From Wikipedia, the free encyclopedia
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