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SORENSON
[CONTRIBUTION
FROM
THE
VOL.
24
PIONEERING
RESEARCH
DIVISION,
TEXTILE
FIBERS
DEPARTMENT,
E. I. DU PONTDE NEMOURS
& co., Ih.C.1
R. SORENSON
The reaction of an aromatic isocyanate or diisocyanate with benzoic acid in dimethyl sulfoxide as solvent has been
found to give the urea or high molecular weight polyurea derived from the amine or diamine precursor of the isocyanate.
The dimethyl sulfoxide takes part in the reaction alw, forming the mcthylthiomethyl ester of benzoic acid. This fact,
plus the observed stoichiometry of the reaction ( 2 : 1 : 1 for isocyanate: carboxylic acid: sulfoxide), precludes the operation in
this case of the usual isocyanate-carboxylic reaction. A mcchanism is proposed which accounts for the products formed.
R-NCO
+ R'-COZH +R-NH-C-0-(!-It'
I1
The decomposition of the mixed anhydride proceeds by two paths to give an amide in A (below),
and in I3 a symmetrical urea and the anhydride of
the acid.2 Carbon dioxide is evolved in both cases.
The products of path B, on heating to higher temperatures (135' or more) can react with each
other to give the amide, path C.* Thus, under
forcing conditions, the ultimate product of the reaction is the amide:
J. Org. Chem.,
JIJLY
1950
C H , - S - - C H ~ - O - & ~ ~+ co2
'37'3
CeH;--NCO
CBS-NHZ
C6Hi-C0JI-+
+ CO,
F=O
0
/I
I+
/I
,C-CaH;
0
I1
CH3-S-CH3
fl
C8H5NH-C-NHC6H5
CtIH5NCO
CaHS-NH-C,
1"
BC-CBHB
0/5=O
980
VOL.
24
has the complete structure of eaeh of these allergenic oils been eltlborated.4~5Because of the extreme sensitivity of these compounds and for other
J. Am. Chem.