Showing papers on "Norbornene published in 1974"

Studies in azide chemistry. Part VI. Some reactions of perfluoroazidobenzene and perfluoro-4-azidotoluene

Abstract: Perfluoroazidobenzene readily undergoes the Staudinger reaction with triphenylphosphine, reacts with dimethyl sulphoxide at elevated temperatures to yield a sulphoximide, partakes in 1,3-dipolar cycloaddition reactions with diphenylacetylene, phenylacetylene, cyclopentadiene dimer, norbornene, and acrylonitrile, and, at 130 °C or above, gives the C–H ‘nitrene insertion’ product C6F5·NHPh with benzene, and, inter alia, the N–H ‘nitrene insertion’ products C6F5·N:NPh, C6F5·N:N·C6H4F-p, and C6F5·N:N·C6F5 with aniline, p-fluoroaniline, and pentafluoroaniline, respectively.Perfluoro-4-azidotoluene reacts with dimethyl sulphoxide, cyclohexane, aniline, and pentafluoroaniline at 160 °C to yield ArFN:S(:O)Me2, ArFNH·C6H11, ArFN:NPh + anilino-substituted derivatives, and ArFN:N·C6F5, respectively (ArF=p-F3C·C6F4).The nitrenoid N–H ‘insertion’ reactions provide a new method for the synthesis of unsymmetrical polyfluorinated aromatic azo-compounds.

Ring-Opening polymerization of cycloolefins with catalysts derived from ruthenium and iridium†

Abstract: An investigation was carried out on the polymerization of norbornene, cyclopentene and cyclooctene by the following iridium and ruthenium compounds: chlorobis(cyclooctene)iridium (1), carbonylchlorobis(cyclooctene)iridium (2), trifluoroacetatobis(cyclooctene)iridium (3), chloroiridic(IV) acid (4), dichloro(2,7-dimethylocta-2,6-diene-1,8-diyl)-ruthenium (5a), and bis(trifluoroacetato)-(2,7-dimethylocta-2,6-diene-1,8-diyl)ruthenium (5b). All the above catalysts were found to be very active for the polymerization of norbornene via ring-opening. Iridium catalysts were practically inactive for the polymerization of cyclopentene and cyclooctene, but gave copolymers of norbornene with cyclopentene and cyclooctene via ring-opening. The ruthenium catalysts displayed no activity for the polymerization of cyclopentene and cyclooctene, but it was found that after treatment with H2 they became active for the polymerization of cyclopentene. The results obtained from the reaction of norbornene and aliphatic olefins suggest that the above catalysts act by metathesis. The particular features of these catalysts were examined. Die Untersuchung der Polymerisation von Norbornen, Cyclopenten und Cycloocten wurde mit folgenden Iridium- und Ruthenium- Verbindungen durchgefuhrt: Chlorobis(cycloocten)iridium (1), Carbonylchlorobis(cycloocten)iridium (2), Trifluoroacetatobis(cycloocten)iridium (3), Chloriridiumsaure (4), Dichloro(2,7-dimethylocta-2,6-dien-1,8-diyl)ruthenium (5a) und Bis(trifluoracetato)-(2,7-dimethylocta-2,6-dien-1,8-diyl)ruthenium (5b). Diese Verbindungen erwiesen sich als sehr aktive Katalysatoren fur die Polymerisation von Norbornen durch Ringoffnung. Die Iridiumverbindungen waren praktisch inaktiv fur die Katalyse der Polymerisation von Cyclopenten und Cycloocten, gaben jedoch Copolymere des Norbornens mit Cyclopenten und Cycloocten uber eine Ringoffnung.Die Rutheniumverbindungen zeigten keinerlei Aktivitat fur die Polymerisation von Cyclo-penten und Cycloocten. Nach Behandlung mit Wasserstoff wurden sie jedoch aktiveKatalysatoren fur die Polymerisation von Cyclopenten. Die bei der Reaktion von Norbor-nen und den aliphatischen Olefinen erhaltenen Ergebnisse lassen darauf schliekn, daB die oben erwahnten Katalysatoren iiber eine Metathesis wirksam sind. Die speziellen Eigenschaften dieser Katalysatoren wurden untersucht.

