Piperonyl aldehyde

Piperonyl aldehyde Basic information
Synthesis
Product Name:Piperonyl aldehyde
Synonyms:HELIOTHROPINE;LABOTEST-BB LT00933538;TIMTEC-BB SBB007752;PIPERONYL ALDEHYDE;PROTOCATECHUIC ALDEHYDE METHYLENE ETHER;1,3-benzodiolole-5-carboxaldehyde;Blue P;Dioxymethylene-protocatechuic aldehyde
CAS:120-57-0
MF:C8H6O3
MW:150.13
EINECS:204-409-7
Product Categories:Food and Feed Additive;Aldehydes;Building Blocks;C8;Carbonyl Compounds;Chemical Synthesis;Organic Building Blocks
Mol File:120-57-0.mol
Piperonyl aldehyde Structure
Piperonyl aldehyde Chemical Properties
Melting point 35-39 °C(lit.)
Boiling point 264 °C(lit.)
density 1.2645 (rough estimate)
vapor pressure 1 mm Hg ( 87 °C)
FEMA 2911 | PIPERONAL
refractive index 1.4500 (estimate)
Fp >230 °F
storage temp. Dark Room
solubility methanol: 0.1 g/mL, clear
form A crystalline solid
Odorat 100.00 %. heliotrope flower sweet powdery coconut vanilla
Odor Typefloral
Water Solubility Slightly soluble
Sensitive Air & Light Sensitive
JECFA Number896
Merck 13,7556
BRN 131691
Stability:Stable, but air and light sensitive. Combustible. Incompatible with strong oxidizing agents, bases.
LogP1.2 at 35℃
CAS DataBase Reference120-57-0(CAS DataBase Reference)
NIST Chemistry ReferencePiperonal(120-57-0)
EPA Substance Registry SystemPiperonal (120-57-0)
Safety Information
Hazard Codes Xi
Risk Statements 38-52/53
Safety Statements 61-24/25
WGK Germany 2
RTECS TO1575000
8-10-23
TSCA Yes
HS Code 29329300
Hazardous Substances Data120-57-0(Hazardous Substances Data)
ToxicityLD50 orally in rats: 2700 mg/kg (Hagan)
MSDS Information
ProviderLanguage
SigmaAldrich English
ALFA English
Piperonyl aldehyde Usage And Synthesis
SynthesisPiperonyl alcohol (0.15 g, 1.00 mmol) was dissolved in EtOAc (7 mL, 0.14 M fifinal concentration), and 1-hydroxy-1,2,benziodoxol-3(1H)-one (IBX 0.84 g, 3.00 mmol) was added. The resulting suspension was immersed in an oil bath set to 80 °C and stirred vigorously open to the atmosphere. After 3.25 h (TLC monitoring), the reaction was cooled to room temperature and fifiltered through a medium glass frit. The fifilter cake was washed with 3 × 2 mL of EtOAc, and the combined fifiltrates were concentrated to yield 0.14 g (90%, > 95% pure by 1 H NMR) of piperonal as a waxy solid.
	Piperonyl aldehyde
Reference: More, J. D.; Finney, N. S. Org. Lett. 2002, 4, 3001−3003.
Chemical PropertiesHeliotropin occurs in a number of essential oils, but only in low concentrations. It forms white crystals (mp 37°C) with a sweet, floral, slightly spicy, heliotrope-like odor.
Chemical PropertiesPiperonal has a sweet, flowery odor reminiscent of heliotrope and a bittersweet taste.
Chemical Propertieswhite crystalline solid
OccurrenceReported found in the essential oils of Robinia pseudo-acacia and Eryngium poterium; in the oils of Spirea ulmaria and of leaves of Doryphora sassafras; also reported found in Tahitian and Bourbon vanilla, camphor wood oil, violet flowers concrete and absolute, burley tobacco, rabbiteye blueberry, melon, pepper, cooked chicken, sherry and dill.
UsesPiperonal is used as fragrance and flavoring agent.
UsesIn perfumery, in cherry and vanilla flavors, in organic syntheses.
UsesPiperonal is an impurity of Tadalafil (T004500). Tadalafil impurity A.
PreparationHeliotropin is produced by two main routes:
1) From isosafrole: For many years, oxidative cleavage of isosafrole was the only route applicable on an industrial scale. Isosafrole [120-58-1] is obtained by isomerization from safrole [94-59-7], which can be isolated from (Chinese) sassafras oil . Examples of oxidants that give good yields of heliotropin are chromium(VI) salts, oxygen, and ozone.
This method is still used currently, but the destructive exploitation of sassafras trees in Southeast Asia has led to a strong decline in the availability of sassafras oil and thus of safrole/isosafrole.
2) From catechol: Several routes have recently been developed for the synthesis of heliotropin from catechol. In one such route, catechol is converted into 3,4-dihydroxymandelic acid with glyoxylic acid in an alkaline medium in the presence of aluminum oxide. 3,4-Dihydroxymandelic acid is oxidized to the corresponding keto acid (e.g., with copper-(II) oxide), which is decarboxylated to 3,4-dihydroxybenzaldehyde. The latter product is converted into heliotropin, for example, by reactionwith methylene chloride in the presence of quaternary ammonium salts.
In another route, catechol is first reacted with methylene chloride and converted into 1,2-methylenedioxybenzene . Reaction with glyoxylic acid in strongly acidic media yields 3,4-methylenedioxymandelic acid . Subsequent oxidation and decarboxylation with nitric acid afford heliotropin.
Alternative routes that start from 1,2-methylenedioxybenzene and use piperonyl chloride as intermediate have been described .

