Uncatalyzed Transfer Hydrogrnation and Transfer Hydrogenolysis : Two Novel Types of Hydrogen-Transfer Reactions

Angewandte Chemie (International Edition in English)

Volumn 36, Issue 13-14, 1997, Pages 1406-1430

  Rüchardt, Christoph ^a   Gerst, Matthias ^b   Ebenhoch, Jochen ^c  

^a UNIVERSITY OF FREIBURG   (Germany)

^b BASF SE   (Germany)

^c WACKER CHEMIE AG   (Germany)

Author keywords

Arenes; Coal liquefaction; Hydrogenations; Radical reactions; Reaction mechanisms

Indexed keywords

EID: 0030768537     PISSN: 05700833     EISSN: None     Source Type: Journal    
DOI: 10.1002/anie.199714061     Document Type: Article

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98. At the same time, the following reactions could be excluded with the results of the deuteration experiments, a) Disproportionate of the 2-phenyl-2propyl radicals 8 with the 9-hydroamhryl radicals 9 to form cumene (3) and anthracene (4) [3]; b) disproportionate of 8 [27]; methathesis reaction of 8 with 1 or 4 [27], see also ref. [19c] and D. M. Camaioni, S. T. Autrey, T. B. Saunas, J. A. Franz, J. Am. Chem. Soc. 1996, 118, 2013-2022; I. W. C. E. Arends, P. Mulder, Energy Fuels 1996, 10, 235-242; J. P. Heuts, A. Pross, L. Radon, J. Phys. Chem. 1996, 100, 17087-17089.
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130. H. Mayr, M. Patz, Angew. Chem. 1994, 106, 990-1010; Angew. Chem. Int. Ed. Engl. 1994, 33, 788-789.
131. See ref. [12c], p. 278.
132. R. A. Jackson, NATO ASI Ser. C. 1986, 189, 325-328.
133. Landoldt-Börnstein, Zahlenwerte und Funktionen aus Physik, Chemie, Astronomie, Geophysik und Technik (Eds.: K. H. Hellwege, A. H. Hellwege), 6th ed., Springer, Berlin. Vol. II, part 6, 1959, p. 618.
134. -1.
135. -1 [32].
136. See Table 5, footnote [d].
137. a) M. Gerst, C. Rüchardt. Chem. Ber. 1993, 126, 1039-1045;
138. b) see also W. R. Roth, C. Unger, T. Wasser, Ltebigs Ann. 1996, 2155-2169.
139. See ref. [31 b]. Special calculation methods were used in some cases [3,27]. The activation parameters were measured in a temperature range of at least 40 K.
140. 1,4-Cyclohexadiene and 1.3-cyclohexadiene could also be employed as H donors with 1. Quantitative investigations were complicated by the thermolability of 1,4-cyclohexadiene with isomerization to the 1,3-isomer, and, in the case of 1,3-cyclohexadiene, by the retrodisproportionation of two molecules, which yielded several by-products that were not further identified; S. W Benson, R. Shaw, J. Am. Chem. Soc. 1967, 89, 5351-5354; G. R. DeMaré, G. Huybrechts, M. Toth, J. Chem. Soc. Perkin Trans. 2 1972, 1256-1258; D. K. Agrafiotis, H. S. Rzepa, J. Chem. Soc. Chem. Commun. 1987, 902-904; G. Huybrechts, B. V. Mele, Int. J. Chem. Kin. 1985, 17, 709-711).
141. 1,4-Cyclohexadiene and 1.3-cyclohexadiene could also be employed as H donors with 1. Quantitative investigations were complicated by the thermolability of 1,4-cyclohexadiene with isomerization to the 1,3-isomer, and, in the case of 1,3-cyclohexadiene, by the retrodisproportionation of two molecules, which yielded several by-products that were not further identified; S. W Benson, R. Shaw, J. Am. Chem. Soc. 1967, 89, 5351-5354; G. R. DeMaré, G. Huybrechts, M. Toth, J. Chem. Soc. Perkin Trans. 2 1972, 1256-1258; D. K. Agrafiotis, H. S. Rzepa, J. Chem. Soc. Chem. Commun. 1987, 902-904; G. Huybrechts, B. V. Mele, Int. J. Chem. Kin. 1985, 17, 709-711).
