26771-06-2

Basic information

• Product Name: (1S-cis)-2,2-dimethyl-3-(2-methylprop-1-enyl)cyclopropanecarboxylic acid
• Synonyms: (1S-cis)-2,2-dimethyl-3-(2-methylprop-1-enyl)cyclopropanecarboxylic acid;(1S)-2,2-Dimethyl-3α-(2-methyl-1-propenyl)cyclopropanecarboxylic acid;(1S)-2β-(2-Methyl-1-propenyl)-3,3-dimethylcyclopropane-1β-carboxylic acid;(1S,3R)-2,2-Dimethyl-3-(2-methyl-1-propenyl)cyclopropanecarboxylic acid
• CAS NO: 26771-06-2
• Molecular Formula: C₁₀H₁₆O₂
• Molecular Weight: 168.23284
• EINECS: 247-994-4
• Mol File: 26771-06-2.mol

Chemical Properties

• Boiling Point: 246.4°Cat760mmHg
• Flash Point: 119°C
• Appearance: /
• Density: 1.077g/cm³
• Vapor Pressure: 0.0088mmHg at 25°C
• Refractive Index: 1.546
• CAS DataBase Reference: (1S-cis)-2,2-dimethyl-3-(2-methylprop-1-enyl)cyclopropanecarboxylic acid(CAS DataBase Reference)
• NIST Chemistry Reference: (1S-cis)-2,2-dimethyl-3-(2-methylprop-1-enyl)cyclopropanecarboxylic acid(26771-06-2)
• EPA Substance Registry System: (1S-cis)-2,2-dimethyl-3-(2-methylprop-1-enyl)cyclopropanecarboxylic acid(26771-06-2)

Safety Data

• Hazardous Substances Data: 26771-06-2(Hazardous Substances Data)

Usage

Uses

Used in Pharmaceutical Synthesis:
(1S-cis)-2,2-dimethyl-3-(2-methylprop-1-enyl)cyclopropanecarboxylic acid is utilized as a key intermediate in the synthesis of various pharmaceuticals. Its distinctive structure and properties contribute to the development of new drugs with potential therapeutic applications.
Used in Agrochemical Production:
In the agrochemical industry, (1S-cis)-2,2-dimethyl-3-(2-methylprop-1-enyl)cyclopropanecarboxylic acid serves as a crucial component in the production of pesticides and other agrochemicals. Its incorporation aids in enhancing the effectiveness and selectivity of these products for agricultural use.
Used in Organic Synthesis Research:
(1S-cis)-2,2-dimethyl-3-(2-methylprop-1-enyl)cyclopropanecarboxylic acid is employed as a valuable building block in organic synthesis research. Its unique structure allows for the exploration of new synthetic pathways and the creation of novel compounds with potential applications across various industries.

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-/m1/s1

Upstream product

• 2935-23-1 cis-Chrysanthemic acid 
• 10453-89-1 chrysanthemumic acid 
• 1083308-98-8 (1S,6R)-2,2,5,5-tetramethyl-7-oxabicyclo[4.1.0]heptan-3-one 
• 865-47-4 potassium tert-butylate 
• 13855-90-8 2,2,5,5-tetramethylcyclohex-3-en-1-one 
• 124-63-0 methanesulfonyl chloride 
• 702-50-1 2,2,5,5-tetramethylcyclohexa-1,3-dione 
• 764-13-6 2,5-Dimethyl-2,4-hexadiene 
• 61057-36-1 (+/-)-trans-2,2-dimethyl-3-(2',2'-dimethylvinyl)cyclopropanecarbonitrile 
• 19902-09-1 (+/-)-cis-2,2-dimethyl-3-(2',2'-dimethylvinyl)cyclopropanecarboxamide 
• 5460-63-9 methyl (dl)-trans-chrysanthemate 
• 27335-32-6 (+)-methyl trans-chrysanthemate 
• 78715-54-5 tert-amyl trans-chrysanthemate 
• 97-41-6 ethyl 2,2-dimethyl-3-(2-methylpropenyl)cyclopropanecarboxylate 

