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Showing papers on "Norbornene published in 1978"



Journal ArticleDOI
TL;DR: In this article, the standard enthalpies of combustion for five C 7 bridged-ring hydrocarbons have been measured in a static combustion bomb calorimeter, based on the dependence of vapour pressures on temperature.

37 citations



Journal ArticleDOI
TL;DR: In this paper, the electrophilicity of 2,4-dinitrobenzenesulphenyl chloride in its addition to norbornene and dimethoxybenzonorbornadiene in formic acid has been studied.

21 citations


Journal ArticleDOI
TL;DR: A cobalt complex, formed by reducing [Co(acac)3] with diethyl-aluminium chloride in the presence of the bidentate ligand bis(1,2-diphenylphosphino)ethane, is an active catalyst for the stereoselective [2 + 2 + 2] cycloaddition of norbornene to norbornadiene as mentioned in this paper.
Abstract: A cobalt complex, formed by reducing [Co(acac)3](Hacac = acetylacetone) with diethyl-aluminium chloride in the presence of the bidentate ligand bis(1,2-diphenylphosphino)ethane, is an active catalyst for the stereoselective [2 + 2 + 2] cycloaddition of norbornene to norbornadiene.

17 citations


Journal ArticleDOI
TL;DR: The photochemical reaction of norbornadiene and α, β-unsaturated nitriles, esters and amides in the presence of Fe(CO)5 was studied in this paper.
Abstract: Iron Pentacarbonyl Induced Reactions of Norbornadiene and Substituted Olefins The photochemical reaction of norbornadiene and α, β-unsaturated nitriles, esters and amides in the presence of Fe(CO)5 was studied. Nitriles furnished the dinorbornenyl ketones 2a-c (Scheme 1). Esters led to an addition of a norbornene moiety to the double bond giving the substituted α, β-unsaturated esters 10a and 10b (Scheme 5). Methacrylamide and methyl β-aminocrotonate gave the cyclopentanone derivatives 14 and 17, respectively (Schemes 7 and 8). The reaction was in all cases highly stereoselective with general exo-substitution on the norbornadiene. The attack on the unsymmetric olefins occurred regiospecifically at that point of the double bond which was furthest away from the functional group. A plausible mechanism for these reactions is suggested in Schemes10and11.

13 citations


Journal ArticleDOI
TL;DR: In this article, the authors showed that exo-norbornenol can be isomerized with potassium hydride in tetrahydrofuran at room temperature, and showed that the process can be extended to exoBicyclo.
Abstract: exo-Bicyclo[3.2.0]hept-2-en-7-ol can be isomerized to exo-norbornenol on treatment with potassium hydride in tetrahydrofuran at room temperature.

13 citations


Journal ArticleDOI
TL;DR: In this article, the chlorination of norbornene and cyclooctadienes with sulfuryl chloride and phosphorus(V) chloride has been investigated mainly in carbon tetrachloride under various conditions.
Abstract: The chlorination of norbornene and cyclooctadienes with sulfuryl chloride and phosphorus(V) chloride has been investigated mainly in carbon tetrachloride under various conditions. From the studies of the product distributions and the effect of radical scavengers, the following facts have been revealed for the first time in olefin chlorination: chlorination with sulfuryl chloride proceeds through an ionic pathway at room temperature or in the presence of silica gel and that with phosphorus(V) chloride through a radical pathway at elevated temperature, and an ionic chlorination with phosphorus(V) chloride in nonpolar solvents does not seem to involve C–P bond formation through the reaction.

10 citations


Journal ArticleDOI
TL;DR: A convenient and reproducible three-step synthesis, starting from norbornene, gives 1,3-cyclopentanedione (6) in excellent purity and 70% overall yield as mentioned in this paper.
Abstract: 1,3-Cyclopentanedione — a Prized Reagent A convenient and reproducible three-step synthesis, starting from norbornene, gives 1,3-cyclopentanedione (6) in excellent purity and 70% overall yield.

9 citations


Patent
28 Jul 1978
TL;DR: A norbornane or norbornene derivative of the formula (I): "STR1" is a derivative with a characteristic odour of sandalwood oil and useful for perfumery; and a process for the production thereof as discussed by the authors.
Abstract: A norbornane or norbornene derivative of the formula (I): ##STR1## wherein the bond represented by the dotted line is present or absent and n is 0 or 1, the norbornane and norbornene derivatives having a characteristic odor of sandalwood oil and useful for perfumery; and a process for the production thereof.

