Acid-catalysed rearrangements between 3,4-dihydro-2H-1,5-benzooxazocine and -benzothiazocine and their macrocyclic (16-membered, 24-membered and 32-membered) oligomers
Acid-catalysed rearrangements between 3,4-dihydro-2H-1,5-benzooxazocine and -benzothiazocine and their macrocyclic (16-membered, 24-membered and 32-membered) oligomers
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3,4-二氢-2H-1,5-苯并恶佐辛和-苯并噻佐辛及其大环（16元、24元和32元）低聚物之间的酸催化重排
DOI：
10.1039/a704255h
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发表时间：
1998
期刊：
影响因子：
--
通讯作者：
S. Wild
中科院分区：
文献类型：
--
作者：
D. Hockless;L. Lindoy;G. Swiegers;S. Wild
用二乙醚中的三苯基膦处理2-（3-叠氮丙氧基）苯甲醛，然后用硫氰酸镍隔离产物，再用氨水从配合物中分离出来，得到16元的3,4-二氢- 2h -1,5-苯并恶唑辛二聚体。二恶二氮二亚胺大环3在溶液中经过酸催化重排成为平衡混合物，该混合物包括三恶三氮三亚胺（24元）8和四恶四氮四胺（32元）9大环以及二亚胺。[2H]氯仿中的低聚物在丙烷-1,3-二烷基连接的中心碳原子上的质子的1H NMR化学位移不同，从而允许研究涉及大环低聚物之间重排的因素。因此，大环聚酰亚胺在7-10分钟内重排成各种低聚物的平衡混合物，但每种情况下的平衡位置取决于溶液的亚胺当量浓度。3,4-二氢- 2h -1,5-苯并噻唑嗪也经历了类似的重排。这种平衡归因于在酸的存在下低聚物之间容易的分子间传递，以及16、24和32元低聚物的热力学稳定性的相似性。报道了相应的大环苯并恶唑类化合物的16元二胺11和32元四胺10衍生物的硝酸铵盐的晶体结构和分子结构。
Treatment of 2-(3-azidopropoxy)benzaldehyde with triphenylphosphine in diethyl ether, followed by sequestration of the products with nickel(II) thiocyanate and subsequent liberation from the complex with aqueous ammonia, produces the 16-membered dimer of 3,4-dihydro-2H-1,5-benzooxazocine. The dioxadiaza diimine macrocycle 3 undergoes an acid-catalysed rearrangement in solution into an equilibrium mixture that includes the trioxatriaza triimine (24-membered) 8 and tetraoxatetraaza tetraimine (32-membered) 9 macrocycles, as well as the diimine. The oligomers in [2H]chloroform differ in the 1H NMR chemical shifts of the protons on the central carbon atoms of the propane-1,3-diyl links, thereby allowing an investigation of the factors involved in the rearrangements between the macrocyclic oligomers. Thus, the rearrangements of the macrocyclic polyimines into equilibrium mixtures of the various oligomers occurs with t>>½>> 7–10 min, but the position of the equilibrium in each case is dependent upon the imine equivalent concentration of the solution. 3,4-Dihydro-2H-1,5-benzothiazocine undergoes a similar rearrangement. The equilibrations have been ascribed to facile intermolecular transiminations between the oligomers in the presence of traces of acid and to the similarities of the thermodynamic stabilities of the 16-, 24- and 32-membered oligomers. The crystal and molecular structures of ammonium nitrate salts of the 16-membered diamine 11 and 32-membered tetraamine 10 derivatives of the corresponding macrocyclic benzooxazocines are reported.