Downstream Products

• 14087-71-9 (-)-cis-dihydrochrysanthemolactone 
• 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) 
• 5460-63-9 methyl (dl)-trans-chrysanthemate 
• 25402-06-6 (S)-3-((Z)-but-2-en-1-yl)-2-methyl-4-oxocyclopent-2-en-1-yl(1R,3R) -2,2-dimethyl-3-(2-methylprop-1-en-1-yl ) -cyclopropane-1-carboxylate 
• 121-21-1 pyrethrin I 
• 121-20-0 cinerin II 
• 1172-63-0 jasmolin II 
• 121-29-9 Pyrethrin II 
• 93132-69-5 (1R,3R)-2,2-Dimethyl-3-((E)-2-methyl-3-oxoprop-1-en-1-yl)cyclopropane-1-carboxylic Acid 
• 1189-99-7 2,5,5-Trimethyl-heptan 

Relevant articles and documents

Molecular chiral recognition in supercritical solvents

The intensity of molecular chiral interactions resulting in differences between physical and chemical properties of diastereomeric molecules is solvent dependent. This difference makes it possible to separate the enantiomers of a given substance by using chiral agents. A solvent of suprcritical state was involved to study its influence on molecular chiral recognition. It was observed that the differences between the diastereomers in supercritical CO2 are so big compared to traditional solvents that a novel, more efficient method for optical resolution can be developed, employing a variety of resolution agents in a much wider range than it was previously assumed.

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).

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.

Competing cyclopropane over epoxide formation from γ-halogeno-δ-hydroxy-ketones

Carbocyclization has been selectively achieved over epoxide formation from a γ-chloro-δ-hydroxy-ketone in the presence of a lithiumamide or using a different strategy in which the related silyloxyenol ether bearing an iodine atom at gamma-position and a silyloxy group in delta-position is reacted with tetrabutylammonium fluoride. These approaches take advantage of (i) the poor reactivity of the intermediate β-halogeno lithiumalkoxide first formed in the former case and (ii) the poorer ability of the fluoride ion to desilylate a silyl ether over a silylenol ether.

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).

Diastereoselective epoxidation of compound bearing a cyclohex-3-enol moiety: Application to the enantioselective synthesis of (1R)-trans-chrysanthemic acid and (1R)-cis-deltametrinic acid

We disclose the synthesis of enantiomeric (1S)-cis- and (1R)-cis-chrysanthemic acids precursors of S-bioallethrin and deltamethrin the most active indoor and outdoor insecticides respectively. It involves an original strategy which takes advantage of the complete stereocontrolled epoxidation of an homoallylalcohol and the synthesis in the same pot of precursors of each of the two enantiomers of cis-chrysanthemic acid, bearing functional groups possessing similar reactivity but having different structural behavior which allow their easy separation.

Selected regiocontrolled transformations applied to the synthesis of (1S)-cis-chrysanthemic acid from (1S)-3,4-epoxy-2,2,5,5-tetramethylcyclohexanol

(1S)-cis-Chrysanthemic acid has been prepared in a few steps with complete control of the relative and absolute stereochemistry using regiocontrolled epoxide ring opening, diol mono-oxidation and cyclopropanation. The Royal Society of Chemistry.

Practical copper-catalyzed asymmetric synthesis of chiral chrysanthemic acid esters

Practical copper salicylaldimine complex catalysts have been developed for the asymmetric synthesis of chiral chrysanthemic acid esters by the cyclopropanation reaction of 2,5-dimethyl-2,4-hexadiene with tert-butyl diazoacetate. First, the effects of the substituents on the salicylaldehyde moiety in the copper salicylaldimine complex (copper Schiff base complex) on the catalytic activity and the stereoselectivities were investigated. As a result, a substitution of hydrogen at the 5-position with the nitro group on the salicylaldehyde moiety was found to enhance the catalytic efficiency. In addtition, a combination catalyst of the copper Schiff base complex with Lewis acid was found to also enhance the catalytic efficiency and achieved 90% chemical yield and 91% ee at 20 °C with 0.1 mol % catalyst loading. Furthermore, the asymmetric induction mechanism of the cyclopropanation reaction catalyzed by the copper Schiff base complex was studied using density functional calculations.