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1
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70649113333
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Common name 4-amino-3,6-dichloropicolinic acid, sold under the tradename Milestone™ (among others): Alexander, A. L.; Balko, T. W.; Bjelk, L. A.; Buysse, A. M.; Fields, S. C.; Keese, R.; Krumel, K. L.; Lo, W. C.; Lowe, C. T.; Richburg, J. S.; Ruiz, J. M. 4-Aminopicolinates and Their Use as Herbicides. U.S. Patent 6,297,197, Oct. 2, 2001; Chem. Abstr. 2001, 135, 107254.
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Common name 4-amino-3,6-dichloropicolinic acid, sold under the tradename Milestone™ (among others): Alexander, A. L.; Balko, T. W.; Bjelk, L. A.; Buysse, A. M.; Fields, S. C.; Keese, R.; Krumel, K. L.; Lo, W. C.; Lowe, C. T.; Richburg, J. S.; Ruiz, J. M. 4-Aminopicolinates and Their Use as Herbicides. U.S. Patent 6,297,197, Oct. 2, 2001; Chem. Abstr. 2001, 135, 107254.
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2
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70649112642
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Johnston, H.; Tomita, M. S. Amino-trichloropicolinic acid compounds. U.S. Patent 3,285,925, Nov. 15, 1966; Chem. Abstr. 1967, 66, 46338.
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Johnston, H.; Tomita, M. S. Amino-trichloropicolinic acid compounds. U.S. Patent 3,285,925, Nov. 15, 1966; Chem. Abstr. 1967, 66, 46338.
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3
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70649093396
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Balko, T. W.; Buysse, A. M.; Epp, J. B.; Fields, S. C.; Lowe, C. T.; Keese, R. J.; Richburg, J. S., III; Ruiz, J. M.; Weimer, M. R.; Green, R. A.; Gast, R. E.; Bryan, K.; Irvine, N. M.; Lo, W. C.-L.; Brewster, W. K.; Webster, J. D. 6-Aryl-4-aminopicolinates and Their Use as Herbicides. U. S. Patent 6,784,137, Aug. 31, 2004; Chem. Abstr. 2003, 138, 153444.
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Balko, T. W.; Buysse, A. M.; Epp, J. B.; Fields, S. C.; Lowe, C. T.; Keese, R. J.; Richburg, J. S., III; Ruiz, J. M.; Weimer, M. R.; Green, R. A.; Gast, R. E.; Bryan, K.; Irvine, N. M.; Lo, W. C.-L.; Brewster, W. K.; Webster, J. D. 6-Aryl-4-aminopicolinates and Their Use as Herbicides. U. S. Patent 6,784,137, Aug. 31, 2004; Chem. Abstr. 2003, 138, 153444.
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4
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70649107340
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Aminopyralid (3) is currently synthesized by the electrochemical reduction of picloram (4) at Dow on production scale.
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Aminopyralid (3) is currently synthesized by the electrochemical reduction of picloram (4) at Dow on production scale.
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5
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70649105904
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Krumel, K. L.; Bott, C. J.; Gullo, M. F.; Hull, J. W., Jr.; Scortichini, C. L. Selective electrochemical reduction of halogenated 4-aminopicolinic acids. U. S. Patent 6,352,635, Mar. 5, 2002; Chem. Abstr. 2001, 135, 98860.
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Krumel, K. L.; Bott, C. J.; Gullo, M. F.; Hull, J. W., Jr.; Scortichini, C. L. Selective electrochemical reduction of halogenated 4-aminopicolinic acids. U. S. Patent 6,352,635, Mar. 5, 2002; Chem. Abstr. 2001, 135, 98860.
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7
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0001635633
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N-F pyridines rearrange to 2-C-F pyridines, however this does not appear to be general:
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N-F pyridines rearrange to 2-C-F pyridines, however this does not appear to be general:. Umemoto T., and Tomizawa G. J. Org. Chem. 54 (1989) 1726
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(1989)
J. Org. Chem.
, vol.54
, pp. 1726
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Umemoto, T.1
Tomizawa, G.2
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8
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0006699233
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Direct nucleophilic substitution of N-F pyridines:
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Direct nucleophilic substitution of N-F pyridines:. Kiselyov A., and Strekowski L. J. Org. Chem. 58 (1993) 4476
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(1993)
J. Org. Chem.
, vol.58
, pp. 4476
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Kiselyov, A.1
Strekowski, L.2
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9
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70649088391
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note
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N-Fluorination of pyridine substrates is a problematic competing reaction because it renders the pyridine less reactive toward ring fluorination.
