Showing papers on "Norbornene published in 1973"
TL;DR: In this article, the 1H n.m. spectra of the products are discussed and the use of an europium shift reagent together with spin decoupling is shown to allow clear distinction of the isomeric methanoindacenediones (VIII) and (IX).
Abstract: Tetra- and hexa-hydro-4,7-methanoinden-1-ones and the analogous indacenediones (VIII)–(X) are formed stoicheiometrically by the title reaction or catalytically from acetylenes, norbornene derivatives, and carbon monoxide in the presence of octacarbonyldicobalt. The process leads stereoselectively to ketones of theexo-series and methyl or phenyl groups derived from the appropriate monosubstituted acetylenes are always found adjacent to the carbonyl group. The 1H n.m.r. spectra of the products are discussed and the use of an europium shift reagent together with spin decoupling is shown to allow clear distinction of the isomeric methanoindacenediones (VIII) and (IX).
323 citations
TL;DR: In this article, a series of tetranuclear arenecobalt carbonyls, ArHCo4(CO)9, are formed by treating hexacarbonylacetylenedicobalt complexes, (R1C2R2)Co2(CO), with arenes in the presence of norbornene derivatives.
Abstract: A series of tetranuclear arenecobalt carbonyls, ArHCo4(CO)9, are formed by treating hexacarbonylacetylenedicobalt complexes, (R1C2R2)Co2(CO)6, with arenes in the presence of norbornene derivatives, or from the cobalt carbonyls Co4(CO)12 and Co2(CO)8 by direct reaction with arenes. Stable complexes are obtained from alkyl- and alkoxy-benzenes, but not from halogeno- or acyl derivatives. The spectroscopic properties of the new complexes are reported.
104 citations
57 citations
TL;DR: In this article, a small degree of polarization of the π-olefin-Pd bond in the transition state for the σ-allyl migration is interpreted in terms of the polarization of a σallylic carbon atom from Pd to the coordinated olefin in a concerted cis-exo addition of PdC across the double bond.
37 citations
30 citations
TL;DR: An improved procedure for the preparation of phenyl(fluorodichloromethyl)mercury involving the reaction of the phenylmercuric chloride with sodium methoxide and fluorodichoromethane in THF/methanol at −40° is described in this paper.
24 citations
TL;DR: In this article, the stereochemistry of the new complexes is deduced from the analysis of the 1H NMR spectra of suitably substituted compounds with the application of double resonance.
24 citations
Patent•
27 Mar 1973
TL;DR: In this article, a ring-opening polymerization of cyano-substituted norbornene derivatives, whose chemical structure may be expressed by the following general formula: radical WHERE:
Abstract: Polymers prepared with a reduced viscosity of 0.1 to 20 by ring-opening polymerization of cyano-substituted norbornene derivatives, whose chemical structure may be expressed by the following general formula: radical WHERE:
17 citations
Patent•
26 Feb 1973TL;DR: In this article, a halogen-containing, sulfur-curable, normally amorphous quadripolymer is produced by contacting a mixture of (1) ethylene, (2) an.alpha.-olefin having the formula, R-CH=CH.
