ORGANIC DISULFIDES AND RELATED SUBSTANCES .27. REACTIONS AND SYNTHETIC UTILITY OF CYCLIC DISULFIDES DIOXIDES AND TETROXIDES
ORGANIC DISULFIDES AND RELATED SUBSTANCES .27. REACTIONS AND SYNTHETIC UTILITY OF CYCLIC DISULFIDES DIOXIDES AND TETROXIDES
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DOI：
10.1021/jo01258a058
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发表时间：
1969-01-01
影响因子：
3.6
通讯作者：
BARBEE, RB
中科院分区：
文献类型：
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作者：
FIELD, L;BARBEE, RB
研究了未取代的五元、六元和七元二硫化物、1，1-二氧化物和1，1，2，2-四氧化物的水解、极谱还原和其它反应。1，1，2，2-四氧化二硫烷与苯硫酚的反应不如1，1-二氧化物，但通过一种可能通用的温和方法将硫醇盐定量氧化为二硫化物;其与亲核试剂的反应性类似于二硫化物，只是对碱更敏感（所有三种四氧化物在pH 8下容易裂解）;其热解得到四氢噻吩二氧化物，但产率低。概括起来很困难，但似乎通常是因为五元系统比六元系统更容易断裂（七元系统可变），并且对自聚合或对更多氧化形式的硫醇攻击有更大的抵抗力，但对水解和电化学还原的抵抗力较小。二氧化物和四氧化物是很有前途的合成中间体。1，2-二硫杂环己烷1，1-二氧化物被硫醇根离子"氧代二硫键裂解"，得到含亚磺酸基的二硫醚1，2和3，它们依次转化为烷基砜（4和5）、芳基砜（6）或磺酸酯（8）。典型的二硫化物产物（4）与耐药类的对称二硫化物发生缩合反应，合成了二硫化物砜。1，2-四氧化二噻烷与碱发生"氧二硫键断裂"，生成含亚磺酸基的磺酸盐（11），再转化为二硫化物（12）。本系列的前一篇文章比较了五、六、七位环状二硫化物（1，2-二硫戊环、1，2-二噻烷、1，2-二硫杂环庚烷）及其1，1-二氧化物和1，1，2，2-四氧化物的合成。本文首先考虑这些物质在各种情况下的相对稳定性和反应性。然后，它证明了这些物质用于合成各种结构的实用性，否则难以获得。未来是否将证明所描述的类型的模型反应的希望将证明一般的cyclicdisulfides和它们的氧化产物还有待观察，但我们乐观地认为，这些原型将建议有用的方法，许多环的大小和环取代的情况。1，2-二硫戊环的不稳定性，显然至少部分是两个硫原子上的非键电子之间排斥的结果，1 2
Hydrolysis, polarographic reduction, and other reactions were studied of the unsubstituted five-, six-, and seven-membered disulfides, the 1, 1-dioxides, and the 1, 1, 2, 2-tetroxides. 1, 2-Dithiane 1, 1, 2, 2-tetroxide reacted less readily with thiophenol than the 1, 1-dioxide but oxidized a thiolate quantitatively to the disulfide by a mild method of possible generaluse; its reactivity with nucleophiles resembled that of a disulfide, except for greater susceptibility to alkali (all three tetroxides were readily cleaved at pH 8); its pyrolysis gave tetrahydrothiophene dioxide but in low yield. Generalizations are difficult but seem usually to be for easier cleavage of the five-membered systems than of the six-membered ones (with the seven-membered systems variable) andfor greater resistance to self-polymerization or to attack of a thiol bythe more oxidized forms but for lesser resistance to hydrolysis and electrochemical reduction. The dioxides and tetroxides are quite promising intermediates for synthesis. 1, 2-Dithiane 1, 1-dioxide underwent “oxodisulfide cleavage” by thiolate ion to give disulfides 1, 2, and 3 containing a sulfinate moiety, which in turn were converted intoalkyl sulfones (4 and 5), an aryl sulfone (6), or a sulfonate (8). A typical disulfide product (4) disproportionated to the symmetrical disulfides com-parably with resistant classes, affording a synthesis of a disulfide sulfone. 1, 2-Dithiane tetroxide underwent “oxodisulfide cleavage” with alkali to give a sulfonate salt containing a sulfinate moiety (11), which was con-verted into a disulfide dioxide (12). Product 3 was active as an antiradiation drug.The previous paper in this series compared syntheses for thefive-, six-, and seven-numbered cyclic disulfides (1, 2-dithiolane, 1, 2-dithiane, and 1, 2-dithiepane), their 1.1-dioxides, and their 1, 1, 2, 2-tetroxides. lc The present paper first considers relative stabilities and reactivities of these substances under various circumstances. It then demonstrates utility of such substances for synthesis of a variety of structures otherwise difficultly obtainable. Whether the future will justify the hope that model reactions of the types described will prove general for cyclicdisulfides and their oxidation products remains to be seen, but we are optimistic that these prototypes will suggest useful approaches for many ring-size and ring-substitution situations. Instability of 1, 2-dithiolane, apparently at least partly a consequence ofrepulsion between nonbonding electrons on the two sulfur atoms, 1 2