Piperonal
Names
Preferred IUPAC name
2H -1,3-Benzodioxole-5-carbaldehyde
Other names
Heliotropin; Heliotropine; Piperonyl aldehyde; Protocatechuic aldehyde methylene ether; 3,4-methylenedioxybenzaldehyde;
Identifiers
131691
ChEBI
ChEMBL
ChemSpider
ECHA InfoCard
100.004.009
EC Number
4186
KEGG
UNII
InChI=1S/C8H6O3/c9-4-6-1-2-7-8(3-6)11-5-10-7/h1-4H,5H2
N Key: SATCULPHIDQDRE-UHFFFAOYSA-N
N
O=Cc1ccc2OCOc2c1
c1cc2c(cc1C=O)OCO2
Properties
C 8 H 6 O 3
Molar mass
150.133 g·mol−1
Appearance
Colorless crystals[ 1]
Density
1.337 g/cm3
Melting point
37 °C (99 °F; 310 K)[ 1]
Boiling point
263 °C (505 °F; 536 K)[ 1]
Soluble in 500 parts[ 1]
Hazards
GHS labelling :
Warning
H317
P261 , P272 , P280 , P302+P352 , P321 , P333+P313 , P363 , P501
Lethal dose or concentration (LD, LC):
2700 mg/kg (orally in rats)[ 1]
Legal status
Except where otherwise noted, data are given for materials in their
standard state (at 25 °C [77 °F], 100 kPa).
Chemical compound
Piperonal , also known as heliotropin , is an organic compound which is commonly found in fragrances and flavors.[ 3] The molecule is structurally related to other aromatic aldehydes such as benzaldehyde and vanillin .
Natural occurrence
Piperonal naturally occurs in various plants. Examples include dill , vanilla , violet flowers , and black pepper .
Preparation
Piperonal can be prepared by the oxidative cleavage of isosafrole or by using a multistep sequence from catechol or 1,2-methylenedioxybenzene . Synthesis from the latter chemical is accomplished through a condensation reaction with glyoxylic acid followed by cleaving the resulting α-hydroxy acid with an oxidizing agent .[ 3] [ 4] [ 5] Synthesis from catechol requires an additional step, Williamson ether synthesis using dichloromethane .[ 6]
Reactions
Piperonal, like all aldehydes , can be reduced to its alcohol (piperonyl alcohol ) or oxidized to give its acid (piperonylic acid ).
Piperonal can be used in the synthesis of some pharmaceutical drugs including tadalafil ,[ 7] L-DOPA ,[ 8] and atrasentan .[ 9]
Fragrance
Piperonal has a floral odor which is commonly described as being similar to that of vanillin or cherry . For this reason it is commonly used in fragrances and artificial flavors .[ 3] The compound was named heliotropin after the 'cherry pie' notes found in the heliotrope flower 's fragrance (even though the chemical is not present in the flower's true aroma).[ 10] Perfumers began to use the fragrance for the first time by the early 1880s.[ 11] It is commonly used to add vanilla or almond nuances, generally imparting balsamic, powdery, and floral aspects to a scent's character.[ 12]
Piperonyl acetate is a synthetic cherry flavoring.[ 13]
Use in MDMA manufacture
Due to their role in the manufacture of MDMA , safrole , isosafrole , and piperonal are Category I precursors under regulation no. 273/2004 of the European Community .[ 14]
References
^ a b c d e Budavari, Susan, ed. (1996). The Merck Index: An Encyclopedia of Chemicals, Drugs, and Biologicals (12th ed.). Merck. ISBN 0911910123 .
^ Anvisa (2023-03-31). "RDC Nº 784 - Listas de Substâncias Entorpecentes, Psicotrópicas, Precursoras e Outras sob Controle Especial" [Collegiate Board Resolution No. 784 - Lists of Narcotic, Psychotropic, Precursor, and Other Substances under Special Control] (in Brazilian Portuguese). Diário Oficial da União (published 2023-04-04). Archived from the original on 2023-08-03. Retrieved 2023-08-15 .
^ a b c Karl-Georg Fahlbusch, Franz-Josef Hammerschmidt, Johannes Panten, Wilhelm Pickenhagen, Dietmar Schatkowski, Kurt Bauer, Dorothea Garbe and Horst Surburg "Flavors and Fragrances" in Ullmann's Encyclopedia of Industrial Chemistry, Wiley-VCH, Weinheim, 2003. doi :10.1002/14356007.a11_141
^ Fatiadi, Alexander & Schaffer, Robert (1974). "An Improved Procedure for Synthesis of DL-4-Hydroxy-3-methoxymandelic Acid (DL-"Vanillyl"-mandelic Acid, VMA)" . Journal of Research of the National Bureau of Standards Section A . 78A (3): 411– 412. doi :10.6028/jres.078A.024 . PMC 6742820 . PMID 32189791 .
^ Nwaukwa, Stephen; Keehn, Philip (1982). "Oxidative cleavage of α-diols, α-diones, α-hydroxy-ketones and α-hydroxy- and α-keto acids with calcium hypochlorite [Ca(OCl)2 ]". Tetrahedron Letters . 23 (31): 3135– 3138. doi :10.1016/S0040-4039(00)88578-0 .
^ Bonthrone, W. & Cornforth, J. (1969). "The methylenation of catechols". Journal of the Chemical Society (9): 1202– 1204. doi :10.1039/J39690001202 .
^ Gilla, G.; Anumula, R.R.; Aalla, S.; Vurimidi, H. & Ghanta, M.R. (2013). "Synthesis and characterization of related substances and metabolite of tadalafil, a PDE-5 inhibitor" (PDF) . Organic Communications . 6 (1): 12– 22. Archived (PDF) from the original on 2018-10-24. Retrieved 2015-01-21 .
^ Yamada, Shun-Ichi; Fujii, Tozo; Shioiri, Takayuki (1962). "Studies on Optically Active Amino Acids. I. Preparation of 3-(3, 4-Methylenedioxyphenyl)-D-, and -L-alanine" . Chemical & Pharmaceutical Bulletin . 10 (8): 680– 688. doi :10.1248/cpb.10.680 . PMID 14002245 .
^ Winn, Martin; von Geldern, Thomas W.; Opgenorth, Terry J.; Jae, Hwan-Soo; Tasker, Andrew S.; Boyd, Steven A.; Kester, Jeffrey A.; Mantei, Robert A.; Bal, Radhika; Sorensen, Bryan K.; Wu-Wong, Jinshyun R.; Chiou, William J.; Dixon, Douglas B.; Novosad, Eugene I.; Hernandez, Lisa; Marsh, Kennan C. (1996). "2,4-Diarylpyrrolidine-3-carboxylic AcidsPotent ETASelective Endothelin Receptor Antagonists. 1. Discovery of A-127722". Journal of Medicinal Chemistry . 39 (5): 1039– 1048. doi :10.1021/jm9505369 . ISSN 0022-2623 . PMID 8676339 .
^ "Essential oils" . Archived from the original on 2019-12-23. Retrieved 2012-09-02 .
^ The Force of Fashion in Politics and Society : Global Perspectives from Early Modern to Contemporary Times By Beverly Lemire ISBN 9781409404927
^ The Good Scents Company database entry for Heliotropin Archived 2020-08-01 at the Wayback Machine
^ Fenaroli's Handbook of Flavor Ingredients.
^ Regulation (EC) No 273/2004 of the European Parliament and of the Council of 11 February 2004 on drug precursors
External links