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• W2323199331 abstract "The bathochromic spectral shift by one of the aminobenzoxazinones, that is 7-dimethylamino-3(4-dimethyl aminostyryl)-l1,4-benzoxazin-2-one, (BOZNMe2) has been measured in 21 nonaqueous solvents. For BOZNMe2 in nonpolar and polar aprotic and hydrogen bonding solvents, the solvatochromic response of the solute conforms exactly to the requirements of the Kamlet-Taft linear solvation free energy model of solvent-solute interactions. Likewise, it follows the generally parallel predictions of a molecular orbital interpretation of the reaction field effects as well. The responses of solvatochromic indicators to changing environments have been used as the phenomenological basis for several general solvent polarity scales. Among such quantitative scales, the Kamlet-Taft system (Kamlet et al., 1983) is the most inclusive with respect to types and it is well supported by theoretical reaction field models for the influences upon the solvatochromic probes (Abboud and Taft, 1979; Brady and Carr, 1982). The fundamental linear solvation free energy relationship (LSFER) in the Kamlet-Taft system is given by equation 1 (Kamlet et al., 1983). XYZ = XYZo + s(r* + db) + aa + bf + hbH + e? (1) Here, the three major intrinsic properties are included: dipolaritypolarizability (-r* and its db-correction); hydrogen bonding acidity (a); and hydrogen bonding basicity (0). The last two terms in Equation (1) are the contributions from the Hildebrand solubility (6H) for enthalpies of transfer between solvents and that for family dependencies assignable to Lewis basicity for particular reactant species; however, for the more usual reactions and equilibria, these two effects are negligible or zero with respect to their influence upon the free energy variable XYZ. A wide variety of spectral probes have been used to determine the lr*, a, and p3 values for solvents in addition to the usual uv-visible bathochromic This content downloaded from 207.46.13.113 on Thu, 06 Oct 2016 04:13:50 UTC All use subject to http://about.jstor.org/terms 122 TRANSACTIONS OF THE KANSAS ACADEMY OF SCIENCE indicators. These include solvent-dependent shifts of ESR spectra for freeradicals and 19Fand 'SN-species as NMR probes of effects (Kolling, 1984). The early work with uv-visible solvatochromic indicators employed relatively simple species, that is the substituted nitroanilines, but these studies were extended to the large molecular merocyanines and betaines as the chromophores (Taft, Abboud, and Kamlet, 1981). More recently, benzophenone and stilbene derivatives have been applied to dipolarity measurements of the alkylbenzenes by Ulrich and Carr (1991). The Kamlet-Taft solvatochromic comparison method (Kamlet and Taft, 1976) utilizes several structurally unique uv-batho-chromic indicators and this investigation extends that procedure to another large solvatochromic species, 7-dimethylamino-3(4-dimethylamino styryl)1,4-benzoxazin-2-one (i.e., BOZNMe2). The total solvent-induced spectral shift for BOZNMe2 is about 33 nm in going from alkane to alkanolic solvents and is comparable in magnitude to other probes in that regard. The 1,4-benzoxazin-2-ones were synthesized first by LeBris (1985) and, although their solvatochromic properties were noted initially, no systematic interpretation of this phenomenon based on the Kamlet-Taft treatment has been reported. Twenty-one solvents ranging from aprotic nonpolar to aromatics and to hydrogen bond donors now are included in this study. EXPERIMENTAL SECTION The solvatochromic compound (BOZNMe2) was prepared by the methods of LeBris (1985) and the orange product was recrystallized twice from ethanol. Product verification was made by spectral comparisons to the LeBris (1985) data. Experimental solvatochromic comparison methods for the determination of dipolarity and hydrogen bonding acidity parameters were the same as reported earlier (Kolling, 1981). Likewise, the spectroscopic grade solvents were redried and purified as before (Kolling, 1984). The triplicate visible spectra were recorded in each solvent, using a Shimadzu UV-1201 instrument, and the uncertainty in all of the Xmax values does not exceed ?0.3 nm. For correlations involving the BOZNMe2 data, two reference indicators used were Phenol Blue and 3-aminofluoren-9-one. RESULTS AND DISCUSSION The experimental results of this investigation can be analyzed within the context of both a generalized reaction field interpretation of solvatochromic indicator behavior and the specific response of BOZNMe2 as a bathochromic species. An MO model for the LSFER. Although the Block-Walker and other reaction field models have provided theoretical support for the Kamlet-Taft LSFER (Abboud and Taft, 1979; Brady and Carr, 1982), an alternative This content downloaded from 207.46.13.113 on Thu, 06 Oct 2016 04:13:50 UTC All use subject to http://about.jstor.org/terms VOLUME 97, NUMBERS 3-4 123 rationale can be restated by using molecular orbital (MO) arguments as well. For the influence on the solute outer-sphere reorganizational energy, the environmental effect experienced by the probe can be formulated in terms of a reaction field Hamiltonian Hf. As an initial first-order molecular orbital perturbation function, the total Hamiltonian assumes the standard form of Equation (2) (Atkins, 1983). Hrf = (Hs)0 + X~pH + ?HHH (2) This is an extension of the formulation of Hf used by Wong, Frisch, and Wiberg (1991) and includes only the two primary additive contributions from dipolar effects and from hydrogen bond donor acidity. For the first effect, the H, function in Equation (3) includes the dipole operator 4 and the Kirkwood g-factor or similar parameter in the static or optical dielectric constants." @default.
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• W2323199331 title "Solvatochromic Response of an Aminobenzoxazinone in the Visible Region" @default.
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