US 2011 O251399A1 (19) United States (12) Patent Application Publication (10) Pub. No.: US 2011/0251399 A1 Dingerdissen et al. (43) Pub. Date: Oct. 13, 2011 (54) METHOD FOR PRODUCING ALDEHYDES (86). PCT No.: PCT/EP10/50772 AND KETONES FROM PRIMARY AND SECONDARY ALCOHOLS S371 (c)(1), (2), (4) Date: Jun. 20, 2011 (75) Inventors: Uwe Dingerdissen, Seeheim (DE); (30) Foreign Application Priority Data Jan Pfeffer, Essen (DE); Thomas Tacke, Alzenau (DE); Thomas Feb. 6, 2009 (DE) ....................... 10 2009 OOO662.1 Haas, Muenster (DE); Harald Publication Classification Schmidt, Muelheim an der Ruhr (51) Int. Cl. (DE); Florian Klasovsky, Haltern C07D 40/04 (2006.01) am See (DE); Roger Sheldon, C07C 45/78 (2006.01) Hoog-Kappel (NL); Michiel C07D 307/68 (2006.01) Janssen, Den Haag (NL); Michael CD7C 45/82 (2006.01) Volland, Duelmen (DE); Michael CD7C 45/38 (2006.01) Rimbach, Herne (DE); Stefanie CD7C 45/6 (2006.01) Rinker, Huenxe (DE) CD7C 45/8 (2006.01) (52) U.S. Cl. ...................... 546/276.4:568/354:568/397; (73) Assignee: EVONIK DEGUSSA GMBH, 568/471; 549/498 ESSEN (DE) (57) ABSTRACT The invention relates to a method for producing aldehydes (21) Appl. No.: and ketones from easily accessible primary and secondary 13/140,921 alcohols by oxidation with atmospheric oxygen or pure oxy gen using a catalyst system which consists of a derivative of (22) PCT Filed: Jan. 25, 2010 a free nitroxyl radical. Patent Application Publication Oct. 13, 2011 Sheet 2 of 10 US 2011/0251399 A1 Fig. 2: Oxidation of isomannitol with with AA-Tempo/nitrite/nitrate Oxygen eeJW Xee 000,000|- 000’00!.-- 000'00/— | 000'009-- 000006, 000'009–-------------------------------------+---- |---- 000'008+/ 000'009–—————————Á----- 000'007-7—~~~ ~~~~---- O-------~~~~4%…• 00?.080907 Š C. O O If u Oeulueouoso Patent Application Publication Oct. 13, 2011 Sheet 3 of 10 US 2011/0251399 A1 Fig. 3 --e-Diketa-e-looketo--sosorbide - - - - --Cyfy. - -- keto -g-konsketc. --S&Soft).ds -- (oft, C 4. 9. 8 gtra 3003) - - - s 5G 2000 t 2 O 2 OQ ... O 10 9. 8 arx 70 60 50 it 208 30an 38 || 58 {{ 2 13 O 30 SO SO 2 EC 80 2G Time (min) Patent Application Publication Oct. 13, 2011 Sheet 4 of 10 US 2011/0251399 A1 Figure 4: Oxidation of 2-propanol with AA-TEMPO/nitric acid/oxygen -e-2-Propanol -a-Acetone.--Isopropyl acetate 100 80 60 40 20 O Timeh) Patent Application Publication Oct. 13, 2011 Sheet 5 of 10 US 2011/0251399 A1 Figure 5: Oxidation of 1-propanol with AA-TEMPO/nitric acid/oxygen -o-1-Propanol -- Propanal -- Propy acetate 100 Timeh Patent Application Publication Oct. 13, 2011 Sheet 6 of 10 US 2011/0251399 A1 Figure 6. Oxidation of cyclohexanol with AA-TEMPO/nitric acid/oxygen |-o- Cyclohexanol -A - Cyclohexanone -- Cyclohexyl acetate 80 60 40 20 O Time (h) Patent Application Publication Oct. 13, 2011 Sheet 7 of 10 US 2011/0251399 A1 Figure 7. Oxidation of furfuryl alcohol with AA-TEMPO/nitric acid/oxygen -o- Furfury alcohol -- Furtural --Furfural acetate 100 80 SS: 60 40 20 O Patent Application Publication Oct. 13, 2011 Sheet 8 of 10 US 2011/0251399 A1 Figure 8. Oxidation of 1,3-dihydroxycyclohexane with AA-TEMPO/nitric acid/oxygen -o- 1 3-Dihydroxycyclohexane -A-3-hydroxycyclohexanone -- 2-Cyclohexenone 100 SS 80 : 60 40 20 O O 1 2 3 Patent Application Publication Oct. 13, 2011 Sheet 9 of 10 US 2011/0251399 A1 Figure 9. Oxidation of nicotinyl alcohol with AA-TEMPO/nitric acid/oxygen -e-Nicotinyl alcohol -- Nicotinaldehyde |-- Nicotinyl acetate 1 OU 80 60 40 20 O Timeh) Patent Application Publication Oct. 13, 2011 Sheet 10 of 10 US 2011/0251399 A1 Figure 10: Oxidation of borneol with AA-TEMPO/nitric acid/oxygen -e-Borneol -d- Menthol -- Bornyl acetate 100 :O O Time (h) US 2011/025 1399 A1 Oct. 13, 2011 METHOD FOR PRODUCING ALDEHYDES wherein nitric acid is used as a further reagent. However, the AND KETONES FROM PRIMARY AND ketone yields reported are below 90% and conversions were SECONDARY ALCOHOLS only between 24 and 72% in the case of the aldehydes. This method is more useful for synthesizing carboxylic acids (U.S. Pat. No. 5,239,116). It is only when nitric acid is used as a 0001. The present invention describes a process for pro Stoichiometric reagent, i.e., when oxygen is omitted as an ducing aldehydes and ketones from inexpensively available inexpensive oxidant (U.S. Pat. No. 5,155,279), conversions primary and secondary alcohols by oxidation with atmo of 42-84% are reported at selectivities of 69-81%. spheric oxygen or pure oxygen using a catalyst system con 0009. The prior art processes have the disadvantage that sisting of a free nitroxyl radical derivative. they are frequently unsuitable for large scale industrial pro 0002 Stable nitroxyl radical derivatives were first duction of aldehydes and ketones owing to the low yields and described by Hoffmann (A. K. Hoffmann, A.T. Henderson, J. many process steps or the Stoichiometric use of costly, cor Am. Chem. Soc. 83 (1961) 4671) and Lebeder (O. L. Leb rosive and poisonous