8 citations


Journal ArticleDOI
TL;DR: In this paper, it was shown that ethyl aluminium dichloride under certain conditions catalyses the ring-opening polymerization of norbornene as well as the formation of oligomers; the possible wider significnce of this observation for Ziegler-Natta polymerization is briefly discussed.
Abstract: Ethyl aluminium dichloride under certain conditions catalyses the ring-opening polymerization of norbornene as well as the formation of oligomers; the possible wider significnce of this observation for Ziegler–Natta polymerization is briefly discussed.

Journal ArticleDOI
TL;DR: The reactivity of cyclopropylalkenes, as well as norbornene and cyclohexene, with p-chlorobenzenesulfenyl chloride in CH2Cl2 at 25 °C have been measured as mentioned in this paper.
Abstract: The reactivity of a series of cyclopropylalkenes, as well as norbornene and cyclohexene, with p-chlorobenzenesulfenyl chloride in CH2Cl2 at 25 °C have been measured. Rates of reaction of several of...

Journal ArticleDOI
TL;DR: In this paper, it has been suggested that the reaction proceeds by syn-E1 and SN1 mechanisms, and that the carboxylates which are produced in the presence of water are derived from an imidatonium ion [R-Amide]+, which is formed by the attack of carboxamide on the intimate ion-pair [R+X−].
Abstract: Solvolysis of exo-2-norbornyl arenesulfonates (RX: X=OTs (1a), –OSO2C6H4–p–OCH3, –OSO2C6H5, and OBs) and the deuterium labeled tosylates (1a-3-endo-d, 1a-3-exo-d, and 1a-3,3-d2) has been carried out in four carboxamides (N-methylformamide, N-methylacetamide, N,N-dimethylformamide, and N,N-dimethylacetamide (DMA) at 25–100 °C. The solvolysis has also been conducted in the solvents containing 0.01–0.2 mol/dm3 water. On the basis of kinetic measurements, product analyses, and the examination of isotopic distribution in the reclaimed substrate and the products (nortricyclene, norbornene, and exo-norbornyl carboxylates) it has been suggested that the reaction proceeds by syn-E1 and SN1 mechanisms, and that the carboxylates which are produced in the presence of water are derived from an imidatonium ion [R-Amide]+, which is formed by the attack of carboxamide on the intimate ion-pair [R+X−]. It has been observed that the isotopic scrambling occurs only between C(3) and C(7) positions of both norbornene and the r...

Journal ArticleDOI
TL;DR: In this article, other color components than those mentioned above and the cause of coloring petroleum resin by cyclopentadiene and methyl derivative were investigated, and the structures of some conjugated systems which color the petroleum resin were inferred from the data of ESR spectra.
Abstract: In a previous report, it was found that some of the color components in the starting material of petroleum resin were cyclopentadiene, methylcyclopentadiene, and their dimers. In the present study, other color components than those mentioned above and the cause of coloring petroleum resin by cyclopentadiene and methyl derivative were investigated. Norbornadiene and ethylidene norbornene were found also to be color components, and the structures of some conjugated systems which color the petroleum resin were inferred from the data of ESR spectra.

Journal ArticleDOI
TL;DR: In this article, the results obtained were compared with those of epoxidation with organic peracids, and it was assumed that such high regioselectivity may be attributable to a steric effect established between the bridge head proton of the norbornene ring in DCP and the epoxidizing agent.
Abstract: Diels-Alder reactions between cyclopentadiene (CP) and butadiene (BD) give a variety of dimers such as 4-vinyl-cyclohexene (VCH), 5-vinyl-2-norbornene (VNB), cis-3a, 4, 7, 7a-tetrahydroindene (THI) and dicyclopentadiene (DCP), and these dimers contain two double bonds of different reactivity.In the present investigation, the epoxidation of these dimers with hydrogen peroxide catalyzed by metal oxides such as SeO2, H2MoO4 and H2WO4 was carried out under various reaction conditions, and the results obtained were compared with those of epoxidation with organic peracids.The reaction of VCH (1) with hydrogen peroxide catalyzed by SeO2 at 40°C for 5hr [Eq. (1)] did not give an epoxide but diol (2) in a 40% yield. In the oxidation of VCH by H2MoO4 and H2WO4 catalysts, diol (2) was also obtained but in lesser yields than by SeO2 catalyst.The epoxidation of VNB (3) with hydrogen peroxide by SeO2 yielded 33% monoepoxide (4), but H2MoO4 and H2WO4 catalysts were less selective [Eq. (2)].When THI (5) was epoxidized with hydrogen peroxide by SeO2 catalyst, monoepoxide (6) and indene (7) were obtained in 27% and 8% yields, respectively [Eq. (3)], while in the epoxidation by H2MoO4 and H2WO4 catalysts only (6) resulted in yields from 10 to 15%.On the other hand, the epoxidation of THI with perbenzoic acid yielded monoepoxides (6) and (8) in a 4:5 molar ratio and diepoxide (9) [Eqs. (4) and (5)].It was found that the present catalytic epoxidation indicated a higher selectivity for the epoxidation of THI compared with that of epoxidation with perbenzoic acid.For the formation of indene (7), it seems reasonable to assume that dehydrogenation is generally observed in the oxidation of cyclic compounds using SeO2.The epoxidation of DCP (10) occurred readily without any side reactions except when a V2O5 catalyst was used to give monoepoxides (11) and (12) as shown in Eq. (6).Effects of various solvents were examined in the reactions with the SeO2 catalyst, and it was found that epoxidation proceeded rapidly in a protonic solvent having a lower polarity such as tert-butyl alcohol.An extremely high ratio of (11)/(12) as compared with that of epoxidation by organic peracid was observed with the catalysts used. It is assumed that such high regioselectivity may be attributable to a steric effect established between the bridge head proton of the norbornene ring in DCP and the epoxidizing agent.

