Trans-chrysanthemic acid

Comments The diene A is symmetrical so it doesn t matter which double bond is attacked by the carbene. On the other hand, it may be difficult to stop carbene addition to the second double bond. The only control over the stereochemistry will be that the trans compound we want is more stable. Japanese chemists have recently synthesised optically active trans chrysanthemic acid by this route (Tetrahedron Letters. 1977, 2599). 

Recently novel methods were reported to make (lR)-trans-chrysanthemic acid including optical resolutions with the (+)-3-caranediol or l,l -binaphthol monoethylether, enzymatic resolution with Arthrobacter globiformis and the asymmetric synthesis with a new Cu catalyst. These methods are reviewed in this section. 

Menthol ester (20) with (l/ S)-frans-2,2-dimethyl-3-(2,2-dichloroethenyl) cyclopropanecarboxylic acid (19) has been utilized to produce ( R)-trans-2, 2-dimethyl-3-(2,2-dichloroethenyl) cyclopropanecarboxylic acid (21), an acid moiety of transfluthrin (22) [9]. Matsuo et al. surveyed various optically active secondary alcohols for their potential in the optical resolution of (lRS)-trans-chrysanthemic acid [10] (Scheme 2). 

Thus, (1 A S Hra/7.v-chrysanthemic acid was condensed with 1,1 -binaphthol derivative using the TsCb/V-methylimidazole reagent to give the corresponding two sets of diastereomers (26) and (27). From the solution, only the (l/ )-trans-chrysanthemic acid ester (26) crystallized from the diastereomer mixtures. The ester was readily... 

Enzymatic Resolution of (lR)-trans-Chrysanthemic Acid with Bacterium... 

Scheme 4 Synthesis of (lR)-trans-chrysanthemic acid with the bacterium...

The synthesis of compounds 39, 41, and 43 by the ODPM rearrangement opens a novel photochemical route to chrysanthemic acid and other cyclopropane carboxylic acids present in pyrethrins and pyrethroids [52]. In fact, aldehyde 43 can be transformed to tran -chrysanthemic acid by simple oxidation. This new synthetic route to ecologically benign insecticides competes with the one previously described by us using the 1-ADPM rearrangement of p,y-unsaturated oxime acetates [30,53]. 

The trans-chrysanthemic acid 88 is an essential component of naturally occurring pyrethrin esters which are present in the flower of Chrysanthenum cinera-riaefolium and has a defense function in these plants [122]. Very effective as an antifeedant for herbivores, it presents a broad spectrum as an insect repellent. 

Much effort this year has been expended on chrysanthemic acid syntheses. Aratani et al. have extended earlier work on asymmetric synthesis (Vol. 6, p. 21) by decomposing various alkyl diazoacetates in 2,5-dimethylhexa-2,4-diene in the presence of chiral copper complexes to yield up to 92% of rrans-chrysanthemic acid in 88% dextrorotatory enantiomeric excess. Mitra has used ozonolysis of (+)-a-pinene to obtain, stereospecifically, the bromo-ketone (104) which undergoes Favorskii rearrangement to yield the anticipated ester (105) from which (+)-trans-chrysanthemic acid is readily obtained a second paper reports another route from (+)-car-3-ene initially to methyl (—)-c/s-chrysanthemate or to (—)-dihydro-chrysanthemolactone (106), both of which are convertible into (+)-rra s-chrysan-... 

Insecticides of the pyrethroid class, such as trans-chrysanthemic acid (190), have significant commercial value (see Chapter 31).241 An asymmetric synthesis of 190 has been achieved through the use of a chiral copper carbenoid reaction (Scheme 12.77).242 243 With ethyl diazoacetate, equal amounts of the cis- and trans-cyclopropanes were formed. However, when the size of the alkyl... 

Details of the preparation of methyl (-)-cis-chrysanthemate from (+)-car-3-ene have appeared (Vol. 5, p. 15 is misleading).159 Both ( )-cis- and (+)-trans-chrysanthemic acids are again reported from (+)-car-3-ene via ozonolysis 160 this work is very similar to that reported (Vol. 5, p. 15) by Sukh Dev and illustrates the lamentable delay from receipt to publication in some journals. The decomposition of ethyl diazoacetate in 2,5-dimethylhexa-2,4-diene in the presence of the chiral copper complex (72) leads to cis- and frvms-chrysanthemic acids in 60—70% optical yield the degree of asymmetric induction is dependent upon the steric bulk of R1 and R2 in (72).161 cis-Chrysanthemic acid has also been prepared from 3,3-dimethylcyclopropene, isoprene, and 2-methylpropenylmagnesium bromide followed by treatment with carbon dioxide.162... 

Three-membered rings are flat with all bonds eclipsed so the dihedral angle is 0° for as Hs and 109° for trans Hs. Looking at the Karplus curve, we expect the as coupling to be larger, and it is. A good example is chrysanthemic acid, which is part of the pyrethrin group of insecticides foimd in the pyrethrum plant. Both cis and trans chrysanthemic acids are important. 