Abstract: Wherein R.sub.1, R.sub.2, R.sub.3 and R.sub.4 are hydrogen atoms, hydrocarbon radicals having one to 20 carbon atoms, halogen atoms, or halogenated hydrocarbon radicals having one to 20 carbon atoms and containing at least one halogen atom as substituent, provided that R.sub.1, R.sub.2, and R.sub.4 have as a whole at least one halogen atom, with a coordinated catalyst comprising an organoaluminum compound of the formula, A1R''.sub.n X.sub.3.sub.-n, wherein R'' is a hydrocarbon radical having 1 to 20 carbon atoms, X is a halogen atom, and n is any number of from 1.5 to 3, and a transition metal compound selected from the group consisting of vanadium compounds and titanium compounds, the molar ratio of said organoaluminum compound to said transition metal compound being from 5 : 1 to 0.5 : 1. The rate of vulcanization of the said quadripolymer is freely controllable by varying the non-conjugated diene content thereof. A halogen-containing, sulfur-curable, normally amorphous quadripolymer is produced by contacting a mixture of (1) ethylene, (2) an .alpha.-olefin having the formula, R-CH=CH.sub.2 wherein R is a hydrocarbon radical having one to 20 carbon atoms, (3) a hydrocarbon compound having a plurality of non-conjugated unsaturated bonds capable of polymerizing with a coordinated catalyst, and (4) a halogenated norbornene compound represented by the formula,
11 citations
Patent•
12 Nov 1973
TL;DR: In this article, a halogenated EPDM terpolymer is cured compatible with unsaturated elastomers such as NR, IR, SBR and BR, and it is shown that the proportion of water to terpolymers crumb in the slurry is critical and must be carefully controlled.
Abstract: In a process whereby ethylene is copolymerized with another alpha-olefin and a norbornene polyene under pressure with a vanadium catalyst to form amorphous vulcanizable elastomers, it is possible to halogenate the terpolymers in a water slurry by the addition of liquid halogen. The proportion of water to terpolymer crumb in the slurry is critical and must be carefully controlled. The halogenated EPDM terpolymer is cure compatible with unsaturated elastomers such as NR, IR, SBR and BR.
10 citations
TL;DR: In this paper, it was concluded that the active species for this catalytic reaction is a nickel hydride and that this reaction proceeds through π-crotyl intermediate.
Patent•
22 Jan 1973TL;DR: Graft copolymers are prepared in a two-stage process by first reacting, for example, 1,2-polybutadiene or an ethylene/propylene/alkylidene norbornene terpolymer with dinitrogen tetroxide to form a nitrated backbone polymer having incorporated therein nitro and nitrite functions which serve, in the second stage of the process, as sites for the subsequent graft copolymerization of an acrylate monomer as discussed by the authors.
Abstract: Graft copolymers are prepared in a two-stage process by first reacting, for example, 1,2-polybutadiene or an ethylene/propylene/alkylidene norbornene terpolymer with dinitrogen tetroxide to form a nitrated backbone polymer having incorporated therein nitro and nitrite functions which serve, in the second stage of the process, as sites for the subsequent graft copolymerization of an acrylate monomer.
TL;DR: In this article, the facility of functional groups to assume cis-coplanarity governs the cleavage of a 2-ammonio-1-nitrosoalkane which is obtained from nitrosamine photoaddition to an olefin.
Abstract: Evidence is presented that the facility of the functional groups to assume cis-coplanarity governs the cleavage of a 2-ammonio-1-nitrosoalkane which is obtained from nitrosamine photoaddition to an olefin.
Patent•
22 Jan 1973TL;DR: Graft copolymers are prepared in a two-stage process by first reacting, for example, 1,2-polybutadiene or an ethylene/propylene/alkylidene norbornene terpolymer, with a mixture of dinitrogen tetroxide and oxygen to form a nitrooxidized backbone polymer having incorporated therein nitro and peroxy nitrate functions which serve, in the second stage of the process, as sites for the subsequent graft polymerization of an acrylate monomer as discussed by the authors.
Abstract: Graft copolymers are prepared in a two-stage process by first reacting, for example, 1,2-polybutadiene or an ethylene/propylene/alkylidene norbornene terpolymer, with a mixture of dinitrogen tetroxide and oxygen to form a nitrooxidized backbone polymer having incorporated therein nitro and peroxy nitrate functions which serve, in the second stage of the process, as sites for the subsequent graft polymerization of an acrylate monomer.
Patent•
29 Jan 1973
TL;DR: In this article, the general formulae of a NORBORNENE in which R is a HYDROGEN, HALOGEN or UNHALOGENATED ALKLY, ARYLALKYL, ALKENYL, or 6-or 7ALKYLIDENE group, X is a hybrid, and N and M are a number of from 0 to 2 SUCH that the some of M and N are never more than 2.