Patent
11 Jan 1978
TL;DR: In this article, a highly active catalystic system composed of specific organo-metallic compounds and specific co-crushed product was used for ring-opening polymerization of norbornene derivatives.
Abstract: PURPOSE:The ring-opening polymerization of norbornene derivatives, etc., by the use of a highly active catalystic system composed of specific organo-metallic compounds and specific co-crushed product, with reduced lowering of the activity caused by the presence of polar groups of the monomers.

Patent
15 May 1978
TL;DR: In this article, a mono or dialkyl substituted norbornenes or cyclic norbornene derivatives are prepared by condensing an appropriate olefin or an ethylenically unsaturated alicyclic compound with dicyclopentadiene or cyclopentadene at an elevated temperature and pressure in the presence of a chlorinated hydrocarbon solvent.
Abstract: Mono or dialkyl substituted norbornenes or cyclic norbornene derivatives are prepared by condensing an appropriate olefin or an ethylenically unsaturated alicyclic compound with dicyclopentadiene or cyclopentadiene at an elevated temperature and pressure in the presence of a chlorinated hydrocarbon solvent.

Patent
07 Sep 1978
TL;DR: In this article, the ring-opening polymerization of norbornene or norbornadiene derivative is conducted in the presence of a specific catalyst, and it is shown that the ring opening polymerization is reversible.
Abstract: PURPOSE:The ring-opening polymerization of norbornene or norbornadiene derivative is conducted in the presence of a specific catalyst.

Patent
02 May 1978
TL;DR: In this paper, the polymer of a norbornene derivative containing COOH group in a mono-(di) alkyl N-substitution product of an organic acid amide of carbon number of 1-2 was dissolved and formed from this solution in the specified condition.
Abstract: PURPOSE:To produce the membrane having high separating capacity and permeability, by dissolving the polymer of a norbornene derivative containing COOH group in a mono-(di) alkyl N-substitution product of an organic acid amide of carbon number of 1-2 and by forming the film from this solution in the specified condition.

Journal ArticleDOI
TL;DR: In this paper, the decay of triplet acetophenone produced in benzene by both pulse radiolysis and pulse laser photolysis techniques was investigated and the dependence of this decay on the concentrations of norbornene andacetophenone was shown.


Patent
02 Mar 1978
TL;DR: In this paper, a resin composition having improved impact resistance, and other mechanical characteristics, comprising a specific norbornene polymer and a vinyl chloride polymer, was proposed, which is a combination of two materials.
Abstract: PURPOSE:A resin composition having improved impact resistance, and other mechanical characteristics, comprising a specific norbornene polymer and a vinyl chloride polymer

Patent
24 Aug 1978
TL;DR: In this paper, a ring-opening polymer of norbornene or its derivative, containing reduced amount of residual monomer, was prepared in a simplified process, wherein the polymer solution was thickened in a stirring-thin membrane evaporator and degassed in a vent type-surface renewal deaerator.
Abstract: PURPOSE:To prepare economically a ring-opening polymer of norbornene or its derivative, containing reduced amount of residual monomer, in a simplified process, wherein the polymer solution is thickened in a stirring-thin membrane evaporator and degassed in a vent type-surface renewal deaerator.