Reaction of Singlet Oxygen with 2‐Methylnorborn‐2‐ene, 2‐Methylidenenorbornane, and their 7,7‐Dimethyl Derivatives. The transition state geometry for hydroperoxidation

Abstract: The dye-sensitized photo-oxygenation of 2-methylnorbonr-2-ene (3), 2-methylidene-norbornane (4) and their 7,7-dimethyl derivatives (5 and 6) has been studied. In all cases allylically rearranged hydroperoxides were formed, except that 4 also gave a little norbornanone (presumably from the dioxetane) and 5 gave some endo-3,7,7-trimethylnorbornan-2-one as a secondary photo-product. It was found that the exo/endo attack ratios by singlet oxygen on 3 and 5 are 66 and 0.19. By exploiting the C (3) monodeuteriated derivatives, 4 and 6 showed ratios of 28 and 0.67. Rates of reactivity of the olefins 3 and 4 were compared to methylidenecyclopentane, 1-methylcyclopentene and 1-methylcyclohexene as monocyclic standards. Additionally, comparative rates between the 7,7-dimethyl olefins and their parents were measured. When further comparison was made of the rate ratios partitioned for exo and endo attack, it was seen that oxygen experienced a 500- to 1000-fold rate retardation on approach to the endo side of 3 compared to that for its monocyclic analogue. Exo rates between the parent norbornene 3 and its 7,7-dimethyl derivative 5 showed a 250-fold decrease. Although four times smaller than the difference reported for epoxidation, the evidence clearly pointed to a one-step cyclic process as the rate determining step for photo-oxygenation. The steric evidence, taken with the low values found for the intermolecular isotope effects of 1.14 ± 0.01 and 1.02 ± 0.01 observed for exo and endo-3-deuterio-2-methylidene-norbornanes, permits the deduction that the transition state is largely dipolar. In the early stages of the addition bonding between one end of the oxygen molecule and the terminal vinyl carbon is advanced. At the same time positive charge is dispersed by hyperconjugation between the central carbon atom and the allylic carbon-hydrogen bond. At a later stage the anionic oxygen atom abstracts the loosened allylic hydrogen atom to create the hydroperoxide. No evidence for the formation of a discrete perepoxide intermediate was obtained.

The Chlorination of Olefins with Antimony(V) Chloride

Abstract: Antimony(V) chloride was revealed to be a good reagent for the cis-chlorination of simple olefins in chlorinated hydrocarbon solvents, such as 1,2-dichloroethane, dichloromethane, chloroform, and carbon tetrachloride. The higher the reaction temperature or the solvent polarity was, the higher the selectivity for cis-chlorination became. From 1,3-butadiene, cis-1,4-dichloro-2-butene was formed together with the trans-1,4- and 1,2-dichloro isomers. In the cases of cyclopentene and norbornene, the trans-1,2-dichloride and other various dichlorides were obtained without any formation of the cis-1,2-isomer. Probable mechanisms for this chlorination are briefly discussed.

Process for producing polymers or copolymers of norbornene-carboxylic acid amides

Abstract: Novel polymers or copolymers of norbornene-carboxylic acid amides can be obtained by contacting, in the presence or absence of an inert solvent, (I) at least one compound selected from the group consisting of 5-norbornene-2-carboxylic acid amide, 5-norbornene-2,3-dicarboxylic acid diamide and substituted derivatives thereof, or (II) a mixture of the said compound (I) with at least one compound selected from the group consisting of norbornenes having at least one substituent selected from the group consisting of ester groups, nitrile groups, esterified hydroxyl groups, acid imide groups, halogens and acid anhydride groups and cyclic olefins, with a catalyst composed of (a) at least one compound selected from the group consisting of compounds of W, Mo and Re and (b) at least one compound selected from the group consisting of compounds of elements of Groups IA, IIA, IIB, IIIA, IVA and IVB of the Deming Periodic Table, said compounds having at least one element-carbon bond or element-hydrogen bond.

