F 1,3,5-Cycloheptatriene

Cyclobutyl 4-methylbenzenesulfonate, 3398a Cyclobutylmethyl methanesulfonate, 2510 c/.v-Cyclododecene, 3345 f Cycloheptane, 2845 f 1,3,5-Cycloheptatriene, 2786 f Cycloheptene, 2833 f 1,3-Cyclohexadiene, 2354 f 1,4-Cyclohexadiene, 2355... 

Finke, H.L., Scott, D.W., Gross, M.E., Messerly, J.F., Waddington, G. (1956) Cycloheptane, cyclooctane and 1,3,5-cycloheptatriene. Low temperature thermal properties, vapor pressure and derived chemical thermodynamic properties. J. Am. Chem. Soc. 78, 5469-5476. 

Photoreactions of [Cr(CO)3( /6-C7H8)] (41) with 6-mono- and 6,6-disub-stituted pentafulvenes (59a-59f) preferentially yield dicarbonyl complexes with substituted tj3 5-2-cyloheptadienylene-2-cyclopentadienylidenemethane chelate ligands (82,83). In the course of the reaction, C-6 of the fulvene forms a C—C bond to C-l of the 1,3,5-cycloheptatriene ligand, and one CO ligand is displaced. This reaction is of the same type as the formation of the f/3 5-[ 1 -(3-butene-1,2-diyl)-7-isopropylidenecycloheptadienyl] complexes 47c, 47e and 47t. The fulvene unit is transformed into a monosubstituted cyclo-pentadienyl entity, / -coordinated to the chromium, with the 1,3,5-cyclo-... 

Ultraviolet activation of the complexes hexacarbonylbis( / 5-cyclopen-tadienyl)dimolybdenum and -ditungsten (135) has been studied in detail (136-138). In addition to homolytic cleavage of the metal-metal bonds, loss of carbon monoxide has also been observed. The products of the photochemical reactions of [(t/5-CH3C5H4)M(CO)3]2 (M = Mo, W) with the dienes la- 1c, lg and It and 1,3,5-cycloheptatriene (68a) differ markedly from those obtained from the thermal reaction of [(f/s-C5Hs)Mo(CO)B]2 (n = 2,3) with dienes (139,140). 

The complexes of type 153 show temperature-dependent carbonyl signals in their 13C-NMR spectra due to hindered movements of the /i-f/2 1-dienyl ligands. This movement can be described as a windshield wiper type oscillation, by which the a and n bonds are interchanged between the two rhenium atoms. For octacarbonyl-fi-ri2 1 -1,3,5-cycloheptatrien-2-yl-/i-hydridodirhe-nium (162) and for octacarbonyl-/ - /2 1 -1,3,5-cycloheptatrien-1 -yl- -hydri-dodirhenium (162 ) activation barriers of AG255 = 48.0 2 kJ/mol and AG207 = 39.9 2 kJ/mol (218) have been determined. 

While norbornene, norbornadiene, 2-triallkylsilylnorbornadiene, and 1,3,5-cycloheptatriene are selectively deprotonated by the LIC-NAOR mixture (butyllithium/sodium /f 7-butoxide), other less acidic substrates such as bicyclo[2.2.2]oct-2-ene, camphene, 3,3-dimethyl-l-butene, and tro/o-dicyclopentadiene require the use of stronger bases constituted by mixtures of pentylsodium/disodium pinacolate (NAC-NAOR) or pentylsodium/ potassium ftrt-butoxide (NAC-KOR). 

CYCLOHEPTATRIENE or 1,3,5-CYCLOHEPTATRIENE (544-25-2) Forms explosive mixture with air (39°F/4°C). Violent reaction with oxidizers. May form unstable peroxides, unless inhibited. Flow or agitation of substance may generate electrostatic charges due to low conductivity. 

Cycloheptatrien-l -amine, 1V-(1 -pheny let hy I)-7 C(l-phenylethyl)imino]-f (R,R) ( ckiramt ) chiral organyl cuprates from, 20-21... 

In an initial step, dibenzo[a,d] cyclohepten-5-one is reacted with the Grignard reagent of 3-di-methylaminopropyl chloride and hydrolyzed to give 5-(3-dimethylaminopropyl)-dibenzo[a,d] -[1,4] cycloheptatriene-5-ol. Then 13 g of that material, 40 ml of hydrochloric acid, and 135 ml of glacial acetic acid is refluxed for 314 hours. The solution is then evaporated to dryness in vacuo and added to ice water which is then rendered basic by addition of ammonium hydroxide solution. Extraction of the basic solution with chloroform and removal of the solvent from the dried chloroform extracts yields the crude product which when distilled in vacuo yields essentially pure 5-(3-dimethylaminopropylidene)-dibenzo[a/f ] [ 1,4] cycloheptatriene, BP 173°C to 177°C at 1.0 mm. 

Ethoxycarbonyl-l/f-azepine forms normal [4+2]7r adducts with 4-phenyl-l,2,4-triazo-line-3,5-dione and with diethyl azodicarboxylate (81H(15)1569, 77JCS(P1)1824), but unlike cycloheptatriene, which yields a [6 + 2]7r adduct, it gives no cycloadduct with AT-ethoxycar-bonylmethyleneimine (CH2=NC02Et) <81JCS(P1)447). The critical solvent dependence of the addition of DMAD to 1H-azepines has been referred to in Section 5.16.3.4 only in hot carbon tetrachloride is the [4+2]7r cycloadduct obtained (80TL1145). 

This type of double dehydrobromination has also been used in a few syntheses of 1,6-methano-annulated systems in which the initially formed norcaradiene isomerizes to the corresponding cycloheptatriene derivative. Thus, a good yield of bicyclo[4.4.1]undeca-l,3,5,7,9-pentaene (11, X = H) was obtained by treating the corresponding tetrabromide (9, X = H) with methanolic potassium hydroxide. The 11,11-difluoro analog 11 (X = F) was likewise obtained in 80% yield. The 11,11-dichloro (X = Cl) and 11,11-dibromo (X = Br) analogs, however, were ob-... 

Epoxy-l,3,5-cyclooctatriene added dropwise with ice-cooling to a soln. of propynylmagnesium bromide prepared from propyne and ethylmagnesium bromide in abs. ether, stirred 2 hrs. at room temp, and 1 hr. under reflux -> l-(2,4,6-cycloheptatrien-l-yl)-2-butyn-l-ol (Y 75%) dissolved in dimethylformamide, ice-cooled, treated dropwise with a soln. of SOClg in dimethylformamide, and stirred 1 hr. at room temp. l-phenyl-l-penten-3-yne (Y 87%). F. e. s. J. Hambredit, H. Straub, and E. Muller, B. 107, 2985 (1974). 

Dehydro-) Cy clisierungen ausgesch lessen ist. So lief ert Dibenzo-[a e]-cycloheptatrien (I) in Cyelohexan 80% des anti-Dimeren II, Tetrabe.nzo-cis-anti-cis-tricyclo [7.5.d.d2>8] tetra-decatetraen-(3,6,10,13) F 341-342° (Zers.)1 ... 

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