Synthesis and Characterization of Ethylene/Carbon Monoxide Copolymers, A New Class of Polyketones<sup>1</sup>

Brubaker, M. M.; Coffman, D. D.; Hoehn, Harvey H.

doi:10.1021/ja01126a047

Cited by 177 publications

(78 citation statements)

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“…[129] There have been several important discoveries including the Rh-catalyzed photocarbonylation of alkanes by Tanaka [130,131] and the carboxylation of methane with CO/O 2 using Pd/ Cu [132] or RhCl 3 [133] catalysts by Fujiwara and Sen et al The carbonylation of adamantanes under the influence of Lewis acid and superacids is also reported. [134,135] Following the first report on the free-radical mediated carbonylation by Coffmann et al in 1952, [136] this type of reaction was not investigated for a long time, probably because the reaction must be conducted under extremely high CO pressure (200-300 atm). [137] In 1990, Ryu performed a successful free-radical carbonylation of alkyl halides with CO mediated by tributyltin hydride.…”

Section: Carboxylation Of Alkanes With Co and Omentioning

confidence: 99%

Innovation of Hydrocarbon Oxidation with Molecular Oxygen and Related Reactions

2001

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An innovation of the aerobic oxidation of hydrocarbons through catalytic carbon radical generation under mild conditions was achieved by using N‐hydroxyphthalimide (NHPI) as a key compound. Alkanes were successfully oxidized with O2 or air to valuable oxygen‐containing compounds such as alcohols, ketones, and dicarboxylic acids by the combined catalytic system of NHPI and a transition metal such as Co or Mn. The NHPI‐catalyzed oxidation of alkylbenzenes with dioxygen could be performed even under normal temperature and pressure of dioxygen. Xylenes and methylpyridines were also converted into phthalic acids and pyridinecarboxylic acids, respectively, in good yields. The present oxidation method was extended to the selective transformations of alcohols to carbonyl compounds and of alkynes to ynones. The epoxidation of alkenes using hydroperoxides or H2O2 generated in situ from hydrocarbons or alcohols and O 2 under the influence of the NHPI was demonstrated and seems to be a useful strategy for industrial applications. The NHPI method is applicable to a wide variety of organic syntheses via carbon radical intermediates. The catalytic carboxylation of alkanes was accomplished by the use of CO and O2 in the presence of NHPI. In addition, the reactions of alkanes with NO2 and SO2 catalyzed by NHPI provided efficient methods for the synthesis of nitroalkanes and sulfonic acids, respectively. A catalytic carbon‐carbon bond forming reaction was achieved by allowing carbon radicals generated in situ from alkanes or alcohols to react with alkenes under mild conditions. 1 Introduction 2 Discovery of NHPI as Carbon Radical Producing Catalyst from Alkanes 2.1 Historical Background 2.2 Catalysis of NHPI in Aerobic Oxidation 3 NHPI‐Catalyzed Aerobic Oxidation 3.1 Oxidation of Benzylic Compounds 3.2 Alkane Oxidations with Molecular Oxygen 3.3 Oxidation of Alkylbenzenes 3.4 Practical Oxidation of Methylpyridines 3.5 Preparation of Acetylenic Ketones via Alkyne Oxidation 3.6 Oxidation of Alcohols 3.7 Selective Oxidation of Sulfides to Sulfoxides 3.8 Production of Hydrogen Peroxide by Aerobic Oxidation of Alcohols 3.9 Epoxidation of Alkenes using Molecular Oxygen as Terminal Oxidant 4 Carboxylation of Alkanes with CO and O2 5 Utilization of NOx in Organic Synthesis 5.1 First Catalytic Nitration of Alkanes using NO2 5.2 Reaction of NO with Organic Compounds 6 Sulfoxidation of Alkanes Catalyzed by Vanadium 7 Carbon‐Carbon Bond Forming Reaction via Catalytic Carbon Radicals Generated from Various Organic Compounds Assisted by NHPI 7.1 Oxyalkylation of Alkenes with Alkanes and Dioxygen 7.2 Synthesis of α‐Hydroxy‐γ‐lactones by Addition of α‐Hydroxy Carbon Radicals to Unsaturated Esters 7.3 Hydroxyacylation of Alkenes using 1,3‐Dioxolanes and Dioxygen 8 Conclusions

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Section: Carboxylation Of Alkanes With Co and Omentioning

confidence: 99%

Innovation of Hydrocarbon Oxidation with Molecular Oxygen and Related Reactions

2001

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“…The polymers. 4,5 norbornene/CO copolymer obtained from 1,4-A series of cationic Pd (II) compounds to catabenzoquinone as oxidant was insoluble in common lyze the copolymerization of carbon monoxide organic solvents such as THF, chlorobenzene, benzene, chloroform, and DMSO. 11 One of the improvements of solubility was to modify norbor-with glass transition temperatures over the range Instruments of 040 to 268ЊC by vinyl addition polymerization…”

Section: Introductionmentioning

confidence: 99%

Copolymerization of carbon monoxide and norbornene derivatives with ester groups by palladium catalyst

Liaw

Tsai

Sang

1998

J. Polym. Sci. A Polym. Chem.

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“…There are two kinds of Copolymerizations of ethylene and carbon monoxpolyketones (ethylene CO copolymers). One is ide have been reported via several methods, such polyketone I with a radical initiator, and the other as conventional Ziegler catalysts, 1 the g-radiation is polyketone II with a Pd catalyst system initiation method, 2 organic peroxides, 3,4 the palla-(Scheme 1). The latter is almost a perfect alterdium catalyst system, 5 metallocene catalyst sysnate copolymer, highly crystalline, has a high tems, 6 and g-rays from a 60 Co source or AIBN.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of poly(hydroxymethylene-co-ethylene) by hydrogenation of the ethylene and carbon monoxide copolymer obtained by radical initiator with Ru/?-alumina and oxygen gas permeability

Takaya¹,

Itoh

Uunno³

1998

J. Polym. Sci. A Polym. Chem.

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Synthesis and Characterization of Ethylene/Carbon Monoxide Copolymers, A New Class of Polyketones¹

Cited by 177 publications

References 0 publications

Innovation of Hydrocarbon Oxidation with Molecular Oxygen and Related Reactions

Innovation of Hydrocarbon Oxidation with Molecular Oxygen and Related Reactions

Copolymerization of carbon monoxide and norbornene derivatives with ester groups by palladium catalyst

Synthesis of poly(hydroxymethylene-co-ethylene) by hydrogenation of the ethylene and carbon monoxide copolymer obtained by radical initiator with Ru/?-alumina and oxygen gas permeability

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Synthesis and Characterization of Ethylene/Carbon Monoxide Copolymers, A New Class of Polyketones1

Cited by 177 publications

References 0 publications

Innovation of Hydrocarbon Oxidation with Molecular Oxygen and Related Reactions

Innovation of Hydrocarbon Oxidation with Molecular Oxygen and Related Reactions

Copolymerization of carbon monoxide and norbornene derivatives with ester groups by palladium catalyst

Synthesis of poly(hydroxymethylene-co-ethylene) by hydrogenation of the ethylene and carbon monoxide copolymer obtained by radical initiator with Ru/?-alumina and oxygen gas permeability

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Synthesis and Characterization of Ethylene/Carbon Monoxide Copolymers, A New Class of Polyketones¹