THERMAL REACTIONS OF SULFONYL AZIDES
THERMAL REACTIONS OF SULFONYL AZIDES
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DOI：
10.1021/ja01037a016
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发表时间：
1969-01-01
影响因子：
15
通讯作者：
RENFROW, WB
中科院分区：
文献类型：
--
作者：
BRESLOW, DS;SLOAN, MF;RENFROW, WB
动力学研究表明，对甲苯磺酰叠氮在各种溶剂中通过清洁的一级反应热分解。速率决定步骤是氮的损失和缺电子氮烯物种的形成。虽然脂肪族磺酰叠氮在二苯醚中的行为类似，但它们在脂肪族烃溶剂中的分解不是一级反应。虽然形成的气体正好是1摩尔，但它含有二氧化硫和氮气。同时发生两种反应：氮的一级消除和氮烯的形成，以及产生二氧化硫的明显的自由基链式反应。自由基反应的其它产物也已确定，加入自由基抑制剂可消除自由基反应。讨论了自由基引发剂的来源。磺酰基氮烯插入饱和烃的碳氢键中，但它们通过夺氢形成很少（如果有的话）的RSG 2NH 2。它们在与一级、二级和三级CH键的反应中比甲酰基氮烯的区别更小。苯对对甲苯磺酰氮烯的反应性是环己烷的两倍，对二甲苯的反应性是对甲苯磺酰氮烯的一半。氮烯的不同反应负责的多重性进行了讨论。结果表明，单重态稳定性福尔斯的顺序为磺酰基>甲酰基>芳基，饱和烃的CH键插入和芳环加成反应为单重态反应，饱和烃的夺氢反应为三重态反应。[3]这里，与叠氮甲酸酯一样，人们认为，如果这些材料由于氮的损失和氮宾的形成而分解，则氮宾可能插入碳-氢键中，并通过使用磺酰叠氮使烃聚合物改性或交联。虽然在我们的工作开始时，有大量关于磺酰叠氮反应的文献4，但几乎全部是关于芳族磺酰叠氮与芳族化合物反应的描述。
p-Toluenesulfonyl azide has been shown by kinetic studies to decompose thermally in a variety of solvents by a clean first-order reaction. The rate-determining step is loss of nitrogen and formation of an elec-tron-deficient nitrene species. Although aliphatic sulfonyl azides behave similarly in diphenyl ether, their de-composition in aliphatic hydrocarbon solvents is not first order. Although exactly 1 mole of gas is formed, it contains sulfur dioxide as well as nitrogen. Two simultaneous reactions occur: first-order elimination of ni-trogen and formation of nitrene, and an apparent radical-chain reaction evolving sulfur dioxide. The other products expected of a radical reaction have been identified, and addition of radical inhibitors eliminates the radi-cal reaction. The origin of the radical initiator is discussed. Sulfonylnitrenes insert into carbon-hydrogen bonds of saturated hydrocarbons, but they form little if any RSG2NH2 by hydrogen abstraction. They are less discriminating in their reactions with primary, secondary, and tertiary CH bonds than are formylnitrenes. Ben-zene is twice as reactive as cyclohexane and half as reactive as p-xylene toward p-toluenesulfonylnitrene. The multiplicities responsible for the different reactions of nitrenes are discussed. It is concluded that singlet stability falls in the order sulfonyl> formyl> aryl, that insertion into the CH bond of a saturated hydrocarbon and addition to an aromatic ring are singlet reactions, and that hydrogen abstractionfrom a saturated hydrocarbon is a triplet reaction.In our continued search for new reactions of saturated hydrocarbons, 2 our attention was focused on the re-actions of sulfonyl azides. 3 Here, as with the azidofor-mates, it was felt that if these materials decomposed by loss of nitrogen and formationof nitrene, the nitrene might insert into a carbon-hydrogen bond and allow the modification or cross-linking of hydrocarbon poly-mers by the use of sulfonyl azides. Although there was a considerable body of literature4 on sulfonyl azide reactions when our work was initiated, it consisted almost entirely of descriptions of the reactions of aromatic sulfonyl azides with aromaticcompounds.