2,3,4,5,6-pentafluorobenzylhydrazine | 163432-96-0

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 2,3,4,5,6-pentafluorobenzylhydrazine
• 英文别名: pentafluorobenzylhydrazine；[(2,3,4,5,6-Pentafluorophenyl)methyl]hydrazine；(2,3,4,5,6-pentafluorophenyl)methylhydrazine
• CAS: 163432-96-0
• 化学式: C₇H₅F₅N₂
• 分子量: 212.122
• InChiKey: KLYFKJKPUDOTND-UHFFFAOYSA-N

物化性质

• 沸点：
  240.2±40.0 °C(Predicted)
• 密度：
  1.522±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1
• 重原子数：
  14
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.14
• 拓扑面积：
  38
• 氢给体数：
  2
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  2,3,4,5,6-pentafluorobenzylhydrazine 在 亚硝酸丁酯 、 sodium ethanolate 作用下， 以 乙醚 、 乙醇 为溶剂， 反应 16.0h， 生成 sodium (E)-(pentafluorophenyl)methanediazoate
  参考文献：
  名称：

  Mechanisms of Benzyl Group Transfer in the Decay of (E)-Arylmethanediazoates and Aryldiazomethanes in Aqueous Solutions

  摘要：

  Rate constants are reported for the buffer-independent decay of ten (E)-arylmethanediazontes in aqueous media at 25 degrees C, ionic strength 1 M (NaClO4), 4% 2-propanol, in the region of pH 4-12. The rate constants are proportional to hydrogen ion concentration at high pH and become pH independent in the low-pH region. Varying concentrations of oxyanion, amine, and hydrazine buffers over the range 0.05-0.2 M increased the pseudo-first-order rate constant for decay of the diazoates by less than 10%. The azide-water selectivities, k(2)/k(5), for partitioning of the benzyl groups in the decay of (E)-(3,5-bis(trifluoromethyl)phenyl)methanediazonate and the (3,5-bis(trifluoromethyl)phenyl)diazomethane are determined to be 0.20 and 0.21 M(-1), respectively, in phosphate buffered water and 0.27 and 0.26 M(-1), respectively, in 20/80 DMSO-water. It is concluded that these two reactants decompose, in these media, via a common free diazonium ion intermediate that is formed in the case of the diazoate upon unassisted N-O bond cleavage of the diazoic acid. A common rate-limiting step is indicated for all the diazoates by the correlation line for the plot of log k(1), the pH independent rate constant, against sigma that has a slope rho = -1.23. Product ratios for trapping of benzyl groups derived from other pairs of arylmethanediazoates and aryldiazomethanes with less electron withdrawing groups are different outside experimental error, indicating the importance of different nitrogen-separated ion pairs in these reactions. The (E)-(p-methoxy)phenyl)methane-(16)-diazoat decomposes in O-16/O-18 water to give alcohol that has an ''excess'' abundance of O-16 compared to solvent, Decomposition of the same compound in 50/50 trifluoroethanol-water with varying concentrations of azide indicates that azide ion appears to trap a limiting amount, similar to 80%, of the p-methoxybenzyl group. Quantitative analysis of the data indicates that 16% of the p-methoxybenzyl cation is trapped by solvent at the nitrogen-separated ion pair stage, in the absence of azide ion, There is a 9-fold enhancement of selectivity for trifluoroethanol at the ion pair stage that is ascribed to a proton switch initiated by the leaving hydroxide ion in the ion pair. The values of k(2)/k(5) similar to 0.2 M(-1) and k(T)/k(H) similar to 0.5-0.6 for the trifluoroethanol-water selectivity and k(ET)/k(T) similar to 1 for the ethanol-trifluoroethanol selectivity are independent of substituent in the decay of arylmethanediazoates (X = H and EWG) in water, water-trifluoroethanol (50/50), and water-trifluoroethanol-ethanol (50/40/10), respectively. It is concluded from this that the product-determining steps do not involve chemical bonding but rather rotational/translational reorientation of the nucleophiles in the first solvation sphere of the carbocation intermediates. It is concluded that the values of k(H)/k(T) = 0.5-0.6 indicate preferential solvation of the cation precursor by trifluoroethanol. It is shown that a preferential interaction for trifluoroethanol of <1 kcal/mol is required to generate the observed selectivities.

