Chemistry of acetylenic ethers. XXIX.: Reactions of acetylenic ethers with some aromatic isocyanates. Formation of derivatives of 2‐quinolone

Abstract

Ethoxyacetylene slowly adds phenyl isocyanate to yield 4-ethoxy2quinolone I (R=H). A similar reac,tion occurs with p-tolyl isocyanate.From the Grignard derivative of ethylfihioacetylene and phenyl isocyanate the anilide of et,hylthiopropynoic acid W I I is obtained. T,he corresponding reaction with ethoxyacetylene does not yield a pure product.In the course of our investigations into ,the reactivity of acetylenic ethers we have also studied the reactions of ethoxyacetylene with aromatic isocyanates.

Rearrangement. II. Pyrolysis and Acetolysis of Cyclohexanemethyl p-Toluenesulfonate

“…The formation of small amounts of alcohols is probably due to the presence of water in the glacial acetic acid used for the acetolysis. Water is known to be much more nucleophilic than acetic acid.12 The formation of the rearranged alcohols and their acetates from the corresponding cycloalkenes, however, (9) This conclusion may be supported by the fact that the pyrolysis of cyclohexanemethyl methanesulfonate also yielded cycloalkenes and methylcyclohexane, but no toluene: unpublished results.…”

Diels-Alder reactions of dienophiles containing iso-cyanate groups

“…The isocyanate function in certain aryl isocyanates will behave as a dienophile toward the highly reactive isoindole system (1); however, this appears to represent an isolated example. In the reaction with alkoxyacetylenes (7), the isocyanate group actually functions in a diene capacity. The highly reactive sulfonyl isocyanates enter into reaction with dienes readily through the isocyanate function, but the products are either anilides of chlorosulfonic acid or four-membered heterocycles formed by cycloaddition (5).…”

“…Dienophiles 1 to 6 contain as a group four different types of unsaturation-namely, a, /3-conjugated (1, 2), strained ring (3,5), cycloalkenyl (4), and acyclic terminal (6). The nine dienes are representative of seven different types-namely, cyclic (7), polyhalogenated cyclic (8,9), monosubstituted acyclic (10,11), aromatic (12), unsubstituted acyclic (13), 2,3-disubstituted acyclic (14), and 1,4-disubstituted acyclic (15). With the exception of those specific cases wherein maximum adduct recovery either was not sought or was especially difficult because of the exceptionally high boiling points of the adducts, surprisingly high yields were obtained in these reactions.…”

“…Bis(2 -isocyanatoethyl) - 5,6,7,8,11,11 -hexachloro -5,7methane -1,2,3,4,5,8,9,10 -octahydronaphthalenetrans -2,3dicarboxylate (27). A mixture of 277 grams (0.9 mole) of adduct 17 and 491 grams (1.8 moles) of hexachlorocyclopentadiene ( 9) was heated with stirring for 18 hours at 150°C.…”

“…of Hg) afforded 271 grams (51.8%) of a reddish-brown viscous liquid, ® 1.5429, having an indicated purity of 99.1% by wet chemical analysis. 5,6,7,8,9,2,3,4,4a,5,8,8a -octahydro -2isocyanatomethyl - 1,4,5,8 -dimethanonaphthalene (30). A mixture of 136.5 grams (0.5 mole) of diene 9 and 74.5 grams (0.5 mole) of 2-isocyanatomethylnorborn-5-ene (5) was heated with stirring in a nitrogen atmosphere for 3.75 Figure 1.…”