Chemistry of N-halo compounds. 30. Regiospecific formation of azoxyaralkanes (diazene N-oxides) from N,N-dibromo compounds and nitrosobenzene

Zawalski, Robert C.; Kovacic, Peter

doi:10.1021/jo01327a019

Cited by 36 publications

(12 citation statements)

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“…The starting compounds for the synthesis of benzo‐1,2,3,4‐tetrazine 1,3‐dioxides (BTDOs) were anilines bearing the tert ‐butyl‐ NNO ‐azoxy group in the ortho ‐position9,10 ( C , Scheme ). The key intermediates in their synthesis were compounds B (X = NO 2 or Hal) obtained by treatment of the appropriate nitrosobenzenes A with N , N ‐dibromo‐ tert ‐butylamine according to the Kovacic method 11. Anilines C were obtained from B by reduction of the nitro group (X = NO 2 ) or by displacement of the halogen with ammonia (X = Hal).…”

Section: Resultsmentioning

confidence: 99%

Benzo-1,2,3,4-tetrazine 1,3-Dioxides: Synthesis and NMR Study

et al. 2002

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Benzo‐1,2,3,4‐tetrazine 1,3‐dioxides (BTDOs) represent fairly stable high‐nitrogen systems, incorporating two head‐to‐tail linked azoxy groups. The synthetic pathway to these heterocycles suggested the use of the tert‐butyl‐NNO‐azoxy group as a building block, allowing the first azoxy group to be incorporated into the ring. The second azoxy group was added with the help of the oxodiazonium ion (−N=N=O+) or its synthetic equivalent. This could be generated by two new methods. The first of these involved treatment of N‐nitroamines with nitrating agents, and the second treatment of diazonium salts with peracids in the presence of a base. The proposed key stage in the tetrazine 1,3‐bis(N‐oxide) ring formation is the reaction between the oxodiazonium ion and the distal nitrogen atom of the tert‐butyl‐NNO‐azoxy group, followed by elimination of the tert‐butyl cation. The syntheses of bromo‐BTDOs 3b−f and nitro‐BTDOs 4a−c are described. The BTDOs were characterized by NMR, including 14N and 15N experiments. (© Wiley‐VCH Verlag GmbH, 69451 Weinheim, Germany, 2002)

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Section: Resultsmentioning

confidence: 99%

Benzo-1,2,3,4-tetrazine 1,3-Dioxides: Synthesis and NMR Study

et al. 2002

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“…The possibilities are that I À coordinates to Br to form [TsN(Br)Br-I] À Na + , facilitating the fission of weaker N À Br bonds; or that I À functions as a reductant to form Ts(Br)NC and Br À . [46] The resulting amidyl radical would react with C 60 to generate fullerene radical C. Because the highest spin density of the monoadduct fullerene radicals is reportedly localized on the carbon adjacent to the [6,6]-junction substituent, [47] it is reasonable that the reaction would proceed from this position. When a considerably bulky and soft halogen substituent, such as iodine, is added to the nitrogen atom, the radical would attack the iodine atom rather than the sterically congested nitrogen atom, giving an N-centered radical with a 1,2 substituent on the fullerene cage (D).…”

Section: Resultsmentioning

confidence: 99%

“…The possibilities are that I − coordinates to Br to form [TsN(Br)Br‐I] − Na + , facilitating the fission of weaker NBr bonds; or that I − functions as a reductant to form Ts(Br)N . and Br − 46. The resulting amidyl radical would react with C 60 to generate fullerene radical C .…”

Section: Resultsmentioning

confidence: 99%

Selective Functionalization of Fullerenes with N,N‐Dihalosulfonamides as an N₁ Unit: Versatile Syntheses of Aza[60]fulleroids and Aziridino[60]fullerenes and their Application to Photovoltaic Cells

Nagamachi

Takeda

Nakayama

et al. 2012

Chemistry A European J

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Highly selective and versatile methods for the synthesis of aza[60]fulleroids and aziridino[60]fullerenes from C(60) have been developed. The reactions utilized N,N-dihalosulfonamides as an N(1) source. The photophysical, electrochemical, and thermal properties of the iminofullerenes were investigated by means of UV/Vis spectroscopy, cyclic voltammetry, and thermogravimetry, respectively. Furthermore, photovoltaic cells based on the synthesized iminofullerenes were fabricated. The power conversion efficiencies (PCEs) of the devices showed moderate values ranging from 1.33 to 2.35 %.

