THE CONVERSION OF META- AND PARA-SUBSTITUTED BENZALDOXIME ARENESULFONATES TO NITRILES

1965 ◽  
Vol 43 (5) ◽  
pp. 1534-1544 ◽  
Author(s):  
Robert J. Crawford ◽  
Charles Woo

The meta- and para-substituted syn-benzaldoxime arenesulfonates were prepared from the reaction between the sodium salt of the oxime and the acid chloride in absolute ether. These oxime esters reacted in aqueous alcohol readily to yield the corresponding nitriles exclusively. The reaction rates can be correlated by a Hammett plot with a slope of −0.77. Several para-substituents tended to deviate from the line. Isotope study gives a kH/kD ratio of 4.51. The rate was found to be sensitive to the change in the ionizing power of the solvent, and to the change in the strength of the esterifying acid. The addition of lithium perchlorate gives rise to a normal salt effect. Sodium acetate brings about a basic elimination having a Hammett p value of + 0.44. A mechanism is proposed in the light of these results.

2020 ◽  
Vol 315 ◽  
pp. 113654
Author(s):  
Sunil H. Ganatra ◽  
Vasim R. Shaikh ◽  
Anushree S. Ujjankar ◽  
Sneha D. Khobragade ◽  
Preeti A. Tomar ◽  
...  

Weed Science ◽  
1989 ◽  
Vol 37 (3) ◽  
pp. 400-404 ◽  
Author(s):  
Gunawan Wanamarta ◽  
Donald Penner ◽  
James J. Kells

The antagonistic effect of bentazon on sethoxydim adsorption and activity was studied in quackgrass. The diffusion of14C-sethoxydim into and through an isolated tomato fruit cuticle was inhibited in the presence of the sodium salt of bentazon. Bentazon also increased the partitioning of14C-sethoxydim into CH2Cl2and water; however, it decreased partitioning into ethyl acetate. Removal of epicuticular wax from quackgrass leaf surfaces did not prevent the antagonism. Addition of sodium acetate or sodium bicarbonate to the sethoxydim spray solution at 10 mM reduced uptake of14C-sethoxydim by quackgrass similar to the effect of bentazon. Sodium ions in the bentazon formulation appeared responsible for the antagonism by exchanging with the H+of the sethoxydim hydroxyl group to form a more polar sodium salt of sethoxydim. The addition of Li+, K+, Cs+, Ca++, and Mg++cations associated with a weak acid also reduced14C-sethoxydim absorption. Addition of organic acids to the spray solution overcame the antagonism by preventing the formation of sodium salt of sethoxydim. In the field, the addition of a 3000 ppm sodium acetate solution delivering 0.56 kg/ha produced the same antagonism as bentazon on quackgrass control with sethoxydim.


2012 ◽  
Vol 47 ◽  
pp. 62-67 ◽  
Author(s):  
G. Ulloa ◽  
C. Coutens ◽  
M. Sánchez ◽  
J. Sineiro ◽  
A. Rodríguez ◽  
...  

2014 ◽  
Vol 2014 ◽  
pp. 1-8 ◽  
Author(s):  
Mohd. Sajid Ali ◽  
Dileep Kumar ◽  
Hamad A. Al-Lohedan

Effect of two amphiphilic drugs (tricyclic antidepressant, nortriptyline hydrochloride (NORT), and nonsteroidal anti-inflammatory drug, sodium salt of ibuprofen (IBF)) on the cloud point of biopolymer hydroxypropylmethyl cellulose (HPMC) was studied. Effect of NaCl was also seen on the CP of HPMC-drug system. CP of HPMC increases uniformly on increasing the (drug). Both drugs, though one being anionic (IBF) and other cationic (NORT), affect the CP in almost the same manner but with different extent implying the role of hydrophobicity in the interaction between drug and polymer. Salt affects the CP of the drug in a dramatic way as low concentration of salt was only able to increase the value of the CP, though not affecting the pattern. However, in presence of high concentration of salts, minimum was observed on CP versus (drug) plots. Various thermodynamic parameters were evaluated and discussed on the basis of the observed results.


Tetrahedron ◽  
1998 ◽  
Vol 54 (11) ◽  
pp. 2631-2646 ◽  
Author(s):  
Yury G. Shtyrlin ◽  
Dmitry G. Murzin ◽  
Natalia A. Luzanova ◽  
Gulnara G. Iskhakova ◽  
Vladimir D. Kiselev ◽  
...  

2018 ◽  
Vol 6 (1) ◽  
pp. 102 ◽  
Author(s):  
I U. Nkole ◽  
C R. Osunkwo ◽  
A D. Onu ◽  
O D. Onu

The kinetics and mechanism of reduction of N-(2-hydroxyethyl) ethylenediaminetriacetatoiron (III) complex (hereafter [Fe(III)HEDTAOH2]) by thioglycol (hereafter RSH) has been studied spectrophotometrically in a bicarbonate buffer medium. The study was carried out under pseudo-first order conditions of an excess of thioglycol concentration at 28 ± 1℃, I = 0.44 mol dm-3 (KNO3) and λmax = 490 nm. The reaction is first order in [Fe(III)HEDTAOH2] and half order in [RSH] and a stoichiometric mole ratio of [Fe(III)HEDTAOH2]: RSH is 2:1. Reaction rates increased with increase in ionic strength (I) and dielectric constant (D) of the reaction medium of the reaction. The reaction displayed positive primary salt effect, which suggests the composition of activated complex are likely charged reactants ions. Test for possibility of an intermediate complex formation shows negative as Michaelis-Menten plot was linear with very negligible intercept. Based on the findings, outer-sphere mechanism is proposed for the reaction. The experimental rate law obtained is; - = k2 [Fe(III)HEDTAOH2][RSH]½   


1989 ◽  
Vol 42 (1) ◽  
pp. 61 ◽  
Author(s):  
EW Della ◽  
J Tsanaktsidis

Bridgehead carboxylic acids can be converted into their corresponding chlorides very efficiently under Barton halodecarboxylation conditions. Addition of the acid chloride to a suspension of the sodium salt of 1-hydroxypyridine-2(1H)- thione in boiling carbon tetrachloride under irradiation leads to excellent yields of the bridgehead chloride via the derived thiohydroxamic ester. In a useful modification for the synthesis of volatile halides, either 1,1,1-trichloro-2,2,2-trifluoroethane or trichlorofluoromethane can be employed as substitute solvents. It is found that the Barton procedure is applicable to the synthesis of labile bromides such as 1-bromobicyclo[3.1.1]heptane for which the usual Hunsdiecker reaction fails. For these, and other brominations , 2-bromo-2-chloro-1,1,1-trifluoroethane ('Halothane') is shown to function as an efficient solvent/bromine atom donor.


1972 ◽  
Vol 27 (5) ◽  
pp. 528-530 ◽  
Author(s):  
Helga Wittmann ◽  
Helmut Rathmayr

Benzylmalonyl Chloride reacts in the presence of sodium acetate in boiling benzene to give tribenzyl-phloroglucinol-triacetate, however with sodium chloroacetate to 3,5-dibenzyl-6-phenethylpyran-2,4-dion. In both cases trimerisation of benzylketene or benzylketene carboxylic acid chloride occurs. On the other hand, benzylmalonylchloride reacts with sodium benzoate and sodium phenylacetate via a dimeric benzylketene carboxylic acid chloride under the loss of phosgene to yield cyclopentadienyl derivatives.


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