Julia, S., Julia, M., Linstrumelle, G. Synthesis of ( )-cis-homocaronic acid and ( )-trans-chrysanthemic acids from substituted bicyclo[3.1.0]hexan-2-one intermediates. Bull. Soc. Chim. France 1964, 2693-2694. 

Sulfur ylides can also be used in the synthesis of chrysanthemate esters (72) from hept-2-enoates (73) (Scheme 27). The natural insecticide pyrethrum is a complex chrysanthemate ester, and the formation of trans-chrysanthemic acid is consequently important for the synthesis of many synthetic pyrethroid insecticides. 

Davies, M S., Chadwick. P.R.. liolborn, J.M.. Sicw-art, D.C, and Wickham, J.C f 1970). Effectiveness of the (-H-trans-chrysanthemic acid ester of (4)-aNethrulone (hin-allethrin) against lour insect species. Pernio. Set. 1, 225-227,... 

Researches on chrysanthemic acid and its derivatives are usually oriented to synthesising esters of trans-chrysanthemic acid, many of which are naturally occurring (and are, therefore, presumably biodegradable) insecticides. The synthesis of pyrethric acid or its mono-ester (65) from chrysanthemic acid has been carried out in two laboratories. Ueda and Matsui prepared all four... 

Car-4-ene derivatives (79) are readily available from car-3-ene, and their ozonolysis leads to (+ )-cis-homocaronic acid dimethyl ester (80), easily convertible into (-l-)-trans-chrysanthemic acid. Purification of mixtures of cis- and trans-chrysanthemic acid by lactonization of the cis-acid with a Lewis acid is reported, as is an improved method for resolving the (+ )-trans-acid using L-lysine. A reinvestigation of the synthesis of pyrethric acid isomers has been carried out. Two studies of the metabolism of the insecticidal esters of... 

The fundamental work on the structure elucidation goes back to Hermann Staudinger (1881-1965) and Leopold Ruzicka (1887-1976) in the 1920s, they isolated pyrethrins from Dalmatian insect-powder, and in particular (+)-trans-chrysanthemic acid [64], and recognised their key structural features (Fig. 8.24). [65, 66]... 

Methylnona-2,3-dienoic acid, X1.9 Iridodial, T13.13 traAW-Pulegenic acid, A38.2 Piperitone oxide, T4.2 c -Chrysanthemic acid, A35.10, T"10 tran -Chrysanthemic acid, A35.6, T"20... 

Hift02, S-(+)-2,2-Diphenylcyclopropanecarboxylic acid, 43B, 171 6H14O2, 2,3-Dicyclopropyl-1,4-naphthoquinone, 45B, 111 sH2oBrNO, (+)-trans-Chrysanthemic acid (p-bromoanilide derivative), 41B, 166... 

The same synthetic approach (i.e., varying the acid, alcohol, or both) resulted in the development of the coirnnercially successful active pyrethroid insecticides covered in this review this same approach also produced a host of relatively inactive isomers. The most potent constituent of resmethrin is the IR, 3R isomer (bioresmethrin), and is formed during the esterification of (-r) cis-, trans-chrysanthemic acid with 5-benzyl-3-furyImethyl alcohol to produce bioresmethrin and three other stereoisomers. Of greater interest to most chemists/biologists is the... 

Ross et al. (2006) studied the hydrolytic metabolism of Type 1 pyrethroids (bioresmethrin, IRS fraws-permethrin, and IRS c/s-permethrin) and several Type II pyrethroids (alpha-cypermethrin and deltamethrin) by pure human CEs (hCE-1 and hCE-2), a rabbit CE (rCE), and two rat CEs (Hydrolases A and B). Hydrolysis rates were based on the formation of 3-phenoxybenzyl alcohol (PBAlc) (CAS no. 13826-36-2) for the cis and trans isomers of permethrin. For bioresmethrin, hydrolysis was based on the production of the trans-chrysanthemic acid (CPCA) (CAS no. 10453-89-1). For alpha-cypermethrin and deltamethrin, hydrolysis was based on the formation of c/s-permethrinic acid (DCCA) (CAS no. 57112-16-0) and 3-phenoxybenzyl aldehyde (PBAld CAS no. 39515-51-0), respectively. Human CE-1 and hCE-2 hydrolyzed trans-permethrin 8- and 28-fold more efficiently (based on kcat/Km values) than did c/s-permethrin, respectively. The kinetic parameters (Fmax> for the hydrolysis of trans- and c/s-permethrin, bioresmethrin and alpha-cypermethrin by rat, mouse, and human hepatic microsomes are given in Table 7. The trans- isomer of permethrin is more readily hydrolyzed by rat, mouse and human hepatic microsomal carboxylesterase than c/s-permethrin (13.4, 85.5 and 56.0 times, respectively). However, the lower for hydrolysis of cis-permethrin in human microsomes suggests that there are both stereoisomer and species-specific differences in metabolism kinetics. 

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