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66249118834
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1,4-Dihydroxy-2,3-dimethoxy-6-methylphenol.
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1,4-Dihydroxy-2,3-dimethoxy-6-methylphenol.
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25
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66249094928
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4 than in the gas phase (see: Ingold, K. U. Can. J. Chem. 1962, 40, 111 - 121), and in this low-dielectric solvent, relative energies are expected to be little changed compared to those in the gas phase. We therefore performed all calculations for isolated (nonsolvated) monomers and complexes.
-
4 than in the gas phase (see: Ingold, K. U. Can. J. Chem. 1962, 40, 111 - 121), and in this low-dielectric solvent, relative energies are expected to be little changed compared to those in the gas phase. We therefore performed all calculations for isolated (nonsolvated) monomers and complexes.
-
-
-
-
26
-
-
66249113326
-
-
+) = 9.24.
-
+) = 9.24.
-
-
-
-
29
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15744383667
-
-
(a) Mulder, P.; Korth, H.-G.; Pratt, D. A.; DiLabio, G. A.; Valgimigli, L.; Pedulli, G. F.; Ingold, K. U. J. Phys. Chem. A 2005, 109, 2647-2655.
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Mulder, P.1
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Pratt, D.A.3
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Valgimigli, L.5
Pedulli, G.F.6
Ingold, K.U.7
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31
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0010378806
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See, e.g, a
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See, e.g.: (a) Bellamy, L. J.; Hallam, H. E. Trans. Faraday Soc 1959, 55, 220-224.
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Bellamy, L.J.1
Hallam, H.E.2
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35
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3543065365
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(e) Vokin, A. I.; Gavrilova, G. A.; Shulunova, A. M.; Krivoruchka, I. G.; Aksamentova, T. N.; Turchaninov, V. K. Zh. Obshch. Khim. (Engl. Transl.) 2004, 74, 239-249.
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Vokin, A.I.1
Gavrilova, G.A.2
Shulunova, A.M.3
Krivoruchka, I.G.4
Aksamentova, T.N.5
Turchaninov, V.K.6
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36
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1842454267
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(f) Chiş, V. Chem. Phys. 2004, 300, 1-11.
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(2004)
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, vol.300
, pp. 1-11
-
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Chiş, V.1
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37
-
-
66249102123
-
-
For an excellent review dealing mainly with intramolecular HBs, including those in ortho-substituted phenols
-
(g) For an excellent review dealing mainly with intramolecular HBs, including those in ortho-substituted phenols
-
-
-
-
38
-
-
27744547412
-
-
see: h
-
see: (h) Sobczyk, L.; Grabowski, S. J.; Krygowski, T. M. Chem. Rev. 2005, 105, 3513-3560.
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Sobczyk, L.1
Grabowski, S.J.2
Krygowski, T.M.3
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39
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3543114916
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See, e.g, a
-
See, e.g.: (a) Magee, M. D.; Walker, S. J. Chem. Phys. 1971, 55, 3068-3071.
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(1971)
J. Chem. Phys
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Magee, M.D.1
Walker, S.2
-
42
-
-
66249115767
-
-
With one exception: 2-nitrophenol in nitrobenzene ref 20b
-
With one exception: 2-nitrophenol in nitrobenzene (ref 20b).
-
-
-
-
43
-
-
66249114773
-
-
The barrier to rotation of the OH group in phenol is 3.5 kcal/mol (ref 24).
-
The barrier to rotation of the OH group in phenol is 3.5 kcal/mol (ref 24).
-
-
-
-
44
-
-
0029731941
-
-
Berden, G.; Meerts, W. L.; Schmitt, M.; Kleinermanns, K. J. Chem. Phys. 1996, 104, 972-982.
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(1996)
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Berden, G.1
Meerts, W.L.2
Schmitt, M.3
Kleinermanns, K.4
-
45
-
-
66249090336
-
-
The sharp IR band at ca. 3100 cm-1 is due to a C3-H stretching mode, see ref 20f
-
3-H stretching mode, see ref 20f.
