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Reaction of methyl alpha‐eleostearate with mercuric acetate
Author(s) -
Planck Ralph W.,
O'Connor Robert T.,
Goldblatt Leo A.
Publication year - 1956
Publication title -
journal of the american oil chemists' society
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.512
H-Index - 117
eISSN - 1558-9331
pISSN - 0003-021X
DOI - 10.1007/bf02665108
Subject(s) - chemistry , alcohol , chloroform , double bond , petroleum ether , acetic acid , saponification , organic chemistry , potassium hydroxide , medicinal chemistry , ether , conjugated system , extraction (chemistry) , polymer
Summary Methyl alpha‐eleostearate has been reacted with mercuric acetate in acetic acid solution. Carrying out the reaction below room temperature gave products having the highest mercury content. Even these products were relatively unstable, gradually decomposing to produce mercury or mercurous acetate or both at room temperature. A typical product obtained at 10°C. is a viscous, pale yellow oil, insoluble in petroleum ether but soluble in alcohol, ether, and chloroform. Each C 18 chain contained, on the average, 1.4 acetoxymercuri‐groups (CH 3 COOHg−), 1.5 acetoxyl groups attached directly to the carbon chain and 0.4 double bonds. For each mole of mercuric acetate added to the methyl eleostearate approximately one mole of mercuric acetate was reduced to mercurous acetate and a double bond in the ester chain was oxidized to an oxygen‐containing group of undetermined structure. Treatment of the acetoxymercuri‐, acetoxy‐ester with aqueous chlorides or bases yielded the corresponding chloromercuri‐ or hydroxymercuri‐derivative. Refluxing the acetoxymercuri‐, acetoxy‐ester in alcoholic potassium hydroxide saponified all the ester linkages and removed the acetoxymercuri‐groups with the formation of an equal number of double bonds, most of which are present in conjugated trans‐trans systems. The Marvel‐Rands chromatographic procedure was modified to permit determination of total acetoxyl groups and of acetoxyl groups attached to mercury atoms. Acetoxyl groups of the latter kind can also be determined by direct titration with standard base.