Showing papers on "Norbornene published in 1983"

Configuration and NMR study of tricyclic oxazines fused to a norbornene or norbornane skeleton

Abstract: Tricyclic oxazines fused with norbornane or norbornane were synthesized for pharmacological and stereochemical purposes. Analogous oxazin-2-ones and -2-thiones were also obtained. The diendo or diexo anellation of the hetero ring to the norbornene or norbornane skeleton was confirmed by 1H and 13C spectral data. The assignment of the proton signals was proved and the proton-proton coupling values were determined by double resonance experiments. With mono- and dichloroacetyl chloride, the oxazines fused to norbornene gave azetidinones which are mixtures of two isomers. The mixtures were separated into homogeneous substances, the configuration and conformation of which were determined via differential NOE experiments.

Benzo[e]isobenzofuran. Formation and reactions of the parent and alkoxy-substituted derivatives

Abstract: Synthese du naphto [1,2-c] furanne a partir des alcoxy-1 ou 3 dihydro-1,3 naphto [1,2-c] furannes; cycloadditions de ces composes avec divers dienophiles

Manufactured products having memory characteristics

Abstract: Produits finis a fonction memoire constitues d'une composition comprenant au moins 25 % en poids d'un polymere choisi parmi les homopolymeres et copolymeres amorphes et semi-cristallins du norbornene et de ses derives alcoyles, cyanes, alcoxyles, mono- ou diesterifies, imides et acides carboxyliques, les homopolymeres et copolymeres du dimethano-octahydronaphtalene et de ses derives, et les copolymeres du dimethano-octahydronaphtalene et d'un monomere choisi parmi le norbornene et ses derives, le styrene, l'acenaphtylene et le dicyclopentadiene. finite memory function products made of a composition comprising at least 25% by weight of a polymer selected from homopolymers and amorphous and semi-crystalline copolymers of norbornene and its derivatives alkylated, cyano, alkoxylated, mono- or diesterifies, imides and carboxylic acids, homopolymers and copolymers of dimethano-octahydronaphthalene and its derivatives, and copolymers of dimethano-octahydronaphthalene and a monomer selected from norbornene and its derivatives, styrene, acenaphthylene and dicyclopentadiene. Leur methode d'utilisation consiste a deformer ledit produit fini a l'etat solide, puis a le refroidir jusqu'a la temperature de transition vitreuse du polymere, et enfin a l'echauffer au-dessus de la temperature de transition vitreuse du polymere pour reprendre sa forme initiale. Their method of use consists in deforming said finished product in the solid state and then cooling it to the glass transition temperature of the polymer, and finally heat it above the glass transition temperature of the polymer for resume its initial shape.

Zur Lenkung der intramolekularen Diels‐Alder‐Reaktion von Cyclopentadienen mit olefinischen Substituenten

Abstract: On the Course of the Intramolecular Diels-Alder-Reaction of Cyclopentadienes with Olefinic Substituents The 1:3 mixture of 4-bromobicyclo [3.2.0]hept-2-en-6-one and -7-one (1/2), available by N-bromosuccinimide bromination of bicyclo [3.2.0]hept-2-en-6-one, reacted rapidly with the organo-magnesium and -zinc reagents 3, 10a, 10b and 10d by cyclobutanone ring opening and bromide ion expulsion to give the 5-substituted cyclopentadienes 5, 12a, 12b/12c, and 12d as non-isolated intermediates. Further transformation occured in situ either by a direct intramolecular Diels-Alder reaction (path a) or by a [1,5]-H-migration prior to the intramolecular Diels-Alder reaction (path b). The intermediate 5 followed only path a to give the bridged norbornene derivative 7, the intermediates 12a, 12b and 12c followed only path b to give the annellated norbornene derivatives 15a, 15b and 15c, respectively, and the intermediate 12d followed both paths to give the bridged 14d and the annellated norbornene derivative 15d (in the ration of about 1.4:1). These observations are discussed in terms of the relative velocities of [1,5]-H-migrations and intramolecular Diels-Alder reactions. The major conclusions are: (1) bridged norbornene derivatives with a six-membered ring C (such as 14d) can be prepared by an intramolecular Diels-Alder reaction from 5-alkenyl-cyclopentadienes 12, as long as the dienophilic double bond is activated by an appropriate substituent (as in 12d); (2) such 5-alkenyl-cyclopentadienes 12 are available from the reaction of the bromo-bicyclo-heptenones 1/2 with suitable C-nucleophiles 10.