142. 1,4-Cyclohexadiene and 1.3-cyclohexadiene could also be employed as H donors with 1. Quantitative investigations were complicated by the thermolability of 1,4-cyclohexadiene with isomerization to the 1,3-isomer, and, in the case of 1,3-cyclohexadiene, by the retrodisproportionation of two molecules, which yielded several by-products that were not further identified; S. W Benson, R. Shaw, J. Am. Chem. Soc. 1967, 89, 5351-5354; G. R. DeMaré, G. Huybrechts, M. Toth, J. Chem. Soc. Perkin Trans. 2 1972, 1256-1258; D. K. Agrafiotis, H. S. Rzepa, J. Chem. Soc. Chem. Commun. 1987, 902-904; G. Huybrechts, B. V. Mele, Int. J. Chem. Kin. 1985, 17, 709-711).
143. 1,4-Cyclohexadiene and 1.3-cyclohexadiene could also be employed as H donors with 1. Quantitative investigations were complicated by the thermolability of 1,4-cyclohexadiene with isomerization to the 1,3-isomer, and, in the case of 1,3-cyclohexadiene, by the retrodisproportionation of two molecules, which yielded several by-products that were not further identified; S. W Benson, R. Shaw, J. Am. Chem. Soc. 1967, 89, 5351-5354; G. R. DeMaré, G. Huybrechts, M. Toth, J. Chem. Soc. Perkin Trans. 2 1972, 1256-1258; D. K. Agrafiotis, H. S. Rzepa, J. Chem. Soc. Chem. Commun. 1987, 902-904; G. Huybrechts, B. V. Mele, Int. J. Chem. Kin. 1985, 17, 709-711).
144. a) I. Murate, Top. Nonbenzenoid Aromat. Chem. 1973, 1, 159-190;
145. b) D. H. Reid, Quart. Rev. 1965, 19, 274-302;
146. W. Broser, H. Kurreck, S. Oestreich-Janzen, G. Schlömp, H.-J. Fey, B. Kirste, Tetrahedron 1979, 35, 1159-1166;
147. J. E. Bennett, Proc. Chem. Soc. 1961, 144-145;
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149. diss or by transition metal/H derivatives. The latter play an important role in the transition metal catalyzed transfer hydrogenation: a) T. E. Nalesnik, J. H. Freudenberger, M. Orchin, J. Organomet. Chem. 1981, 221, 193-197; b) R. L. Sweany, S. C. Butler, J. Halpern, ibid. 1981, 213, 487-492; R. L. Sweany, J. Halpern, J. Am. Chem. Soc. 1977, 99, 8335-8337; J. Halpern, Pure Appl. Chem. 1979, 51, 2171-2182; see also ref. [20, 35c].
150. diss or by transition metal/H derivatives. The latter play an important role in the transition metal catalyzed transfer hydrogenation: a) T. E. Nalesnik, J. H. Freudenberger, M. Orchin, J. Organomet. Chem. 1981, 221, 193-197; b) R. L. Sweany, S. C. Butler, J. Halpern, ibid. 1981, 213, 487-492; R. L. Sweany, J. Halpern, J. Am. Chem. Soc. 1977, 99, 8335-8337; J. Halpern, Pure Appl. Chem. 1979, 51, 2171-2182; see also ref. [20, 35c].
151. diss or by transition metal/H derivatives. The latter play an important role in the transition metal catalyzed transfer hydrogenation: a) T. E. Nalesnik, J. H. Freudenberger, M. Orchin, J. Organomet. Chem. 1981, 221, 193-197; b) R. L. Sweany, S. C. Butler, J. Halpern, ibid. 1981, 213, 487-492; R. L. Sweany, J. Halpern, J. Am. Chem. Soc. 1977, 99, 8335-8337; J. Halpern, Pure Appl. Chem. 1979, 51, 2171-2182; see also ref. [20, 35c].
