of sulphuric acid of the specific gravity 1·249. The author next instituted a series of experiments to ascertain whether the evaporation of water from dilute sulphuric acid is capable of being carried on to the same extent in air as in vacuo, and found that the evaporating force of air exerted upon such acid is less than that of a vacuum at the same temperature. He observes that his experiments offer conclusive evidence that the evaporation of water is not owing to the existence of a chemical affinity between the vapour of the liquid and atmospheric air; but thinks that they favour the notion that the obstruction to this process in the open atmosphere is rather owing to the pressure than to the inertiæ of the particles of air. He is also of opinion that improvements will hereafter arise from this inquiry with regard to the economical management of the process of manufacturing sulphuric acid, which process would be greatly expedited by the regulated admission of steam into the condensing chambers kept at a constant high temperature.


2016 ◽  
Vol 19 (4) ◽  
pp. 511 ◽  
Author(s):  
Yoh Takekuma ◽  
Haruka Ishizaka ◽  
Masato Sumi ◽  
Yuki Sato ◽  
Mitsuru Sugawara

PURPOSE. Storage under high temperature and humid conditions has been reported to decrease the dissolution rate for some kinds of tablets containing polyvinylpolypyrrolidone (PVPP) as a disintegrant. The aim of this study was to elucidate the properties of pharmaceutical formulations with PVPP that cause a decrease in the dissolution rate after storage under high temperature and humid conditions by using model tablets with a simple composition. METHODS. Model tablets, which consisted of rosuvastatin calcium or 5 simple structure compounds, salicylic acid, 2-aminodiphenylmethane, 2-aminobiphenyl, 2-(p-tolyl)benzoic acid or 4.4’-biphenol as principal agents, cellulose, lactose hydrate, PVPP and magnesium stearate as additives, were made by direct compression. The model tables were wrapped in paraffin papers and stored for 2 weeks at 40°C/75% relative humidity (RH). Dissolution tests were carried out by the paddle method in the Japanese Pharmacopoeia 16th edition. RESULTS. Model tablets with a simple composition were able to reproduce a decreased dissolution rate after storage at 40°C/75% RH. These tablets showed significantly decreased water absorption activities after storage. In the case of tablets without lactose hydrate by replacing with cellulose, a decreased dissolution rate was not observed. Carboxyl and amino groups in the structure of the principal agent were not directly involved in the decreased dissolution. 2-Benzylaniline tablets showed a remarkably decreased dissolution rate and 2-aminobiphenyl and 2-(p-tolyl)benzoic acid tablets showed slightly decreased dissolution rates, though 4,4’-biphenol tablets did not show a decrease dissolution rate. CONCLUSIONS. We demonstrated that additives and structure of the principal agent were involved in the decreased in dissolution rate for tablets with PVPP. The results suggested that one of the reasons for a decreased dissolution rate was the inclusion of lactose hydrate in tablets. The results also indicated that compounds as principal agents with low affinity for PVPP may be easily affected by airborne water under high temperature and humid conditions. This article is open to POST-PUBLICATION REVIEW. Registered readers (see “For Readers”) may comment by clicking on ABSTRACT on the issue’s contents page.


2021 ◽  
Vol 9 ◽  
Author(s):  
Xingqiao Wu ◽  
Xiao Li ◽  
Yucong Yan ◽  
Sai Luo ◽  
Jingbo Huang ◽  
...  

Pt-based multimetallic nanorings with a hollow structure are attractive as advanced catalysts due to their fantastic structure feature. However, the general method for the synthesis of such unique nanostructures is still lack. Here we report the synthesis of Pd@PtM (M = Rh, Ni, Pd, Cu) multimetallic nanorings by selective epitaxial growth of Pt alloyed shells on the periphery of Pd nanoplates in combination with oxidative etching of partial Pd in the interior. In situ generation of CO and benzoic acid arising from interfacial catalytic reactions between Pd nanoplates and benzaldehyde are critical to achieve high-quality Pt-based multimetallic nanorings. Specifically, the in-situ generated CO promotes the formation of Pt alloyed shells and their epitaxial growth on Pd nanoplates. In addition, the as-formed benzoic acid and residual oxygen are responsible for selective oxidative etching of partial Pd in the interior. When evaluated as electrocatalysts, the Pd@PtRh nanorings exhibit remarkably enhanced activity and stability for ethanol oxidation reaction (EOR) compared to the Pd@PtRh nanoplates and commercial Pt/C due to their hollow nanostructures.


1965 ◽  
Vol 18 (7) ◽  
pp. 1023 ◽  
Author(s):  
ALJ Beckwith ◽  
JE Goodrich

Various branched-chain carboxylic acids have been oxidized with the following reagents: (A) potassium manganate in dilute alkali; (B) potassium permanganate in concentrated alkali; (C) potassium peroxydisulphate in dilute alkali; (D) potassium peroxydisulphate in dilute acid. In most cases hydroxy-acids were formed by oxidation at the tertiary position but the yields were poor. None of these reagents appears to provide a general method for the preparation of lactones from branched-chain saturated carboxylic acids.


1976 ◽  
Vol 54 (14) ◽  
pp. 2213-2219 ◽  
Author(s):  
Nick Henry Werstiuk ◽  
Tonu Kadai

The hydration of norbornene (1) and nortricyclane (2) under the high temperature and dilute acid (HTDA) conditions of aqueous acetic acid at 250 °C gives as products exo-2-norborneol, endo-2-norborneol, exo-2- and endo-2-norbornyl acetate, and a mixture of stereoisomeric dinorbornyl ethers 4. When the reactions are carried out in deuterated medium perdeuteration (>90% in one cycle) of the [2.2.1]-products is accomplished. Respectable overall yields (50–70%) of the products are obtained. Solvolysis of the products exo-norborneol, and endo-norbornyl acetate under HTDA(D) conditions also leads to perdeuterated 3a, 3b, 3c, 3d, and 4.


2016 ◽  
Vol 30 (27) ◽  
pp. 1650305 ◽  
Author(s):  
Hong Li ◽  
Yinhai Wang ◽  
Lei Li ◽  
Haiju Huang ◽  
Hui Zhao ◽  
...  

Zn2GeO4:Mn[Formula: see text],[Formula: see text]Eu[Formula: see text] and Zn2GeO4:Mn[Formula: see text] powders were synthesized by a high-temperature solid-state reaction. X-ray powder diffraction (XRD) and scanning electron microscopy (SEM) were used to characterize the structures and morphologies of the synthesized powders, respectively. The photocatalytic properties and long persistent luminescence performance were improved by Eu[Formula: see text] doping. Thermoluminescent (TL) curves showed that the trap concentration in the material was increased with Eu[Formula: see text] doping, which formed trap centers in Zn2GeO4:Mn[Formula: see text]. The trap centers can capture the electrons or holes and subsequently increase the separation of photogenerated electrons and holes by suppressing the recombination of captured electrons and holes; thus, resulting in an improved photocatalytic activity and a prolonged persistent luminescence. The present strategy may be used as a general method to improve the photocatalytic activity and persistent luminescence.


2013 ◽  
Vol 338 ◽  
pp. 217-223 ◽  
Author(s):  
Niti Sunsandee ◽  
Sira Suren ◽  
Natchanun Leepipatpiboon ◽  
Milan Hronec ◽  
Ura Pancharoen

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