Showing papers on "Norbornene published in 1982"
TL;DR: The oxanickelacyclopentanone-derivate (I) can easily be prepared from norbornene (bicyclo[2.2.1]heptene), CO2 and nickel(0) compounds.
72 citations
TL;DR: The Diels-Alder reaction product of cyclopentadiene and maleic anhydride (CPD-MA) exists in both endo and exo -isomeric forms as mentioned in this paper.
62 citations
TL;DR: In this article, the reaction of the palladium complex with norbornene in acetone leads to the quantitative formation of the metallacycle, which can be isolated as a yellow solid, and decomposition of this metallatricycle under nitrogen in toluene solution produces exo-epoxynorbornene (ca 90% yield) at an initial rate of 3%/h.
Abstract: Reaction of the palladium complex with norbornene in acetone leads to the quantitative formation of the metallacycle, which can be isolated as a yellow solid. Decomposition of this metallatricycle under nitrogen in toluene solution produces exo-epoxynorbornene (ca 90% yield) at an initial rate of 3%/h. Part of this stability and change in product selectivity is attributed to the allycyclic bridgeheads. Intrametallacyclic ..beta..-hydrogen is restricted by the rotational rigidity of the bicyclic norbornane skeleton and by the attendant reintroduction of ring strain. 1 table.
58 citations
Patent•
07 Jul 1982TL;DR: Silylnorbornane anhydrides are provided by effecting reaction between a silicon hydride and a norbornene carboxylic acid anhydride in the presence of a platinum catalyst as discussed by the authors.
Abstract: Silylnorbornane anhydrides are provided by effecting reaction between a silicon hydride and a norbornene carboxylic acid anhydride in the presence of a platinum catalyst. The resulting silicon functionalized norbornane monoanhydrides or dianhydrides can be used to synthesize a variety of tough organosilicon polyimide copolymers and polydiorganosiloxane polyimide block polymers.
48 citations
TL;DR: The anomalous reactivity of the bicyclo [2.2.1] double bond is interpreted in terms of hyperconjugative effects, leading to an exceptionally low endo out-of-plane deformation potential as mentioned in this paper.
45 citations
TL;DR: In this paper, (±)-Sinularene and 5-epi-sinularenes were synthesized in a stereocontrolled manner from the norbornene 2 in overall yields of 4% and 8%, respectively, using a regio-and stereoselective intramolecular reaction.
29 citations
TL;DR: In this article, new syntheses of condensed cyclopentanes are described, based on insertion into a sufficiently stable PdC bond of molecules able to provide an easy reductive elimination step.
24 citations
Patent•
29 Sep 1982TL;DR: Impact modified polycycloolefin is made by ring opening bulk polymerization of at least one monomer containing at least 1 norbornene group in presence of an organoammonium molybdate or tungstate catalyst and an alkoxyalkyl- aluminium halide cocatalyst as discussed by the authors.
Abstract: Impact modified polycycloolefin is made by ring opening bulk polymerization of at least one monomer containing at least one norbornene group in presence of an organoammonium molybdate or tungstate catalyst and an alkoxyalkyl- aluminium halide cocatalyst as well as a sufficient amount of an impact modifier selected from polyolefin powders and halogen-containing polyolefin powders.
23 citations
TL;DR: In this article, ring-opening copolymerization studies were made on the systems cyclopentene (CPE)/norbornene (NBE), cyclooctene (COE)/ norbornene, 1,5-cyclooctadiene (COD)/nor bornene, cyclopentsene/cycloheptene (CHP), and cyclopenene/ 1, 5-cycloxadiene using olefin metathesis catalysts, showing either a random or blocky distribution of monomeric units.
Abstract: Ring-opening copolymerization studies were made on the systems cyclopentene (CPE)/ norbornene (NBE), cyclooctene (COE)/ norbornene, 1,5-cyclooctadiene (COD)/norbornene, cyclopentene/cycloheptene (CHP), and cyclopentene/ 1,5-cyclooctadiene using olefin metathesis catalysts.13C NMR spectra of the copolymers permit direct determination of the reactivity ratios in most cases, as well as the proportion of cis double bonds in each type of dyad. For CPE/NBE, COD/NBE and CPE/CHP the reactivity ratios vary widely with the catalyst system and sometimes with the catalyst/cocatalyst ratio and method of mixing. There is no correlation between composition of the copolymer and cis content. The copolymers show either a random or blocky distribution of monomeric units. The results are discussed in terms of a mechanism in which the metal carbenes formed in the propagation processes are initially coordinated to the polymer chain and can add further monomeric units stereospecifically while in this form. These propagation processes compete with a relaxation process leading to a metal carbene in which the polymer chain is no longer coordinated at the vacant site and which adds monomer in a less stereospecific fashion.
21 citations
21 citations
TL;DR: In this paper, a technique for measuring enthalpies of sublimation with the LKB 8721-3 Vaporization Calorimeter, designed originally for liquid samples, was described.