reagents. Particularly the addition of eder, S.N. Kazarnovski, Zh. Obshch. Khim. 30 (1960) 1631; halogen Sources which is needed in the nitroxyl radical-cata O. L. Lebeder, S. N. Kazarnovski, C A 55 (1961) 1473a.). lyzed reaction of alcohols, in conjunction with carboxylic They were first used as radical Scavengers. Their usefulness acids, but also in organic solvents, is an extremely corrosive as catalysts for the oxidation of alcohols was only discovered system which makes implementation on an industrial scale recently (e.g., J. M. Bobbitt, C. L. Flores, Heterocycles 27 difficult. Alternatively, poisonous and difficult-to-remove (1988) 509 or A. E. J. de Nooy, A. C. Besemer, H. van transition metals are frequently used as catalyst constituent. Bekkum, Synthesis (1996) 1153). 0010. It is an object of the present invention to provide a 0003. One disadvantage with this type of catalysis is that process for producing aldehydes and ketones which allows the oxygen required for oxidation frequently is generated the use of primary or secondary alcohols as a starting material from expensive sources of oxygen. The use of hypochlorite, and which is such that the addition of halogen sources, more chloroperbenzoic acid, peroxomonosulfuric acid, periodic particularly bromine sources and the use of transition metals acid or trichloroisocyanuric acid for example has been can be dispensed with. reported (e.g. L. Anelli, C. Biffi, F. Montanari, S. Quici, J. 0011 We have found that this object is achieved, surpris Org. Chem. 52 (1987) 2559; J. A. Cella, J. A. Kelley, E. F. ingly, by a process for producing aldehydes and ketones Kenehan, J. Org. Chem. 40 (1975) 1850; S. D. Rychovsky, R. which allows the use of primary and secondary alcohols as a Vaidyanathan, J. Org. Chem. 64 (1999) 310: Bolm, Carsten; starting material and which overcomes precisely the above Magnus, Angelika S.; Hildebrand, Jens P. Organic Letters mentioned disadvantages of the prior art. (2000), 208), 1173-1175: S. S. Kim, K. Nehru, Synletter 0012. The present invention accordingly provides a pro (2002) 616; De Luca, Lidia; Giacomelli, Giampaolo; cess for producing aldehydes and ketones comprising the Porcheddu, Andrea. Organic Letters (2001), 3(19), 3041 oxidation of primary or secondary alcohols with an oxygen 3043). In addition, many of the reagents mentioned contain containing gas in the presence of a catalyst composition com halogens (chlorine, bromine and iodine in particular) which, prising at least one nitroxyl radical, one or more NO sources under the reaction conditions, can have a corrosive effect and and at least one or more carboxylic acids oranhydrides and/or often lead to undesired secondary reactions. mineral acids or anhydrides, optionally in the presence of one 0004. The oxidation of alcohols with oxygen by using or more solvents, characterized in that the primary and sec nitroxyl radical derivatives is accomplished through addition ondary alcohols used have a value of less than 2 for the of transition metals, for example cobalt, copper, tungsten, decadic logarithm of the n-octanol-water partition coefficient ruthenium, manganese and iron (e.g., Sheldon Roger A.; (log P), and in that the aldehydes and ketones are preferably Arends, Isabel W. C. E. Journal of Molecular Catalysis A: obtained in a yield of more than 92%, based on the alcohol Chemical (2006), 251(1-2), 200-214; Minisci, Francesco; used. Punta, Carlo: Recupero, Francesco. Journal of Molecular 0013 The process of the present invention has the advan Catalysis A: Chemical (2006), 251(1-2), 129-149). One dis tage that the alcohol is oxidized using a mild method in the advantage with this method is the frequently difficult removal presence of nitroxyl radicals in a single process step. This of the transition metal salts and their toxic properties. mild method Surprisingly makes it possible to oxidize even 0005 Augustine (U.S. Pat. No. 7,030,279) describes in sterically hindered alcohols which are not available using general the oxidation of primary or secondary alcohols with other methods. This oxidation frequently provides almost oxygen as oxidant to the corresponding aldehydes and quantitative conversions and selectivities, i.e., the high yields ketones using a catalyst system consisting of a free nitroxyl testify to the high efficiency of the process according to the radical derivative, a nitrate Source, a bromine source and a present invention. This high efficiency is completely Surpris carboxylic acid, which is acetic acid in all cases. ing on the basis of the prior art. 0006 Xinquan Hu et al. describe in J. AM. CHEM. SOC. 0014 More particularly, corrosive sources of halogen are 2004, 126, 4112-41 13 the alcohol oxidation using nitroxyl avoided as is the use of transition metals, and the Substrate radical derivative and oxygen, wherein the nitrate source was which constitutes the NO source is adjusted to the particular replaced by a nitrite source.