133320-07-7Relevant articles and documents
In situ hydrogenation of terminal halogen in poly(methyl methacrylate) by ruthenium-catalyzed living radical polymerization: Direct transformation of "polymerization catalyst" into "hydrogenation catalyst"
Terashima, Takaya,Ouchi, Makoto,Ando, Tsuyoshi,Sawamoto, Mitsuo
, p. 11014 - 11015 (2006)
An in situ, selective, and quantitative hydrogenation of the terminal chlorine (α-haloester) in living PMMA-Cl into PMMA-H was achieved via direct transformation of a "polymerization catalyst" into a "hydrogenation catalyst" in the Ru(II)-catalyzed living radical polymerization, where the polymerization mixture of MMA was directly treated in situ with K2CO3 as a base and 2-propanol as a hydrogen donor. The reaction terminated the polymerization and, more importantly, the terminal chlorine was quantitatively hydrogenated, as confirmed by SEC, 1H NMR, and MALDI-TOF MS. Copyright
Synthesis of Pd catalysts based on a nonbornene - CO copolymer and their properties in the carbomethoxylation of propylene
Korneeva,Kerov,Ibragimova,Kurkin,Makovetsky,Slivinsky
, p. 360 - 362 (1998)
It was found that carboxylation of norbornene (nbn) in the presence of the PdCl2 -PPh3 - HCl catalytic system is accompanied by alternating copolymerization of nbn with carbon monoxide to form norbornanecarboxylic acid (yield -20%) and a nbn-CO copolymer (yield -80%, Mw = 1600, Mw/Mn = 1.6). The PdII salt of poly(norbornaneketone)carboxylic acid is a highly active catalyst for the carbomethoxylation of propylene.
Selective carbonylation of Propane in Superacid Media via Hydride Abstraction by the Chlorocarbocations: CCl3+ and CHCl2+
Culmann, Jean-Christophe,Simon, Michael,Sommer, Jean
, p. 1098 - 1100 (1990)
Carbonylation of propane in HF-SbF5 (5:1 molar ratio) superacid in the presence of carbon tetrachloride (or chloroform) at -30 deg C yields exclusively the isobutyryl ion (isopropyloxocarbenium ion), analysis of the gaseous fluorocarbons generated as side products showing both hydride abstraction by CCl3+ (or CHCl2+) and Cl/F exchange on the tri- and di-chloromethane formed; in the absence of CCl4 (or(CHCl3) no reaction takes place under the same experimental conditions.
ASYMMETRIC HYDROFORMYLATION OF UNSATURATED ESTERS WITH PtCl(SnCl3) CATALYST
Kollar, Laszlo,Consiglio, Giambattista,Pino, Piero
, p. 305 - 314 (1987)
Dimethyl 2-(formylmethyl)butanedioate (2e) has been synthesizes regioselectively with an enantiomeric excess of more than 82percent by the homogeneous catalytic hydroformylation of dimethyl itaconate (1e) with PtCl(SnCl3) as the catalyst precursor.Under the conditions used a competitive hydrogenation to dimethyl 2-methylsuccinate (3e) takes place.This reaction occurs with an optical yield of up to 51percent.For other vinylidene esters 1 the asymmetric induction was lower both in the hydroformylation and in the competitive hydrogenation.The relationship between the absolute configuration of the predominant antipodes and the possible transition states responsible for the enantioface discrimination is discussed in terms of a model developed and successfully used for olefinic hydrocarbons as substrates.
Thermochemical Studies of Carbonyl Compounds. 3. Enthalpies of Hydrolysis of Ortho Esters
Wiberg, Kenneth B.,Martin, Eric J.,Squires, Robert R.
, p. 4717 - 4720 (1985)
The enthalpies of hydrolysis of a series of ortho esters have been measured in aqueous dioxane.The largest effect on ΔHr was found with α-branching, in contrast to the previously reported hydrolysis of ketals which gave the larger effect with β-branching.Possible reasons for this difference in behavior are discussed.
