Showing papers on "Norbornene published in 1976"
73 citations
Patent•
07 Sep 1976TL;DR: Methylenemalonates are prepared by reacting a substituted norbornene with an electrophilic material in the presence of a lithium amide complex and pyrolyzing.
Abstract: Methylenemalonates are prepared by reacting a substituted norbornene with an electrophilic material in the presence of a lithium amide complex and pyrolyzing. The resulting acrylates are useful as fast setting, polymerizable adhesives.
47 citations
Patent•
16 Aug 1976TL;DR: In this paper, a process of producing a ring-opening polymerization product of a norbornene derivative containing at least one polar group or aromatic group using a catalyst system prepared from an organometallic compound was described.
Abstract: A process of producing a ring-opening polymerization product of a norbornene derivative containing at least one polar group or aromatic group, a norbornadiene derivative containing at least one of said groups or a cycloolefin using a catalyst system prepared from an organometallic compound and the reaction product of tungsten oxide or molybdenum oxide and a phosphorus pentahalide or phosphorus oxytrihalide or these compounds and other third components. The catalyst system possesses a high polymerization activity.
46 citations
TL;DR: In this paper, the authors provide evidence of steric control resulting in preferred substitutions at positions 2 and 5 and placement of the larger substituent at position 2 if the acetylenic precursor is disubstituted.
Abstract: Numerous new examples of the annelation reactions leading to cyclopentenone derivatives are reported They provide evidence of steric control resulting in preferred substitutions at positions 2 and 5 and placement of the larger substituent at position 2 if the acetylenic precursor is disubstituted A pathway accounting for such preference is suggested and the bulky trimethylsilyl group is utilized as a removable direction-determining group to allow synthesis of the 3- instead of 2-substituted cyclopentenones More remote substituents in the norbornene are shown to exert a significant but no longer decisive effect, so that mixtures of isomers result A 1H nmr study has shown that the ferrocenyl substituent in 7a-ferrocenyl-3a,4,5,6,7,7a-hexahydro-4,7-methanoinden-1-one (IX) cannot rotate about the bond joining it to position 7a
33 citations
TL;DR: In this article, a cross-addition of norbornene derivatives and dimethyl acetylenedicarboxylate to give exo-tricyclo[4.2.1.02,5]nonenes is described.
Abstract: [H2Ru(PPh3)4] catalyses the [2+2] cross-addition of norbornene derivatives and dimethyl acetylenedicarboxylate to give exo-tricyclo[4.2.1.02,5]nonenes.
32 citations
Patent•
13 Oct 1976
TL;DR: An organic solvent- or water-developable photosensitive composition consisting of a ring-opened polymer or copolymer of at least one norbornene derivative having at least a substituent selected from the group consisting of ester groups, nitrile groups, carboxyl groups, amide groups, imide groups and hydroxyl groups is presented in this paper.
Abstract: An organic solvent- or water-developable photosensitive composition consisting essentially of a ring-opened polymer or copolymer of at least one norbornene derivative having at least one substituent selected from the group consisting of ester groups, nitrile groups, carboxyl groups, amide groups, imide groups, hydroxyl groups, halogens and carboxylic acid anhydride groups, or a ring-opened copolymer of at least one said norbornene derivative and at least one cycloolefin other than cyclohexene, or a hydrolysis product of said ring-opened polymer or copolymer and a photosensitive crosslinking agent or photosensitizer soluble in organic solvents or water. The above photosensitive composition is excellent in sensitivity, adhesion and stability.
31 citations
TL;DR: In this paper, the authors investigated the title reaction in both directions in a static system and showed that at temperatures in the range 521-570 K the addition of ethylene to cyclopentadiene (CPD) results in the formation solely of norbornene (NB) and the decomposition of the latter produces only ethylene and CPD.
Abstract: The title reaction has been investigated in both directions in a static system. At temperatures in the range 521–570 K the addition of ethylene to cyclopentadiene (CPD) results in the formation solely of norbornene (NB) and the decomposition of the latter produces only ethylene and CPD. In a vessel of high surface : volume ratio, small quantities of nortricyclene are formed heterogenously. Kinetic studies support second and first orders for the addition and decomposition respectively. The mechanism C2H4+ CPD[graphic omitted]NB is almost certainly homogeneous and molecular in nature. Least means squares analysis of the data yields equations (i) and (ii). Equilibrium log(k1/s–1)=(14.26 ± 0.28)–(44.54 ± 0.72 kcal mol–1)/RTln10 (i) log (k1/l mol–1s–1)=(7.59 ± 0.63)–(23.67 ± 1.56 kcal mol–1)/RTln10 (ii) studies suggest that, for the addition, these Arrhenius parameters may be slightly high. Higher temperature investigations on this system (at equilibrium) indicate that no significant homogeneous molecular isomerisation of NB occurs with an activation energy < ca. 54 kcal mol–1.