DefinitionChEBI: An arenecarbaldehyde that is 1,3-benzodioxole substituted by a formyl substituent at position 5. It has been isolated from Piper nigrum.
Aroma threshold valuesDetection: 62 ppb to 1 ppm. Aroma characteristics at 1.0%: sweet, anise-like, almond vanilla, floral, black cherry pit, berry raspberry, powdery coumarin-like with a hint of hay.
Taste threshold valuesTaste characteristics at 10 to 50 ppm: ripe black cherry fleshy, ripe berry, sweet, macaroon, Jordan almond, creamy vanilla, spicy cream soda, courmarin, slight floral with hay nuances.
Synthesis Reference(s)Canadian Journal of Chemistry, 64, p. 225, 1986 DOI: 10.1139/v86-039
The Journal of Organic Chemistry, 48, p. 4053, 1983 DOI: 10.1021/jo00170a036
Tetrahedron Letters, 33, p. 5909, 1992 DOI: 10.1016/S0040-4039(00)61086-9
General DescriptionColorless lustrous crystals.
Air & Water ReactionsSlightly water soluble .
Reactivity ProfilePiperonyl aldehyde is an aldehyde. Aldehydes are frequently involved in self-condensation or polymerization reactions. These reactions are exothermic; they are often catalyzed by acid. Aldehydes are readily oxidized to give carboxylic acids. Flammable and/or toxic gases are generated by the combination of aldehydes with azo, diazo compounds, dithiocarbamates, nitrides, and strong reducing agents. Aldehydes can react with air to give first peroxo acids, and ultimately carboxylic acids. These autoxidation reactions are activated by light, catalyzed by salts of transition metals, and are autocatalytic (catalyzed by the products of the reaction). The addition of stabilizers (antioxidants) to shipments of aldehydes retards autoxidation. Piperonyl aldehyde is sensitive to light. Piperonyl aldehyde may react with oxidizing materials.
Fire HazardFlash point data for Piperonyl aldehyde are not available. Piperonyl aldehyde is probably combustible.
Flammability and ExplosibilityNotclassified
Safety ProfileModerately toxic by ingestion and intraperitoneal routes. Can cause central nervous system depression. A human skin irritant. Mutation data reported. Combustible when exposed to heat or flame; can react with oxidizing materials. See also ALDEHYDES.
SynthesisBy the oxidation of isosafrole with potassium dichromate and sulfuric acid and subsequent steam distillation of piperonal
MetabolismIn the animal body heliotropin undergoes the expected metabolic reaction involving oxidation to the corresponding acid (Williams, 1959).
Purification MethodsCrystallise piperonal from aqueous 70% EtOH or EtOH/water. [Beilstein 19/4 V 225.]
5-Bromo-2,3-methylenedioxybenzaldehyde 6-AMINO-1,3-BENZODIOXOLE-5-CARBOXYLIC ACID Piperonyl acetone 2-Methyl-3-(3,4-methylenedioxyphenyl)propanal MELICOPINE 7-Bromobenzo[1,3]dioxole-5-carbaldehyde MELICOPIDINE ALLOCRYPTOPINE 1-Nonanal Piperonyl aldehyde Neoheliotropine MYRISTICIN ALDEHYDE 4-(Trifluoromethyl)benzaldehyde Aristolochic acid Cuminaldehyde 3,4-(METHYLENEDIOXY)PROPIOPHENONE cyclamen aldehyde Protopine

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