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Phenanthrene, 9-vinyl

B. HCl, m.p. 242-3°). The methiodide, m.p. 104-7°, of this, on treatment with potassium hydroxide in methyl aleohol, yielded 5 6-pimethoxy-8-vinylphenanthrene, m.p. 86-7°, along with dimethyl-de-iV-methylnorroemerine, oil, [aju + 13-55° (EtOH) the methiodide, m.p. 278°, of this, on like treatment also yielded 5 6-dimethoxy-8-vinyl-phenanthrene, whose identity was established by its oxidation by permanganate to 5 6-dimethoxyphenanthrene-8-earboxylie aeid. Rcemerine is, therefore, 5 6-methylenedioxy-iV-methylaporphine, and this eon-stitution has been confirmed by Marion and Grassie s synthesis of the alkaloid. [Pg.315]

Dihydrovinylphenanthrenes are more reactive than the corresponding vinyl phenanthrenes and undergo Diels-Alder reactions easily. They have been used in the synthesis of polycyclic aromatic compounds and helicenes. Examples of cycloaddition reactions of the 3,4-dihydro-1-vinylphenanthrene (70), [61] 3,4-dihydro-2-vinylphenanthrene (71) [68] and l,2-dihydro-4-vinylphenanthrene (72) [69] are reported in Equation 2.22 and Schemes 2.27 and 2.28. [Pg.55]

The chemical sensitization effect was 0.006 (calculated from the quantum yield of the photochemical transformation of 130 to 131, the yield of 131 obtained with the oxalate/hydrogen peroxide reaction, and the moles of oxalate employed). Higher chemical sensitization efficiencies (about 0.04) were observed when the oxalate/hydrogen-peroxide system was used in the addition of ethyl vinyl ether onto phenanthrene quinone... [Pg.130]

Takasu et al. found that at high temperature a free radical reaction of polyolefinic vinyl iodides leads to phenanthrene derivatives via a 6-endo-6-exo-polycyclization while at low temperature a mono-cyclized product is obtained through a 5-exo mode.1501... [Pg.50]

Other examples of determination of the absolute configuration of bichromophoric molecules having two or more rotamers in the equilibrium include naphthalene/A -vinyl carbamate in a 1,2,3,4-tetrahydropyridine derivative123, naphthalenc/purine in deoxyadenosine adducts124-126, phenanthrene/purine in deoxyadenosine and deoxyguanosine adducts127 and pyrene/purine in adenosine adducts128. [Pg.519]

Phenanthrene has also a reactive 9,10-double bond, in agreement with the Clar structure having two aromatic sextets and a C=C fixed double bond in the median ring. On co-ozonolysis with formaldehyde, acetyl cyanide, or benzoyl cyanide, phenanthrene reacted accordingly, affording an aldehydic ozonide 112, which in a separate co-ozonolysis with vinyl acetate that produced formaldehyde oxide (H2C-0-0) gave rise to a diozonide 113 (Scheme 35 and Table 14). [Pg.221]

In the case of pyrene, there are two sextets and two fixed double bonds similar to the phenanthrenic double bond. In agreement with this argument and with the result for phenanthrene, co-ozonolysis of pyrene with formaldehyde or acetyl cyanide afforded the expected normal ozonide 114 and the cross-ozonide 115 with an aldehydic group. In a separate co-ozonolysis of 115 with vinyl acetate, diozonides 116 were prepared. No cross-ozonide was obtained in the presence of benzoyl cyanide, which afforded only the normal mono-ozonide 114 (Scheme 36 and Table 15). [Pg.221]

The final polycyclic aromatic hydrocarbon that was investigated <2000EJ0335> is benzo[fixed double bond like phenanthrene. Its cross-ozonolysis with formaldehyde gave none of the normal ozonide 120, but mainly the aldehydic ozonide 117. At room temperature, a substantial amount of opening of the ozonide ring occurred with the formation of the acid aldehyde 121. Both products 117 and 121 could be stabilized by treatment with O-methylhydroxylamine, yielding products 118 and 122, respectively. The separate co-ozonolysis of compound 117 with vinyl acetate afforded the diozonide 119 (Scheme 37 and Table 16). The cross-ozonolysis with acetyl cyanide followed by treatment of the crude reaction mixture with O-methylhydroxylamine yielded the O-methyloxime of the cross-product. Cross-ozonolysis with benzoyl cyanide was not successful, and only the normal mono-ozonide 120 was formed. [Pg.222]