24 citations
TL;DR: The sulphonyl chlorides have been characterized as a series of polychlorobenzene- sulphonamides, some of which have been converted into N-trichloromethylsulphenyl derivatives as discussed by the authors.
Abstract: 2,3,5,6-Tetrachlorobenzenesulphonyl chloride (2) and pentachlorobenzenesulphonyl chloride (4) have been obtained from the corresponding sulphonic acids (3) and (5) by treatment with phosphorus pentachloride. The sulphonyl chlorides have been characterized as a series of polychlorobenzene- sulphonamides, some of which have been converted into N-trichloromethylsulphenyl derivatives. The reaction of 1,2,4,5-tetrachlorobenzene with chlorosulphonic acid has been reinvestigated; comparatively short reaction periods gave mainly bis(pentachloropheny1) sulphide, and prolonged heating afforded hexachlorobenzene. Possible routes to these products are briefly discussed. Attempts to obtain 2,3,5,6-tetrachlorobenzenesulphonohydrazide (10) were unsuccessful; but the corresponding sulphonyl azide (11) has been prepared and its reactions with triphenylphosphine, norbornene and cyclohexene investigated.
21 citations
TL;DR: Low molecular-weight products have been obtained during ring-opening polymerization of norborene catalysed by several transition-metal halides; their identities and other evidence show that hydridometal complexes are involved in both dimerization reactions and carbene initiation.
Abstract: Low molecular-weight products have been obtained during ring-opening polymerization of norborene catalysed by several transition-metal halides; their identities and other evidence show that hydridometal complexes are involved in both dimerization reactions and carbene initiation.
20 citations
16 citations
TL;DR: In this article, Brained bicyclic olefins were found to undergo facile 1,3-cycloaddition reaction with trimethylsilyl azide.
Patent•
09 Feb 1976
TL;DR: In this article, a flame resistant composition of a ring-opening polymerization product of a norbornene derivative and a halogen-containing multicyclic compound or bromine-containing aromatic compound was proposed.
Abstract: A flame-resistant composition of (a) a ring-opening polymerization product of a norbornene derivative and (b) a halogen-containing multicyclic compound or bromine-containing aromatic compound The composition is employed in shaped articles and structural materials which are subjected to flame and heat exposure
Patent•
08 Apr 1976
TL;DR: In this paper, a ring-opening copolymerization of norbornene derivatives and cycloolefines was proposed to obtain the membrane for separation which can separate easily unsaturated compounds from the mixed solution of organic compounds.
Abstract: PURPOSE: To obtain the membrane for separation which can separate easily unsaturated compounds from the mixed solution of organic compounds, by forming film from the polymer obtained by carrying out the ring-opening (co)polymerization of norbornene derivatives having polar substituents in the specified positions or by carrying out the ring-opening copolymerization of these norbornene derivatives and cycloolefines COPYRIGHT: (C)1977,JPO&Japio
TL;DR: In this article, the effect of cyclic olefin adduct stereochemistry on the multiplicity pattern in the aromatic region of the proton spectrum is discussed as a probe to adduct stereoochemistry with this diene system.
Patent•
05 Apr 1976
TL;DR: In this paper, a ring opening polymers with high yields by the ring opening polymerization of norbornene derivatives using catalysts obtained from organometal compounds, reaction products of oxides of W and/or Mo with lewis acids and halogen-containing metal compounds.
Abstract: PURPOSE: To prepare ring opening polymers with high yields by the ring opening polymerization of norbornene derivatives using catalysts obtained from (a) organometal compounds, (b) reaction products of oxides of W and/or Mo with lewis acids and (c) halogen-containing metal compounds. COPYRIGHT: (C)1977,JPO&Japio
TL;DR: The reaction of norborn-2-ene with thallium(I) acetate-iodine in several solvents has been investigated in this article, and the products have been compared with those arising from similar treatment of Norbornene with silver-I acetate−iodine, which is indicative of an ionic pathway involving initial electrophilic addition of iodine followed largely by skeletal rearrangement characteristic of the bicyclo[2.2.1]heptyl system.
Abstract: The reaction of norborn-2-ene with thallium(I) acetate–iodine in several solvents has been investigated, and the products have been compared with those arising from similar treatment of norbornene with silver(I) acetate–iodine. The product distribution in each case is indicative of an ionic pathway involving initial electrophilic addition of iodine followed largely by skeletal rearrangement characteristic of the bicyclo[2.2.1]heptyl system.
