Piperonal

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Piperonal
Piperonal structure.png
Names
IUPAC name
1,3-Benzodioxole-5-carbaldehyde
Other names
Heliotropin; Heliotropine; Piperonyl aldehyde; Protocatechuic aldehyde methylene ether; 3,4-methylenedioxybenzaldehyde;
Identifiers
3D model (JSmol)
ChEBI
ChemSpider
ECHA InfoCard 100.004.009
UNII
Properties
C8H6O3
Molar mass 150.13 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
Lethal dose or concentration (LD, LC):
2700 mg/kg (orally in rats)[1]
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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Infobox references

Piperonal, also known as heliotropin, is an organic compound which is commonly found in fragrances and flavors.[2] The molecule is structurally related to other aromatic aldehydes such as benzaldehyde and vanillin.

Natural occurrence[edit]

Piperonal naturally occurs in various plants. Examples include dill, vanilla, violet flowers, and black pepper.

Preparation[edit]

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.[2][3][4] Synthesis from catechol requires an additional step, Williamson ether synthesis using dichloromethane.[5]

Reactions[edit]

Piperonal, like all aldehydes, can be reduced to its alcohol (piperonyl alcohol) or oxidized to give its acid (piperonylic acid).

Piperonal can be used to synthesize:

  1. In the book PIHKAL, 3,4-methylenedioxyamphetamine (MDA), BOH (drug), and MDOH were the target molecules made from heliotropin.
  2. Piperonal is also used in the synthesis of tadalafil.[6]
  3. Olmidine
  4. Stiripentol
  5. Heliotropin can be used to make piperonyl acetone. This in-turn is used to prepare Safrazine.
  6. L-DOPA synthesis:[7]
  7. Reductive amination with piperazine would give Methylenedioxybenzylpiperazine.
  8. Nitroaldol reaction with nitromethane followed by reduction of the nitrostyrene gives 3,4-Methylenedioxyphenethylamine.
  9. Monomethylation of the above product gives Homarylamine.
  10. Hydrastinine is cyclization of the above product with formaldehyde.
  11. 1-(4-chlorobenzhydryl)-4-(3,4-methylenedioxybenzalamino)piperazine (Ex25 in Ropizine patent U.S. Patent 3,178,422).
  12. The nitrostyrene between heliotropin & nitromethane is used in a published synthesis of Atrasentan.[8] & also Cephalotaxine.[9]
  13. Canadine
  14. Via the cinnamic acid, heliotropin was used to make Cinoxopazide, as well as Oxmetidine
  15. Piperic acid amides such as piperine.[10]
  16. Guineesine
  17. Piribedil
  18. Niperotidine

Fragrance[edit]

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.[2] 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).[11] Perfumers began to use the fragrance for the first time by the early 1880s.[12] It is commonly used to add vanilla or almond nuances, generally imparting balsamic, powdery, and floral aspects to a scent's character.[13]

Piperonyl acetate is a synthetic cherry flavouring.[14]

References[edit]

  1. ^ a b c d e Budavari, Susan, ed. (1996), The Merck Index: An Encyclopedia of Chemicals, Drugs, and Biologicals (12th ed.), Merck, ISBN 0911910123 
  2. ^ 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
  3. ^ 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. 
  4. ^ 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. 
  5. ^ Bonthrone, W. & Cornforth, J. (1969). "The methylenation of catechols". Journal of the Chemical Society: 1202–1204. doi:10.1039/J39690001202. 
  6. ^ 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. 
  7. ^ 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.
  8. ^ 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. ISSN 0022-2623. doi:10.1021/jm9505369. 
  9. ^ Ishibashi, Hiroyuki; Okano, Masahiko; Tamaki, Hiroshi; Maruyama, Kazumi; Yakura, Takayuki; Ikeda, Masazumi Journal of the Chemical Society, Chemical Communications, 1990 , # 20 p. 1436 - 1437
  10. ^ Wani, Naiem Ahmad; Singh, Samsher; Farooq, Saleem; Shankar, Sudha; Koul, Surrinder; Khan, Inshad Ali; Rai, Rajkishor (2016). "Amino acid amides of piperic acid (PA) and 4-ethylpiperic acid (EPA) as NorA efflux pump inhibitors of Staphylococcus aureus". Bioorganic & Medicinal Chemistry Letters. 26 (17): 4174–4178. ISSN 0960-894X. doi:10.1016/j.bmcl.2016.07.062. 
  11. ^ http://www.bojensen.net/EssentialOilsEng/EssentialOils13A/EssentialOils13A.htm
  12. ^ The Force of Fashion in Politics and Society: Global Perspectives from Early Modern to Contemporary Times By Beverly Lemire ISBN 9781409404927
  13. ^ The Good Scents Company database entry for Heliotropin
  14. ^ Fenaroli's Handbook of Flavor Ingredients.

External links[edit]