Formation of N-coordinated 4H-benzo[d][1,3]oxazine from 2-(trimethylsiloxymethyl)- and 2-(hydroxymethyl)-phenyl isocyanides promoted by dirhodium(II) acetate

Marino Basato; Andrea Biffis; Gianluca Martinati

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Formation of N-coordinated 4H-benzo[d][1,3]oxazine from 2-(trimethylsiloxymethyl)- and 2-(hydroxymethyl)-phenyl isocyanides promoted by dirhodium(II) acetate

机译：由乙酸（II）促进的2-（三甲基甲硅烷氧基甲基）-和2-（羟甲基）-苯基异氰酸酯形成N-配位的4H-苯并[d] [1,3]恶嗪

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The neutral dirhodium(II) acetate [Rh2(OAc)4] and the related cationic complex [Rh2(OAc)2(MeCN)6](BF4)2 react with 2-(trimethyl-siloxymethyl)phenyl isocyanide (I) and/or 2-(hydroxymethyl)phenyl isocyanide (II) to give the corresponding adducts,in which the entering isocyanide occupies the axial position at the two rhodium centres.These complexes are stable in toluene,but they evolve in chloroform as a consequence of an intramolecular ligand rearrangement via oxygen attack to the coordinated carbon atom.With the neutral dirhodium acetate species the cyclization reaction affords the well characterized benzoxazine complex [Rh2(OAc)4(NC6H4-2-CH2OC(H))2] (4),whereas the cationic acetonitrile derivative rapidly evolves into a complex mixture.

机译：中性乙酸乙二铵（II）[Rh2（OAc）4]和相关的阳离子络合物[Rh2（OAc）2（MeCN）6]（BF4）2与2-（三甲基-甲硅烷氧基甲基）苯基异氰酸酯（I）和/或2-（羟甲基）苯基异氰酸酯（II）生成相应的加合物，其中进入的异氰酸酯在两个铑中心处占据轴向位置。这些配合物在甲苯中稳定，但由于分子内作用而在氯仿中生成配体通过氧攻击重排到配位的碳原子上。利用中性乙酸乙二胺酯，环化反应可提供特征明确的苯并恶嗪配合物[Rh2（OAc）4（NC6H4-2-CH2OC（H））2]（4），阳离子乙腈衍生物迅速演变成复杂的混合物。

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《Inorganic Chemistry Communications》 |2007年第4期|共3页
作者
Marino Basato; Andrea Biffis; Gianluca Martinati;
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正文语种 eng
中图分类无机化学;
关键词
Rhodium(II); Functionalized isocyanides; Benzod1; 3oxazine complex;

机译：铑（II）;功能化异氰化物;苯并[d] [1;3]恶嗪配合物;

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1. Formation of N-coordinated 4H-benzo[d][1,3]oxazine from 2-(trimethylsiloxymethyl)- and 2-(hydroxymethyl)-phenyl isocyanides promoted by dirhodium(II) acetate [J] . Marino Basato, Andrea Biffis, Gianluca Martinati Inorganic Chemistry Communications . 2007,第4期

机译：由乙酸（II）促进的2-（三甲基甲硅烷氧基甲基）-和2-（羟甲基）-苯基异氰酸酯形成N-配位的4H-苯并[d] [1,3]恶嗪
2. Ferrocene Compounds. XXVIII. Synthesis of 2-(Ferrocenylalkyl)- and 2-[Ferrocenyl(phenyl)alkyl]-1,3-propanediols and Their Acetates [J] . Lapi? Jasmina, Rapi? Vladimir Croatica chemica acta . 2000,第3期

机译：二茂铁化合物。二十八。 2-（二茂铁基烷基）-和2- [二茂铁基（苯基）烷基] -1,3-丙二醇及其乙酸酯的合成
3. tert-Butyl 2-(6-{2-[2-(4-fluorophenyl)-5-isopropyl-3-phenyl-4-(phenylcarbamoyl)pyrrol-1-yl]ethyl}-2,2-dimethyl-1,3-dioxan-4-yl)acetate [J] . Wu Y.-M. Acta Crystallographica Section E: Crystallographic Communications . 2013,第11期

机译：叔丁基2-（6- {2- [2-（4-氟苯基）-5-异丙基-3-苯基-4-（苯基氨基甲酰基）吡咯-1-基]乙基} -2,2-二甲基-1， 3-二恶烷-4-基）乙酸酯
4. THE NEW REARRANGEMENT OF N-ACYLATED 2- HYDROXYMETHYL-2-AMINO ACIDS TO 4,5- DIHYDRO-1,3-OXAZOLE-4-CARBOXYLIC ACIDS [C] . Janina E. Kaminska, Sebastian Olczyk, Beata Kolesinska the European Peptide Symposium . 2007

机译：N-酰化的2-羟甲基-2-氨基酸的新重排至4,5-二氢-1,3-氧唑-4-羧酸
5. Solid state chemistry: Part I. Mechanistic studies on the decomposition of didecanoyl peroxide. Part II. Possible insights into mechanisms of crystal growth through the crystalline packing of 2-(hydroxymethyl)-2-methyl-1,3-propanediol [D] . Carter, Randall Lee 1993

机译：固态化学：第一部分。过氧化双癸酰分解的机理研究。第二部分通过2-（羟甲基）-2-甲基-1,3-丙二醇的晶体堆积对晶体生长机理的可能见解
6. Bis{μ-1,3-bis[2-(5-bromo-2-oxidobenzylideneamino)ethyl]-2-(5-bromo-2-oxidophenyl)-1,3-imidazolidine}dineodymium(III) N,N-dimethylformamide hexasolvate [O] . Qing-Fan Xie, Miao-Ling Huang, Yan-Min Chen 2016

机译：双{μ-1,3-双[2-（5-溴-2-氧化苄叉亚氨基）乙基] -2-（5-溴-2-氧化苯基）-1,3-咪唑烷}钕（III）N，N-二甲基甲酰胺六溶剂化物
7. (Z)-4-(Carbomethoxymethylene)-2-(4-fluorophenyl)-4H-benzo[d][1,3]oxazine [O] . Francesco Pancrazzi, Elena Motti, Mirco Costa, 2017

机译：（Z）-4-（Carbomethoxymethylene）-2-（4-氟苯基）-4H-苯并[d] [1,3]恶嗪
8. Initial Submission: Toxicity Study of 2-(hydroxymethyl)-2-nitro-1,3-propanediol with Cover Letter dated 09/10/92. [R] . 1992

机译：初始提交：2-（羟甲基）-2-硝基-1,3-丙二醇的毒性研究，封面信函日期为09/10/92。

Formation of N-coordinated 4H-benzo[d][1,3]oxazine from 2-(trimethylsiloxymethyl)- and 2-(hydroxymethyl)-phenyl isocyanides promoted by dirhodium(II) acetate

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