-
-
-
-
46
-
-
66249107558
-
-
Intramolecular HB strengths were computed (ref 27), to a first approximation (ref 28), by taking the difference in enthalpy between the OH toward the ortho substituent H-bonded minimum enthalpy structure and the OH away minimum enthalpy structure following a 180° rotation of the OH group about the HO- C bond.
-
Intramolecular HB strengths were computed (ref 27), to a first approximation (ref 28), by taking the difference in enthalpy between the OH "toward the ortho substituent" H-bonded minimum enthalpy structure and the OH "away" minimum enthalpy structure following a 180° rotation of the OH group about the HO- C bond.
-
-
-
-
47
-
-
66249135440
-
-
By calculating the stabilization enthalpies for 2-XC6H 4OH (2,4-X2C6H4OH, C 6H6 → 2-XC6H5 (2,4-X 2C6H5, C6H5OH at the B971/6- 311++G(2d,2p) level of theory
-
5OH at the B971/6- 311++G(2d,2p) level of theory.
-
-
-
-
48
-
-
66249120139
-
-
This is only a first approximation of the intramolecular HB strength because it incorporates enthalpies associated with resonance and inductive interactions between the OH group and the other substituents on the ring
-
This is only a first approximation of the intramolecular HB strength because it incorporates enthalpies associated with resonance and inductive interactions between the OH group and the other substituents on the ring.
-
-
-
-
51
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0000992504
-
-
(b) Berthelot, M.; Laurence, C.; Lucon, M.; Rossignol, C.; Taft, R. W. J. Phys. Org. Chem. 1996, 9, 626-630.
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J. Phys. Org. Chem
, vol.9
, pp. 626-630
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Berthelot, M.1
Laurence, C.2
Lucon, M.3
Rossignol, C.4
Taft, R.W.5
-
52
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66249127009
-
-
There would appear to be no 2,6-diacylphenols commercially available, and no easy synthesis of any of them was discovered in the literature. It was not possible, therefore, to look for a bifurcated hydrogen bond with DMSO using such a phenol.
-
There would appear to be no 2,6-diacylphenols commercially available, and no easy synthesis of any of them was discovered in the literature. It was not possible, therefore, to look for a bifurcated hydrogen bond with DMSO using such a phenol.
-
-
-
-
53
-
-
66249096457
-
-
H value for nitrobenzene is 0.34, whereas the values for benzaldehyde and acetophenone are significantly greater, 0.42 and 0.51, respectively (ref 5).
-
H value for nitrobenzene is 0.34, whereas the values for benzaldehyde and acetophenone are significantly greater, 0.42 and 0.51, respectively (ref 5).
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-
-
-
59
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-
0037136807
-
-
Korth, H.-G.; de Heer, M. I.; Mulder, P. J. Phys. Chem. A 2002, 106, 8779-8789.
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(2002)
J. Phys. Chem. A
, vol.106
, pp. 8779-8789
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Korth, H.-G.1
de Heer, M.I.2
Mulder, P.3
-
60
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0347218098
-
-
(a) Detoni, S.; Hadzi, D.; Juranji, M. Spectrochim. Acta 1974, 30A, 249-253.
-
(1974)
Spectrochim. Acta
, vol.30 A
, pp. 249-253
-
-
Detoni, S.1
Hadzi, D.2
Juranji, M.3
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61
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66249121192
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-
In this paper, the band maxima for 2-acetyl, 2-formyl, and 2-nitro-phenol were reported to be 3050, 3150, and 3240 cm-1, respectively
-
-1, respectively.
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-
-
-
62
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66249095450
-
-
The ortho- para method (ref 38) for estimating the enthalpy of this intramolecular HB from the difference in the calculated ground- state energies of 2-hydroxybenzaldehyde and 4-hydroxybenzaldehyde yielded values of 5.5 (CBS-QB3) and 5.6 (B3LYP/6-311+G(dp)) kcal/mol (ref 38b). As appears to be usual (ref 38), the ortho-para method gives lower (often much lower) intramolecular HB strengths than the cis- trans method we employed. There appears to be no compelling reason for choosing one method over the other. The ortho-para method yielded intramolecular HB strengths in 2-acetylphenol of 5.9 (CBS-QB3) and 6.3 (B3LYP/6-311+G(dp)) kcal/mol (ref 38b).