Abstract: AN INTERPOLYMER FORMED BY THE ADDITION POLYMERIZATION OF ETHYLENE, AT LEAST ONE MONOOLEFIN HAVING THE GENERAL FORMULA CH2=CH-R, WITHOUT A POLYENE AND A SILYL NORBORNENE HAVING THE GENERAL FORMULA 1,3,7-TRI(R),2-((Y)M-SI(-X(3-(M+N)))(-(R'')N)-5-NORBORNENE IN WHICH R IS HYDROGEN, HALOGENATED OR UNHALOGENATED ALKLY, ARYLALKYL, ALKENYL OR 6- OR 7-ALKYLIDENE GROUP, R'' IS AN ALKYL, ARYL OR ALKENYL GROUP, X IS HYDROGEN AND Y IS HALOGEN, AND N AND M IS A NUMBER OF FROM 0 TO 2 SUCH THAT THE SOME OF M AND N IS NEVER MORE THAN 2.
TL;DR: Some norbornanes carrying fused heterocycles have been synthesized by 1,3-dipolar additions to substituted norbornenes as mentioned in this paper, but these were unsuccessful due to the occurrence of rearrangements.
Abstract: Some norbornanes carrying fused heterocycles have been synthesised by 1,3-dipolar additions to substituted norbornenes. Attempts to prepare heterocycles by reactions of electrophilic reagents with the strained double bond in norbornenes were unsuccessful owing to the occurrence of rearrangements. In the reaction of iodine with 5-endo-aminomethylnorborn-2-ene, rearrangement may be prevented by prior nucleophilic attack of the amine group on the cation intermediate to give a 5-azatricyclo[4.2.1.0]nonane (32).
Patent•
09 Mar 1973
TL;DR: In this article, an ester of an N-protected amino acid or peptide with N-hydroxy-5-norbornene-2,3 dicarboxyimide is reacted with an amino acid having a free amino gp.
Abstract: In the title processes, an ester of an N-protected amino acid or peptide with N-hydroxy-5-norbornene-2,3 dicarboxyimide is reacted with an amino acid or peptide having a free amino gp. in the presence of a carbodiimide. The reaction is effected with reduced racemisation and by product formation and may also be effected in an aq. medium. Prefd. processes lead to Pyroglu-His-ProNH2 and Pyroglu-His-Trp-Ser-Tyr-Gly-Leu-Alg-Pro-Gly-NH2.
TL;DR: The photoelectron spectra of 5-methylenenenorborn-2-2ene (I, II, and III) and norbornene (III) showed that the π-orbitals in the diene (II) interact strongly but the interacation leads to little or no stabilization of the system as discussed by the authors.
Abstract: The photoelectron spectra of 5-methylenenorborn-2-ene (I), 2-methylenenorborane (III), and norbornene show that the π-orbitals in the diene (I) interact strongly but the interacation leads to little or no stabilization of the π-system; simple HMO arguments and consideration of the photoelectron spectrum of norbornadiene (II) suggest that the interaction is mostly π-bonding through-space.
Patent•
04 Oct 1973
TL;DR: The homo-and copolymers can be used in the form of compression, extrusion, injection and blow moldings and castings, e.g. as bottles, films, bags, packing materials, machine parts and for electrical purposes, including lighting as discussed by the authors.
Abstract: Polymers with reduced viscosity 0.1 - 20 are produced by ring fission polymerisation of cyano-substd. norbornene derivs. (I) of formula: (in which W, X, Y and Z are H, CN, substits. contg. CN, 1-20C alk(en)yl or 1 - 20C ar(alk)yl, >=1 of these gps. being CN or a substit. contg. CN). The homo- and copolymers can be used in the form of compression, extrusion, injection and blow mouldings and castings, e.g. as bottles, films, bags, packing materials, machine parts and for electrical purposes, including lighting. They exhibit ease of degradation in sunlight in conjunction with excellent surface hardness. impact and tensile strength, solvent resistance and impermeability to gases.
