Abstract
The synthesis of a diverse series of novel insecticidally active carboxylic acid N’ -benzoyl-N’ -tert -butyl-N -(4-chlorobenzo-yl)hydrazinocarbonyloxy methyl and ethyl esters as well as carboxylic acid N’ -benzoyl-N’ -tert -butyl-N -(4-chlorobenzoyl)hydrazino methyl esters are reported.
Key words
carboxylic acids - drugs - esters - diacyl hydrazines - parallel synthesis
References
1 Thomson WT.
Agricultural Chemicals, Book 1
14th ed.:
Thomson Publications;
Fresno:
1998.
Insecticides.
p.142-144
2 James WN, and Aller HE. inventors; U.S. Patent 5358966.
; Chem. Abstr. 1994 , 122 , 3593
3 The Presidential Green Chemistry Award for Rohm and Haas diacyl hydrazines can be found on the following web pages: http://www.turfnet.com/news/rohm_haas.asp and http://www.epa.gov/greenchemistry/past.htm.
4 Tomlin CDS.
The Pesticide Manual
British Crop Protection Council;
Farnham, Surrey, GU9 7PH, UK:
1997.
11th ed..
p.388-389
5a Silverman RB.
The Organic Chemistry of Drug Design and Drug Action
Academic Press;
San Diego, CA:
1992.
p.361-375
5b Omar FA.
Farag HH.
Bodor N.
Journal of Drug Targeting
1994,
2:
309
5c Gogate US.
Repta AJ.
Alexander J.
Int. J. Pharm.
1987,
40:
235
5d Gogate US.
Repta AJ.
Int. J. Pharm.
1987,
40:
249
5e Folkmann M.
Lund FJ.
Synthesis
1990,
1159
6a 2 and 3 , respectively, have been reported as carbonyl equivalents in the synthesis of carbamates: Barcelo G.
Senet JP.
Sennyey G.
Synthesis
1986,
627
6b We recently reported the novel cyclization reaction in which treatment of the potassium salt of N ’- benzoyl-N ’-tert- butyl-N -(4-chloro-benzoyl)hydrazide 1b with a carbonyl equivalent such as phosgene at -78 °C afforded 3-(4-chlorobenzoyl)-5-phenyl-3H -[1,3,4]oxadiazol-2-one: Mulvihill, M. J.; Nguyen, D. V.; MacDougall, B. S.; Weaver, D. G.; Mathis, W. D. Synthesis 2001 , 1965.
6c In light of these results, it was to our pleasant surprise that treatment of the potassium salt of halofenozide (1b ) with known carbonyl equivalents such as chloroformates 2 and 3 did not afford cyclized oxadiazol-2-one products but afforded stable isolable compounds 4 , 5 and 6 which were further reacted to afford stable isolable esters 7 and 8 .
7a Roberts WJ.
Sloan KB.
J. Pharm. Sci.
2000,
89:
1415
7b Madec-Lougerstay R.
Florent JC.
Monneret C.
J. Chem. Soc., Perkin Trans. 1
1999,
10:
1369
7c Redden PR.
Melanson RL.
Jo-Anne E.
Dick AJ.
Int. J. Pharm.
1999,
180:
151
7d Falch E.
Perregaard J.
Frolund B.
Sokilde B.
Buur A.
Hansen LM.
Frydenvang K.
Brehm L.
Bolvig T.
Larsson OM.
Sanchez C.
White HS.
Schousboe A.
Krogsgaard-Larsen P.
J. Med. Chem.
1999,
42:
5402
7e Davidsen SK.
Summers JB.
Albert DH.
Holms JH.
Heyman RH.
Magoc TJ.
Conway RG.
Rhein DA.
Carter GW.
J. Med. Chem.
1994,
37:
4423
7f Alexander J.
Renyer ML.
Rork GS.
J. Pharm. Sci.
1994,
83:
893
7g Waranis RP.
Sloan KB.
J. Pharm. Sci.
1988,
77:
210
7h Bundgaard H.
Buur A.
Int. J. Pharm.
1987,
37:
185
7i Buur A.
Bundgaard H.
Falch E.
Int. J. Pharm.
1985,
24:
43
7j Bodor N.
Woods R.
Raper C.
Kearney P.
Kaminski JJ.
J. Med. Chem.
1980,
23:
474
8a Ozawa N, and Yazawa N. inventors; WO 9308152 A1.
; Chem. Abstr. 1993 , 119 , 138756
8b Benneche T.
Strande P.
Wiggen U.
Acta Chem. Scand.
1989,
43:
74
8c Grynkiewicz G.
Tsien RY.
Pol. J. Chem.
1987,
61:
443
8d Gruszecki W, Gdulewicz-Gruszecka M, Dunajska B, Kolodziejczyk P, and Borowski E. inventors; PL 78-206892.
; Chem. Abstr. 1984 , 102 , 45492
9a Finkelstein H.
Ber.
1910,
43:
1528
9b Ingold CK.
Structure and Mechanism in Organic Chemistry
Cornell Univ. Press;
London:
1969.
2nd ed..
p.435
10 Treatment of thiocarbonates with sulfuryl chloride typically affords the respective chloroformates (ref.
[5e 10 with sulfuryl chloride afforded chloromethyl derivative 11 with no trace of the respective chloroformate. Chloromethyl derivative 11 was not stable to silica gel column chromatography. However, chloromethyl derivative 11 could be recrystallized from hot hexanes to afford the pure product, which was stored at -20 °C.
