SYNTHESIS OF 1,5-DIAMINO-1,5-DIHYDROBENZO[1,2-D-4,5-D']BISTRIAZOLE (DABT) AND ITS USE AS A 1,4-BENZADIYNE EQUIVALENT
SYNTHESIS OF 1,5-DIAMINO-1,5-DIHYDROBENZO[1,2-D-4,5-D']BISTRIAZOLE (DABT) AND ITS USE AS A 1,4-BENZADIYNE EQUIVALENT
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DOI：
10.1021/jo00357a005
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发表时间：
1986-04-04
影响因子：
3.6
通讯作者：
OK, D
中科院分区：
文献类型：
--
作者：
HART, H;OK, D
结果DABT的制备。得到3的最直接途径是通过已知的6，7 - 1，5-二氢苯并[1，2-d：4，5-d]双三唑（8）的胺化，其由间二氯苯经五步反应制得，总产率为54%，如方案I所示。如参考文献8中所述制备化合物5，并乙酰化为6.6789。在我们掌握的文献中，将6转化为87的方法总是得到非常低的产率（报道为60%，但我们得到的产率< 10%），我们在实验部分描述了一种改进的方法，该方法一致地从6得到93%的产率8。主要的变化是用乙醇代替乙酸进行氢化，使用更多的催化剂，以及用0 ℃代替室温进行7（未分离）的重氮化。如所述进行8至9的转化。7在66-68 ℃下用羟胺-O-磺酸在碱水溶液中直接胺化9，得到五种产物的混合物，三种可能的二氨基衍生物3、10和11以及两种单氨基衍生物12和13（方案II）。二氨基和单氨基产物的总收率分别为45%和48%，后者可以在相同的反应条件下循环使用，从而大大提高了二氨基衍生物的收率。3的比例：10点整：11的NMR积分结果为53：12：35（3的芳香质子信号积分值分别为8.24、8.69和7.71，11的芳香质子信号积分值分别为8.59和7.96）。异构体11在热乙醇中极易溶解，而3的溶解度低于10。根据光谱数据指定了结构。化合物3，熔点292 ℃，在NMR中仅显示两种类型的质子，芳香族质子在8.24处，NH质子在7.18处; 13 C NMR谱仅显示三个信号，在144.16、131.40和97.43处。这些数据仅与3的C2 h对称性一致。3的红外光谱在3386和3610 cm-1处显示出强的伯胺吸收。
Results Preparation of DABT. The most direct route to 3 is via amination of the known6, 7 l, 5-dihydrobenzo [1, 2-d: 4, 5-djbistriazole (8), which is prepared from m-dichloro-benzene in five steps and 54% overall yield as shown in Scheme I. Compound 5 was prepared as described in ref 8 and acetylated to 6.6 7 89The literature method for con-version of 6 to 87 in our hands always gave very low yields (reported 60%, but we obtained< 10%), and we describe in the Experimental Section an imporved procedure which consistently gives a 93% yield of 8 from 6. The major changes were to use ethanol in place of acetic acid for the hydrogenation, to use more catalyst, and to use 0 C in-stead of room temperature for the diazotization of 7 (not isolated). Conversion of 8 to 9 proceeded as described. 7 Direct amination of 9 in aqueous base with hydroxylamine-0-sulfonic acidat 66-68 C gave a mixture of five products, the three possible diamino derivatives 3, 10, and 11 and the two monoamino derivatives 12 and 13 (Scheme II). The combined yields of diamino and monoamino products were 45% and 48%, respectively; the latter could by recycled using the same reaction conditions, thus sub-stantially increasing the yields of diaminoderivatives. The ratio of 3: 10: 11 was determined by NMR integration to be 53: 12: 35 (the aromatic proton signals which were integrated appeared at 8.24 for 3, 8.69 and 7.71 for 10, and 8.59 and 7.96 for 11).The three diamino derivatives were separated in ex-cellent purity by fractional crystallization from ethanol. Isomer 11 is very soluble in hot ethanol and 3 is less soluble than 10. The structures were assigned from spectral data. Compound 3, mp 292 C dec, showed only two types of protons in the NMR, aromaticprotons at 8.24 and NH protons at 7.18; the 13C NMR spectrum showed only three signals, at 144.16, 131.40, and 97.43. These data are only consistent with the C2h symmetry of 3. The infrared spectrum of 3 showed strong primary amine ab-sorption at 3386 and 3610 cm" 1.