Organic Process Research & Development
Communication
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7) (a) Bewert, W. D.; Kiefer, H. D. (BASF AG). EP 0205131, 1986.
ASSOCIATED CONTENT
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b) Bewert, W. D. ; Littmann, D. W. (BASF AG). EP 0001760, 1979.
8) Felber, A.; Spruijtenburg R. (DSM Nutritional Products). WO/
003/087041, 2003.
(9) Nishihira, K. C. U. C. F.; Fujikawa, S. C. U. C. F.; Yamashita, M.
C. T. M. O. (Ube Industries Ltd.). EP 0279556, 1988.
10) (a) Bewert, W.; Littmann, W. (BASF AG). DE 2748153, 1979.
b) Littmann, W. DE 2818156, 1979. (c) Ernst, H.; Littmann, W.;
Paust, J. (BASF AG). DE 3431270, 1986.
11) Ernst, H.; Paust, J. (BASF AG). DE 3511273, 1985.
(12) Bonrath, W.; Harter, R.; Karge, R.; Letinois, U. (DSM
Nutritional Products). WO/2008/087021, 2008.
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S
Supporting Information
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2
Experimental procedures for all synthesized compounds and
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(
AUTHOR INFORMATION
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*
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́
Present Address
DSM Biotechnology Centre China, 476 Li Bing Road,
Shanghai-Pudong 201203, Peoples Republic of China.
†
(13) Values in water; scale according to Smith, M. B.; Mar, J. March’s
Advanced Organic Chemistry, 5th ed.; Wiley Interscience: New York,
2
001; pp 329.
Notes
(14) Classification according to Kobayashi: Kobayashi, S.; Busujima,
T.; Nagayama, S. Chem. Eur. J. 2000, 6, 3491.
The authors declare no competing financial interest.
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(
15) Anastas, P. T.; Kirchhoff, M. M. Acc. Chem. Res. 2002, 35, 686.
16) The program, STAVEX, 5.1; Aicos Technologies AG: Basel,
ACKNOWLEDGMENTS
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Switzerland, wasused for this purpose.
We thank Dr. Gerhard Schiefer and Dieter Gossweiler for
analytical support, and Dr. Rene
Medlock for fruitful discussion.
(17) Ege, G.; Pross, M. DE 4333688, 1995; Harada, K.; Choshi, T.;
Sugino, E.; Sato, K.; Hibino, S. Heterocycles 1994, 38, 1119. Gluncic,
B.; Kovacevic, K. (PLIVA Tvornica Farmaceutskih i Kemijskih
Proizvoda). DE 2248631, 1973.
́
Stemmler and Dr. Jonathan
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18) Alberola, A.; Gonzal
Pulido, F. J. Tetrahedron Lett. 1986, 27, 2027.
19) Bonrath, W.; Fischesser, J.; Giraudi, L.; Karge, R. (DSM
́ ́
ez, A. M.; Gonzalez, B.; Laguna, M. A.;
ADDITIONAL NOTES
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a
The conditions as disclosed in the BASF patent application
have also been tried, leading to 35% yield. Unfortunately, under
these conditions the reaction mixture also sticks to the flask
walls, and the final product mixture is not homogeneous. The
inhomogeneity of the crude product may be the reason why
yields of >50% are reported in the patent application but not
found in our study.
(
Nutritional Products). WO/2006/079504, 2006.
(20) (a) Akalin, E.; Akyuz, S. Vib. Spectrosc. 2008, 48, 233.
(b) Nat
21) Prince, B. J.; Turnbull, M. M.; Willett, R. D. J. Coord. Chem.
003, 56, 441.
22) (a) Malandrinos, G.; Louloudi, M.; Koukkou, A. I; Sovago, I.;
Drainas, C.; Hadjiliadis, N. J. Biol. Inorg. Chem. 2000, 5, 218.
b) Talbert, P. T.; Weaver, J. A.; Hambright, P. J. Inorg. Nucl. Chem.
970, 32, 2147.
23) (a) Habib, U.; Badshah, A.; Flo
̈
her, C.; Bhosekar, G.; Jess, I. Eur. J. Inorg. Chem. 2007, 5353.
(
2
(
b
One reviewer asked if 0.26 equiv of zinc- or copper salts is
(
acceptable in fine chemical synthesis. According to several
patents, the use of 20 mol % or more of zinc- or copper salts is
quite common in the production of fine chemicals. For
example, in vitamin E production, copper salts are used in 50
mol % or more in the oxidation of trimethylphenol to
trimethyquinone (see patents from various vitamin E
manufacturers such as BASF in EP 1132367, 0.75 equiv
1
(
̈
rke, U.; Qureshi, R.; Mirza, B.;
Nazar-ul-Islam, A. K. J. Chem. Crystallogr. 2009, 39, 730. (b) Kulkarni,
D. R.; Mulay, M. R.; Rodge, J. K.; Deshpande, M. N.; Ardhapurkar, S.
S. Int. J. Pharm. Biosci. 2010, 1, 1.
(
24) Reichle, R. A.; McCurdy, K. G.; Hepler, L. G. Can. J. Chem.
1
975, 53, 3841.
(
(
25) Elementary analysis by AAS.
26) Patterson, J. W.; Boice, R. E.; Marani, D. Environ. Sci. Technol.
CuCl and in DE 4029198, from Mitsubishi Gas Chemical
2
Company in EP 127888, 1 mol equiv CuCl ; from Eisai in EP
2
1
991, 25, 1780.
2
94584, 0.5 equiv CuCl High loadings of zinc salts are used in
2.
the condensation of trimethylhydroquinone (see U.S. patent
,020,505 from Eisai). Recycling and handling of the transition
6
metal waste is not the subject of the current manuscript, and
therefore this point is not explained in the text.
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E
dx.doi.org/10.1021/op300190s | Org. Process Res. Dev. XXXX, XXX, XXX−XXX