Heliotropin; Heliotropine; Piperonyl aldehyde; Protocatechuic aldehyde methylene ether; 3,4-methylenedioxybenzaldehyde;
3D model (Jmol)
|Molar mass||150.13 g·mol−1|
|Melting point||37 °C (99 °F; 310 K)|
|Boiling point||263 °C (505 °F; 536 K)|
|Soluble in 500 parts|
|Lethal dose or concentration (LD, LC):|
LD50 (median dose)
|2700 mg/kg (orally in rats)|
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
|what is ?)(|
Piperonal, also known as heliotropin, is an organic compound which is commonly found in fragrances and flavors. The molecule is structurally related to other aromatic aldehydes such as benzaldehyde and vanillin.
Piperonal can be prepared by oxidizing 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. Synthesis from catechol requires an additional step, Williamson ether synthesis using dichloromethane.
Piperonal can be used to synthesize:
- 3,4-methylenedioxyamphetamine (MDA), an illegal psychoactive drug reported to have entactogenic and stimulant properties.
- Piperonal is also used in the synthesis of tadalafil.
- Heliotropin can be used to make piperonyl acetone. This in-turn is used to prepare Safrazine.
- L-DOPA synthesis:
- Reductive amination with piperazine would give Methylenedioxybenzylpiperazine.
- Nitroaldol reaction with nitromethane followed by reduction of the nitrostyrene gives 3,4-Methylenedioxyphenethylamine.
- Monomethylation of the above product gives Homarylamine.
- Hydrastinine is cyclization of the above product with formaldehyde.
- 1-(4-chlorobenzhydryl)-4-(3,4-methylenedioxybenzalamino)piperazine (Ex25 in Ropizine patent U.S. Patent 3,178,422).
Piperonal has a floral odor which is commonly described as being similar to that of vanillin or cherry. For this reason it commonly used in fragrances and artificial flavors. 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). Perfumers began to use the fragrance for the first time by the early 1880s. It is commonly used to add vanilla or almond nuances, generally imparting balsamic, powdery, and floral aspects to a scent's character.
- Budavari, Susan, ed. (1996), The Merck Index: An Encyclopedia of Chemicals, Drugs, and Biologicals (12th ed.), Merck, ISBN 0911910123
- 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.
- 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: 1202–1204. doi:10.1039/J39690001202.
- Shulgin, Alexander; Manning, Tania; Daley, Paul (2011). The Shulgin Index, Volume One: Psychedelic Phenethylamines and Related Compounds (1st ed.). Berkeley, CA: Transform Press. p. 165. ISBN 9780963009630.
- Shulgin, Alexander & Shulgin, Ann (1991). PiHKAL: A Chemical Love Story. Lafayette, CA: Transform Press. ISBN 9780963009609.
- 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.
- 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. ISSN 0009-2363.
- 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
|Wikisource has the text of the 1911 Encyclopædia Britannica article Piperonal.|