Di phenyl methane

Eine N-Alkylierung wird bei der Reaktion von 2-Mercapto-l,3,4-oxadiazolen mit Diazo-di-phenyl-methan beobachtet598. 

Hexa-chlor benzene is formed by the chlorination not only of benzene itself, but also of other more complex hydrocarbons, e.g, naphthalene, anthracene, phenanthrene, di-phenyl methane (but not diphenyl). Penta-chlor benzene is of interest because it was at one time supposed to exist in isomeric forms which is contrary to the Kekule theory. 

Benzo phenone is a solid which is di-morphous, i.e.j it exists in two forms which are not isomeric as they possess the same formula in every respect. One form is a solid, m.p. 26°, while the other is a solid, m.p. 46 . On reduction with zinc dust benzo phenone yields first the corresponding secondary alcohol, CeHs—CH(OH)—CeHs, and then the hydrocarbon di-phenyl methane, CeHs—CH2—CeHs. 

This hydrocarbon, di-phenyl methane, is a member of another series which will be considered later and, strictly speaking, benzo phenone does not belong to the group of aromatic ketones which we have been studying. Because of its close analogy to the other aromatic ketones... 

In this compound the benzyl group is linked to the phenyl group or the two benzene rings are linked by an intervening methylene group. Considering the methylene group as a residue of methane the compound is plainly di-phenyl methane. This is the name by which it is known. 

Eluorene.—We stated that when benzene is passed through a red hot tube two molecules lose two hydrogens with the formation of diphenyl. Di-phenyl methane acts in the same way, one molecule losing two hydrogens, one from each ring from the positions ortho to the methylene linkage, the new hydrocarbon being known as fluorene. 

Dyes. Auramine.—K hydrocarbon which is very closely related to di-phenyl methane and which we shall study very soon is tri-phenyl methane. It is the mother substance of a large and very valuable group of dyes. While di-phenyl methane also yields dyes they are few in number. They are known as auramine dyes. The dye known as auramine O is made as follows Michler s ketone (p. 667), which is tetra-methyl di-amino benzo phenone, is heated with ammonium chloride and anhydrous zinc chloride. The ammonium chloride yields ammonia which reacts with the ketone with the loss of water, the zinc chloride being the dehydrating agent. 

Synthesis.—This hydrocarbon is by far the most important of those in which two or more benzene rings are linked together by intervening aliphatic carbon groups. Just as methyl chloride and benzene by the Friedel-Craft reaction yield phenyl methane (methyl benzene or toluene) and methylene chloride, di-chlor methane, with benzene yields di-phenyl methane so by the same reaction tri-chlor methane, chloroform, yields with benzene a hydrocarbon which by this synthesis must be tri-phenyl methane. 

Methane Character.—Tri-phenyl methane is the hydrocarbon mother substance from which the dyes are derived. The relation between the hydrocarbons, methane, toluene, di-phenyl methane and tri-phenyl methane is clearly seen if we write their formulas as derivatives of methane. 

Oxidation Products.—Methane stands at one end, as a pure aliphatic hydrocarbon, while the others are phenyl derivatives becoming more strongly aromatic in character, but retaining, even in tri-phenyl methane, at least one methane hydrogen. Thus toluene, di-phenyl methane and tri-phenyl methane exhibit, in the order given, a grad-... 

In making di-phenyl methane benzyl chloride reacts with phenyl chloride in the presence of sodium. 

Di phenyl methane-4,4 -di isocyanate trimellic anhydride. SeeTrimellitic anhydride Diphenylmethanol. See Benzhydrol Diphenyl methanone. See Benzophenone Diphenylmethyl alcohol. See Benzhydrol Diphenylmethylcyanide. See Diphenylacetonitrile Di (phenylmethyl) disulfide. See Benzyl disulfide... 

The insoluble material consists of silica, l,l-di-(/)-chloro-phenyl)-ethylene and a small amount of di-(/>-chlorophenyl)-methane (melting at 54-55° when purified), formed by decarboxylation of the acid. 

With 4,4-diarylcyclohexenones, the di-Tc-methane rearrangement occcurs. In compounds in which the two aryl groups are substituted differently, it is found that substituents which stabilize radical character favor migration. Thus, the p-cyanophenyl substituent migrates in preference to the phenyl substituent in 4 ... 

A phenyl group may be substituted for one of the vinyl groups 1,2 in the di-7r-methane rearrangement as follows ... 

When the central substituents are phenyl the di-ir-methane rearrangement does take place,<25)... 

Again the di-7r-methane reaction is regiospecific but this time it is competing with phenyl migration,... 

A study on mechanistic aspects of di-ir-methane rearrangements has been published recently [72]. The kinetic modeling of temperature-dependent datasets from photoreactions of 1,3-diphenylpropene and several of its 3-substituted derivatives 127a-127d (structures 127 and 128) show that the singlet excited state decays via two inactivated processes, fluorescence and intersystem crossing, and two activated processes, trans-cis isomerization and phenyl-vinyl bridging. The latter activated process yields a biradical intermediate that partitions between forma-... 

Man erhalt auf diese Weise z.B. mit Phenyllithium aus Thiobenzoesaure-morpholid Di-phenyl-morpholino-methan in einer Ausbeute von 72% an isoliertem Produkt2 weitere Beispiele s.Tab. 107 (S. 991). 

To examine the viability of CIM a number of photoreactions (electrocyclic reactions, Zimmerman (di-n) reaction, oxa-di-7i-methane rearrangement, Yang cyclization, geometric isomerization of 1,2-diphenyl-cyclopropane derivatives, and Schenk-ene reaction) which yield racemic products even in presence of chiral inductors in solution have been explored (Sch. 40) [187,189-200]. Highly encouraging enantiomeric excesses (ee) on two photoreactions within NaY have been obtained photocyclization of tropolone ethylphenyl ether (Eq. (1), Sch. 40) and Yang cyclization of phenyl benzonorbornyl ketone (Eq. (3), Sch. 40). The ability of zeolites to drive a photoreaction that gives racemic products in solution to ee >60% provides... 

Aminomethyl-benzol- XII/1, 379 Amino-(3,4-methylendioxy-phenyl)-methan- -di-... 

Dibutylamino-carbonyl- -dicthylester XII/1. 457 Dibutylamino-methan- -diphenylester XII/1, 484 (3,5-Di-tert.-butyl-4-hydroxy-phenyl)-methan- -diethylester E2, 369... 

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