TL;DR: Benzonorbornadiene and four related aryl-substituted derivatives of norbornene are shown to undergo metathesis ring-opening polymerization; whereas, neither indene nor acenaphthalene appears to be susceptible to ring opening.
TL;DR: In this paper, the trans/cis ratios of 2-butenes and 3-hexenes extrapolated to zero percent conversion were determined by 1H NMR and 13C NMR.
TL;DR: In this paper, the substitution of the olefin proceeds via a dissociative mechanism, the meridional isomers rearrange back to the facial ones prior to the rupture of the metal-olefin bond.
Abstract: Monoolefin-Komplexe M(CO)3(R2PC2H4PR2)(ol) (M = Cr, Mo, W; R = CH3, C6H5; ol = Maleinsaureanhydrid, Dimethylfumarat, Dimethylmaleat, Methylacrylat, Ethylen, Styrol, Norbornen) sind photochemisch aus den Tetracarbonyl-Chelatphosphan-Derivaten zuganglich. Es entstehen zunachst faciale Komplexe, die sich zum Teil rasch intramolekular in die meridionalen Isomeren umlagern. Die Substitution des Olefins verlauft nach einem dissoziativen Mechanismus, der Spaltung der Metall-Olefin-Bindung geht bei den meridionalen Derivaten die intramolekulare meridional-facial-Isomerisierung voraus.
Carbonyl Monoolefin Derivatives of the Group VI Transition Metals, III. Preparation and Reaction and Reactivity of Tricarbonyl Chelate Phosphane Olefin Derivatives
Monoolefin complexes M(CO)3(R2PC2H4PR2)(ol) (M = Cr, Mo, W; R = CH3, C6H5; ol = maleic anhydride, dimethyl fumarate, dimethyl maleate, methyl acrylate, ethylene, styrene, norbornene) are obtained photochemically from the tetracarbonyl chelate phosphane derivatives. Facial complexes are formed primarily, some of which rearrange intramolecularly to the meridional isomers. The substitution of the olefin proceeds via a dissociative mechanism, the meridional isomers rearrange back to the facial ones prior to the rupture of the metal-olefin bond.
Patent•
29 Sep 1982
TL;DR: Impact modified polycycloolefin is made by ring opening bulk polymerization of at least one monomer containing at least 1 norbornene group in presence of an organoammonium molybdate or tungstate catalyst and an alkoxyalkylaluminum halide cocatalyst as well as a sufficient amount of a polyolefin powder and a rubbery material to produce ductile polycyclOOlefin this paper.
Abstract: Impact modified polycycloolefin is made by ring opening bulk polymerization of at least one monomer containing at least one norbornene group in presence of an organoammonium molybdate or tungstate catalyst and an alkoxyalkylaluminum halide cocatalyst as well as a sufficient amount of a polyolefin powder and a rubbery material to produce ductile polycycloolefin.
TL;DR: In this paper, the 13NMR signals of α-pinene and camphene were reassigned unequivocally. And the J(CH) values of 1, 2, bornene, norbornene and norbornadiene were reported.
Abstract: The 13NMR signals of camphene (1) and α-pinene (2) are reassigned unequivocally. J(CH) values of 1, 2, bornene, norbornene and norbornadiene are reported.
TL;DR: The photochemical hydrogenation of norbornadiene (NBD) in the presence of Cr(CO)6 or Cr( CO)4NBD at normal pressure yields nortricyclene and norbornene in a ratio of 3/1.
TL;DR: In this article, the 1H NMR Spectra of NorphosO and MeNorphosO are assigned with respect to the norbornene skeleton. But this is not the case for MeNoptosO.
TL;DR: In this article, cross-linked poly(styrene-4-vinylpyridine) beads, containing 40% of pyridine rings, were transformed with bromine to provide three types of brominating agents (1), (2), and (3).
Abstract: Cross-linked poly(styrene–4-vinylpyridine) beads, containing 40–43% of pyridine rings, were transformed with bromine to provide three types of brominating agents (1), (2), and (3). Reactions of cis- and trans-1-phenylpropene with (1), (2), and (3) resulted in a high degree of anti-stereoselectivity. The reactivity increases from (1) to (3); solvent polarity has no significant effect on stereoselectivity, but affects the reactivity, being significantly greater in acetonitrile and chloroform than in cyclohexane and dioxan. Bromination of 1-phenylcyclohexene with (1) and (3) resulted in the formation of trans-1,2-dibromo-1-phenylcyclohexane (9) and 3-bromo-2-phenylcyclohexene (10), the temperature affecting only the ratio of the products. Bromination of norbornene with the reagents (1), (2), and (3) resulted in the formation of seven products: 2-exo-bromonorbornane (12), 7-bromonortricyclane (13), 2-exo, 3-endo-dibromonorbornane (14), 2-exo-7-anti-dibromonorbornane (15), 2-exo, 5-endo-dibromonorbornane (16), 2-exo, 5-exo-dibromonorbornane (17), and 2-exo, 7-syn-dibromonorbornane (18).
