Xi:Irritant;
591-50-4Relevant articles and documents
Microwave synthesis of charge-compensated dodecaborates bearing exohedral boron-phosphorus connectivities
Dopke, Joel A.,Lincoln, Zachary S.,Blazejewski, Jacob,Staples, Richard J.,Lee, Mark E.
, p. 263 - 267 (2018)
Solution pyrolysis of arylphosphonium salts of B12H122?,1, utilizing microwave heating provided charge-compensated monophosphine dodecaborate derivatives of general formula B12H11(PPhnR3-n)? (n = 1, R = Me; n = 2, R = Me, Et) in high yield. The resulting anions B12H11(PPh2Me)? (2), B12H11(PPhMe2)? (3), and B12H11(PPh2Et)? (4) were characterized by 11B, 1H, 13C, and 31P NMR spectroscopy, and by negative mode ESI-TOF mass spectrometry. A single-crystal X-ray diffraction study of [Ph3PMe]2 confirmed an icosahedral boron cluster fragment appended by a PPh2Me moiety through a P-B bond.
GENERATION, TRAPPING AND FATE OF ALKYLIDENECARBENE-IODONIUM YLIDES FROM THE ADDITION OF NaN3 TO ALKYNYLPHENYLIODONIUM TOSYLATES
Kitamura, Tsugio,Stang, Peter J.
, p. 1887 - 1890 (1988)
Addition of NaN3 to RCCIPh(1+)*OTs(1-) results in novel alkylidenecarbene-iodonium ylides, 5, R(N3)C=C=IPh, that by either protonation, ylide transfer or insertion of the derived carbene R(N3)C=C: give unique functionalized vinyl azides.
Gold-catalyzed synthesis of iodofulvenes
Noesel, Pascal,Lauterbach, Tobias,Rudolph, Matthias,Rominger, Frank,Hashmi, A. Stephen K.
, p. 8634 - 8641 (2013)
We report the gold-catalyzed synthesis of highly functionalized iodofulvenes from iododialkynes under mild conditions. The catalytic cycle involves the formation of gold acetylides and vinylgold intermediates. These intermediates can then undergo an unprecedented iodine/gold exchange. This new pathway for catalyst transfer in dual gold catalysis opens up the possibility of highly regioselective transformations directed by the gold in the organogold intermediates. The resulting products are well suited for further metal-mediated coupling reactions, allowing the synthesis of extended π-systems. Iodine/gold exchange: A gold-catalyzed iodine transfer allows the efficient synthesis of benzofulvenes with iodo substituents on the fulvene core (see scheme). The new dual-activation catalysts are efficient catalysts for this new type of cycloisomerization. Copyright
Stereoselective synthesis of (Z)-enethiols and their derivatives: Vinylic SN2 reaction of (E)-alkenyl(phenyl)-λ3-iodanes with thioamides
Ochiai, Masahito,Yamamoto, Shinji,Suefuji, Takashi,Chen, Da-Wei
, p. 2753 - 2756 (2001)
(Equation presented) Exposure of (E)-β-alkylvinyl(phenyl)-λ3-iodanes to thioamides in dichloromethane at room temperature was found to result in a bimolecular nucleophilic substitution (SN2) at the vinylic carbon atom to give inverted (Z)-enethiols and/or (Z)-S-vinylthioimidonium salts. Vinylic SN2 reactions with thioureas are also discussed.
(Diacetoxyiodo)benzene-Mediated Transition-Metal-Free Amination of C(sp3)-H Bonds Adjacent to Heteroatoms with Azoles: Synthesis of N-Alkylated Azoles
Sun, Bin,Yan, Zhiyang,Jin, Can,Su, Weike
, p. 2432 - 2436 (2018)
A novel PhI(OAc) 2 -mediated cross-dehydrogenative coupling reaction of α-C(sp 3)-H bonds adjacent to a hetero atom with various azoles has been developed, which provides an alternative method for constructing C-N bonds with high atom efficiency. This new protocol requires no metal catalyst and it provides ready access to a wide range of N-alkylated azole derivatives in moderate to excellent yields by using commercially available PhI(OAc) 2 as the sole oxidant. Furthermore, the method is effective on a gram scale, which highlights the practicality of this transformation. The result of radical-captured experiments indicated that the transformation might involve a free-radical pathway.
KINETICS AND MECHANISM OF IODODESTANNYLATION OF STANNATRANES
Ravenscroft, M. D.,Roberts, R. M. G.