Only a few additional examples of intermolecular photochemical vinylations of (hetero)aromatic compounds have been forthcoming. Coupling products are formed in the irradiation of dichloro- and dibromo-A-methylmaleimide in the presence of 1,3-dimethyluracils341 and of 3-bromocoumarin in the presence of naphthalene, phenanthrene, 1-methylpyrrole and other aromatic compounds342. The former reaction is accompanied by cyclobutane adduct formation, which is the mode of reaction of A-methylmaleimide itself. The mechanism of these vinylation reactions is not clear, but most probably an exci-plex (cf equation 20a) or a charge-transfer complex (cf equation 20b) is involved. [Pg.902]

C-3 of the naphthalene nucleus that controls the electrophilic ring-closure of the vinyl ketene intermediate moreover, the degree of aromaticity of the angular rings in the phenanthrene skeleton exceeds that in the anthracene analogues. This regioselectivity observed in the benzannulation of chromium carbenes is paralleled by results observed for 2-naphthyl cyclo-butenones [77] and for the palladium-catalyzed cyclocarbonylation of 2-naphthyl allyl acetates [78]. [Pg.280]

The intramolecular reaction can be extended to the cross-annulation reaction of aryl halides with unsaturated compounds [31,33]. For example, 2-halo-biphenyls react with alkynes to give phenanthrene derivatives [96,97]. By using the method, the analogs of hypericin known as antiviral agent (Eq. 45) [98] and indolocarbazoles (Eq. 46) [99] have been prepared. In these reactions, vinyl-palladium intermediates are involved. [Pg.226]

As mentioned above, an increase in the steric hindrance between the substituents at positions 1 and 11 of the starting aporphine leads to the formation of a greater proportion of dihydrophenanthrene (154) relative to phenanthrene alkaloid (153). With few exceptions (22,38,45,89), when either or both substituents are hydrogen, no vinyl phenanthrene is formed. The presence of bulky substituents at C-1 and C-11 causes the generation of variable amounts of 153 and 154 (20,30,85,88,115). Thus, boiling of O-methylisocorydine methiodide (168) in methanolic potassium hydroxide yields 85% 169 and 7% 170 (20). [Pg.124]

The mass spectra of phenanthrene alkaloids are very informative regarding the nature of the side chains. The two main fragmentations correspond to the loss of CH2NR,R2 and to the CH2=N + R,R2 cation. This cation is usually the base peak and allows the identification of R, and R2. Thus, phenanthrenes with a 2-dimethylaminoethyl side chain present the base peak at 58 mass units, whereas ones with a 2-monomethylaminoethyl side chain show the base peak at 44 mass units. In the case of the V-oxides there is a Cope elimination in the mass spectrometer, giving rise to a strong peak corresponding to a vinyl phenanthrene. [Pg.134]

In helium quantitative yield of HCI. remainder residue and hydrocarbons, benzene is major volatile hydrocarbons product aliphatic hydrocarbons, benzene (major product), toluene, ethylbenzene, o-xyiene, monochlorobenzene styrene, vinyl tcriuerre. p-dichlorobenzene, o-dichlorobenzene, indene, 1,3.5-trichlorobenzene 1.2.4. richlorobenzene. naphthalene, u-methylnaphthalene. p-methylnaphthatene effect of ZnO. SnOj, and Ab03 on the yields of products Is also recorded HCI. CO2. ethene. ethane, propane, 1-butene. 2-butene. 1-pentene. cydopentene, n-pentane, 2-methylbulane, 1,3-pentadiene. 2-methyl-1,3-pentadiene, complex series (60 Identlfled) of aromatic and polyaromatic species including benzene, styrene, methylstyrenes, toluene, o-xytene, m-xylene, p-xylene, biphenyl, naphthalene, anthracene, phenanthrene. pyrene, etc. [Pg.279]