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13
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10844284516
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Gakh A.A., Nikishin K.G., Kagramanov N.D., and Semenov V.V. Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya 10 (1991) 2403
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(1991)
Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya
, vol.10
, pp. 2403
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Gakh, A.A.1
Nikishin, K.G.2
Kagramanov, N.D.3
Semenov, V.V.4
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18
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0000601660
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Umemoto reagents are supplied by Allied Signal Inc., Buffalo Research Laboratories, Buffalo, NY:
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Umemoto reagents are supplied by Allied Signal Inc., Buffalo Research Laboratories, Buffalo, NY:. Umemoto T., Fukami S., Tomizawa G., Harasawa K., Kawada K., and Tomita K. J. Am. Chem. Soc. 112 (1990) 8563
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(1990)
J. Am. Chem. Soc.
, vol.112
, pp. 8563
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Umemoto, T.1
Fukami, S.2
Tomizawa, G.3
Harasawa, K.4
Kawada, K.5
Tomita, K.6
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20
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0001421078
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Appears to be effective on Grignards and electron rich phenols, but no specific mention of heterocycles:
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Appears to be effective on Grignards and electron rich phenols, but no specific mention of heterocycles:. Barnette W.E. J. Am. Chem. Soc. 106 (1984) 452
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(1984)
J. Am. Chem. Soc.
, vol.106
, pp. 452
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Barnette, W.E.1
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21
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0001168749
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Des Marteau reagents:
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Des Marteau reagents:. Singh S., Des Marteau D., Zuberi S., Witz M., and Huang H.N. J. Am. Chem. Soc. 109 (1987) 7194
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(1987)
J. Am. Chem. Soc.
, vol.109
, pp. 7194
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Singh, S.1
Des Marteau, D.2
Zuberi, S.3
Witz, M.4
Huang, H.N.5
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24
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70649094727
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Also known as SELECTFLUOR, and Banks' Reagent: Banks, R. E. Preparation of N-fluorodiazoniabicycloalkanes as fluorinating agents. U. S. Patent 5,086,178, Feb. 4, 1992; Chem. Abstr. 1992, 116, 194355. Supplied by Air Products and Chemicals Inc., 7201 Hamilton Blvd, Allentown, PA 18195.
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Also known as SELECTFLUOR, and Banks' Reagent: Banks, R. E. Preparation of N-fluorodiazoniabicycloalkanes as fluorinating agents. U. S. Patent 5,086,178, Feb. 4, 1992; Chem. Abstr. 1992, 116, 194355. Supplied by Air Products and Chemicals Inc., 7201 Hamilton Blvd, Allentown, PA 18195.
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26
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70649103382
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note
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F-TEDA is a white salt which is safe, stable, and easily handled in air.
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29
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0037189251
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F-TEDA also has been used deliberately to effect chlorination and other electrophilic substitutions:
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F-TEDA also has been used deliberately to effect chlorination and other electrophilic substitutions:. Syvret R.G., Butt K.M., Nguyen T.P., Bulleck V.L., and Rieth R.D. J. Org. Chem. 67 (2002) 4487
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(2002)
J. Org. Chem.
, vol.67
, pp. 4487
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Syvret, R.G.1
Butt, K.M.2
Nguyen, T.P.3
Bulleck, V.L.4
Rieth, R.D.5
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32
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70649097776
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note
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Honeywell scientists, led by Dr. Andy Poss, attempted a fluorination of 3 with divalent fluorine in aqueous suspension at 25 °C and observed similar results, with respect to mass balance and picloram formation (personal communication).
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33
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0001859676
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There has been a noted solvent dependence with these reagents:
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There has been a noted solvent dependence with these reagents:. Zupan M., Iskra J., and Stavber S. J. Fluorine Chem. 70 (1995) 7
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(1995)
J. Fluorine Chem.
, vol.70
, pp. 7
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Zupan, M.1
Iskra, J.2
Stavber, S.3
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35
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70649094728
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note
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24 additional work is now underway to provide more details on the origin of 4. Our results will be forthcoming.
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