2,4-Dinitrophenyl phenyl ether

The number of reactions that fit into this second class are manifold. Some typical examples are the amine-catalyzed reactions of 2,4-dinitrochlorobenzene with n-butylamine in chloroform (k"/k = 2.59 l.mole-1)23, with allylamine in chloroform (k"jk — 4.60 l.mole-1)24 and with allylamine in ethanol (k"fk =0.36 l.mole-1)25 and the amine-catalyzed reaction of p-nitrofluorobenzene with piperidine in polar solvents (k"/k < 3.2 l.mole-1)26. A typical example of a strongly catalyzed system is the reaction of 2,4-dinitrophenyl phenyl ether with piperidine in 60 % dioxan-40 % water27. 

If one limits the consideration to only that limited number of reactions which clearly belong to the category of nucleophilic aromatic substitutions presently under discussion, only a few experimental observations are pertinent. Bunnett and Bernasconi30 and Hart and Bourns40 have studied the deuterium solvent isotope effect and its dependence on hydroxide ion concentration for the reaction of 2,4-dinitrophenyl phenyl ether with piperidine in dioxan-water. In both studies it was found that the solvent isotope effect decreased with increasing concentration of hydroxide ion, and Hart and Bourns were able to estimate that fc 1/ for conversion of intermediate to product was approximately 1.8. Also, Pietra and Vitali41 have reported that in the reaction of piperidine with cyclohexyl 2,4-dinitrophenyl ether in benzene, the reaction becomes 1.5 times slower on substitution of the N-deuteriated amine at the highest amine concentration studied. 

Figure 2. Reaction of 2,4-dinitrophenyl phenyl ether with piperidine, catalysed by NaOH.

Table 3. Reaction between piperidine and 2,4-dinitrophenyl phenyl ether.

A similar twisting was expected to occur with the phenoxy ether to explain the greater reactivity of the 2,6-isomer in recent studies of the reactions of 2,4-dinitro and 2,6-dinitrophenyl phenyl ethers with zz-butylamine109. Nevertheless, in this case, the authors... 

C13H7NsO, mw 409.23, N 17.12%. Two compds, presumably 2,4-Dinitrobenzyl-2,4,6-trinitro-phenyl Ether, (02N)2CgH3.CH2.0.CgH2(N02)3( ) and 2,4,6- Trinitrobenzyl-2,4-dinitrophenyl Ether, (02N)3CgH2.CH2.0.CgH3(N02)2( ) were reported prepd by nitration of either 4-nitrobenzyl-2,4-di-nitrophenyl etber(mp 207-8°) or 2-nitrobenzyl -2,4-dinitrophenyl ether(mp 188°), using mixed nitric-sulfuric acids. A product of mp 146 (dec), but not further identified, was obtd on recrystn from chlf. Attempts to prep a hexanitro deriv led to formation of decompn products Refs l)Beil- not found 2)H.Ryan J.Keane,Sci-ProcRoyDublinSoc 17,287(1924) CA 18,1654 (1924)... 

Stability of the compounds 86 varies dramatically with the nitrogen substituent. Methyl" and phenyl s derivatives (86 R = Me or Ph) are moderately stable crystalline solids—often hydrated (87 or 88 X = OH). The 2,4-dinitrophenyl derivative [86 R = C6H3(NO2)2, R = H] is less stable but can be isolated as orange prisms (mp 112°C)5° It readily rearranges to the diaryl ether 96 (mp 128°C) with which it was originally confused.5The monomeric 5-nitro-2-pyridyI derivative is similarly unstable and in solution dimerizes giving adduct 97a. 5 5 The 4,6-di-methylpyrimidin-2-yl derivative can only be isolated as the dimers 97b and... 

Ethanol, 2-[(1,7,7-trimethylbicyclo [2.2.1] hept-2-yl) oxy], exo-. See (exo)-2-Camphanyl-P-hydroxyethyl ether Ethanol, undenatured. See Alcohol Ethanone, 1-(2,3-dihydro-1,1,2,3,3,6-hexamethyl-1H-inden-5-yl)-. See Acetyl hexamethyl indan Ethanone, 2,2-dimethoxy-1,2-diphenyl-. See 2,2-Dimethoxy-2-phenylacetophenone Ethanone, 1-(4-(1,1-dimethylethyl)-2,6-dimethyl-3,5-dinitrophenyl)-. See Musk ketone Ethanone, 1-[4-(1,1-dimethylethyl) phenyl]-. See p-t-Butyl acetophenone Ethanone, 1-(4-ethylphenyl)-. See4-Ethylacetophenone... 

---