Tricyanovinyl-N,N-dimethylaniline has been prepared by adding hydrogen cyanide to -dimethylaminobenzalmalono-nitrile and oxidizing the adduct.3 The present procedure, an adaptation of one that has been published,3 is the more convenient preparative method. It can be applied to a wide variety of secondary and tertiary aromatic amines to give />-tricyanovinyl-arylamines that, like the present one, are dyes.3 Other types of aromatic compounds also condense with tetracyanoethylene in this manner. Thus one can obtain 4-tricyano vinyl-2,6-dimethyl-phenol from 2,6-dimethylphenol, 2-tricyanovinylpyrrole from pyrrole, and 9-tricyanovinylphenanthrene from phenanthrene.4... [Pg.96]

Three novel phenanthrenes have been isolated from the wetland plant Juncus acutus. The structures of the novel phenanthrenes were established as 2-hydroxy-l,6-dimethyl-5-vinyl-phenanthrene (320), 2,7-dimethoxy-l,6-dimethyl-5-vinylphenanthrene (321) and 2-hydroxy-6-hydroxymethyl-l-methyl-5-vinyl-phenanthrene (322) [164, 165]. In spite of the great number of 9,10-dihydrophenanthrenes, only quite a small number of phenanthrenes have been reported until now as constituents of Juncaceae. [Pg.494]

Oxygen Quenching in Poly(vinyl acetate) Particles. In order to study a system in which fluorescent groups could be Introduced into both the stabilizer and core polymers, we turned our attention to poly(vinyl acetate) [PVAc] particles sterically stabilized by poly(2-ethylhexyl methacrylate) [PEHMA] (14,15). Phenanthrene [Phe] was chosen as the fluorescence sensor. It was Introduced into the stabilizer by mixing a small amount (ca. 1%) of 9-phenanthrylmethyl methacrylate 1. with EHMA in the synthesis of PEHMA. It was introduced into the core polymer by mixing a trace (ca. 0.01%) of J with VAc in the presence of unlabelled PEHMA in the particle synthesis step. [Pg.12]

Photocyclisation to phenanthrenes competes with the photosubstitution reactions of the anisyl substituted arylvinyl bromides (201)however, with the corresponding thioanisyl arylvinyl bromides photosubstitution is the favoured reaction. The products of photosubstitution of (201) are the acetates (202) these also photocyclise to phenanthrenes and no products from fragmentation of the vinyl acetate (as seen for (194) ) were observed. [Pg.230]

Bei der Belichtung von 3-(trans-2-Phenyl-vinyl)-phenanthren (I) in Methanol wird als einziges Dimeres das Kopf/Sehwanz-Addukt II erhalten, welches seinerseit.s photolabil ist1 ... [Pg.332]

Bei der Beliehtung von l,4-Bis-[2-phenyl-vinyl]-benzol kann 3-(2-Phenyl-vinyl)-phenanthren (III) mitseinen Folgeprodukten Difoenzo-[c g]-phenanthrm (IV) bzw. Benzo-[g,h,i]-perylen (V) nurauf dem... [Pg.514]

J) Bei der Belichtung von l,3-Bis-12-phenyl-vinyl]-benzol ist keine intermediare Dimerisierang zur Bildung von 1- und 2-Bis-[2-phenyl-vinyl]-phenanthren (VIII, IX), 4-Ftienyl-pyren (X) und Benzo-[c]-c irysen (XI) notwendig ... [Pg.516]


See other pages where Phenanthrene, 9-vinyl is mentioned: [Pg.229]    [Pg.307]    [Pg.322]    [Pg.27]    [Pg.348]    [Pg.290]    [Pg.290]    [Pg.469]    [Pg.154]    [Pg.74]    [Pg.26]    [Pg.290]    [Pg.259]    [Pg.493]    [Pg.493]    [Pg.238]    [Pg.180]    [Pg.264]    [Pg.7]    [Pg.388]    [Pg.228]    [Pg.265]    [Pg.95]    [Pg.336]   
See also in sourсe #XX -- [ Pg.736 ]




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