152. diss or by transition metal/H derivatives. The latter play an important role in the transition metal catalyzed transfer hydrogenation: a) T. E. Nalesnik, J. H. Freudenberger, M. Orchin, J. Organomet. Chem. 1981, 221, 193-197; b) R. L. Sweany, S. C. Butler, J. Halpern, ibid. 1981, 213, 487-492; R. L. Sweany, J. Halpern, J. Am. Chem. Soc. 1977, 99, 8335-8337; J. Halpern, Pure Appl. Chem. 1979, 51, 2171-2182; see also ref. [20, 35c].
153. -32 also occurs with other H donors and is usually small, so that the rate constants of the retrodisproportionation and particularly the activation parameters change only to a minor extent (see Table 4).
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158. T. Dockner, Angew. Chem. 1988, 100, 699-702; Angew. Chem. Int. Ed. Engl. 1988, 27, 679-682.
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164. H.-H. King, L. M. Stock. Fuel 1981, 60, 748-749.
165. J. Fleming. Grenzorhitale und Reaktionen organischer Verbindungen, 1st ed., VCH, Weinheim, 1979, p. 217.
166. -11 [64a].
167. diss(C-H)[33] = 98.6[32b] - 9.0[64d] - 89.6;
168. -1
169. -1 was given for 31 and 2: D. G. Hendry, D. Schuetzle, J. Am. Chem. Soc. 1975, 97,7123-7127.
170. diss(C-H) of 31.
171. J. B. Pedley, R. D. Naylor, S. P. Kirby, Thermochemical Data of Organic Compounds, 2nd ed., Chapman und Hall, London, 1986, p. 460.
172. -1 [2 b]. All calculated results for the substituted dihydroanthracenes and the acridans (see Table 4) were calibrated accordingly.
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209. In the reaction of fluorenone with 2, fluorene and fluorenol were formed in approximately equimolar amounts. The decrease in fluorenone was not a first-order reaction, as was the case for H acceptors containing C=C bonds (see Section 2.2.2.).
210. W. Bradley, L. J. Watkinson, J. Chem. Soc. 1956, 319-327: the authors describe the hydrogenation of azobenzene (85 a) by an throne, which leads to the formation of hydrazobenzene and aniline.
211. G. Koga, N. Koga, J.-P. Anselme, The Chemistry of Hydrazo-, Azo- and Azoxygroups (Ed.: S. Patai), 1st ed., Wiley, New York, 1975, Vol. 1, part 2, pp. 921-922.
212. -1]: azobenzene (85a): 96.6 [65]; 1,2-diphenylhydrazyl radical: 98.9, see S. Ingemann, R. H. Fokkens, N. M. M. Nibbering, J. Org. Chem. 1991, 56, 607-612; DHA(2): 38.2 [651; [9]: 69.1, see ref. [64a, 34a].
213. -1]: azobenzene (85a): 96.6 [65]; 1,2-diphenylhydrazyl radical: 98.9, see S. Ingemann, R. H. Fokkens, N. M. M. Nibbering, J. Org. Chem. 1991, 56, 607-612; DHA(2): 38.2 [651; [9]: 69.1, see ref. [64a, 34a].
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219. b) P. Kapferer, unpublished results.
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225. We thank Prof. M. Goez (Halle, Germany) and Prof. A. G. Davies (London, UK) for performing these experiments.
