Labeled Compound Synthesis, Synthesis of d-trans-Chrysanthemumic Acid-1-C¹⁴ and Its Antipode on a Semimicro Scale

Abstract

c//-/rans-Chrysanthemurmc acid-1 -C14 was prepared in 45% yield from 4 mmoles of ethyl glycinate-1-C14. Yield of the trans-acid was increased by isomerization of methyl c/schrysanthemumate-1 -C14 with sodium ferf-amylate. Geometrical isomers of the acid were

Metabolic fate of pyrethrin I, pyrethrin II, and allethrin administered orally to rats

“…Chrysanthemic acid labeled in the isobutenyl methyl groups 2C=] with a specific activity of 0.055 mCi per mmol and chrysanthemum dicarboxylic acid labeled in the side chain carboxy group [designated CDCA-HO(O)-14C(CH3)C=] with a specific activity of 0.009 mCi per mmol were provided by Leslie Crombie (Crombie et a!., 1970). The radiochemical purities of these three samples of labeled acids all exceeded 98%, as determined by tic with the BFE1 solvent system described later and, in the chrysanthemic acid samples, also with the isopropyl acetate-ammonia-methanol system of Nishizawa and Casida (1965).…”

“…PyII-l4CH30acid (located in uv light, Rt 0.54) separated adequately from the isomeric ester (Ri 0.45) and it was extracted from the upper band with ether, the extract was concentrated in nitrogen, and the residue was dissolved in hexane. Chrysanthemic acid labeled in the cyclopropane carboxy group [designated CA-14C(0)0] had a specific activity of 1.3 mCi per mmol (Nishizawa and Casida, 1965). Chrysanthemic acid labeled in the isobutenyl methyl groups 2C=] with a specific activity of 0.055 mCi per mmol and chrysanthemum dicarboxylic acid labeled in the side chain carboxy group [designated CDCA-HO(O)-14C(CH3)C=] with a specific activity of 0.009 mCi per mmol were provided by Leslie Crombie (Crombie et a!., 1970).…”

Conversion of (S)-allethrolone to pyrethrin I, jasmolin I, cinerin I, and [propenyl-3-13C]- and [propenyl-3-14C]-(S)-bioallethrin

“…Radiosyntheses are reported for [14C]-and [3H]-(S)-bioallethrin (la) and -pyrethrin I [(Z)-lb] prepared from [14C]-(17? )trans-chrysanthemic acid (Nishizawa and Casida, 1965;Yamamoto and Casida, 1968) and [377]-(S)-allethrolone and -pyrethrolone (Elliott and Casida, 1972) and for [14C]bioallethrin from [ 14C]-(RS)-allethrolone (Yamamoto and Casida, 1968). Unlabeled (7?S)-allethrolone has been converted to (7?S)-jasmolone and -cinerolone (Pattenden and Storer, 1974) and to (RS)-pyrethrolone and (RS)-pyrethrin I (Sasaki et al, 1979) by protection of the hydroxyl or hydroxyl and carbonyl functions, oxidative cleavage of the propenyl group, and reconstruction of the butenyl, pentenyl, and pentadienyl substituents by a Wittig reaction.…”

Photodecomposition of resmethrin and related pyrethroids

“…Various samples of isomerically and optically pure [14C]resmethrin, -tetramethrin, and -allethrin, each of greater than 99% radiochemical purity, were utilized (Figure 1). The ( + )-and (-)-isomer preparations were used interchangeably in different photochemical experiments with resmethrin and tetramethrin because no difference is expected with these antipodes and in fact none was observed on comparing ( + )-and (-)trans-resmethrin, trans-and cis-[l-14C]chrysanthemic acid prepared by a described procedure (Nishizawa and Casida, 1965) were each resolved with ( + )-and (-)-a-(pchlorobenzyl)benzylamine to obtain the optically pure isomers of [l-14C]chrysanthemic acid. Conversion of these acids to the acid, chlorides and esterification with 5-benzyl-3-furylmethanol (BFA) gave the optically pure isomers of acid-labeled (14C) resmethrin.…”