TL;DR: In this paper, the photofragmentation reactions from the excited singlet state and, depending on the substitution pattern, may undergo rearrangement to norbornene derivatives from both singlet and triplet states.
Abstract: 4-Methylenebicyclo[3,2,0]hept-2-enes are shown to undergo photofragmentation reactions from the excited singlet state and, depending on the substitution pattern, may undergo rearrangement to norbornene derivatives from both singlet and triplet states.
TL;DR: Some derivatives known to be metabolites of the pesticide Endosulfan® show a high intrinsic toxicity to houseflies if the oxidative metabolism is inhibited, and the intrinsic toxicity of the compounds studied shows up under these conditions.
Abstract: The aspects of molecular-structure and biological conversion have been studied for 12 derivatives of the endosulfan ether 1 [4, 5, 6, 7, 8, 8- hexachloro- 1, 3, 3a, 4, 7, 7a- hexahydro- 4, 7-methanoisobenzofuran]. Adults of a normal house-fly strain (Musca domestica) have been used in the assay. Derivatives of 1 monosubstituted in position I are found to be converted substantially faster than products disubstituted in position I and 3, respectively. Metabolism is inhibited for all compounds studied after application of piperonyl butoxide as a synergist. Besides proving that on oxidative metabolism has to be discussed and in fact could be proved for some derivatives, the intrinsic toxicity of the compounds studied shows up under these conditions. Some derivatives known to be metabolites of the pesticide Endosulfan® show a high intrinsic toxicity to houseflies if the oxidative metabolism is inhibited.
Patent•
26 Jan 1973
TL;DR: In this paper, the authors proposed a method for stabilisation of the NORBORNENES, which consists of finding at least one PHENOL of either one of the two forms of the formulae: 4-((4-(HO)-),R3,R4-PHENYL)-X-),R1,R2PHENOL 2-((2-(HO-,R7,R8-PHenyl)-X'' -),R5,R6PHENol and 2-R9,3-R10,4-R
Abstract: A METHOD FOR STABILIZATION OF NORBORNENES WHICH COMPRISES INCORPORATING AT LEAST ONE PHENOL OF EITHER ONE OF THE FORMULAE: 4-((4-(HO-),R3,R4-PHENYL)-X-),R1,R2-PHENOL 2-((2-(HO-),R7,R8-PHENYL)-X''-),R5,R6-PHENOL AND 2-R9,3-R10,4-R11,5-R12,6-R13,7-R14,8-R15-1-NAPHTHOL WHEREIN X AND X'' ARE EACH ALKYLIDENE HVING 1 TO 6 CARBON ATOMS, CYCLOALKYLIDENE HAVING 3 TO 6 CARBON ATOMS, THIO, SULFINYL OR SULFONYL, R1, R2, R3, R4, R5, R6, R7 AND R8 ARE EACH HYDROGEN, ALKYL HAVING 1 TO 9 CARBON ATOMS OR CYCLOALKYL HAVING 3 TO 6 CARBON ATOMS AND R9, R10, R11, R12, R13, R14 AND R15 ARE EACH HYDROGEN, ALKYL HAVEING 1 TO 9 CARBON ATOMS OR PHENYL INTO A NORBORNENE SELECTED FROM THE GROUP CONSISTING OF ALKENYLNORBORNENES AND ALKYLIDENENORBORNENES.
Abstract: Preparation of new kinds of norbornene episulfides by use of arenethiosulfenyl chlorides has been investigated. Norbornene and 7,7-dimethylnorbornene afforded exo and endo epithio derivatives, respectively. Norbornadiene gave a mixture of exo and endo monoepithio compounds. The structure of the episulfides and of the intermediately formed adducts of the norbornenes with the chlorides is discussed on the basis of nmr spectra.