- The standard enthalpy of formation of silver pivalate
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The standard enthalpy of combustion of crystalline silver pivalate, (CH3)3CC(O)OAg (AgPiv), was determined in an isoperibolic calorimeter with a self-sealing steel bomb, Δc H 0 (AgPiv, cr)= -2786.9±5.6 kJ mol-1. The value of standard enthalpy of formation was derived for crystalline state: Δf H 0(AgPiv,cr)= -466.9±5.6 kJ mol-1. Using the enthalpy of sublimation, measured earlier, the enthalpy of formation of gaseous dimer was obtained: Δf H 0(Ag2Piv 2,g)= -787±14 kJ mol-1. The enthalpy of reaction (CH3)3CC(O)OAg(cr)=Ag(cr)+(CH3) 3CC(O)O.(g) was estimated, Δr H 0=202 kJ mol-1.
- Lukyanova,Papina,Didenko,Alikhanyan
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Read Online
- MANUFACTURING METHOD OF BIPYRIDYL COMPOUND
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PROBLEM TO BE SOLVED: To provide various bipyridyl compounds by a reaction less in process number with a relief condition and short time. SOLUTION: A compound represented by the general formula, where Y represents a hydrogen atom or a nitrogen atom, R1 represents a cyano group, a halogen atom, an alkyl group which may be substituted, an alkoxy group which may be substituted, an aryl group which may be substituted, a heteroaryl group which may be substituted or a silyl group which may be substituted, n represents an integer of 0 to 4 and 2 R1 binding same benzene ring may bind each other to form a ring when n is 2 or more. SELECTED DRAWING: None COPYRIGHT: (C)2017,JPOandINPIT
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Paragraph 0080
(2017/09/16)
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- Palladium-Catalyzed, Site-Selective Direct Allylation of Aryl C-H Bonds by Silver-Mediated C-H Activation: A Synthetic and Mechanistic Investigation
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We describe a method for the site-selective construction of a C(aryl)-C(sp3) bond by the palladium-catalyzed direct allylation of arenes with allylic pivalates in the presence of AgOPiv to afford the linear (E)-allylated arene with excellent regioselectivity; this reaction occurs with arenes that have not undergone site-selective and stereoselective direct allylation previously, such as monofluorobenzenes and non-fluorinated arenes. Mechanistic studies indicate that AgOPiv ligated by a phosphine reacts with the arene to form an arylsilver(I) species, presumably through a concerted metalation-deprotonation pathway. The activated aryl moiety is then transferred to an allylpalladium(II) intermediate formed by oxidative addition of the allylic pivalate to the Pd(0) complex. Subsequent reductive elimination furnishes the allyl-aryl coupled product. The aforementioned proposed intermediates, including an arylsilver complex, have been isolated, structurally characterized, and determined to be chemically and kinetically competent to undergo the proposed elementary steps of the catalytic cycle.
- Lee, Sarah Yunmi,Hartwig, John F.
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supporting information
p. 15278 - 15284
(2016/12/06)
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- Ligand-promoted alkylation of C(sp3)-H and C(sp2)-H bonds
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9-Methylacridine was identified as a generally effective ligand to promote a Pd(II)-catalyzed C(sp3) - H and C(sp2) - H alkylation of simple amides with various alkyl iodides. This alkylation reaction was applied to the preparation of unnatural amino acids and geometrically controlled tri- and tetrasubstituted acrylic acids.
- Zhu, Ru-Yi,He, Jian,Wang, Xiao-Chen,Yu, Jin-Quan
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supporting information
p. 13194 - 13197
(2015/03/30)
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- Redox-controlled selectivity of C-H activation in the oxidative cross-coupling of arenes
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Gold brings us together: Taking advantage of the orthogonal reactivities of AuI and AuIII towards C-H activation of electron-poor and electron-rich arenes, respectively, a novel approach for the synthesis of biaryls through double C-H activation is proposed. Stoichiometric studies demonstrate that these oxidative couplings occur with high selectivity at low temperature. Copyright
- Cambeiro, Xacobe C.,Boorman, Tanya C.,Lu, Pengfei,Larrosa, Igor
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supporting information
p. 1781 - 1784
(2013/04/10)
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- Dinuclear palladium(II) compounds with bridging cyclometalated phosphines. Synthesis, crystal structure and electrochemical study
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The structural characterization of bis-cyclometalated palladium(ii) compounds of formula Pd2[(-(C6X4)PPh 2]2(-O2CR)2 [X = H, R = CH 3 (3), CF3 (4), C(CH3)3 (5) and C6F5 (6); X = F, R = CH3 (7) and CF 3(8)], has confirmed its paddle wheel structure with two palladium atoms bridged by two acetates and two metalated phosphines in a head-to-tail arrangement. The Pd...Pd distances are in the range 2.6779(16)-2.7229(8) A. Under cyclic voltammetric conditions, compounds 3-6, in CH 2Cl2 solution, were found to undergo a reversible oxidation peak in the range of potential values 0.84-1.25 V. A second partially-reversible oxidation is observed at more positive potentials (1.37-1.55 V). For compounds 3-5 in the presence of chlorides, the first oxidation becomes a two-electron process presumably leading to a neutral [Pd(iii)-Pd(iii)] species with a metal-metal bond. The Royal Society of Chemistry 2006.