Furazan N-oxides. Part 2. Synthesis and structure of some strained furazan N-oxides

Abstract: The strained furazan N-oxides (5) and (6) have been synthesised from norbornene and dicyclopentadiene by treatment with N2O3, thermal isomerisation of the resulting nitronitroso-adducts to the nitro-oximes [e.g.(9)], and subsequent dehydration at ambient temperature using SO3–DMF or CISO3H–DMF. Characterisation of the products is based on analytical and spectroscopic evidence by comparison with the known analogues (2) and (3), and in the case of (6) by X-ray crystal structure analysis. Compound (6) has endo-stereochemistry and is shown by 13C n.m.r. spectroscopy to be, like (2), a mixture of isomers, (6A) and (6B). X-Ray crystal structure analysis also showed that (3) has exo-stereochemistry and that for both (3) and (6) the O1–N2 bond of the oxadiazole is long (1.47 and 1.54 A).

Preparation of formylnorbornane containing polar functional group

Abstract: PURPOSE: To obtain the titled compound, by subjecting a norbornene containing a polar functional group to hydroformylation in the presence of a specific catalyst, bringing an aqueous solution of a bisulfite into contact with the prepared reaction mixture so that a formylnorbonane containing a polar functional group is extracted in the form of an addition product in the aqueous solution, separating it from a catalytic phase. CONSTITUTION: A norbornene shown by the formula I (X is polar functional group such as cyano, carbomethoxy, etc.) containing a functional group is subjected to hydroformylation with a mixed gas of H 2 and CO in an organic solvent immiscible with water in the presence of a catalyst consisting of a rhodium complex and a triarylphosphine. After the reaction is over, an aqueous solution of a bisulfite is brought into contact with the reaction mixture, formylnorbornane containing a polar functional group is extracted in the aqueous solution in the form of a bisulfite addition product, an organic solvent phase containing the catalyst is separated, to give the desired compound shown by the formula II. The organic solvent phase containing the separated catalyst is recycled to the reaction zone. USE: Various intrmediates useful in polymer fields such as polyester, etc. COPYRIGHT: (C)1985,JPO&Japio

The influence of conjugated dienes on the metathetical polymerization of cycloolefins

Abstract: Polymerisation du norbornene en presence de NCl 3 /Su(CH 3 ) 4 et de differentes quantites d'isoprene

Stereochemical versatillity in synthesis of substituted cycloalkanes from acyclic unsaturated sugars

Abstract: Acyclic unsaturated sugars obtained by Wittig extension of aldehydo arabinose precursors undergo stereoselective Diels–Alder addition of cyclopentadiene, permitting isolation of a single, crystalline, opticallly pure norbornene adduct whose stereochemistry may be controlled by the enantiomeric form of the sugar used and the conditions of the cycloaddition reaction.

Orbital interactions. XII: Product studies and competition kinetic measurements of the Birch reduction of a series of hexahydrodimethanonaphthalenes and their interpretation in terms of orbital interactions through space and through bonds

Abstract: Relative rate constants for the Birch reduction (Li/liq. NH3/ButOH) of the three isomeric hexahydrodimethanonaphthalenes (3)-(5) and the octahydro analogues (10)-(13) were obtained and compared with those obtained for the reduction of norbornadiene and norbornene from an earlier study. Diene (5) was reduced almost 2000 times more rapidly than norbornene and 20000 times more rapidly than the monoene (13). Rate-enhancement factors for dienes (3) and (4) were less substantial but meaningful: 19 for (3) [compared with (10)] and 35 for (4) [compared with (12)]. These rate enhancements were attributed to the operation of π* orbital interactions through space in diene (5) and to the presence of π* orbital interactions through four bonds in dienes (3) and (4). The existence of a linear relationship between the natural logarithm of the rate of reduction of a substrate and its LUMO energy (obtained from either gas-phase electron affinities or ab initio MO calculations) supports this conclusion. The only-fair correlation of the above relationship was attributed to the neglect of other factors, such as the electronic structure and the geometry of the anion radical, which contribute to the overall rate of the Birch reduction. These two factors were explored by using PMO theory and ab initio MO calculations. In particular, full geometry optimizations (UHF, STO-3G basis set) on the anion radicals of norbornadiene (1) (C2v symmetry constraint) and norbornene (22) (Cs symmetry constraint) were carried out, and their geometries reported. Noteworthy is the strong pyramidalization of the olehic centres of (1) and (22) in the endo direction. These pyramidalizations explain the observed stereoselective exo protonation of the anion radical of (1), and also the much faster rate of reduction of (1) compared with (5), since the pyramidalization in the anion radical of (5) is such as to hinder protonation. The geometries of anion radicals appear to have a profound effect on rates, on stereoselectivity of protonation, and on the structures of the final products, and this is discussed in detail. The synthesis of the diene (3) is also described.

