Non-methylated Analogue Research Articles

Syntheses and characterizations of adenosine 5′-(α,β- N-methylimido)di and triphosphates and adenosine 5′-(β,γ- N-methylimido)triphosphate—Comparisons with their nonmethylated analogs

N-Methylimidodiphosphate [PN(Me)P] has been synthesized for the first time by hydrolysis of N-methylimidodiphosphoryl tetrachloride. PN(Me)P was coupled with 5′-tosyladenosine to produce adenosine 5′-[α,β- N-methylimido]diphosphate [AMPN(Me)P] which in turn was treated with phosphocreatine in the creatine kinase reaction to generate adenosine 5′-[α,β- N-methylimido]triphosphate [AMPN(Me)PP]. Using the Michelson synthesis, PN(Me)P was coupled with adenosine 5′-monophosphate to produce adenylyl N-methylimidophosphate [AMP · PN(Me)P]. All three new purine nucleotide analogs were characterized by mass spectrometry and 31P NMR spectroscopy. Their enzyme kinetic parameters ( V max and K m values) were measured in the creatine kinase reaction and directly compared to similar kinetic parameters obtained for the corresponding nonmethylated analogs and ADP and ATP. AMPN(Me)P was shown to have a V max value ca. 40% of that of ADP although its K m value is ca. 100 times greater than that for ADP. AMPN(Me)PP was also a substrate, whereas AMP · PN(Me)P showed no detectable inhibitory properties.

Crystal structure of (η 5-pentamethylcyclopentadienyl) (O,O′-diisopropyldithiophosphato) (dicarbonyl)-iron(II), FeS2PO4C18H29

Abstract Mr = 460.36, monoclinic. P21/c, a = 13.718(1), b = 11.090(1), c = 14.985(1) Å, β = 98.162(2)°, V = 2256.67(9) Å3, Z = 4, Dx = 1.355 Mgm−3, μ = 0.933 mm−1, F(000) = 968, room temperature, final R = 0.047 (Rw = 0.048) for 3184 [I ⩾ 3 σ(I)] observed reflections. The title compound has the “three-legged piano stool” geometry, i.e. the coordination geometry of the iron can be regarded as a distorted octahedron with aη 5 – C5Me5 group occupying three coordination sites. Like its nonmethylated analogue it contains an unusually monodentate dithiophosphate ester ligand.

Synthesis, structure, and spectroscopic properties of copper(II) compounds containing nitrogen–sulphur donor ligands; the crystal and molecular structure of aqua[1,7-bis(N-methylbenzimidazol-2′-yl)-2,6-dithiaheptane]copper(II) perchlorate

The linear quadridentate N2S2 donor ligand 1,7-bis(N-methylbenzimidazol-2′-yl)-2,6-dithiaheptane (bmdhp) forms mono- and di-hydrate 1 : 1 copper(II) complexes which are significantly more stable toward autoreduction than those of the non-methylated analogue. The deep green monohydrate of the perchlorate salt crystallises as the mononuclear aqua-complex, [Cu(bmdhp)(OH2)][ClO4]2, in the monoclinic space group P21/n, with Z= 4, a= 18.459(3), b= 10.362(2), c= 16.365(3)A, and β= 117.14(1)°. The structure was solved and refined by standard Patterson, Fourier, and least-squares techniques to R= 0.047 and R′= 0.075 for 3 343 independent reflections with l > 2σ(l). The compound consists of [Cu(bmdhp)(OH2)]2+ ions and ClO4– counter ions. The co-ordination around copper is intermediate between trigonal bipyramidal and square pyramidal, with Cu–N distances of 1.950(4) and 1.997(4)A, Cu–O(water) 2.225(4)A, and Cu–S 2.328(1) and 2.337(1)A. In the solid state, the perchlorate dihydrate's co-ordination sphere may be a topoisomer of the monohydrate's. A new angular structural parameter, τ, is defined and proposed as an index of trigonality, as a general descriptor of five-co-ordinate centric molecules. By this criterion, the irregular co-ordination geometry of [Cu(bmdhp)(OH2)]2+ in the solid state is described as being 48% along the pathway of distortion from square pyramidal toward trigonal bipyramidal. In the electronic spectrum of the complex, assignment is made of the S(thioether)→ Cu charge-transfer bands by comparison with those of the colourless complex Zn(bmdhp)(OH)(ClO4). E.s.r. and ligand-field spectra show that the copper(II) compounds adopt a tetragonal structure in donor solvents.