  DOI：

  10.1021/ja00120a004
• 作为产物：
  描述：

  2,3,4,5,6-五氟苄基氯 在 肼 作用下， 以 甲醇 为溶剂， 反应 2.0h， 以70%的产率得到2,3,4,5,6-pentafluorobenzylhydrazine
  参考文献：
  名称：

  Reaction of Malondialdehyde−DNA Adducts with HydrazinesDevelopment of a Facile Assay for Quantification of Malondialdehyde Equivalents in DNA

  摘要：

  Malondialdehyde is a ubiquitous product of lipid peroxidation that reacts with DNA to form premutagenic lesions. Principal among them is pyrimido-[1,2-alpha]purin-10(3H)-one (M(1)G). M(1)G has recently been found to be a reactive electrophile in DNA that couples with amines at basic pH or hydroxylamines at neutral pH. We explored the reaction of M(1)G with hydrazines because of the possibility that the latter could act as bifunctional nucleophiles to strip the malondialdehyde equivalent from DNA. Pentafluorophenylhydrazine reacted rapidly with M(1)G to form a hydrazone conjugate. This hydrazone was stable at room temperature and did not cyclize to form the corresponding pyrazole. In contrast, phenylhydrazine and benzylhydrazine reacted with M(1)G to form phenylpyrazole and benzylpyrazole, respectively. Pentafluorobenzylhydrazine reacted rapidly with M(1)G to form pentafluorobenzylpyrazole and dG in near quantitative yield. This reaction formed the basis for a quantitative assay for the presence of M(1)G or M(1)G equivalents in DNA or protein that utilized gas chromatography/negative chemical ionization mass spectrometry. The assay was extended to the oxopropenyl donors, M(1)A, base propenal, and N-epsilon-3-oxopropenyl-lysine. Analysis of DNA treated with bleomycin demonstrated a linear increase in the level of oxopropenyl groups that plateaued at approximately 1 oxopropenyl group/100 bases at a bleomycin concentration of 200 muM. Parallel analysis of M(1)G in the samples revealed that this adduct represents a small fraction of the total oxopropenyl units generated in DNA by treatment with bleomycin.

  DOI：

  10.1021/tx010105v

文献信息

• Microwave‐Assisted Synthesis and Antiprotozoal Activity of Pyridazines Carrying Polyfluoro Substituents
  作者：J. Kaminski、Rosa Moo‐Puc、R. Cedillo‐Rivera、Z. Kazimierczuk

  DOI：10.1080/00397910600764758

  日期：2006.9

  A number of 4,5-dichloro- and 4,5-dibromopyridazin-3-ones and - 3,6-diones with polyfluoro substituents at position 2 were obtained in good yields by microwave-assisted method. The oxopyridazines as well as their respective 5-dimethylaminoethylamino derivatives were tested for antibacterial, antiviral, and antiprotozoal activity.
• PYRIDAZINO QUINOLINE COMPOUNDS
  申请人：ZENECA LIMITED