Umwandlung von Bicyclo [3.2.0]hept-2-en-6-on in Cyclopentadienessigsäure-Derivate

Abstract: Conversion of Bicyclo [3.2.0]hept-2-en-6-one into Cyclopentadienylacetic Acid Derivatives The reaction of a mixture of 4exo-bromobicyclo [3.2.0]hept-2-en-6-one (2) and -7-one (3) with O- or N-nucleophiles yielded cyclopentadien-5′-yl-acetates 4a–f or-acetamides 4g–h. Due to their rapid isomerization, the products 4 were not isolated, but some of them were demonstrated spectroscopically or captured in situ with maleimide as 10′-substituted norbornene derivatives 7. The formation of 4 from 2/3 involves a fragmentation of the bond between the carbonyl and the bridge-head C-atom, induced by the attacking nucleophile and the leaving Br-ion and aided by the relief of the four-membered ring strain. Some of the isomerization products of 4, i.e. the cyclopentadiene-1′-yl- and 2′-yl-acetyl derivatives were captured with maleimide as the 1′- and 8′-substituted norbornene-derivatives 8 and 9. Two C-nucleophiles did not induce the fragmentation: sodium acetylacetonate substituted the Br-atom and sodium (diethoxyphosphoryl)ethoxycarbonylmethide condensed with the carbonyl group of 2/3, yielding 11/12 and 13/14, respectively.

The [4 + 2]cycloaddition reactions of aromatic thiones with maleic anhydride, norbornene, and norbornadiene

Abstract: The reactions of aryl 1-naphthyl thiones and aryl 2-naphthyl thiones with maleic anhydride, norbornene, and norbornadiene gave the 1,4-cycloadducts containing 3,4-dihydro-2 H-thiopyran rings. 7H-Benz[de]anthracene-7-thione also reacted with norbornene and norbornadiene to give similar 1,4-cycloadducts. In the reaction of aryl phenyl thiones with norbornene, initially formed cycloadducts rearranged to aromatized compounds. In these reactions, the aromatic thiones reacted with the olefins as a heterodiene system.

Cis-Dihydroxylation of Dimers obtained from Cyclopentadiene and Butadiene

Abstract: Diels-Alder reaction of cyclopentadiene and butadiene gives several dimers, which are considered to be valuable materials for various organic preparations. The cis-dihydroxylation of these dimers with N-methylmorpholine-N-oxide in the presence of a catalytic amount of osmium tetroxide was investigated to examine the regio- and stereoselectivities of the reaction. The hydroxylation of 4-vinyl-1-cyclohexene occurred exclusively at the double bond of cyclohexene ring to give two stereoisomeric mixture of cis-diols 2a and 2b. 5-Vinyl-2-norbornene led to the cis-diol 4 which was hydroxylated regio- and stereoselectively. The same reaction of cis-3a, 4, 7, 7a-tetrahydroindene gave cis-diols, 6 and 7, and tetrol 8 with a high stereoselectivity. On the other hand, the cis-hydroxylation of endo-dicyclopentadiene gave diols, 10 and 11, but that of exo-isomer afforded only cis-diol 13. Cis-dihydroxylation of norbornene ring and that of cyclopentene ring proceeded stereoselectively by one side attack, but that of cyclohexene ring occurred at both side of double bonds. It was assumed that these selectivities depended on the reactivity of double bond and on the steric effect between the substrate and oxidizing reagent in the transition state.

