PREPARATION + REACTIONS OF HYDRAZINO PERFLUOROAROMATIC COMPOUNDS
PREPARATION + REACTIONS OF HYDRAZINO PERFLUOROAROMATIC COMPOUNDS
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DOI：
10.1021/jo01029a069
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发表时间：
1964-01-01
影响因子：
3.6
通讯作者：
TAMBORSKI, C
中科院分区：
文献类型：
--
作者：
HOLLAND, DG;MOORE, GJ;TAMBORSKI, C
六氯苯与肼的反应。在二氧杂环己烷里。-将六氯苯（37.2g.，0.20摩尔）和95+%无水肼（38.4克，1.20摩尔）在125毫升中加热。对二氧六环在约1200 cc回流温度下16小时后。(27%）。从反应溶液中蒸馏得到沸点低于溶剂的馏分（bp 88-92）。汽相色谱显示该馏出物是六氟苯（13.4%）、五氟苯（7.6%）和1，2，4，5-正-苯（IV，78.9%）的混合物。石油醚（bp 60-90）。将难处理的棕褐色固体（10.5g，25%，mp 156.5-162 dec.）通过过滤除去。从甲苯中重结晶三次，得到少量淡黄色针状物，mp 148.5-152.5 dee。Anal.对于C6 HeF 4 N4计算：C，34.29; H，2.88; F，36.2; N，26.66。实测值：0，34.56; H，2.92; F，36.3; N，26.76。在二甲基甲酰胺中的难处理的棕褐色固体的F19核磁共振谱表明它是1，4-和1，3-二肼基四氟苯的1：1混合物。在74.7、88.7（双重峰）和93.9（三重峰）ppm处的吸收归因于Meta异构体，而在83.0 ppm处的单一吸收归因于帕拉异构体。从甲苯中重结晶的样品的光谱显示出相似的吸收，其摩尔异构比近似为12.5：1.0间-对位。粗混合物产生双-1，4-苯乙酮腙衍生物，白色针状物（来自乙醇），mp 167，5-168。Anal. C22 H，8 F4 N4的计算值：C，63.76; H，4.38; F，18.3; N，13.52。实测值：C，63.82; F，4.40; F，18.6; N，13.60。双腙在丙酮中的F_（19）NMR谱在79.8ppm处有吸收
The Reaction of Hexafluorobenzene with Hydrazine. In Dioxane.—Hexafluorobenzene (37.2 g., 0.20 mole) and 95+% anhydrous hydrazine (38.4 g., 1.20 moles) were heated in 125 ml. of p-dioxane. After 16 hr. at reflux temperature approximately 1200 cc.(27%) of nitrogen hadbeen evolved. Distillation from the reaction solution yielded a fraction (bp 88-92) boiling below the solvent. A vapor phase chromatogram8 showed this distillate to be a mixture of hexafluorobenzene (13.4%), pentafluorobenzene (7.6%), and 1, 2, 4, 5-tetrafluoro-benzene (IV, 78.9%).The cooled reactionmixture was stirred with 400 ml. of ligroin (bp 60-90). The intractable tan solid (10.5 g., 25%, mp 156.5-162 dec.) was removed by filtration. Recrystallization three times from toluene afforded a small amount of pale yellow needles, mp 148.5-152.5 dee. Anal. Caled, for CeHeF4N4: C, 34.29; H, 2.88; F, 36.2; N, 26.66. Found: 0, 34.56; H, 2.92; F, 36.3; N, 26.76. The F19 nmr spectrum of the intractable tan solid in dimethyl-formamide showed it to be a 1: 1 mixture of 1, 4-and 1, 3-dihydrazinotetrafluorobenzenes. Absorption'at 74.7, 88.7 (doublet), and 93.9 (triplet) ppm is attributed to the meta isomer, while a single absorption at 83.0 ppm is attributed to the para isomer. The spectrum of the sample recrystallized from toluene exhibited similar absorption with the approximate molar isomeric ratio of 12.5: 1.0 meta-para. The crude mixture yielded a bis-1, 4-acetophenone hydrazone derivative, white needles (from ethanol), mp 167, 5-168. Anal. Caled, for C22H, 8F4N4: C, 63.76; H, 4.38; F, 18.3; N, 13.52. Found: C, 63.82;, 4.40; F, 18.6; N, 13.60. The F19 nmr spectrum of the bishydrazone in acetone ex-hibits absorption at 79.8 ppm