4638-92-0

Basic information

• Product Name: TRANS-(+)-CHRYSANTHEMIC ACID
• Synonyms: (1R,3R)-TRANS-2,2-DIMETHYL-3-(2-METHYL-1-PROPENYL)CYCLOPROPANE-1-CARBOXYLIC ACID;(+)-(1r,3r)-2,2-dimethyl-3-(2-methylpropenyl)cyclopropanecarboxylicacid;(1r-trans)-chrysanthemicacid;2,2-dimethyl-3-(2-methyl-1-propenyl)-cyclopropanecarboxylicaci(1r-trans;2,2-dimethyl-3-(2-methyl-1-propenyl)-cyclopropanecarboxylicaci(1theta-tr;2,2-dimethyl-3-(2-methylpropenyl)-,(1r,3r)-(+)-cyclopropanecarboxylicaci;(1R-trans)-2,2-dimethyl-3-(2-methylprop-1-enyl)cyclopropanecarboxylic acid;trans-(+)-Chrysanthemic acid, 99+%
• CAS NO: 4638-92-0
• Molecular Formula: C₁₀H₁₆O₂
• Molecular Weight: 168.23
• EINECS: 225-067-5
• Mol File: 4638-92-0.mol
• Article Data: 28

Chemical Properties

• Melting Point: 17-21 °C
• Boiling Point: 255.81°C (rough estimate)
• Flash Point: 119 °C
• Appearance: Clear colorless to yellow/Liquid
• Density: 0.9934 (rough estimate)
• Vapor Pressure: 0.0088mmHg at 25°C
• Refractive Index: n20/D 1.477
• Storage Temp.: 0-6°C
• PKA: 4.90±0.33(Predicted)
• BRN: 4904351
• CAS DataBase Reference: TRANS-(+)-CHRYSANTHEMIC ACID(CAS DataBase Reference)
• NIST Chemistry Reference: TRANS-(+)-CHRYSANTHEMIC ACID(4638-92-0)
• EPA Substance Registry System: TRANS-(+)-CHRYSANTHEMIC ACID(4638-92-0)

Safety Data

• Hazard Codes: Xi
• Statements: 36/38
• Safety Statements: 26
• WGK Germany: 3
• RTECS: GZ1280000
• F: 10-23
• Hazardous Substances Data: 4638-92-0(Hazardous Substances Data)

Usage

Uses

Used in Pheromone Synthesis:
TRANS-(+)-CHRYSANTHEMIC ACID is used as a reactant in the synthesis of (1R,3R)-[2,2-dimethyl-3-(2-methylprop-1-enyl)cyclopropyl]methyl (R)-2-acetoxy-3-methylbutanoate, which is the sex pheromone of Pseudococcus calceolariae, also known as the citrophilous mealybug. This application aids in the control and management of these pests in the agricultural industry.
Used in Insecticide Production:
TRANS-(+)-CHRYSANTHEMIC ACID is used as a building block for the preparation of (+)-trans-pyrethric acid, which is an essential component in the synthesis of rethrin II, a type of synthetic pyrethroid insecticide. This application is crucial in the chemical industry for the development of effective insect control solutions.
Used in Chemical Synthesis:
TRANS-(+)-CHRYSANTHEMIC ACID is utilized as a key intermediate in the synthesis of various chemical compounds, contributing to the advancement of the chemical industry and the development of new products with potential applications in different fields.

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)/p-1/t7-,8+/m1/s1

Upstream product

• 97-41-6 ethyl 2,2-dimethyl-3-(2-methylpropenyl)cyclopropanecarboxylate 
• 97-41-6 ethyl trans-(+/-)-chrysanthemate 
• 10453-89-1 chrysanthemumic acid 
• 764-13-6 2,5-Dimethyl-2,4-hexadiene 
• 35059-50-8 t-butyl diazoacetate 
• 61057-36-1 (+/-)-trans-2,2-dimethyl-3-(2',2'-dimethylvinyl)cyclopropanecarbonitrile 
• 5460-63-9 methyl (dl)-trans-chrysanthemate 
• 76-02-8 trifluoroacetyl chloride 
• 19165-55-0 2,2,5,5-tetramethylcyclohex-3-en-1-ol 
• 15500-76-2 Dimethyl-dimedon-mono-(toluol-4-sulfonyl-hydrazon) 
• 702-50-1 2,2,5,5-tetramethylcyclohexa-1,3-dione 
• 13855-90-8 2,2,5,5-tetramethylcyclohex-3-en-1-one 
• 78779-89-2 (+/-)-trans-2,2-dimethyl-3-(2',2'-dimethylvinyl)cyclopropanecarboxamide 
• 2198-88-1 (+/-)-cis-2,2-dimethyl-3-(2',2'-dimethylvinyl)cyclopropanecarbonitrile 