Donor-Acceptor Complexes in Copolymerization. LXIII. Alternating Diene-Dienophile Copolymers. 15. Copolymerization of Cyclopentadiene and the Isomeric N-Phenyl-5-norbornene-2,3-dlcarboximides with N-Phenylmaleimide

Abstract: The copolymerization of cyclopentadiene (CPD) and N-phenyl-maleimide (NPMI) at 80–195°C, in the presence of a radical catalyst having a short half-life at the reaction temperature and less than 25% solvent, yields a 1:2 CPD-NPMI copolymer (DP 2–3) which is identical (IR, NMR) to the endo 1:1 copolymer (DP 18) obtained under the same conditions from the copolymerization of the endo CPD-NPMI Diels-Alder adduct and NPMI. The exo CPD-NPMI adduct copolymerizes with NPMI under the same conditions to yield an exo 1:1 copolymer (DP 8). Under the same conditions the homopolymerization of the endo and exo CPD-NPMI adducts is effected in the melt at temperatures up to 260°C and in solution at 120–155°C. The homopolymers (DP 3–7) prepared below 210°C retain the configuration of the adducts while the homopolymers prepared at 260°C from either isomer contain both endo and exo configurations due to isomerization. The participation of excited species is suggested by the requirement for high-speed decomposition o...

Process for the production of polymers and copolymers of vinyl chloride by suspension polymerization and their use as viscosity reducing agents in plastisol processing

Abstract: Production of suspension polyvinyl chloride suitable for reducing the viscosity of polyvinyl chloride plastisols is effected by suspension polymerization in the presence of small amounts of (a) an ethylene/propylene/ethylidene norbornene terpolymer having a propylene content of 40-50% by weight, with 5-15 double bonds per 1,000 carbon atoms and with a viscosity of 4-20 mPa s, measured with 2% solutions in trichloroethylene at 25° C; and/or (b) a polyvinyl isobutyl ether having a K value of 80-150, measured with 05% solutions in isooctane at 20° C, wherein the catalysts, the ethylene/propylene/ethylidene norbornene terpolymer and/or the polyvinyl isobutyl ether and the monomer or comonomer mixture are added to the polymerization batch before adding the suspension agent or the suspension agent mixture These suspension polymers are used as additives for polyvinyl chloride plastisols

Resin composition having excellent impact resistance

Abstract: PURPOSE:To prepare a resin composition having improved thickness dependence of impact strength, by compounding a norbornene resin with an ethylene-propylene-diene copolymer grafted with vinyl chloride to improve the compatibility CONSTITUTION:The objective resin is prepared by mixing (A) 100ptswt of a norbornene ring-opening polymer resin composed of 100-5mol% of a norbornene ring-opening polymer unit having carboxylic acid group and 0-95mol% of a norbornene ring-opening polymer unit having carboxylic acid ester group with (B) 2-40ptswt, preferably 3-20ptswt of an ethylene-propylene-diene copolymer grafted with 30-80wt%, preferably 40-60wt% of vinyl chloride

Removing or recovery of oil

Abstract: PURPOSE:To remove or recover oil efficiently, by adding slurry made by dispersing powdery norbornene polymer in water containing surface active agent to oil floating on water or sea water. CONSTITUTION:A surface active agent is dissolved in water and powdery norbornene polymer such as ring-opening polymer etc. of bicyclo(2.2.1)heptene 2 is added to this aqueous solution agitated to prepare a slurry solution. For the surface active agent, any one of anionic active agent, cationic active agent, non- ionic active agent can be used, and >=2wt.% of the weight of norbornene polymer is added. The slurrylike norbornene polymer thus prepared is scattered by adequate means on the surface of water or sea water on which oil is floating and brought into contact with the oil to adsorb and remove the oil.

Foam of norbornene ring-opening polymer

Abstract: PURPOSE:The titled foam excellent in shape retention and suitable as a heat- insulating material for refrigeration pipes, prepared by foaming a polymer consisting of a ring-opening polymer of norbornene containing carboxylate ester groups and a ring-opening polymer of norbornene containing carboxylic acid groups. CONSTITUTION:A 5-norbornene-2-carboxylate ester is polymerized with the aid of a metathesis catalyst and, if required, a part of the carboxylate ester groups of the polymer are hydrolyzed. Thus, there is obtained a norbornene ring- opening polymer which consists substantially of 100-10mol% norbornene ring- opening polymer composed of repeating units of formula I , wherein R1 is H, an alkyl or a phenyl, R2 is H or an alkyl and R3 is an alkyl, and 0-90mol% norbornene ring-opening polymer composed of repeating units of formula II, and in which the content of an isomer having trans double bonds is at least 40%. Then, this polymer is foamed to obtain the titled foam.