ChemInform Abstract: CRYSTAL AND MOLECULAR STRUCTURE OF BIS(DICARBONYL(Π‐PENTAMETHYLCYCLOPENTADIENYL)IRON), (η5‐C5ME5)2FE2(CO)4, AND STRUCTURAL COMPARISONS WITH THE NONMETHYLATED ANALOG

Chemischer InformationsdienstVolume 11, Issue 48 Physical Organic Chemistry ChemInform Abstract: CRYSTAL AND MOLECULAR STRUCTURE OF BIS(DICARBONYL(Π-PENTAMETHYLCYCLOPENTADIENYL)IRON), (η5-C5ME5)2FE2(CO)4, AND STRUCTURAL COMPARISONS WITH THE NONMETHYLATED ANALOG R. G. TELLER, R. G. TELLERSearch for more papers by this authorJ. M. WILLIAMS, J. M. WILLIAMSSearch for more papers by this author R. G. TELLER, R. G. TELLERSearch for more papers by this authorJ. M. WILLIAMS, J. M. WILLIAMSSearch for more papers by this author First published: December 2, 1980 https://doi.org/10.1002/chin.198048082AboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinkedInRedditWechat No abstract is available for this article. Volume11, Issue48December 2, 1980 RelatedInformation

Crystal and molecular structure of bis[dicarbonyl(.pi.-pentamethylcyclopentadienyl)iron], (.eta.5-C5Me5)2Fe2(CO)4, and structural comparisons with the nonmethylated analog

The molecular structure of (eta/sup 5/-C/sub 5/Me/sub 5/)/sub 2/Fe/sub 2/(CO)/sub 4/ has been determined via x-ray diffraction. The dimer has a monoclinic unit cell of space group P2/sub 1//n with a = 8.372 (4) A, b = 9.864 (5) A, c = 13.872 (5) A, ..beta.. = 93.13 (1)/sup 0/, V = 1144 (1) A/sup 3/, d/sub calcd/ = 1.43 g/cm/sup 3/, d/sub obsd/ = 1.46 g/cm/sup 3/, and Z = 2. The molecule contains two terminal and two bridging carbonyl ligands with a normal Fe-Fe single bond separation of 2.560 (1) A. The most unusual finding in this study is that, unlike the case for the unsubstituted analogue (eta/sup 5/-C/sub 5/H/sub 5/)/sub 2/Fe/sub 2/(CO)/sub 4/, no significant variations in the cyclopentadienyl ligand C-C bond lengths are observed. This result may bear directly on the catalytic activity, or lack of it, observed in certain permethylated-cyclopentadienyl complexes.

OESTROGENIC, ANTI‐OESTROGENIC AND FERTILITY EFFECTS OF SOME TRIPHENYLETHANES AND TRIPHENYLETHYLENES RELATED TO ETHAMOXYTRIPHETOL (MER 25)

Five triphenylethylenes, a triphenylethane and a triphenylethanol, carrying methyl substituents ortho to one or both of the ring oxygen functions, have been examined for oestrogenic, and antioestrogenic activity in mice, and three of the compounds, alpha-[4-(beta-diethylaminoethoxy)-3, 5-xylyl]-alpha-phenyl-beta-4-methoxyphenyl-ethanol (IV), alpha'-[4-(beta-diethylaminoethoxy)-3, 5-xylyl]-4-methoxy-bibenzyl (V) and alpha'-[4-(beta-diethylaminoethoxy)-3, 5-xylyl]-4-methoxy-stilbene (VI), were tested for their effects on fertility in mice. 2 Orthomethylation reduces oestrogenic and/or anti-oestrogenic activity compared with the reported activities of non-methylated analogues. 3 The anti-oestrogenic ethamoxytriphetol (MER 25) reduced fertility in mice whereas its inactive dimethylated analogue (IV) was ineffective. The weakly active anti-oestrogens, V and VI, did not affect fertility in mice.