Efficient oxidative cleavage of olefins to carboxylic acids with hydrogen peroxide catalyzed by methyltrioctylammonium tetrakis(oxodiperoxotungsto)phosphate(3-) under two-phase conditions. Synthetic aspects and investigation of the reaction course

Journal of Organic Chemistry

Volumn 63, Issue 21, 1998, Pages 7190-7206

  Antonelli, Ermanno ^a   D'Aloisio, Rino ^a   Gambaro, Mario ^a   Fiorani, Tiziana ^a   Venturello, Carlo ^a  

^a ENI S P A   (Italy)

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EID: 0000732404     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo980481t     Document Type: Article

References (131)

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36. Oxidation of trisubstituted and internal disubstituted olefins to acids obeys a 1:3 and 1:4 substrate-to-hydrogen peroxide stoichiometry, respectively. The molar ratio required becomes 1:5 with monosubstituted terminal olefins as the coproduced formic acid can be further oxidized to carbon dioxide.
37. 2 (3 mmol) at low conversion (18%, 1 h). Pentanal (7d), which forms in equimolar amounts with pentanoic acid (8d) from the oxidative cleavage of 4d, was found to be present in the reaction mixture in a molar ratio of 1:1.75 to 8d and of at least 20:1 to 5,6-decanedione.
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43. 10) peroxides and ethers. They presumably result from further reaction of, respectively, the β-hydroperoxy alcohols (see ahead in the text) and vic-diols previously formed with the respective starting epoxides.
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50. The found value of the molar ratio (in favor of the 1,2-diol/α-ketol pair) is misleading because of the high reactivity of β-hydroperoxy alcohols 5c,d under the reaction conditions (see section III).
51. 33b
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53. A nearly 1:1 regioisomeric mixture of 5-hydroxy-4-decanone (4Ic) and 4-hydroxy-5-decanone (4IIc) was obtained from the epoxide trans-2c, as determined by GC and GC-MS (after silylation with BSTFA). Regioisomer 4Ic eluted first.
54. 35b As amphiphiles, in the present two-phase system, the former should be regarded as being more suitably oriented than the latter to contact their polar head with the nucleophiles water and hydrogen peroxide. This might contribute to their much faster hydrolysis/perhydrolysis.
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58. 2 under the same conditions. This is due to the fact that, starting from 2f, heating of the substrate/catalyst Ia/water mixture prior to addition of hydrogen peroxide according to the procedure adopted (cf. Experimental Section) favors an early hydrolysis of the epoxide.
59. For a definition of "normal" and "abnormal" product with regard to the direction of ring opening by a nucleophile in unsymmetrical epoxides, see: Parker, R. E.; Isaacs, N. S. Chem. Rev. 1959, 742 and references therein.
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61. In addition to detection as the silyl derivative (for details, see Experimental Section), 6d could also be revealed as such by GC (cold on-column injector), without appreciable decomposition. Its formation during the progress of transformation 5d → 8d was quantitated by GC as the α-ketol, after reduction in situ with triphenylphosphine.
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67. 47b
68. Analogously, under the same conditions the silyl derivative of the secondary α-hydroperoxy ketone 6d was found to gradually convert into the corresponding α-diketone (see Experimental Section).
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79. 2. In any case, it speaks for way a" as well. A priori, we cannot exclude, for both 5IIb and 5d, that the found α-ketol may in part arise also from decomposition of the corresponding α-hydroperoxy ketone formed by the alternative way a' (cf. text and Scheme 2 for the case of 5d). However, since (i) the figures considered refer to experiments at low/partial conversion, where the intermediate α-hydroperoxy ketone formed is present to the extent of 78-82%, and (ii) decomposition of the latter leads only to minor amounts of a-ketol (cf. text and Scheme 2 for the case of 6d), the possible contribution of way a' to the formation of the found α-ketol (due to the decomposed α-hydroperoxy ketone) is insignificant.
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91. 4 (the first one in the same molar amount, the other two in a molar amount 5-fold greater), under identical conditions. This points to the importance of the lipophilic character of the used acid catalyst for a satisfactory oxirane opening under two-phase reaction conditions.
92. 60b
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105. Due to its syrupy nature, complex la was preferably employed as a dichloromethane solution of known concentration, with the solvent subsequently removed.
106. 2, and combined with the crystals precipitated from the aqueous layer.
107. Acheson, R. M. J. Chem. Soc. 1956, 4232.
108. Thoma, H.; Spiteller, G. Liebigs Ann. Chem. 1983, 1237.
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110. Osowska-Pacewicka, K.; Alper, H. J. Org. Chem. 1988, 53, 808.
111. 2:substrate molar ratio (5:1) used in these experiments was chosen to simulate the reaction conditions (volume ratio of the organic versus aqueous phase) as close as possible.
112. 2 was omitted.
113. Determined by GC (after silylation) and NMR.
114. Determined by NMR.
115. +), 75 (60), 61 (38).
116. Rigby, W. J. Chem. Soc. 1950, 1911.
117. +), 138 (1), 136 (2.5), 123 (52), 121 (65), 106 (63), 105 (100), 77 (58).
118. Purity was determined after converting 6d into the corresponding α-ketol.
119. +).
120. 2.
121. (b) Dickey, F. H.; Rust, F.; Vaughan, W. E. J. Am. Chem. Soc. 1949, 71, 1432.
122. The value of the ratio decidedly in favor of 8d parallels the trend observed in the blank decomposition of 5d (see Experimental Section) and discussed in ref 83a.
123. For the formation of 1,2,4-trioxanes by the reaction of aldehydes with β-hydroperoxy alcohols in the presence of acids or dehydrating agents, see: (a) Swern, D. Organic Peroxides; Wiley-Interscience: New York, 1970; Vol. 3, Chapter 2, pp 108-110.
124. (b) Singh, C. Tetrahedron Lett. 1990, 31, 69.
125. Refs 28 and 29.
126. 4, 20.6 and 48 mg/L, respectively).
127. (87) This value does not include the quota due to the phosphoric acid already contained in hydrogen peroxide itself (cf. ref 86).
128. Through the use of procedure B (85 °C, 30 min) but with water alone in place of aqueous hydrogen peroxide, from cyclohexene and styrene oxides (2e and 2f) the corresponding 1,2-diols were easily obtained in 85-86% yields (GC analysis). In contrast, from epoxyalkanes 2a,b only small or negligible amounts of the respective 1,2-diols were formed under the same conditions.
129. 71
130. Most of the glutaric and adipic acid formed (about 5% and 1%, respectively) is found in the mother liquor from acid extraction.
131. The GC-mass spectrum (as dimethyl ester) was consistent with published data: Heller, J.; Yogev, A.; Dreiding, A. S. Helv. Chim. Acta 1972, 55, 1003.