-
The "ortho- para method" (ref 38) for estimating the enthalpy of this intramolecular HB from the difference in the calculated ground- state energies of 2-hydroxybenzaldehyde and 4-hydroxybenzaldehyde yielded values of 5.5 (CBS-QB3) and 5.6 (B3LYP/6-311+G(dp)) kcal/mol (ref 38b). As appears to be usual (ref 38), the ortho-para method gives lower (often much lower) intramolecular HB strengths than the "cis- trans method" we employed. There appears to be no compelling reason for choosing one method over the other. The ortho-para method yielded intramolecular HB strengths in 2-acetylphenol of 5.9 (CBS-QB3) and 6.3 (B3LYP/6-311+G(dp)) kcal/mol (ref 38b).
-
-
-
-
63
-
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10844251015
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(a) Estacio, S. G.; Cabral do Couto, P.; Costa Cobral, B. J.; Minas da Piedade, M. E.; Martinho Simoes, J. A. J. Phys. Chem. A 2004, 108, 10834-10843.
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Estacio, S.G.1
Cabral do Couto, P.2
Costa Cobral, B.J.3
Minas da Piedade, M.E.4
Martinho Simoes, J.A.5
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67
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0033617162
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Dorrestijn, E.; Kranenburg, M.; Ciriano, M. V.; Mulder, P. J. Org. Chem. 1999, 64, 3012-3018.
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Dorrestijn, E.1
Kranenburg, M.2
Ciriano, M.V.3
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68
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66249101360
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-
Private communication
-
Mendenhall, G. D. Private communication.
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-
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Mendenhall, G.D.1
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69
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66249125166
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-
The ratio of the free phenol to the HB form was estimated (ref 39) to be 4:96, possibly from peak heights (our own peak height ratio is 5:95, Figure 9). However, this ratio overestimates the amount of the free phenol because HB bands are broader and generally of lower height than an equal quantity of a free phenol. A better measure of free phenol is given by the ratio of the integrated areas of the two bands, viz., 1.9:98.1. However, this ratio will underestimate the amount of free phenol because the integrated areas of the O-H stretching bands of phenols are greater when the phenol forms a HB than when it is free.
-
The ratio of the "free" phenol to the HB form was estimated (ref 39) to be 4:96, possibly from peak heights (our own peak height ratio is 5:95, Figure 9). However, this ratio overestimates the amount of the "free" phenol because HB bands are broader and generally of lower height than an equal quantity of a "free" phenol. A better measure of "free" phenol is given by the ratio of the integrated areas of the two bands, viz., 1.9:98.1. However, this ratio will underestimate the amount of "free" phenol because the integrated areas of the O-H stretching bands of phenols are greater when the phenol forms a HB than when it is "free".
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-
-
-
70
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38349078273
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-
See, for example
-
See, for example: Amorati, R.; Catarzi, F.; Menichetti, S.; Pedull, G. F.; Viglianisi, C. J. Am. Chem. Soc. 2008, 130, 237-244.
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Amorati, R.1
Catarzi, F.2
Menichetti, S.3
Pedull, G.F.4
Viglianisi, C.5
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72
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4243664295
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Hansch, C.; Leo, A.; Taft, R. W. Chem. Rev. 1991, 91, 165-195.
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(1991)
Chem. Rev
, vol.91
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Hansch, C.1
Leo, A.2
Taft, R.W.3
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73
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66249091736
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-
4. A very similar equilibrium constant should apply to phenol (see text), indicating that for phenol in neat CCl4 about 20% of the hydroxyl groups will be hydrogen-bonded to a solvent molecule. This phenomenon is not distinguishable by IR, but it is in excellent agreement with earlier kinetic measurements (ref 3).
-
4. A very similar equilibrium constant should apply to phenol (see text), indicating that for phenol in neat CCl4 about 20% of the hydroxyl groups will be hydrogen-bonded to a solvent molecule. This phenomenon is not distinguishable by IR, but it is in excellent agreement with earlier kinetic measurements (ref 3).
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