  公开号：EP0724583A1

  公开（公告）日：1996-08-07
• PYRIDAZINOQUINOLINE COMPOUNDS
  申请人：ZENECA LIMITED

  公开号：EP0790996A1

  公开（公告）日：1997-08-27
• [EN] PYRIDAZINO QUINOLINE COMPOUNDS<br/>[FR] COMPOSES DE PYRIDAZINO QUINOLEINE
  申请人：——

  公开号：WO1995011244A1

  公开（公告）日：1995-04-27

  [EN] The present invention relates to compounds, pharmaceutical compositions and methods of using compounds of formula (I) in the treatment and/or prevention of certain diseases or conditions. In formula (I), A is chosen from ortho substituted aryl or heteroaryl species, X is chosen from -OH, -SH, NHR and R<1> or R<2> is chosen from -(CH2)nL wherein L may be selected from a variety of substituents including aryl, heteroaryl and heterocyclic groups. The compounds are useful in treating and/or preventing neurological disorders associated with excitatory amino acids.
  [FR] L'invention concerne des composés, des compositions pharmaceutiques et des procédés d'utilisation des composés représentés par la formule (I), dans le traitement et/ou la prévention de certaines maladies ou de certains états pathologiques. Dans la formule (I), A est sélectionné à partir d'espèces aryle ou hétéroaryle orthosubstituées, X est sélectionné à partir de -OH, -sh, NHR et R<1> ou R<2> est sélectionné à partir de -(CH2)nL où L peut être sélectionné à partir d'une variété de substituants, y compris des groupes aryle, hétéroaryle et hétérocycliques. Ces composés sont efficaces dans le traitement et/ou la prévention de troubles neurologiques associés à des acides aminés excitateurs.
• Mechanisms of Benzyl Group Transfer in the Decay of (E)-Arylmethanediazoates and Aryldiazomethanes in Aqueous Solutions
  作者：Jari I. Finneman、James C. Fishbein

  DOI：10.1021/ja00120a004

  日期：1995.4

  Rate constants are reported for the buffer-independent decay of ten (E)-arylmethanediazontes in aqueous media at 25 degrees C, ionic strength 1 M (NaClO4), 4% 2-propanol, in the region of pH 4-12. The rate constants are proportional to hydrogen ion concentration at high pH and become pH independent in the low-pH region. Varying concentrations of oxyanion, amine, and hydrazine buffers over the range 0.05-0.2 M increased the pseudo-first-order rate constant for decay of the diazoates by less than 10%. The azide-water selectivities, k(2)/k(5), for partitioning of the benzyl groups in the decay of (E)-(3,5-bis(trifluoromethyl)phenyl)methanediazonate and the (3,5-bis(trifluoromethyl)phenyl)diazomethane are determined to be 0.20 and 0.21 M(-1), respectively, in phosphate buffered water and 0.27 and 0.26 M(-1), respectively, in 20/80 DMSO-water. It is concluded that these two reactants decompose, in these media, via a common free diazonium ion intermediate that is formed in the case of the diazoate upon unassisted N-O bond cleavage of the diazoic acid. A common rate-limiting step is indicated for all the diazoates by the correlation line for the plot of log k(1), the pH independent rate constant, against sigma that has a slope rho = -1.23. Product ratios for trapping of benzyl groups derived from other pairs of arylmethanediazoates and aryldiazomethanes with less electron withdrawing groups are different outside experimental error, indicating the importance of different nitrogen-separated ion pairs in these reactions. The (E)-(p-methoxy)phenyl)methane-(16)-diazoat decomposes in O-16/O-18 water to give alcohol that has an ''excess'' abundance of O-16 compared to solvent, Decomposition of the same compound in 50/50 trifluoroethanol-water with varying concentrations of azide indicates that azide ion appears to trap a limiting amount, similar to 80%, of the p-methoxybenzyl group. Quantitative analysis of the data indicates that 16% of the p-methoxybenzyl cation is trapped by solvent at the nitrogen-separated ion pair stage, in the absence of azide ion, There is a 9-fold enhancement of selectivity for trifluoroethanol at the ion pair stage that is ascribed to a proton switch initiated by the leaving hydroxide ion in the ion pair. The values of k(2)/k(5) similar to 0.2 M(-1) and k(T)/k(H) similar to 0.5-0.6 for the trifluoroethanol-water selectivity and k(ET)/k(T) similar to 1 for the ethanol-trifluoroethanol selectivity are independent of substituent in the decay of arylmethanediazoates (X = H and EWG) in water, water-trifluoroethanol (50/50), and water-trifluoroethanol-ethanol (50/40/10), respectively. It is concluded from this that the product-determining steps do not involve chemical bonding but rather rotational/translational reorientation of the nucleophiles in the first solvation sphere of the carbocation intermediates. It is concluded that the values of k(H)/k(T) = 0.5-0.6 indicate preferential solvation of the cation precursor by trifluoroethanol. It is shown that a preferential interaction for trifluoroethanol of <1 kcal/mol is required to generate the observed selectivities.