Fulven

Meuche, Doris; Neuenschwander, Markus; Schaltegger, H.; Schlunegger, H. U.

doi:10.1002/hlca.19640470514

Cited by 44 publications

(16 citation statements)

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“…Fulvene was prepared by the method of Meuche (15). The benzene containing all solid products from the reactor and pot residue was reduced to 30 ml.…”

Section: Methodsmentioning

confidence: 99%

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Chemical Reactions in a Corona Discharge I. Benzene

Ranney¹,

O’Connor²

1969

Advances in Chemistry

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Excitation of benzene vapor in a 15 kv. corona discharge reactor at atmospheric pressure and 45°C. gives an 8.5% conversion to identifiable products. This over-all yield is comparable to that reported for the glow discharge reactions of benzene initiated by radiofrequency and microwave energy sources. Low molecular weight products (up to C18) which have been quantitatively determined in this study include biphenyl, o-, m-, and p-terphenyl, phenylbenzylcycloalkenes, fulvene, 1,3 and 1,4-cyclohexadiene, cyclohexene, and acetylene. Approximately 80% of the product yield is a yellow polymeric material, largely soluble in benzene, with a major fraction having a molecular weight of 4,000. A phenyl and/or benzyl substituted cyclopentene system is indicated as the average repeating unit. /^orona discharges (silent) have been used to initiate chemical reactions for well over 150 years with much of the early work being confined to inorganic gases (10).However, the only commercially sig nificant development over the years has been the process for synthesizing ozone (17) by subjecting oxygen to a corona discharge (ozonizer). Most early investigators encountered serious difficulties in studying the inter action of high voltage electricity with organic molecules. Equipment was unreliable and dangerous, and the complexity of the reaction product mass precluded definitive performance evaluation. Since World War II, technology has advanced to the point where high frequency power can be generated and controlled at reasonable cost and many new dielectric materials such as fused quartz, alumina, and mica mat are available (5).

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“…Fulvene was prepared by the method of Meuche (15). The benzene containing all solid products from the reactor and pot residue was reduced to 30 ml.…”

Section: Methodsmentioning

confidence: 99%

“…In a typical run, the benzene reservoir temperature is set at 55°C., the helium is adjusted to 100 ml./min. and after a two minute purge, an electrical potential of 15 …”

Section: Apparatusmentioning

confidence: 99%

Chemical Reactions in a Corona Discharge I. Benzene

Ranney¹,

O’Connor²

1969

Advances in Chemistry

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“…Thus even derivatives of azete are difficult to prepare and are very reactive [9,10], while 2-azirine and oxirene are still unknovvn [11]. Cyclopentadienone (ER--5.3 kcal/mole) has been obtained only as an extremely reactive intermediate which cannot be isolated since it dimerizes so readily [12]; note that the isoconjugate hydrocarbon, fulvene, for which ER = 1.1 kcal/mole, is relatively stable [13][14][15], Similar remarks apply to cyclopropenone (Er = -3.0 kcal/mole) which has only recently been prepared and resisted ali attempts to isolate it from solution because it polymerized so readily [16]; cyclopropenone bears the same relation to the aromatic ion, cyclopropenium, that tropone does to tropylium, and it had been suggested that it might, like tropone, be aromatic. It has, however, become increasingly evident that tropone is not an aromatic compound, a conclusion confirmed by calculations which will be reported elsevvhere [17].…”

Section: Fij = K S Tjmentioning

confidence: 99%

Resonance energies of some compounds containing nitrogen or oxygen

Dewar

Trinajstić

1970

Theoret. Chim. Acta

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“…Finally parent 2a could be separated from solvents by preparative GC (yield 0.6%!) [ 23]. -B ecause of the disappointing results of the Thiele synthesis and due to the fact that parent fulvenes and Scheme 3.…”

mentioning

confidence: 99%

Low‐Temperature Olefin Syntheses in View of Parent Fulvenes and Fulvalenes

Neuenschwander

2015

Helvetica Chimica Acta

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Parent fulvenes and fulvalenes are thermallyu nstable cross-conjugated olefins for which lowtemperature syntheses are indispensable. In this review 5syntheses (inthe temperature range between À 100 and À 108)are discussed:1. Reaction of sodium cyclopentadienidew ith 1-acetoxy-1-chloroalkanes or 1-acetoxy-1-bromoalkanes (26)gives acetoxy-alkyl-cyclopentadienes (27)which are easily converted to pentafulvenes (2)by low-temperature HOAc-elimination with NEt 3 .T his synthesis has been applied to parent pentafulvene (2a), heptafulvene(3a), nonafulvene (4a)a nd sesquifulvalene (19a)(Schemes 8 -11).2. Based on an early quantitative oxidative coupling of cyclononatetraenide (8)t og ive dihydrononafulvalene (38)( Scheme 10), ag eneral synthetic plan for fulvalenes has been outlined (Scheme 11)a nd applied to the synthesis of pentafulvalene (12), nonapentafulvalene (16)a nd nonafulvalene (14). Several applications of oxidative couplings of Hückel anions are discussed (Schemes 20 and 21).3. Tr ifunctional cyclopropanes 67 (inm ost cases 1,1-dibromo-2-X-cyclopropanes) are attractive precursors of parent triafulvene (1a)a nd calicene (17)(Scheme 18). Contrary to classical procedures they are transformed into nucleophiles (67 ! 68)b yh alogen-lithium exchange,m ethylation( 68 ! 69) and HBr-eliminationt og ive 1-methylidene-2-X-cyclopropaneso ft ype 71.B ys ubsequentH Xeliminationtriafulvene (1a)has been synthesized and trapped as a[4þ2]-cycloadduct 73 (Scheme 20). Furthermore,c alicene precursors 77 are available by using cyclopentenone as an electrophilic cyclopentadiene equivalent.4. Similarly,1 -lithio-1-bromo-2-X-cyclopropanes 68 are directly transformed into triafulvalene precursors 81 (Scheme 26)b yanovel CuCl 2 -catalyzed oxidative coupling.5. In view of the synthesiso fp arent triafulvene( 1a), triafulvalene( 11)a nd calicene (17), retroDielsÀAlder reactionso fs table precursors -p repared by low-temperature reactions( described in chapters 3 and 4)-have been explored.

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Fulven

Abstract: Feinsprit &24zmp/&36rmp = 49.0 (drei Tage altes Produkt) &242mp/&360mp = 51.4.

Cited by 44 publications

References 7 publications

Chemical Reactions in a Corona Discharge I. Benzene

Chemical Reactions in a Corona Discharge I. Benzene

Resonance energies of some compounds containing nitrogen or oxygen

Low‐Temperature Olefin Syntheses in View of Parent Fulvenes and Fulvalenes

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