Method of polymerizing carbonimide norbornene derivatives

Abstract: A method of polymerizing imide type norbornene derivatives which comprises the ring-opening polymerization of imide type norbornene derivatives containing at least one N-substituted cyclic imide group or a mixture consisting of said norbornene derivatives as the main component and cycloolefins in the presence of a catalytic system comprising organic aluminum compounds and tungsten and/or molybdenum compounds

Molybdenum(V) Chloride as a Reagent for cis Chlorination of Olefins

Abstract: Treatment of nonconjugated olefins such as cis- and trans-2-butenes, cis-2-octene, and cyclohexene with MoCl5 in CCl4 gave vic-dichloroalkanes whose cis-isomer was formed predominantly, the ratio of cis- to trans-addition being 4.9–12.1, together with monochloroalkanes. Preferential formation of exo-cis-dichloride was observed in the case of norbornene and norbornadiene. Bromochlorination and chloroiodination of olefins, and aromatic bromination and iodination were carried out with mixtures of MoCl5 and halogens. The reaction scheme for chlorination is discussed.

Participation of Non‐Conjugated Double Bonds in Diels‐Alder Reactions. A kinetic study of the addition of tropone to norbornens

Abstract: A kinetic study of Diels-Alder additions between norbornene derivatives acting as dienophiles and the dienes tropone, perchlorocyclopentadiene and 9,10-dimethylanthracene is presented. The results suggest that tropone thereby acts as an electron acceptor, classifying these reactions then as Diels-Alder additions with ‘inverse electron demand’. The role of non-reacting double bonds was investigated using 7-alkylidenorbornene derivatives as dienophiles. These show comparable reactivity in ‘normal’ but enhanced reactivity in ‘inverse electron demand’ Diels-Alder additions. This outcome is interpreted in terms of frontier orbital interactions between the reactants using photoelectron spectroscopical results as a basis for the qualitative perturbation treatment. It is suggested that the enhanced reactivity in the case of the 7-alkylidene derivatives does not necessitate the consideration of a direct (‘through-space’) participation of the non-reacting double bond.

NMR studies of bridged ring systems: XIX—13C1H spin coupling and 13C chemical shift of the bridge methylene in benzonorbornene and benzonorbornadiene†

Abstract: Data on 13C chemical shifts and 13C1H spin coupling constants of norbornane (1), norbornene (2), norbornadiene (3), benzonorbornene (4) and benzonorbornadiene (6) are reported. The non-equivalence in J(13CH) values determined from the two bridge methylene proton signals in 2,2,3,3-tetradeuteriobenzonorbornene (5) and 6 is briefly discussed. The extraordinary deshielding of the bridge methylene carbon in 6 has been noted.

Copolymers of ethylene with norbornene derivatives—dynamic mechanical properties

Abstract: The dynamic mechanical properties have been determined and the β relaxation temperatures Tβ have been located for a series of copolymers of ethylene with norbornene, methylnorbornene, dicyclopentadiene, and octahydrodimethanonaphthalene The Tβ values show discontinuous changes with changing comonomer content The several levels of Tβ observed apparently can be associated with the sequence of close multiplets of norbornane moieties ranging from isolated units through pairs to triads and higher For isolated norbornane units Tβ is around 10°C, while for pairs of these units, probably separated by a C2H4 unit, it is 55°C The size of the norbornene-type comonomer has a small but measurable effect on these values of Tβ The bearing of these results on the problem of defining a value of Tg for polyethylene is discussed

The synthesis and reactions of some polychloroaromatic azides, sulphonyl azides and sulphonohydrazides

Abstract: Azidopentachlorobenzene (2) and 4-azidotetrachloropyridine (4) react with norbornene to give the aziridines (6) and (7); with cyclohexene the enamines (10) and (11) are formed. 1,2,3,4-Tetrachlorobenzene reacts with chlorosulphonic acid to give 2,3,4,5-tetrachlorobenzenesulphonyl chloride (14), but the reported chlorosulphonation of 1,2,4,5-tetrachlorobenzene could not be effected, and under drastic conditions the reaction afforded hexachlorobenzene. The sulphonyl chloride (14) reacts with hydrazine to give the sulphonohydrazide (15). However, in contrast to previous work, reaction of polychloroaromatic sulphonyl chlorides with ammonia and phenylhydrazine gave only the normal sulphonamides and N'-phenyl sulphonohydrazides.