- Koshevoy, Igor O.,Lahuerta, Pascual,Sanau, Mercedes,Ubeda, M. Angeles,Domenech, Antonio
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p. 5536 - 5541
(2007/10/03)
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- Prodrugs of GABA analogs, compositions and uses thereof
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The present invention provides prodrugs of GABA analogs, pharmaceutical compositions of prodrugs of GABA analogs and methods for making prodrugs of GABA analogs. The present invention also provides methods for using prodrugs of GABA analogs and methods for using pharmaceutical compositions of prodrugs of GABA analogs for treating or preventing common diseases and/or disorders.
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Page/Page column 36
(2010/11/24)
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- Prodrugs of GABA analogs, compositions and uses thereof
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The present invention provides prodrugs of GABA analogs, pharmaceutical compositions of prodrugs of GABA analogs and methods for making prodrugs of GABA analogs. The present invention also provides methods for using prodrugs of GABA analogs and methods for using pharmaceutical compositions of prodrugs of GABA analogs for treating or preventing common diseases and/or disorders.
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- Palladium nitrosyl carboxylate complexes X-ray structures of Pd 4(μ-NO)2(μ-OCOCMe3)6
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Two types of palladium nitrosyl carboxylate complexes were synthesized and their structures were characterized by several methods including an X-ray diffraction analysis. The tetranuclear complexes Pd4(μ-NO) 2(OCOR)6 (R=CMe3, Me, Ph, CHMe2, CH2Cl, IIa-e, respectively) were synthesized by the reaction of Pd(NO)Cl with silver carboxylates Ag(OCOR). The structure of IIa was determined by a single crystal X-ray diffractometry. Crystals of IIa are monoclinic, space group P21/n, a=12.104(7), b=23.970(8), c=15.495(4) A?, β=90.30(4)°, V=4496(4) A?3. The least-square structure refinement on F2 was converged to R=0.0714 for 6228 reflections [I>2σ(I)]. In IIa the palladium atoms form near regular rectangle Pd4, with the edges bridged by the ligands. Two bridging NO groups occupying the opposite sides of the rectangle are in the cis-positions with respect to the Pd4 plane. These groups are symmetric, with the Pd-N-O angles ranging from 120.4(5) to 121.8(5)°. The coordination polyhedrons of the Pd atoms are close to square planar ones. The reaction of the Pd4(CO)4(OCOCF3)4 clusters with nitrogen monoxide leads to a substitution of the carbonyl groups and formation of the low stable complex Pd4(NO)4(OCOCF3) 4 (III) that was characterized by the spectroscopic and analytical data. The transformation of III during slow recrystallization from toluene gives Pd3(NO)2(OCOCF3) 4·2C6H5Me (IV) and palladium black. The structure of IV was determined by an X-ray diffraction analysis. Crystals of IV are monoclinic, space group P21/n, a=9.2340(2), b=9.2859(2), c=18.0460(4) A?, β=92.339(1)°, V=1546.08(6) A?3. The least-square refinement on F2 was converged to R=0.0205 for 3209 reflections [I>2σ(I)]. In the linear tri-nuclear molecule of IV, any adjacent metal atoms are linked with a couple of the CF3CO 2 ligands and are separated by 3.0755(2) A?. Additionally, the terminal Pd atoms bear the NO and the η2-toluene ligands. The configuration of the N atoms corresponds to the ideal sp2- hybridization. The Pd-N-O angle is 117.2(2)°. The N atoms form short contacts with the aromatic rings. The distance between the center of the ring and the nitrogen atom is 2.70 A?. Complex IV is the first example of the Pd complex with the terminal nitrosyl ligand. The scheme of transformation of complex III to complex IV was proposed.
- Stromnova, Tatiana A.,Paschenko, Denis V.,Boganova, Lyubov' I.,Daineko, Mikhail V.,Katser, Sergei B.,Churakov, Andrei V.,Kuz'mina, Lyudmila G.,Howard, Judith A.K.
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p. 283 - 288
(2008/10/08)
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- Administrative agents via the SMVT transporter
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Disclosed herein are conjugates comprising a therapeutic agent (e.g., a drug) which is linked to a conjugate moiety that is itself, or itself in combination with the agent, is a good substrate for the sodium dependent multi-vitamin transporter (SMVT). The
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- Aerosol-assisted chemical vapour deposition (AACVD) of silver films from triorganophosphine adducts of silver carboxylates, including the structure of [Ag(O2CC3F7)(PPh3)2]
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Silver carboxylates [Ag(O2CR): R = Me, tBu, 2,4,6-Me3C6H2], fluorocarboxlyates [Ag(O2CRf): rf = c3f7, C6F13, C7F15] and their phosphine adducts [Ag(O2CR)·nPR3′: r = me, tBu, 2,4,6-Me3C6H2, R′ = Me, Ph, n = 2; R = Me, R′ = Me, n = 3; Ag(O2CRf).2PPh3, Rf = C3F7, C6F13, C7F15] have been synthesised, characterised spectroscopically and used as precursors in the aerosol-assisted chemical vapour deposition of silver films. All the phosphine adducts produced films, though in general PMe3 adducts, proved more successful than PPh3 analogues. The fluoro-carboxylates and their PPh3 adducts all generated silver films, though the growth rate for the adducts was lower. All these latter films showed carbon impurities while fluorine was also evident in most cases. The X-ray structure of AgO2CC3F7·2PPh3 is also reported.
- Edwards, Dennis A,Harker, Robert M,Mahon, Mary F,Molloy, Kieran C
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p. 134 - 146
(2008/10/08)
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