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234. Calculations of the transition state by J. W. Verhoeven, W. van Gerresheim, F. M. Martern, S. M. van der Kerk, Tetrahedron 1986, 42, 975-992 suggest that the hydrogen carries only a 10% positive charge in the transition state. However, this phenomenon was also found for proton transfer between carbon atoms (C. F. Bernasconi, J. P. Wenzel, J. Am. Chem. Soc. 1996, 118, 10494-10504) and for hydride transfer of allylic hydrogen onto carbenium ions (G. Lange, H. Mayr (Munich, Germany), private communication);
235. Calculations of the transition state by J. W. Verhoeven, W. van Gerresheim, F. M. Martern, S. M. van der Kerk, Tetrahedron 1986, 42, 975-992 suggest that the hydrogen carries only a 10% positive charge in the transition state. However, this phenomenon was also found for proton transfer between carbon atoms (C. F. Bernasconi, J. P. Wenzel, J. Am. Chem. Soc. 1996, 118, 10494-10504) and for hydride transfer of allylic hydrogen onto carbenium ions (G. Lange, H. Mayr (Munich, Germany), private communication);
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249. 1,2-dihydronaphthalene (H donor)/1,2-dihydronaphthalene (H acceptor): see ref. [13b, 58-61];
250. 1,2-dihydronaphthalene (H donorj/anthracene and phenanthrene (H acceptors): see ref. [13a];
251. e) 1,4-dihydronaphthalene (H donor)/arenes (H acceptor): see also c);
252. f) tetraline (H donorj/indene, cy- clohexene, and trans-stilbene (H acceptors): see ref. [13a];
253. g) tetraline (H donor)/coal (H acceptor): see ref. [55 b]; K. R. Brower, J. Org. Chem. 1982, 47, 1889-1893;
254. h) tetraline (H donor)/furan, indole, and thiophene derivatives (H acceptors): see f);
255. tetraline (H donor)/ketones and aldehydes (H acceptors): see
256. f) and B. M. Benjamin, V. F. Raaen, P. H. Maupin, L. L. Brown, C. J. Collins, Fuel 1978, 57, 269-272;
257. j) tetraline (H donor)/ quinones (9,10-phenanthrenedione, 9,10-anthraquinone; H acceptors): see f) and ref. [55b];
258. k) tetraline (H donor)/with nitroso derivatives and maleic esters (H acceptors): see j);
259. cyclohexane (H donor)/olefins, alkynes, or carbonyl derivatives (H acceptors): see f);
260. 2-propanol (H donor)/carbonyl derivatives (H acceptors): D. Malwitz, J. O. Metzger, Chem. Ber. 1986, 119, 3558-3575;
261. n) o- and p-isotoluene (simultaneously H donor and H acceptor): ref. [18a]; W. J. Bailey, R. A. Baylouny, J. Org. Chem. 1962, 27, 3476-3478; D. Hasselmann, K. Loosen, Angew. Chem. 1978, 90, 641-642; Y. W. Andemichael, K. K. Wang, J. Org. Chem. 1992, 57, 796-798;
262. n) o- and p-isotoluene (simultaneously H donor and H acceptor): ref. [18a]; W. J. Bailey, R. A. Baylouny, J. Org. Chem. 1962, 27, 3476-3478; D. Hasselmann, K. Loosen, Angew. Chem. 1978, 90, 641-642; Y. W. Andemichael, K. K. Wang, J. Org. Chem. 1992, 57, 796-798;
263. n) o- and p-isotoluene (simultaneously H donor and H acceptor): ref. [18a]; W. J. Bailey, R. A. Baylouny, J. Org. Chem. 1962, 27, 3476-3478; D. Hasselmann, K. Loosen, Angew. Chem. 1978, 90, 641-642; Y. W. Andemichael, K. K. Wang, J. Org. Chem. 1992, 57, 796-798;
264. p) dimethylaminoethyl acrylate (simultaneously H donor and H acceptor): see ref. [14e];
265. q) peroxides or halides with alkenes: see ref. [17].