Origin and direction of nonequivalent orbital extension and stereochemical behaviors of plane-asymmetric olefins. exo -electrophilic addition to norbornene

Abstract: Origin and direction of nonequivalent extending of orbitals with symmetric density distribution under influence of weakly conjugative entity was considered in a general manner. An application of the obtained results was found to shed new light on exo-stereoselectivity in electrophilic addition to norbornene.

Polymers of acid anhydride type norbornene derivatives and a method of preparing the same

Abstract: Polymers or copolymers of acid anhydride type norbornene derivatives and a method of preparing the same, said polymers or copolymers being formed with a reduced viscosity of 0.1 to 20 by ring-opening polymerization of acid anhydride type norbornene derivatives having at least one carboxylic anhydride group or a mixture of said norbornene derivatives and cycloolefins.

Cyano-substituted norbornene polymers blended with polyvinyl chloride resins

Abstract: A resin composition is prepared from 5 to 95 parts by weight of a polymer prepared by ring-opening polymerization of cyano-substituted norbornene derivatives having at least one nitrile group or substituents including nitrile group and 95 to 5 parts by weight of (a) homopolymer or copolymer of vinyl chloride, (b) styrene homopolymer or vinyl copolymer containing at least 50 per cent by weight of at least one vinyl compound selected from the group consisting of styrene, acrylonitrile and methyl methacrylate, (c) said homopolymer or copolymer compounded with elastomer, or (d) graft copolymer obtained by grafting at least one of said vinyl compounds to said elastomer.

The use of n-hydroxy-5-norbornene-2,3-dicarboximide active esters in peptide synthesis

Abstract: N-Hydroxy-5-norbornene-2, 3-dicarboximide (HONB) was found to be an excellent reagent to be used in couple with N, N'-dicyclohexylcarbodiimide (DCC) for the peptide synthesis. Various racemization tests by the use of this reagent were conducted to see the degree of racemization during the peptide synthesis. The newly employed reagent (HONB) decreases racemization, prohibits formation of N-acylurea and affords peptides in excellent yields and a high state of purity. To evaluate this new reagent, luteinizing hormone releasing hormone (LH-RH) was prepared by the new active ester method.

Block copolymers containing olefin sulfur dioxide segments and process for their preparation

Abstract: The instant invention relates to novel block copolymers containing olefin sulfur-dioxide segments and a process for their preparation. The olefin of choice is a "strained" olefin thus capable of reaction with SO 2 in the presence of radicals at very high rates. Examples of strained olefins include cyclopropene, cyclobutene, norbornene, and the derivatives thereof. The novel block copolymers are prepared by contacting the olefin and the sulfur dioxide with a polymer under conditions of shearing degradation whereby said polymer is broken down into radical-containing segments which subsequently combine with the olefin and sulfur dioxide to form the novel copolymers described above. The polymer may be selected from the group consisting of polyisobutylene, poly(ethylene oxide), ethylene-propylene copolymers, poly(propylene oxide), polybutadiene, polyisoprene, etc. A novel block polymer formed by this preferred process shows improved properties as compared to physical mixtures of said polymer and olefin-sulfur dioxide copolymers. For example, the novel polymers formed by the preferred process of the instant invention show higher moduli and may be plasticized to higher levels while retaining good physical properties.

Acrylate-butadiene graft copolymers and reinforced plastic compositions containing such copolymers

Abstract: Acrylate graft copolymers prepared in a two-stage process by first reacting a backbone polymer, such as 1,2-polybutadiene, an alkylidene norbornene polymer or an ethylene/propylene/alkylidene norbornene terpolymer, with, for example, a mixture of dinitrogen tetroxide and oxygen to form a nitrooxidized 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 are disclosed. The thus-formed graft copolymers comprise from about 5 to about 80 weight percent of the backbone polymer with the balance being furnished by the acrylate monomer.