Patent•
25 May 1976
TL;DR: In this article, a ring opening polymers in high yields, by ring opening polymerization of norbornene derivatives, etc., was presented by the use of a specific catalyst system containing a metal alkoxide compound.
Abstract: PURPOSE: To prepare ring opening polymers in high yields, by ring opening polymerization of norbornene derivatives, etc. by the use of a specific catalyst system containing a metal alkoxide compound. COPYRIGHT: (C)1977,JPO&Japio
TL;DR: The acid-catalysed addition of acetic acid to some cyclic and strained bicyclic olefins has been investigated using trifluoromethanesulphonic acid as the catalyst as discussed by the authors.
Abstract: The acid-catalysed addition of acetic acid to some cyclic and strained bicyclic olefins has been investigated using trifluoromethanesulphonic acid as the catalyst. For norbornene and related derivatives, the reaction rate was first order with respect to the catalyst acid but for cyclohexene there was evidence of a small contribution from a secondorder term. The addition was essentially non-stereospecific. Values of the kinetic isotope effect were less than unity for cyclic substrates but greater than unity for norborriene suggesting a change to rate-determining proton transfer. Activation parameters are reported together with new values for the acidity function H0 for CF3SO3H in acetic acid. The addition is discussed in terms of intimate and solvent-separated ion-pairs.
Patent•
30 Nov 1976
TL;DR: In this article, copolymers of the endo and exo cyclic adducts of maleic anhydride and cyclic conjugated dienes such as cyclopentadiene are presented.
Abstract: Novel copolymers of the endo and exo cyclic adducts of maleic anhydride and cyclic conjugated dienes such as cyclopentadiene The copolymers are prepared by heating either of the cyclic adducts in the presence of a free radical precursor, such as a peroxygen compound, at a temperature at which endo-exo isomerization of the adduct occurs
TL;DR: In this paper, the Stockmayer-Fixman relation was used to obtain from Δ[η] a molecular-weight independent function of composition, which is indeed negative for propylene-rich copolymers and zero for a 56% ethylene copolymer.
Abstract: Intrinsic viscosities have been measured at 25° on five ethylene–propylene copolymer samples ranging in composition from 33 to 75 mole-% ethylene. The solvents used were n-C8 and n-C16 linear alkanes and two branched alkanes, 2,2,4-trimethylpentane and 2,2,4,4,6,8,8-heptamethylnonane (br-C16). This choice was based on the supposition that the branched solvent would prefer the propylene segments and the linear solvent the ethylene segments, due to similarity in shape and possibly in orientational order. It was found that [η]n − [η]br ≡ Δ[η] is indeed negative for propylene-rich copolymers, zero for a 56% ethylene copolymer, and positive for ethylene-rich copolymers. The Stockmayer–Fixman relation was used to obtain from Δ[η] a molecular-weight independent function of composition. The quantities (Δ[η]/[η])(1 + aM−1/2) and Δ[η]/M are linear with the mole percent ethylene in the range investigated with 200 ≤ a ≤ 2000. The possibility of using these results for composition determination in ethylene–propylene copolymers is discussed. Intrinsic viscosities in the same solvents are reported for two samples of a terpolymer with ethylidene norbornene.
Patent•
30 Apr 1976
TL;DR: In this paper, a method for producing vinyl norbornene at a high yield preventing the formation of Diels-Alder reaction by-products which is characterized in that cyclopentadiene and butadiene are reacted in the presence of p-phenylenediamine compounds such as N-isopropyl-N'-phenyl-p-phenyi, N,N-diphenyl-P-phenylediamine and the like.
Abstract: A method for producing vinyl norbornene at a high yield preventing the formation of Diels-Alder reaction by-products which is characterized in that cyclopentadiene and butadiene are reacted in the presence of p-phenylenediamine compounds such as N-isopropyl-N'-phenyl-p-phenylenediamine, N,N'-diphenyl-p-phenylenediamine and the like.
TL;DR: In the presence of a silylating agents the sulphenic acid intermediate can be trapped as the trimethylsilyl derivative but this, in turn, under-goes a thermal rearrangement to give the enol ether.
Abstract: When the title compound (4) is heated for 1 ½ h in refluxing benzene a mixture of ring-expanded products, (6a)(25%) and (7)(67%), is obtained. In acetic anhydride, compounds (4) gives the acetate (6b) 77% as the only significant product, and in norbornene, dinorbornyl sulphoxide (12a) 35% is formed. In the presence of a silylating agents the sulphenic acid intermediate (5a) can be trapped as the trimethylsilyl derivative (5b) but this, in turn, under-goes a thermal rearrangement to give the enol ether (13).
