26771-11-9

Usage

Uses

Used in Pesticide Synthesis:
(1R-cis)-2,2-dimethyl-3-(2-methylprop-1-enyl)cyclopropanecarboxylic acid is used as an intermediate in the synthesis of (+)-cis-Phenothrin (P318100), an isomer of Phenothrin (P318095). (1R-cis)-2,2-dimethyl-3-(2-methylprop-1-enyl)cyclopropanecarboxylic acid is a pesticide that is utilized for the control of pests and insects in various agricultural and domestic settings. Its effectiveness in pest control is attributed to its ability to interfere with the nervous systems of insects, leading to paralysis and death.

InChI:InChI=1/C10H16O2/c1-6(2)5-7-8(9(11)12)10(7,3)4/h5,7-8H,1-4H3,(H,11,12)/t7?,8-/m0/s1

Upstream product

• 111902-48-8 cis-Chrylanthemylaldehyd 
• 78780-10-6 2,2-dimethyl-3-(2-methylprop-1-enyl)-cis-1-hydroxymethylcyclopropane 
• 55701-01-4 (+)-(1R,2S)-cis-2,2-dimethyl-3-(2-methylprop-1-enyl)cyclopropanoate 
• 2935-23-1 cis-Chrysanthemic acid 
• 127851-86-9 2,2-dimethyl-3-(1-hydroxy-2-methyl-2-propen-1-yl)-1-cyclopropanecarboxylic acid lactone 
• 10453-89-1 chrysanthemumic acid 
• 2198-88-1 (+/-)-cis-2,2-dimethyl-3-(2',2'-dimethylvinyl)cyclopropanecarbonitrile 
• 19902-09-1 (+/-)-cis-2,2-dimethyl-3-(2',2'-dimethylvinyl)cyclopropanecarboxamide 
• 937027-93-5 2,4,6-triisopropyl-benzenesulfonic acid 3,3,6,6-tetramethyl-4-oxo-bicyclo[3.1.0]hex-2-yl ester 
• 140624-24-4 Acetic acid (1S,2S,5R)-3,3,6,6-tetramethyl-4-oxo-bicyclo[3.1.0]hex-2-yl ester 
• 97-41-6 ethyl 2,2-dimethyl-3-(2-methylpropenyl)cyclopropanecarboxylate 
• 67911-21-1 6,6-dimethyl-3-oxabicyclo[3.1.0]hexane-2,4-dione 
• 82442-72-6 (1S,5R)-(-)-6,6-dimethyl-3-oxabicyclo[3.1.0]hexan-2-one 
• 81706-69-6 (4R,trans)-2,2,α,α,α',α'-hexamethyl-1,3-dioxolane-4,5-dimethanol 

Downstream Products

• 14087-70-8 (+)-Dihydrochrysanthemolactone 
• 53179-78-5 2,2-dimethyl-3R-(2',2'-dibromovinyl)-cyclopropane-1R-carboxylic acid 
• 5460-63-9 methyl (dl)-trans-chrysanthemate 
• 97-41-6 ethyl trans-(+/-)-chrysanthemate 
• 2259-14-5 (1S,3S)-trans-chrysanthemic acid 
• 4638-92-0 (1R,3R)-trans-chrysanthemic acid 
• 454-25-1 (+/-)-trans-Homochrysanthemsaeure 
• 497-96-1 (+/-)-trans-(E)-pyrethricsaeure 
• 94672-92-1 (+/-)-2.2-dimethyl-3t-(2-methyl-propenyl)-cyclopropane-carbanilide-(1r) 
• 18228-69-8 rac-trans-1-(-2,2-dimethyl-3-(2-methylprop-1-enyl)cyclopropyl)ethanone 
• 2861-25-8 trans-chrysanthemyl alcohol 
• 29172-41-6 trans-chrysanthemyl acetate 
• 3972-20-1 allethrin I 
• 78715-47-6 (2-Isopropenyl-4-methyl-1-methylene-pent-3-enylsulfanyl)-benzene 

Relevant academic research and scientific papers

Novel Enantioselective Syntheses of Optically Active (1R)-cis- and (1R)-trans-Chrysanthemic Acids.

Dimethyl dimedone, a non chiral and cheap compound, has been converted to the optically actives 1-(R)-cis- and 1-(R)-trans-chrysanthemic acids possessing high economic value.These processes involve as the key steps (i) a cyclopropanation reaction (ii) a Grob fragmentation and (iii) a lipase monitored hydrolysis of a prochiral diacetate.

Total Syntheses of All Six Chiral Natural Pyrethrins: Accurate Determination of the Physical Properties, Their Insecticidal Activities, and Evaluation of Synthetic Methods

Chiral total syntheses of all six insecticidal natural pyrethrins (three pyrethrin I and three pyrethrin II compounds) contained in the chrysanthemum (pyrethrum) flower were performed. Three common alcohol components [(S)-cinerolone, (S)-jasmololone, and (S)-pyrethrolone] were synthesized: (i) straightforward Sonogashira-type cross-couplings using available (S)-4-hydroxy-3-methyl-2-(2-propynyl)cyclopent-2-en-1-ones (the prallethrin alcohol) for (S)-cinerolone (overall 52% yield, 98% ee) and (S)-pyrethrolone (overall 54% yield, 98% ee) and (ii) traditional decarboxylative-aldol condensation and lipase-catalyzed optical resolution for (S)-jasmololone (overall 16% yield, 96% ee). Two counter acid segments [(1R,3R)-chrysanthemic acid (A) and (1R,3R)-second chrysanthemic acid precursor (B)] were prepared: (i) C(1) epimerization of ethyl (±)-chrysanthemates and optical resolution using (S)-naphthylethylamine to afford A (96% ee) and (ii) concise derivatization of A to B (96% ee). All six pyrethrin esters (cinerin I/II, jasmolin I/II, and pyrethrin I/II) were successfully synthesized utilizing an accessible esterification reagent (TsCl/N-methylimidazole). To investigate the stereostructure-activity relationship, all four chiral stereoisomers of cinerin I were synthesized. Three alternative syntheses of (±)-jasmololone were investigated (methods utilizing Piancatelli rearrangement, furan transformation, and 1-nitropropene transformation). Insecticidal activity assay (KD50 and IC50) against the common mosquito (Culex pipiens pallens) revealed that (i) pyrethrin I > pyrethrin II, (ii) pyrethrin I (II) > cinerin I (II) ? jasmolin I (II), and (iii) "natural" cinerin I ? three "unnatural" cinerin I compounds (apparent chiral discrimination).