Downstream Products

• 5458-67-3 1R-trans-Chrysanthemsaeure-sec.-butylester 
• 26767-71-5 (1R)-trans-3-[(E)-(2-methoxycarbonyl-1-propenyl)]-2,2-dimethylcyclopropanecarboxylic acid 
• 4489-14-9 (1R)-trans-3-(2-methyl-1-propenyl)-2,2-dimethylcyclopropanecarboxylic acid chloride 
• 5458-68-4 (+)-trans-chrysanthemumic acid isobutyl ester 
• 454-25-1 (+)-trans-Homochrysanthemsaeure 
• 94672-92-1 (1R)-2.2-dimethyl-3t-(2-methyl-propenyl)-cyclopropane-carbanilide-(1r) 
• 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 
• 2259-14-5 (1S,3S)-trans-chrysanthemic acid 
• 454-25-1 (+/-)-trans-Homochrysanthemsaeure 

Relevant articles and documents

Metabolism of (S)-bioallethrin and related compounds in humans

Chrysanthemate insecticides like (S)-bioallethrin, natural pyrethins, and related pyrethroids are subjected to extensive hydrolytic and oxidative degeneration by the mammalian metabolism, leading to a complex series of metabolites partially conjugated and finally eliminated in the urine. The major oxidation products of chrysanthemic acid, cis-(E)- and trans-(E)-chrysanthemumdicarboxcylic acid (cis-(E) and trans-(E)-CDCA), were synthesized and their structures were established by nuclear magnetic resonance spectrometry (H1-NMR) and mass spectrometry (MS). Diastereoselective separation was by high performance liquid chromatography (HPLC) and capillary gas chromatography (GC). An analytical method for extraction and identification of CDCA from human urine was developed. Quantitation was by gas chromatography and electron-impact mass spectrometry (GC/MS). The limit of detection was 20 μg/l for cis-(E)-CDCA and 10 μg/l for trans-(E)-CDCA. To test the applicability of the presented method, urine samples of humans exposed to (S)-bioallethrin were investigated. Urinary peak excretion of trans-(E)-CDCA occurred within 24 h after exposure. Copyright (C) 1999 Elsevier Science Ireland Ltd.

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.

Identification of the catalytic residues of carboxylesterase from arthrobacter globiformis by diisopropyl fluorophosphate-labeling and site-directed mutagenesis

The role of amino acid residues in the enzymatic activity of carboxylesterase from Arthrobacter globiformis was analyzed by diisopropyl fluorophosphate (DFP) labeling and site-directed mutagenesis. The electrospray ionization mass spectrometric (ESI-MS) analysis of the esterase, covalently labeled by DFP, showed stoichiometric incorporation of the inhibitor into the enzyme. The further comparison of endopeptidase-digested fragments between native and DFP-labeled esterase by fast atom bombardment mass spectrometric (FAB-MS) analysis as well as site-directed mutagenesis indicated that Ser59 in the consensus sequence Ser-X-X-Lys, which is conserved exclusively in penicillin-binding proteins and some esterases, served as a catalytic nucleophile. In addition, the results obtained from analysis of the mutants at position 62 suggested the importance of the basic amino acid side chain at this position, and suggested the significance of this residue acting directly as a general base rather than its involvement in the maintenance of the optimum hydrogenbonding network at the active site.

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).

Practical method for crystalline-liquid resolution of chrysanthemic acids utilizing chiral 1,1′-binaphthol monoethyl ethers directed for process chemistry

We have developed an efficient practical resolution method for (1R,3R)-trans-chrysanthemic acid 1 and (1R,3S)-trans-2,2-dimethyl-3-(2,2-dichloroethenyl)cyclopropanecarboxylic acid 2, based on the preliminary results of the simpler analogues, (1R)-2,2-dichlorocyclopropanecarboxylic acid 3 and (1R)-2,2-dimethylcyclopropanecarboxylic acid 4, using a crystalline-liquid separation procedure (without column chromatography) with chiral 1,1′-binaphthol monoethyl ethers (R)-5b as the key auxiliary. Direct esterifications of 1, 2, 3, and 4 with (R)-5b gave four sets of (1R)- and (1S)-diastereomeric esters 8, 9, 6, and 7, respectively, with markedly different melting points. All of these diastereomers were easily obtained using a simple and one-step crystalline-liquid separation. The separated diastereomers 8 and 9 were easily hydrolyzed to the desired enantiopure acids 1 (>98%) and 2 (>99%), respectively, with recovery of (R)-5b (>90%).

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.