TL;DR: In this paper, a new reaction involving oxidative addtion of aromatic bromides to palladium(O), two successive insertions of norbornene, and ring closure to the aromatic carbon ortho to the carbon originally bearing the bromine was described.
TL;DR: In this article, a new concept, "Orbital tilting" leading to hybridization change, was introduced on the basis of the destabilizing and the stabilizing secondary orbital interaction.
Abstract: A new concept, “Orbital Tilting,” leading to hybridization change, was introduced on the basis of the destabilizing and the stabilizing secondary orbital interaction. The predominant π-MO extension of norbornene in the exo-direction was elucidated by application of the concept to the orbital system.
Patent•
22 Oct 1982TL;DR: In this paper, heat resistant resins are prepared containing unsaturated polyester resins or polyesteramide resins terminated with a norbornene type group, an ethylenically unsaturated group, and a dicyclopentadiene ester of an uns saturated polycarboxylic acid.
Abstract: Heat resistant resin compositions are prepared containing unsaturated polyester resins or polyesteramide resins terminated with a norbornene type group, an ethylenically unsaturated group, and a dicyclopentadiene ester of an unsaturated polycarboxylic acid.
TL;DR: Norbornene was selectively fluorinated with xenon difluoride by photochemical means as discussed by the authors, which represents a novel example of controlled XeF 2 radical fluorination by light initiation.
Patent•
08 Nov 1982
TL;DR: A compound of the formula (I) is useful as electrical insulation and as heat shrinkable parts or as other plastic parts to improve the retention of mechanical and/or electrical properties of the insulation or parts.
Abstract: A compound of the formula (I) ##STR1## Polymer compositions including antioxidants and the compounds or the compound alone are useful as electrical insulation e.g., for copper cable, as heat shrinkable (heat recoverable) parts or as other plastic parts to improve the retention of mechanical and/or electrical properties of the insulation or parts.
Patent•
20 Sep 1982
TL;DR: In this article, the authors proposed a method to provide a titled formed product recoverable in shape through temperature change even without incorporating of much oil, useful for wide range of applications in cludning medical supplies such as gypsum, composed of a specific nurbornene-based polymer.
Abstract: PURPOSE: To provide titled formed product recoverable in shape through temperature change even without incorporating of much oil, useful for wide range of applications in cludning medical supplies such as gypsum, composed of a specific nurbornene-based polymer. CONSTITUTION: The objective product recoverable in shape composed of a norbornene-based polymer with a glass transition temperature of 10°C or higher and number-average molecular weight ≥1,000,000 [e.g., polynorbornene, namely a ring-opened polymer of bicyclo (2,2,1) heptene-2]. USE: Applicable to a wide range of fields, because of deformability below the forming temperature, settability of the deformation when cooled below its glass transition temperature, and also recoverability of the original shape on heating to temperatures higher than said glass transition temperature and below the forming temperature. COPYRIGHT: (C)1984,JPO&Japio
Patent•
22 Sep 1982
TL;DR: In this paper, a mixture of a norbornene and a tetracyclododecene is prepared in any desired desired mole ratio in the range of 95/5 to 5/95, which comprises heating an olefin, cyclopentadiene, and a Norbornene in the respective mole ratio of 1-20/1-5/1 -5, at a temperature of 100 DEG to 400 DEG C., 100 to 5000 psi, and 0.1 to 5 hours of residence time.
Abstract: A product mixture of a norbornene and a tetracyclododecene is prepared in any desired mole ratio in the range of 95/5 to 5/95 which comprises heating an olefin, cyclopentadiene, and a norbornene in the respective mole ratio of 1-20/1-5/1-5, at a temperature of 100 DEG to 400 DEG C., 100 to 5000 psi, and 0.1 to 5 hours of residence time.
TL;DR: In this article, photoadditions of NNOD to various olefins under oxygen lead to 2-dimethylamino-1-nitrate esters in good yields as primary products.
Abstract: Photoadditions of NNOD to various olefins under oxygen lead to 2-dimethylamino-1-nitrate esters in good yields as primary products. The amino-nitrates are stable in acidic solution but their stability towards bases varies over a wide range depending on configuration. In most cases, the crude photoaddition products were reduced with lithium aluminium hydride to give good yields of the alcohols. The nitrates derived from cyclododeca-1,5,9-trienes were stable and reduced by lithium aluminium hydride to give, quite unexpectedly, the acyclic α,ω-dimethylamino-alcohols. The oxidative photoaddition to cis,trans,trans-cyclododecatriene occurred preferentially at the trans-double bond and that to dicyclopentadiene at the norbornene double bond. In both cases, good regioselectivity was observed. The precursors to the nitrates were suggested to be the corresponding peroxynitrites which might also undergo various ionic or light-induced reactions.