Method for preparing chiral trans-chrysanthemic acid

The invention provides a method for preparing chiral trans-chrysanthemic acid, belongs to the field of organic synthesis, and relates to a method for synthesis of chiral ethyl chrysanthemumate from 2,5-dimethyl-2,4-hexadiene and ethyl diazoacetate by an asymmetric cyclopropanation reaction and for hydrolysis to form chiral chrysanthemic acid. A chiral copper catalyst adopted is prepared in situ from a copper salt and a chiral tridentate P,N,N-ligand in various polar and non-polar solvents. The chiral trans-chrysanthemic acid can be conveniently synthesized, and the percentage of enantiomeric excess is as high as 95%. The method has the characteristics such as simple operation, easy availability of raw materials, wide application range of substrates and high enantioselectivity.

Cyclopropanation of Terminal Alkenes through Sequential Atom-Transfer Radical Addition/1,3-Elimination

An operationally simple method to affect an atom-transfer radical addition of commercially available ICH2Bpin to terminal alkenes has been developed. The intermediate iodide can be transformed in a one-pot process into the corresponding cyclopropane upon treatment with a fluoride source. This method is highly selective for the cyclopropanation of unactivated terminal alkenes over non-terminal alkenes and electron-deficient alkenes. Due to the mildness of the procedure, a wide range of functional groups such as esters, amides, alcohols, ketones, and vinylic cyclopropanes are well tolerated.

Syntheses of racemic and scalemic cis-chrysanthemic acid from β,γ-unsaturated cyclohexanol

2,2,5,5-Tetramethylcyclohexane-1,3-dione is a valuable starting-material precursor of cis-chrysanthemic acid. The (1S)-stereoisomer is a precursor of pyrethrin I, the most active natural insecticide from Chrysanthemum cinerariifolium, whereas the (1R)-stereoisomer is efficiently transformed to deltamethrin, the most active commercially available pyrethroid insecticide. Several intermediates have been identified and used with variable success for that purpose.

An enantiospecific route to (+)-(1R,3S)-cis-chrysanthemic acid from (-)-d-pantolactone

In this paper, a novel route for the synthesis of (+)-(1R,3S)-cis- chrysanthemic acid is described. The use of readily available (-)-d-pantolactone as a starting point, application of ring-closing metathesis to form the cyclopentene intermediate, and Haller-Bauer/Grob-type fragmentation to form the target compound are the highlights of the present synthesis. Georg Thieme Verlag Stuttgart.

Unprecedented dual reactivity of anhydrous potassium hydroxide in cascade cyclopropannelation/Haller-Bauer-scission/Grob-fragmentation reactions

We report an unprecedented type of reactivity of 'anhydrous potassium hydroxide' ('APH') in which it plays, over a large variety of related educts, sequentially the role of base and nucleophile. Some insight into the structure of reactive species as well as comparative reactivity of related reagents prepared by fusion of commercially available potassium hydroxide or by adding stoichiometric amount of water to potassium hydride is provided.

A practical method for O-acylation of N -hydroxythiazole-2(3 H)-thiones

O-Acylation of 4- and 4,5-substituted N-hydroxythiazole-2(3H)-thiones occurred in solutions of acetone upon treatment with solid K2CO3 and a variety of neat acyl chlorides (primary, secondary, and tertiary alkyl, aryl; 60-87% yield; ～10 g scale).

Novel synthesis of (d,l)-cis-chrysanthemic acid involving α,α′-dibromination of 2,2,5,5-tetramethylcyclohexane-1,3-dione: application to the enantioselective synthesis of (1R)-cis-chrysanthemic acid

cis-Chrysanthemic acid has been prepared in a few steps from dimethyldimedone via dibromination at alpha positions of each carbonyl carbons. The trans-dibromide which is almost exclusively formed has been isomerized to its cis-stereoisomer by highly chemoselective tandem H/K-K/H exchanges involving potassium bases at low temperature (-40 °C). Carbocyclization of the potassium enolate intermediate takes place at around -30 °C and provide the bicyclo[3.1.0]-hexane skeleton. Lithiated bases behave differently and mainly lead to Br/M rather than to H/M exchange. We have been unsuccessful in using state of the art enantioselective metallation reactions to achieve the enantioselective synthesis of (1R)-cis-chrysanthemic acid using the disclosed strategy. This therefore still remains challenge.

Diastereoselective bromination of compounds bearing a cyclohex-3-enol moiety: Application to the enantioselective synthesis of (1R)-cis-deltamethrinic acid

(Chemical Equation Presented) (1R)-cis-Chrysanthemic acid has been prepared in a few steps with complete control of the relative and absolute stereochemistry. Some mechanistic aspect of the addition of bromine to the C,C double bond of 2,2,5,5-tetramethylcyclohex-3-enol is disclosed.