Phenyl Chloride Derivatives

AMI calculations suggested that in the formation of methyl 4-phenyl-l, 6-dioxo-l,3,4,6,7,8-hexahydropyrido[2,l-c][l,4]oxazine-9-carboxylates (28) from acroyl chloride derivatives 26 and 1,4-oxazine 27 is favored over the hetero-Diels-Alder condensation (96JOC5736). 

The easily available 4-(4 -bromophenyl)-2,6-diphenylphenol has been used to make an interesting water soluble persistant and oxygen stable phenoxyl radical132). It has been synthesized by reacting the (4 -bromo-4-phenyl)-phenol derivative with butyllithium in ether and dry sulfuryl chloride. 

Maroz A, Hermann R, Naumov S, Brede O. (2005) Ionization of aniline and its N-methyl and N-phenyl substituted derivatives by (free) electron transfer to n-butyl chloride parent radical cations. JPhys Chem A 109 4690 696. 

Tri-phenyl Methane Derivative.—That this compound is a derivative of tri-phenyl methane is proven by the following series of relationships. When phthalyl chloride is reduced with hydrogen we obtain phthalide (p. 693). 

In a related phthalein dye, however, this condition is fully met. The dye fluorescein is resorcinol phthalein and is made from phthalic anhydride or phthalyl chloride and resorcinol just as phenol phthalein is made from phthalic anhydride and phenol (p. 750). These relationships may be expressed as follows writing the final dye salt both as a tri-phenyl methane derivative (B) and as a pyronine (C). The reactions are exactly analogous to those given for the preparation of phenolphthalein and its dye salt (p. 750), some of the intermediate steps being omitted in the present case. 

The interaction of indenyl- and fluorenyl-lithium and phenyl-sub-stituted plumbic chlorides produces the corresponding phenyl lead derivatives ( ), but attempts to prepare difluorenyl lead and diindenyl lead were not successful. 

The direct selenoacetalization of carbonyl compounds by selenols is by far the shortest and most convenient route to selenoacetals. The reaction is usually carried out at 20 C with zinc chloride (0.5 equiv. versus the carbonyl con x>und) and delivers rapidly (<3 h) and in reasonably good yields methyl and phenyl selenoacetals derived from aliphatic aldehydes and ketones and cyclic ketones (Scheme 69). Selenoacetalization is more difficult to achieve with hindered ketones, such as adamantanone and diisopropyl ketone, and with hindered aromatic carbtmyl compounds. In these cases the reaction is best achieved with titanium tetrachloride instead of zinc chloride and is often limited to the methylseleno derivatives (Scheme 78). Tris(methylseleno)borane offers the advantage of not requiring an acid catalyst and is particularly useful for the selenoacetalization of acid labQe aldehydes such as citronellal (Scheme 70, e). 

The 4-phenyl substituted derivatives (243, 245) have also been prepared via this methodology starting from 5-chloro-2-methyl-6-phenylpyridazin-3(2TZ)-one (241). Remarkably, Buchwald-Hartwig reaction of 241 with 2-bromoaniline worked smoothly and no homocoupling of the bromoaniline was observed. The C—Cl bond of 241 seems to be more reactive in the oxidative addition step than the C—Br bond of 2-bromoaniline. The preferential reaction of the C—Cl bond can be explained by taking into account that this C—Cl bond is part of a vinylogous carbamoyl chloride which dramatically increases... 

Diarylketones are also the important fine chemical intermediates, which could be prepared by the acylation of aromatic hydrocarbon with benzoyl chloride and benzoic anhydride. The ionic liquids have also been used to catalyze the synthesis of diarylke-tone. Earle et al. [105] have reported the benzoylation of benzene, derivants of benzene (toluene, anisole, isobutyl benzene, phenyl chloride and fluoride) to synthesize the diarylketone by use of chloroindate (III) ionic liquids as the green dual catalysts and solvents. As a result, good yields (75-96%) were obtained under proper conditions with the ionic liquids as the clean reaction medium and recyclable catalysts. 

The chlorides derived from the reaction of aroyl phenylhydrazines with phosphorus pentachloride are recorded in the literature under a variety of names. While Chemical Abstracts lists these compounds as the phenyl-hydrazones of the corresponding acid chlorides (for example, benzoyl chloride phenylhydrazone for C H5CiCl)=NNHC H5), Beilstein uses the terms a-chlorobenzyliden phenylhydrazine or a-chlorobenzal phenyl-hydrazine for this compound. In view of the relationship of the chlorides I with the corresponding acid hydrazides (II), their hydrolysis products, the names hydrazide chlorides or hydrazidoyl chlorides are more appropriate. In order to preserve conformity of nomenclature, the latter name is used in this book. 

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