Patent
14 Aug 1978
TL;DR: In this article, the saturated exo-exo hexacyclic dimer of norbornadiene and nobornene is codimerized to a three-component homogeneous catalytic system consisting of cobaltic or cobaltous acetylacetonate, 1,2-bisdiphenylphosphino ethane and an alkyl aluminum chloride.
Abstract: Norbornadiene and nobornene are catalytically codimerized to the saturated exo-exo hexacyclic dimer of norbornadiene. Used is a three-component homogeneous catalytic system consisting of cobaltic or cobaltous acetylacetonate, 1,2-bisdiphenylphosphino ethane and an alkyl aluminum chloride. Resulting dimer can be used as a component of high energy fuel.

Patent
15 May 1978
TL;DR: In this paper, the authors proposed a copolymer prepared by grafting a vinyl compound onto a rubber-like material and a graft or block copolymers obtained from a rubberlike polymer and a norbornene derivative.
Abstract: PURPOSE: The title composition having improved impact resistance, comprising a copolymer prepared by grafting a vinyl compound onto a rubber-like material and a graft or block copolymer obtained from a rubber-like polymer and a norbornene derivative. CONSTITUTION: A rubber-like material (A) or a copolymer (B) obtained by grafting 70W15 parts by wt. of a vinyl compound, e.g. a vinyl cyanide, aromatic vinyl or methacrylate compound, onto the material (A) or both are incorporated with a graft or block copolymer (C) obtained by bringing a mixture of a norbornene derivative having a polar group, e.g. a nitrile, ester, or N-substituted imido group, and a rubber-like polymer (D) having corbon-carbon double bonds into contact with a metathesis catalyst to give the total content of the material (A) and the polymer (D) in the composition of 30W85 wt.%. COPYRIGHT: (C)1979,JPO&Japio

Patent
07 Sep 1978
TL;DR: In this article, a norbornene polymer molded article with an acrylic resin paint diluted with a specific diluent was used to obtain a coating film easily, having high glossiness and adhesivity, without lowering the mechanical properties of the substrate.
Abstract: PURPOSE:To obtain a coating film easily, having high glossiness and adhesivity, without lowering the mechanical properties of the substrate, by coating a norbornene polymer molded article with an acrylic resin paint diluted with a specific diluent.

Patent
12 Aug 1978
TL;DR: In this paper, a tin-containing organic compound and a phosphite ester are incorporated to a polymer containing norbornene derivatives to provide a ring-opening polymer composition of good heat-discoloration resistance.
Abstract: PURPOSE:A tin-containing organic compound and a phosphite ester are incorporated to a polymer containing norbornene derivatives to provide a ring-opening polymer composition of good heat-discoloration resistance.

Journal ArticleDOI
TL;DR: In this paper, the addition of diethyl N, N -dichlorophosphoroamidate (DCPA) to α-pinene and norbornene has been described.

Patent
20 Sep 1978
TL;DR: A rubber composition with high green strenth giving vulcanized rubber with improved wear and wet skid resistance and tensile strength, which is composed of a polymer rubber and a ring-opening polymer of a norbornene derivative, was proposed in this article.
Abstract: PURPOSE:A rubber composition with high green strenth giving vulcanized rubber with improved wear and wet skid resistance and tensile strength, which is composed of a polymer rubber and a ring-opening polymer of a norbornene derivative.

Journal ArticleDOI
TL;DR: In this paper, the cyclopentanone was always formed in these reactions and the reaction of disubstituted acetylenes such as dimethyl acetylenedicarboxylate and ethyl phenylpropiolate, respectively.
Abstract: Photochemical reactions of norbornadiene with substituted acetylenes in the presence of Fe(CO)5 gave various products of different types, depending on the nature of the acetylene. The results are summarized in Table 1. The cyclopentanone 1 was always formed in these reactions. In the reaction of disubstituted acetylenes such as dimethyl acetylenedicarboxylate and ethyl phenylpropiolate, the cyclopentenones 2 and 5 were formed, respectively. By contrast, propiolic esters produced the cyclohexenones 3 and 4, in which the ester group was attached on the β carbon with respect to the keto group. Plausible mechanisms for the formation of these products are shown in Schemes 7 and 8. The reaction of diphenylacetylene gave the cyclohexendione 7 as well as the cyclopentenone 6. Two enedione products 8 and 9 were obtained from the reaction of phenylacetylene. Compound 9 was converted to the aromatic diacetate 13 by heating with acetic anhydride in pyridine. On irradiation in the presence of Fe(CO)5 norbornene reacted similarly with dimethyl acetylenedicarboxylate and phenylacetylene to give the cyclopentenone 14 and the cyclohexenone 15, respectively. Compound 15, upon heating, isomerized to hydroquinone 16, which on acetylation gave the diacetate 17.