Stoichiometric hydrogenation of α,β-unsaturated ketones by HCo(CO)4
Roth, Jerome A.,Grega, Kevin,Orchin, Milton
, p. 129 - 136 (1988)
A study of the kinetics of the stoichiometric hydrogenation of α,β-unsaturated ketones by HCo(CO)4 led to the rate expression rate = kobs2-1.The reaction is catalyzed by Co2(CO)8 and shows a small inverse isotope effect with DCo(CO)4.Although the analogous reaction with the α,β-unsatureted ester dimethyl α-methylidenesuccinate (dimethyl itaconate, DMI) is also catalyzed by Co2(CO)8 and also shows an inverse isotope effect, the rate expression involves a first order dependence on HCo(CO)4.Furthermore, contrary to the behavior of simple acrylates, which have been shown elsewhere to conform to the same kinetic expression, no aldehydic product is produced.A mechanism consistent with the results is proposed.
Transition Metal Ketene Complexes as Active Intermediate for Catalytic Carbonylation of Geminal Dibromoalkanes
Miyashita, Akira,Kihara, Takehiro,Nomura, Kotohiro,Nohira, Hiroyuki
, p. 1607 - 1610 (1986)
MX2(PPh3)2 (M=Ni, Pd, Pt; X=Cl, Br) and Co2(CO)8 catalyze alkoxy- and aminocarbonylation of geminal dibromoalkanes, R1R2CBr2 (R1, R2=H and CH3).In the course of the catalysis, initial formation of the transition metal ketene complexes, M(CH2=C=O)L2, was followed by the reaction with alcohols to yield carbalkoxymethyl metal intermediate leading to esters.
A bulky phosphite modified rhodium catalyst for efficient hydroformylation of disubstituted alkenes and macromonomers in supercritical carbon dioxide
Koeken, Ard C. J.,Smeets, Niels M. B.
, p. 1036 - 1045 (2013)
The hydroformylation of disubstituted alkenes and related macromonomers in supercritical CO2 is demonstrated. Higher turnover frequencies were observed for the 1,2-disubstituted alkenes than for the 1,1-disubstituted alkenes. The turnover frequency for poly(styrene) macromonomer hydroformylation compares well with that observed for cyclohexene. The turnover frequency observed for poly(methyl methacrylate) macromonomer hydroformylation is considerably lower than that observed for methyl methacrylate. Unprecedented turnover frequencies are observed in comparison with previous studies where CO2 has been applied as a solvent. This is achieved using rhodium modified with a readily available bulky phosphite ligand without the need of ligand modification to improve solubility in supercritical CO2.
Ozonolytic decyclization of (R)-4-menthen-3-one
Kharisov,Gazetdinov,Botsman,Muslukhov,Ishmuratov,Tolstikov
, p. 1005 - 1008 (2002)
Ozonolytic decyclization of (R)-4-menthen-3-one is accompanied by fragmentation of the isobutyl group, leading to ω-functionalized 3-methylpentanoic acid derivatives.
C(9)-C Bonds of 10-Methyl-9-alkyl-9,10-dihydroacridines Acting Like Metal-Carbon Bonds in the Reactions with Electrophiles
Fukuzumi, Shunichi,Tokuda, Yoshihiro,Fujita, Morifumi,Otera, Junzo,Chanon, Michel,et al.
, p. 1701 - 1704 (1992)
The C(9)-C bonds of 10-methyl-9-alkyl-9,10-dihydroacridines (AcrHR: R = CMe2COOMe, CMe(H)COOEt, But, CHPh2) are readily cleaved by electrophiles (perchloric acid, oxygen, and iodine) in acetonitrile at 298 K, acting like metal-carbon bonds to yield the corresponding alkane, alkyl hydroperoxide, and alkyl iodide, respectively.
