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The synthesis, characterization, and reactivity of some ruthenocene-fused heterocycles.

机译：某些钌茂茂稠合杂环的合成，表征和反应性。

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摘要

The preparation and characterization of 1', 2 ', 3', 4', 5 ' pentamethylruthenocene-fused heterocycles were studied. This work was divided into several parts: first, the syntheses of ruthenocene-fused pyridazines; second, the attempted syntheses of ruthenocene-fused thiophenes and pyrroles; and third, the synthesis of 1,3-dimethyl-4H-cyclopenta[ c]thiophene and its attempted metallation.; The first examples of the convenient, versatile ruthenocene-fused heterocycle precursors, 1, 2-diacyl-1',2',3 ',4',5'-pentamethylruthenocenes were synthesized from reaction of [Tl{lcub}1,2-C5H3(COR) 2{rcub}] (R = H, Me, Ph, But, Tp (thiophene)) with 1/4 [Ru( m 3-Cl)(Cp*)]4. The first examples of 1 ',2',3',4' ,5'-pentamethylruthenocene-fused pyridazines were easily synthesized by reactions of 1,2-diacyl-l',2 ',3',4',5' -pentamethylruthenocenes with hydrazine hydrate. The diacyl and pyridazine compounds were characterized by X-ray crystallography.; Reactions of 1,2-diacyl-1',2',3 ',4',5'-pentamethylruthenocenes with thiating reagents or primary amines failed to give any isolated 1 ',2',3',4' ,5'-pentamethylruthenocene-fused thiophenes or pyrroles. The reaction of 1,2-diformyl-1',2' ,3',4',5'-pentarnethylruthenocene with Lawesson's Reagent gave a ruthenocene-fused dithiolactone in 55% yield. Methylation of the thiocarbonyl of the dithiolactone with methyl triflate gave &sqbl0;Ru&cubl0;h5 -1,2- C5H3C&parl0;SCH3&parr0; SCH2&cubr0; (Cp*)][OTf], the first example of a protonated ruthenocene-fused thiophene. Hydride addition using NaBH4 gave neutral [Ru{lcub} h 5-1,2-C5 H3CH&parl0;SCH3&parr0;SC H2&cubr0;&parl0;Cp*&parr0;&sqbr0; , {09}a {09}ruthenocene-fused dihydrothiophene. Loss of MeSH by addition of trifluoroacetic acid led to [Ru{lcub} h 5-1,2- C5H3CHOC&parl0;O&parr0;CF 3SCH2&cubr0;&parl0;C p*&parr0;&sqbr0;.; A modification of Helmers' synthesis was used to synthesize 1,3-dimethyl-5,6-dihydro-4H-cyclopenta[ c]thiophene-5-one. Reduction of 1,3-dimethyl-5,6-dihydro-4H-cyclopenta[ c]thiophene-5-one, chloride substitution, and elimination led to 1,3-dimethyl-4H-cyclopenta[c]thiophene. 1,3-Dimethyl-4H-cyclopenta[ c]thiophene was easily deprotonated with n-BuLi. Attempted transmetallation with TIOEt led to oxidative coupling through the cyclopentadienyl unit of 1,3-dimethyl-4H-cyclopenta[c]thiophene. Attempted transmetallations of 1,3-dimethyl-4H-cyclopenta[c]thiophene lithium with ruthenium failed.
机译：研究了1'，2'，3'，4'，5'五甲基茂茂茂稠合杂环的制备和表征。这项工作分为几个部分：首先，钌茂茂融合的哒嗪的合成；其次，尝试合成钌茂茂稠合的噻吩和吡咯。第三，1，3-二甲基-4H-环戊[c]噻吩的合成及其尝试的金属化。便利的，通用的钌茂茂稠合的杂环前体的第一个例子是从[Tl {lcub} 1,2-的反应中合成1,2-二酰基-1'，2'，3'，4'，5'-五甲基钌烯具有1/4 [Ru（m 3-Cl）（Cp *）] 4的C 5 H 3（COR）2 {rcub}]（R ＝ H，Me，Ph，但是，Tp（噻吩））。 1'，2'，3'，4'，5'-五甲基茂茂茂并茂的哒嗪的第一个实例很容易通过1,2-二酰基-1'，2'，3'，4'，5'的反应合成-五甲基钌与水合肼。二酰基和哒嗪化合物通过X射线晶体学表征。 1,2-二酰基-1'，2'，3'，4'，5'-五甲基钌烯与噻吩试剂或伯胺的反应未能产生任何孤立的1'，2'，3'，4'，5'-五甲基钌茂金属稠合的噻吩或吡咯。 1，2-二甲酰基-1′，2′，3′，4′，5′-戊烯乙基钌茂茂与Lawesson's试剂的反应得到了钌茂茂稠合的二硫代内酯，产率为55％。二硫代内酯的硫代羰基与三氟甲磺酸甲酯的甲基化得到＝ Ru ＝ h5 -1，2-C5H3C＆parl; SCH3＆parr0; SCH2＆cubr0; （Cp *）] [OTf]，质子化的钌茂金属稠合噻吩的第一个例子。使用NaBH 4的氢化物加成得到中性的[Ru {lcub} h 5-1,2-C5 H3CH＆SCHl0; SCH3＆parr0; SC H2＆cubr0;＆parl0; Cp *＆parr0;＆sqbr0; ，{09} a {09}钌茂金属稠合的二氢噻吩。通过添加三氟乙酸而损失MeSH导致[Ru {lcub} h 5-1,2-C5H3CHOC＆amp; O＆parr0; CF 3SCH2＆cubr0;＆amp; Cp *＆parr0;＆sqbr ;;。 Helmers合成方法的改进用于合成1，3-二甲基-5，6-二氢-4H-环戊[c]噻吩-5-酮。 1,3-二甲基-5,6-二氢-4H-环戊[c]噻吩-5-酮的还原，氯取代和消除导致1,3-二甲基-4H-环戊[c]噻吩。 1,3-二甲基-4H-环戊[c]噻吩很容易用正丁基锂去质子化。尝试用TIOEt进行金属转移会导致通过1,3-二甲基-4H-环戊[c]噻吩的环戊二烯基单元进行氧化偶联。尝试将1,3-二甲基-4H-环戊[c]噻吩锂与钌进行金属转移失败。

著录项

  • 作者

    Wallace, Chad Everett.;

  • 作者单位

    University of Kentucky.;

  • 授予单位 University of Kentucky.;
  • 学科 Chemistry Inorganic.; Chemistry Organic.
  • 学位 Ph.D.
  • 年度 1998
  • 页码 196 p.
  • 总页数 196
  • 原文格式 PDF
  • 正文语种 eng
  • 中图分类 无机化学;有机化学;
  • 关键词

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