Patent•
13 Jul 1976
TL;DR: In this paper, a homo-or copolymer of norbornene derivative using a coordination compound of W or Mo and titanium teterahalide as an highly active catalyst without using a dangerous-to-handle and expensive organometal compound.
Abstract: PURPOSE: To prepare homo-or copolymer of norbornene derivative using a coordination compound of W or Mo and titanium teterahalide as an highly active catalyst without using a dangerous-to-handle and expensive organometal compound. COPYRIGHT: (C)1978,JPO&Japio
TL;DR: In this article, the preferred endo-addition to 1,4-diphenyl-2-benzopyran-3-one (2; R1= R2= Ph) was attributed to inhibition of secondary interactions by non-coplanar phenyl substituents.
Abstract: Buta-1,3-diene, isoprene, cyclopenta-1,3-diene, dimethyl maleate, norbornadiene, norbornene, cis-but-2-ene, and cyclopentene add to 1,4-diphenyl-2-benzopyran-3-one (2; R1= R2= Ph) to give mostly exo-adducts; only for the addition of furan is the endo-adduct preferred. By comparison with the preferred endo-addition to 2-benzopyran-3-one, its 1-phenyl derivative (2; R1= Ph, R2= H), and 1,3-diphenylinden-2-one (15) the exo-selectivity in additions to (2; R1= R2= Ph) is attributed to inhibition of secondary interactions by non-coplanar phenyl substituents.
TL;DR: The reaction of solvated iodine oxide, prepared by ozonising a solution of iodine in acetic anhydride, with alkenes has been examined in this article, leading to vic-iodo-acetates, iodohydrins, and iodo-ketones.
Abstract: The reaction of solvated iodine oxide, prepared by ozonising a solution of iodine in acetic anhydride, with alkenes has been examined. The reaction is regiospecific and leads to vic-iodo-acetates, iodohydrins, and iodo-ketones. In some cases di- and tri-acetates and 2,2′-di-iodo-ethers are formed. The products from norbornene are similar to those formed with thallium(I) acetate and iodine. The mode of formation of the products is discussed and the effect of non-polar solvents is investigated.
TL;DR: In this paper, the hydration of norbornene (1) and nortricyclane (2) under the high temperature and dilute acid (HTDA) conditions of aqueous acetic acid at 250 °C gives as products exo-2-norborneol, endo- 2-norbornol, exo 2- and endo 2norbornyl acetate, and a mixture of stereoisomeric dinorbornyl ethers 4.2.
Abstract: The hydration of norbornene (1) and nortricyclane (2) under the high temperature and dilute acid (HTDA) conditions of aqueous acetic acid at 250 °C gives as products exo-2-norborneol, endo-2-norborneol, exo-2- and endo-2-norbornyl acetate, and a mixture of stereoisomeric dinorbornyl ethers 4. When the reactions are carried out in deuterated medium perdeuteration (>90% in one cycle) of the [2.2.1]-products is accomplished. Respectable overall yields (50–70%) of the products are obtained. Solvolysis of the products exo-norborneol, and endo-norbornyl acetate under HTDA(D) conditions also leads to perdeuterated 3a, 3b, 3c, 3d, and 4.
Patent•
14 Sep 1976
TL;DR: In this article, the authors proposed a method to remove a catalytic system from a title polymeric polymer using a coordination compound of W, W, a titamium halide, an acid amide, etc.
Abstract: PURPOSE: Easy removal of catalytic system from the title (co) polymer, using a catalytic system obtained by combining a coordination compound of W, etc., a titamium halide, an acid amide, etc. COPYRIGHT: (C)1978,JPO&Japio
Patent•
17 Feb 1976TL;DR: An acrylic copolymer composition capable of being vulcanized with sulfur comprising the radical polymerization product of (1) a monomer mixture comprising an acrylic acid ester, ethylidene norbornene, and acrylonitrile as mentioned in this paper.
Abstract: An acrylic copolymer composition capable of being vulcanized with sulfur comprising the radical polymerization product of (1) a monomer mixture comprising an acrylic acid ester and ethylidene norbornene, (2) a monomer mixture comprising an acrylic acid ester, ethylidene norbornene and acrylonitrile, (3) a monomer mixture comprising an acrylic acid ester and vinyl norbornene, or (4) a monomer mixture comprising an acrylic acid ester, vinyl norbornene and at least one unsaturated compound selected from the group consisting of monovinyl compounds, monovinylidene compounds and monovinylene compounds.