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“…The stability of N,N-dibromamines is variable; tertiary compounds are more stable than secondary (91) (92). N,N-Dichloramines are rapidly converted to N,N-dibromamines by reaction with Br À in acetonitrile (93). N-Chloroalkylamines are useful for the preparation of substituted hydrazines by reaction with excess amine in the presence of base.…”

Section: Aliphatic Compoundsmentioning

confidence: 99%

N‐Halamines

Worley¹,

Wojtowicz²

2004

Kirk-Othmer Encyclopedia of Chemical Technology

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N ‐Halamines are inorganic and organic compounds in which oxidative halogen is chemically bonded to nitrogen. They have both research and commercial importance, particularly in the areas of disinfection of water and stabilization of free halogen. The N ‐halogen bond is formed by reaction of an amine, imine, amide, or imide with halogen, hypohalous acid, or hypochlorite. Only the chloro and bromo derivatives are of commercial importance. The physical and chemical properties, preparation, manufacture, uses, safety and handling, toxicity, and economic aspects of chloramines and bromamines are discussed. The chemistry of chloramines and bromamines is diversified not only because nitrogen and halogen act as reaction sites, but because of the different modes by which these functionalities react. Research activity on synthetic applications of chloramines and bromamines continues to be high. In aqueous solution, the chloramines and bromamines generally undergo hydrolysis to varying degrees forming hypochlorous and hypobromous acids. Thus generally these N ‐halamines can be considered as halogen release agents, and many, eg, chloroisocyanurates, find use in bleaching, disinfecting, and sanitizing applications. Others, such as halogen derivatives of ammonia, are important because they are industrial process intermediates (monochloramine) or of significance in water treatment (mono‐, di‐, and trichloramine). The most recent work has concerned covalent attachment of N ‐halamine moieties to insoluble polymers so as to create biocidal materials with excellent potential for commercial utilization.

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Chemistry of N-halo compounds. 30. Regiospecific formation of azoxyaralkanes (diazene N-oxides) from N,N-dibromo compounds and nitrosobenzene

Cited by 36 publications

References 3 publications

Benzo-1,2,3,4-tetrazine 1,3-Dioxides: Synthesis and NMR Study

Benzo-1,2,3,4-tetrazine 1,3-Dioxides: Synthesis and NMR Study

Selective Functionalization of Fullerenes with N,N‐Dihalosulfonamides as an N₁ Unit: Versatile Syntheses of Aza[60]fulleroids and Aziridino[60]fullerenes and their Application to Photovoltaic Cells

N‐Halamines

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Chemistry of N-halo compounds. 30. Regiospecific formation of azoxyaralkanes (diazene N-oxides) from N,N-dibromo compounds and nitrosobenzene

Cited by 36 publications

References 3 publications

Benzo-1,2,3,4-tetrazine 1,3-Dioxides: Synthesis and NMR Study

Benzo-1,2,3,4-tetrazine 1,3-Dioxides: Synthesis and NMR Study

Selective Functionalization of Fullerenes with N,N‐Dihalosulfonamides as an N1 Unit: Versatile Syntheses of Aza[60]fulleroids and Aziridino[60]fullerenes and their Application to Photovoltaic Cells

N‐Halamines

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Product

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Selective Functionalization of Fullerenes with N,N‐Dihalosulfonamides as an N₁ Unit: Versatile Syntheses of Aza[60]fulleroids and Aziridino[60]fullerenes and their Application to Photovoltaic Cells