, p. 45 - 52 (1986)
A detailed kinetic study of iododestannylation of phenylstannatranes is reported.Reaction rates were compared with reference systems PhSnBu3, PhSn(OMe)3.No evidence was found for iodide catalysis.The reaction is interpreted as involving rate determining Sn-C bond fission.Rates for the stannatranes are some seven times greater than those for PhSn(OMe)3 indicative of increased Sn-N coordination in the transition state.Salt effects were significantly smaller for the stannatranes commeasurate with decreased charge on the electrofugal tin.For PhSn(OMe)3, the reaction was followed in the absence of iodide ion, enabling the evaluation of the association constant for the species +I- formed during the reaction.
Remote Para-C-H Acetoxylation of Electron-Deficient Arenes
Li, Minghong,Shang, Ming,Xu, Hui,Wang, Xing,Dai, Hui-Xiong,Yu, Jin-Quan
, p. 540 - 544 (2019)
One formidable challenge in sp2 C-H activation is how to achieve high para selectivity on electron-deficient arenes because such site selectivity is disfavored by the electronic bias induced by the electron-withdrawing groups. The first highly selective para-C-H acetoxylation of various benzoic acids using a nitrile-based template was realized. Removal of the template leads to para-hydroxylated benzoic acids, which are versatile intermediates for a wide range of synthetically useful transformations.
Preparation of Bis(arylthio)iodobenzene and Reaction with 1-Alkynes. A Novel Route to 1,2-Bis(arylthio)alkenes
Kita, Yasuyuki,Okuno, Takayuki,Tohma, Hirofumi,Akai, Shuji,Matsumoto, Keita
, p. 2717 - 2720 (1994)
The in situ reaction of a novel hypervalent iodine reagent 2b having an arylthio ligand, prepared from phenyliodine diacetate and 2,3,5,6-tetrafluorothiophenol 1b in pyridine, with 1-alkynes 3 gave 1,2-bis(arylthio)alkenes 4 in good yields.
Reactions of Unsaturated Compounds with Iodine and Bromine on γ-Alumina
Pagni, Richard M.,Kabalka, George W.,Boothe, Richard,Gaetano, Kevan,Stewart, Lyman J.,et al.
, p. 4477 - 4482 (1988)
Iodine reacts with a diverse group of unsaturated substrates in the presence of dehydrated alumina.Aromatic substrates, for example, are iodinated at room temperature by electrophilic aromatic substitution.The yields of the iodinated products can be improved dramatically by running the reaction at 110 deg C.Aniline, even at 100 deg C, is unreactive, presumably because its nitrogen lone pair is complexed to surface aluminum cation or protons.Alkenes react readily with HI, formed in the reaction of surface hydroxyls with I2, to form alkyl iodides by an ionic mechanism involving carbocations.This is an excellent method for the synthesis of alkyl iodides from alkenes.Alkynes, on the other hand, add I2 (stereospecific, anti) under very mild conditions to form vinyl diiodides in excellent yield.The behavior of Br2 with cyclohexene on alumina is considerably different than that of I2 withcyclohexene.Two products are formed: trans-1,2-dibromocyclohexane (1), which is formed in solution during workup, and trans-1-bromo-2-chlorocyclohexane (2), which is formed on the surface.The chlorine in 2 arise from intrinsic chloride already on the alumina and CCl4, the solvent used to adsorb Br2 onto alumina.Further experiments demonstrate that cyclohexene undergoes intergranular hopping, but that Br2 does not.
On the mechanism of photoinduced addition of acetonitrile to phosphonium-iodonium ylides
Nekipelova, Tatiana D.,Kuzmin, Vladimir A.,Matveeva, Elena D.,Gleiter, Rolf,Zefirov, Nikolay S.
, p. 137 - 143 (2013)
Recently, a novel photochemical reaction of pseudocycloaddition of nitriles to mixed phosphonium-iodonium ylides 1 was found. Nitriles R1CN give corresponding oxazoles (2) with a high yield, with PhI (3) being a leaving group. The mechanism of the photoinduced cycloaddition of acetonitrile to mixed phosphonium-iodonium ylide 1 was studied by steady-state and time-resolved methods with resolution from 10 ns to 20 μs. The formation of photolysis products, substituted oxazole 2, and phosphonium salt 4, occurs in parallel reactions. The primary photochemical processes for the formation of 2 and 4 are the heterolytic and homolytic C-I+Ph bond cleavage in the excited singlet state of 1, respectively. Three transient species with lifetimes on microsecond and millisecond time scales were observed. The mechanism of the formation of major and minor products of the photolysis was suggested. Addition of water to the reaction mixture in acetonitrile changes the ratio of the products in favor of the phosphonium salt formation. The effect of water was accounted for by the acid catalysis of the homolytic C-I+Ph bond cleavage and the acceleration of the salt formation. Copyright
