A SYNTHESIS OF 1-HYDROXY-2-NAPHTHOIC NITRILE

1937 ◽  
Vol 15b (11) ◽  
pp. 480-485 ◽  
Author(s):  
John A. McRae ◽  
Léo Marion

The neutral product of the condensation of phenylacetaldehyde with ethyl sodiocyanoacetate when distilled under low pressures loses the elements of ethyl alcohol and forms 1-hydroxy-2-naphthoic nitrile. This is identical with the synthetic substance prepared through a series of reactions from α-naphthol. The methyl ether has been prepared from both the synthetic substance and the product of the condensation. 1-Hydroxy-2-naphthoic nitrile can be coupled readily with p-nitrobenzenediazonium chloride. The evidence relating to the structure of the neutral condensation product is reviewed.

1930 ◽  
Vol 2 (3) ◽  
pp. 214-217 ◽  
Author(s):  
Harold Hibbert ◽  
J. G. Morazain

Isopropylidene glycerol, prepared in neutral medium by the action of anhydrous copper sulphate as condensing agent, was methylated with silver oxide and methyl iodide; the product yielded only glycerol α-methyl ether on hydrolysis, thus proving the absence of any six-membered ketal in the condensation product of glycerol and acetone.The properties of both glycerol α- and β-methyl ethers have been carefully redetermined.A table of the isomeric acetals and ketals summarising their physico-chemical constants is given, in view of their usefulness as "type compounds" in investigations relating to fats, carbohydrates and polysaccharides.


A detailed analytical investigation has been made of the reactions occurring during the early stages of the oxidation of ethyl alcohol (ethanol) in the temperature region 270 to 370° C. During an induction period the alcohol is converted quantitatively into acetaldehyde until a critical concentration of this intermediate has accumulated. The pressure then begins to rise autocatalytically, and methanol, formaldehyde and carbon monoxide become detectable; evidence is presented to show that these compounds arise from the further oxidation of acetaldehyde. The amount of ethanol consumed and of acetaldehyde formed at the end of the induction period are largely independent of the initial reactant pressures, except at low pressures of the alcohol. A study of the effect of added acetaldehyde shows that the minimum quantity required to eliminate the induction period is the same as that normally present at the end of the induction period. Hydrogen peroxide is the only product, other than acetaldehyde, detected during the induction period. Under optimum surface conditions the yields of hydrogen peroxide are equivalent to those of the aldehyde. A moderate increase in surface shortens the induction period, but a further increase retards reaction. In vessels of large surface: volume ratio, the yields of hydrogen peroxide are much reduced, while in a potassium chloride-coated vessel peroxides are invariably absent; in each case, the other products are unchanged. The mechanisms of the chain-initiating and propagating reactions are considered and the role of the surface in initiating and terminating chains is discussed.


1932 ◽  
Vol 7 (6) ◽  
pp. 629-642 ◽  
Author(s):  
Muriel E. Platt ◽  
Harold Hibbert

The work represents an extension of the "Hibbert-Michael ring partition theory" to the interaction of α-phenyl glycerol with acetone and p-nitrobenzaldehyde respectively. The α-phenyl glycerol was prepared in the form of a pure crystalline product from cinnamyl alcohol and on condensation with acetone yielded the two expected, isomeric, five-membered (dioxolane) ring compounds. These two isopropylidene derivatives were isolated and their structures definitely determined by the usual hydrolysis and methylation technique. In this manner the corresponding α- and γ-methyl ethers of α-phenyl glycerol were isolated, the identity of which had been previously settled by direct synthesis employing well-established reactions.The β-methyl ether of α-phenyl glycerol was obtained by methylating crystalline 1:3 p-nitrobenzylidene α-phenyl glycerol and then hydrolyzing the ether.Condensation of p-nitrobenzaldehyde with α-phenyl glycerol should yield, according to the "ring partition principle", one six- and two five-membered cyclic acetals.The crystalline isomer separating from the crude condensation product was shown to be the six-membered cyclic acetal. Removal of this left a viscous oil containing the five-membered acetals which, on methylation, and subsequent hydrolysis, yielded a small amount of the γ-methyl ether of α-phenyl glycerol, thus indicating the presence of some 1:2 p-nitrobenzylidene glycerol in the original reaction product. Due to the large number of theoretically possible five-membered rings it was not found possible to isolate, or prove the presence of, both five-membered acetals in the oil left after removal of the crystalline six-membered acetal. Presumably both of the structural five-membered acetals were formed, but due to their mutual solubility relations it was not possible to bring about a separation of crystalline forms.


Author(s):  
B. J. Grenon ◽  
A. J. Tousimis

Ever since the introduction of glutaraldehyde as a fixative in electron microscopy of biological specimens, the identification of impurities and consequently their effects on biologic ultrastructure have been under investigation. Several reports postulate that the impurities of glutaraldehyde, used as a fixative, are glutaric acid, glutaraldehyde polymer, acrolein and glutaraldoxime.Analysis of commercially available biological or technical grade glutaraldehyde revealed two major impurity components, none of which has been reported. The first compound is a colorless, water-soluble liquid with a boiling point of 42°C at 16 mm. Utilizing Nuclear Magnetic Resonance (NMR) spectroscopic analysis, this compound has been identified to be — dihydro-2-ethoxy 2H-pyran. This impurity component of the glutaraldehyde biological or technical grades has an UV absorption peak at 235nm. The second compound is a white amorphous solid which is insoluble in water and has a melting point of 80-82°C. Initial chemical analysis indicates that this compound is an aldol condensation product(s) of glutaraldehyde.


Author(s):  
Q.Z. Chen ◽  
X.F. Wu ◽  
T. Ko

Some butterfly martensite nuclei were observed in an Fe-27.6Ni-0.89V-0.05C alloy. The alloy was austenitized at 1200°C for 1 hour. Some samples were aged at 850° C for 40 minutes and quenched in 10% brine at room temperature. All the samples were cooled in ethyl alcohol for martensite transformation.A nucleus in an unaged specimen is shown in Fig.1. The nucleus has certain contrast different from the matrix and is shaped like one wing of a butter fly martensite. The SADP of the circled region is measured to be: da=dh, and approximate to dγ(111) and dm(110) with ∠AOB = 55° . It is similar to [011]f.c.c and b patterns in the anglez ∠AOB and the ratio ra/rb, respectively. The SADP shows that the structure of the nucleus is between f.c.c and b.c.c. The dislocation structure within the nucleus is shown in Fig.2. Their Burgers vectors and line directions are also given in it. There are many long dislocations near it without dislocations piled up as shown in Fig.3.Long dislocations are closed at one end as an envelope.


1955 ◽  
Author(s):  
Saul B. Sells ◽  
John R. Barry ◽  
David K. Trites ◽  
Herman I. Chinn
Keyword(s):  

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