Ethylene–propylene terpolymers based on methylcyclopentadienyl‐5‐norborn‐2‐enylmethane derivatives

Abstract: The terpolymerization of ethylene, propylene, and methylcyclopentadienyl-5-endonorborn-2-enylmethane (III) by means of different vanadium-based coordination catalysts was investigated. The structure of III and its isomeric composition was studied by using vapor-phase chromatography, mass spectrometry, and NMR, infrared, and ultraviolet spectroscopy. The catalyst system V Acac3–Et2AlCl was used under different conditions, and the influence of several variables regulating the terpolymerization process were related to the properties of the resulting terpolymers (EPTM). The insertion of III into EPTM chains takes place randomly and does not influence the random distribution of comonomers. The selective opening of the norbornene double bond of III has been demonstrated by use of 2,3-dihydro-III as model compound. Tritiated III gave a radiochemical titer of unsaturation in excellent agreement with the value deduced from ultraviolet measurements. The influence of Lewis bases added to VAcac3–Et2AlCl catalyst is discussed.

Process for producing amorphous olefin interpolymer

Abstract: A substantially amorphous ethylene-α-olefin-diolefin rubbery interpolymer is obtained by interpolymerizing ethylene, an α-olefin, and as a third component a specified diolefin having a norbornene ring with a catalyst system comprising a specified combination of an ether or ester compound, an organoaluminum compound, and a transition metal compound. The resulting rubbery interpolymer has an excellent extrudability and gives a cured product having favorable physical properties.

Olefin interpolymers method of making a metal pattern on a substrate

Abstract: 1422299 After-treated unsaturated silane copolymers COPOLYMER RUBBER & CHEMICAL CORP 31 July 1974 33792/74 Heading C3P An interpolymer of an ethylenically unsaturated silane having at least one highly hydrolysable group, such as halogen or tertiary amino, ethylene and a C 3-20 mono olefin or a polyolefin hydrocarbon or halohydrocarbon is reacted to replace at least one of the highly hydrolysable groups with an alternative, nucleophilic substituent. The after-treatment may introduce alkoxy groups (by alcohol treatment), halogenated alkoxy groups or dye groups. Any residual highly hydrolysable groups may be replaced by further alcohol treatment to convert them to alkoxy groups. In the examples, ethylene - propylene - 5 - trichlorosilyl - 2 - norbornene terpolymers and quater-polymers with 5-ethylidene-2-norbornene are obtained using Ziegler catalysts and treated with water, methanol, allyl alcohol, 1,2,3,4,7,7-hexachloro- 2-hydroxymethyl norbornene-5,2,6-di-t-butyl-4- hydroxymethylphenol, rayon (to produce a graft polymer), or diphenylamine, in some cases followed by a further alcohol treatment to replace the remaining hydrolysable groups and to prevent undesirable hydrolytic cross-linking.

Norbornene derivs. prodn. - by reacting dicyclopentadiene with unsatd. cpds. esp. acrylonitrile, in liq. phase

Abstract: Norbornene derivs. (I): where R1 and R3 = H or lower alkyl gp., which may be substd. by non-reactive substnts.; R2 = carboxy gp. or deriv. of this and R4 has the same meaning as R1, R2 or R3; are made by reacting dicyclopentadiene with a cpd. (II) or (III): in the liq. phase, by passing the reaction components (opt. premixed) directly into a reaction zone at 160-240 degrees C and pressures greater than autogenic pressure, and working up the resulting reaction mixt. Process is esp. useful for prodn. of exo-2-cyano-bicyclo 1,2,2 heptene-(5) (IV) from dicyclopentadiene and acrylonitrile with reduced by-prodt. formation and higher yields than known processes.

Polyalkenmers from monomers of norbornene structure containing polar groups

Abstract: A novel polymer is produced by the ring opening polymerization of a 5-substituted-norbornene-2 in which the 5-substituent is a nitrile group or a nitrile group pendant that position through an alkylene radical, e.g., poly(5-cyanonorbornene-2).

Epimination of olefins by means of 3,3-pentamethyleneoxaziridine — A one-step synthesis of aziridines

Abstract: 3,3-Pentamethyleneoxaziridine, which is readily obtained by treatment of cyclohexanone with ammonia and sodium hypochlorite or hydroxylamine-O-sulfonic acid, reacts with olefins with transfer of the NH group to give aziridines. Aziridines were obtained from styrene, ring- or side-chain-substituted styrenes, norbornene, and acrylonitrile in 20–70% yields. Cyclohexene is doubly aminated to give N-aminoaziridine. Nitriles are formed from phenylacetylene and diphenylacetylene as a result of rearrangement.