Diphenyl- -amid

Enolates of NN-disubstituted amides react with halobenzenes on photolysis in liquid ammonia to give a-aryl derivatives, e.g. (213) from iV-methyl-iV-phenylacetamide and chlorobenzene, often in good yields, although the a,a-diphenyl amide is often a contaminant. Most likely, an SrnI mechanism is involved perhaps many more useful reactions will come to light by studying the photochemistry of anions. 

Condensa.tlon, This term covers all processes, not previously iacluded ia other process definitions, where water or hydrogen chloride is eliminated ia a reaction involving the combination of two or more molecules. The important condensation reactions are nitrogen and sulfur heterocycle formation, amide formation from acid chlorides, formation of substituted diphenyl amines, and misceUaneous cyclizations. 

The conversion of a 4-arylazo-5-oxazolone into a 1,2,4-triazole by reaction with a Grignard reagent is mentioned in Section II, B, 3. In HiTnilar fashion, the rearrangement of compound 30 to derivatives of 3-carboxy-l,5-diphenyl-lfl -l,2,4-triazoles (40) proceeds readily in the presence of strong nucleophiles [Eq. (26)]. This transformation undoubtedly occurs by ring opening and dehydrative cychzation, and, indeed, the acyclic amide and hydrazide 41 have been isolated. ... 

Nucleophilic aromatic substitution of the anthranilic acid derivatives, 72, on ortho-bromonitrobenzene affords the diphenyl-amine, 73. The ester is then saponified and the nitro group reduced to the amine (74). Cyclization of the resulting amino acid by heat affords the lactam (75). Alkylation on the amide nitrogen with 2-dimethylaminoethyl chloride by means of sodium amide affords dibenzepine (76). ... 

Unlike the parent system, 5-methyl-5//-dibenz[c,e]azepine (1, R1 = Me R2 = H) on treatment with lithium diisopropyl amide fails to yield the tautomeric phenanthridine-imine (see Section 3.2.1.5.4.2.), but forms the 5-carbanion, which on quenching with deuterium oxide furnishes 5-methyl-[5-2H,]-5//-dibenz[e,e]azepine (l).83 5,7-Diphenyl-5//-dibenz[r,e]azepine (1. R1 = R2 = Ph) behaves similarly. In contrast, however, 5,7-dimethyl-5//-dibcnz[c,e]azepine (1, R1 = R2 = Me) yields theazaallyl anion 3, which on addition of deuterium oxide deuterates regiospecifically at the 7-methyl group to give derivative 4. 

We have investigated the reaction of NH phosphinous amides with diphenyl-cyclopropanone. The products were unequivocally identified as the corresponding p-phosphinyl carboxamides 27 resulting from the hydrolysis of a presumed heterocyclic intermediate (Scheme 28) These results await publication. 

Chiral phosphinous amides have been found to act as catalysts in enantio-selective allylic alkylation. Horoi has reported that the palladium-catalyzed reaction of ( )-l,3-diphenyl-2-propenyl acetate with the sodium enolate of dimethyl malonate in the presence of [PdCl(7i-allyl)]2 and the chiral ligands 45 gave 46 in 51-94% yields and up to 97% ee (Scheme 38). It is notorious that when the reaction is carried out with the chiral phosphinous amide (S)-45a, the product is also of (S) configuration, whereas by using (R)-45b the enantiomeric (R) product is obtained [165]. 

Diamine 108 led to 95% ee for the alkylation of l,3-diphenyl-2-propenyl acetate with 90% yield. By polycondensation with a diacid chloride or polyaddition with a diisocyanate, this ligand led, respectively, to an insoluble poly(amide) 109 or poly(urea) 110 with excellent yields. Poly(amide) 109 gave a better ee (80%) than poly(urea) 110 (38%), albeit with a lower conversion (respectively, 38 and 72%), when they were used as palladium hgands... 

Carboxylic acids can also be activated by the formation of mixed anhydrides with various phosphoric acid derivatives. Diphenyl phosphoryl azide, for example, is an effective reagent for conversion of amines to amides.140 The proposed mechanism involves formation of the acyl azide as a reactive intermediate. 

The zinc complexes with diphenyl-2-pyridylmethane, ZnL2Cl2 and ZnL2Br2, have been characterized by IR spectroscopy and conductivity measurements.107 The [(pyridyl)2P(NSi Mc3)2] ligand forms an aminoiminophosphoranate complex with zinc which structural characterization shows to be four-coordinate bound to two pyridyl and two amide nitrogen donors (3).108... 

Methodical details of crystal calculations have been published by several authors (8, 95-98). As applications we only mention the calculation of the crystal structure of diphenyl (98, 99) which has a planar structure in the solid state (100) whereas gaseous diphenyl is twisted around the CC-bond, which links both benzene rings, by about 40° (101). The calculations reproduce satisfactorily the experimental findings. A further application is the calculation of the crystal structures of a series of amides (102), with the object of deriving suitable functions for the description of hydrogen bonds (cf. previous Section). 

This is further accentuated by the surprising results of the reaction between aziridine and diphenyl cyclopropenone which was elucidated by Dehmlow224. In aprotic media two molecules of aziridine react with a cyclopropenone moiety eliminating ethylene and forming enamino amide 527, whereas in protic media one molecule of aziridine reacts with the exclusive formation of the aziridide 326 ... 

The bicyclic enamine 383 deviates from the above reaction scheme when interacting with diphenyl cyclopropenone the betaine 384 formed initially does not iso-merize to the amide 385, but to the a-amino cyclopentenone 386, possibly favored by steric reasons248. ... 

Diphenylcyclopropane has been prepared in 24% yield by the Simmons-Smith reaction,2 in 78% yield by treatment of 3,3-diphenylpropyltrimethylammonium iodide with sodium or potassium amide,3 in 61% yield by reaction of 1,1-diphenyl-ethylene with dimethylsulfonium methylide,4 and in unspecified yields from 1,1-diphenylethylene by reaction with diazomethane followed by pyrolysis of the resulting pyrazoline or by reaction with ethyl diazoacetate followed by distillation of the corresponding acid over calcium oxide.5... 

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