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{{chembox |
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{{chembox |
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| verifiedrevid = 306855349 |
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| verifiedrevid = 394986228 |
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| Name = Piperonal |
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| Name = Piperonal |
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| ImageFile = Piperonal structure.png |
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| ImageFile = Piperonal structure.png |
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| ImageClass = skin-invert |
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| ImageSize = 200px |
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| ImageName = |
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| ImageName = |
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| IUPACName = 1,3-benzodioxole-5-carbaldehyde |
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| PIN = 2''H''-1,3-Benzodioxole-5-carbaldehyde |
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| OtherNames= heliotropine, protocatechuic aldehyde methylene ether |
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| OtherNames= Heliotropin; Heliotropine; Piperonyl aldehyde; Protocatechuic aldehyde methylene ether; 3,4-methylenedioxybenzaldehyde; |
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| Section1 = {{Chembox Identifiers |
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|Section1={{Chembox Identifiers |
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| UNII_Ref = {{fdacite|correct|FDA}} |
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| UNII = KE109YAK00 |
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| UNII = KE109YAK00 |
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| ChEBI_Ref = {{ebicite|correct|EBI}} |
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| ChEBI = 8240 |
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| ChEMBL_Ref = {{ebicite|correct|EBI}} |
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| ChEMBL = 271663 |
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| StdInChI_Ref = {{stdinchicite|changed|chemspider}} |
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| StdInChI = 1S/C8H6O3/c9-4-6-1-2-7-8(3-6)11-5-10-7/h1-4H,5H2 |
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| StdInChIKey_Ref = {{stdinchicite|changed|chemspider}} |
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| StdInChIKey = SATCULPHIDQDRE-UHFFFAOYSA-N |
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| SMILES1 = c1cc2c(cc1C=O)OCO2 |
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| CASNo_Ref = {{cascite|correct|CAS}} |
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| CASNo_Ref = {{cascite|correct|CAS}} |
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| CASNo = 120-57-0 |
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| CASNo = 120-57-0 |
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| Beilstein = 131691 |
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| ChemSpiderID = 8130 |
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| ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}} |
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| SMILES = O=Cc1ccc2OCOc2c1 |
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| ChemSpiderID = 13859497 |
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| EC_number = 204-409-7 |
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| Gmelin = 4186 |
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| KEGG = C10812 |
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| PubChem = 8438 |
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| SMILES = O=Cc1ccc2OCOc2c1 |
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| Section2 = {{Chembox Properties |
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|Section2={{Chembox Properties |
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| C=8 | H=6 | O=3 |
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| Formula = C<sub>8</sub>H<sub>6</sub>O<sub>3</sub> |
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| Appearance = Colorless crystals<ref name=Merck>{{Merck12th}}</ref> |
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| MolarMass = 150.13 g/mol |
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| Density = |
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| Density = 1.337 g/cm<sup>3</sup> |
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| MeltingPt = 35-37 °C |
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| MeltingPtC = 37 |
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| MeltingPt_ref = <ref name=Merck/> |
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| BoilingPtC = 264 |
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| BoilingPtC = 263 |
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| SolubleOther = THF 7.44 M, ethanol 4.99 M, methanol 7.29 M <ref>{{Verify credibility|date=December 2009}}</ref> |
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| BoilingPt_ref = <ref name=Merck/> |
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| Solvent = ], ], ] |
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| Solubility = Soluble in 500 parts<ref name=Merck/> |
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|Section3={{Chembox Hazards |
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| GHSPictograms = {{GHS07}} |
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| GHSSignalWord = Warning |
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| HPhrases = {{H-phrases|317}} |
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| PPhrases = {{P-phrases|261|272|280|302+352|321|333+313|363|501}} |
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| MainHazards = |
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| FlashPt = |
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| AutoignitionPt = |
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| LD50 = 2700 mg/kg (orally in rats)<ref name=Merck/> }} |
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|Section4={{Chembox Legal status |
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| legal_AU = |
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| legal_BR = D1 |
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| legal_BR_comment = <ref>{{Cite web |author=Anvisa |author-link=Brazilian Health Regulatory Agency |date=2023-03-31 |title=RDC Nº 784 - Listas de Substâncias Entorpecentes, Psicotrópicas, Precursoras e Outras sob Controle Especial |trans-title=Collegiate Board Resolution No. 784 - Lists of Narcotic, Psychotropic, Precursor, and Other Substances under Special Control|url=https://www.in.gov.br/en/web/dou/-/resolucao-rdc-n-784-de-31-de-marco-de-2023-474904992 |url-status=live |archive-url=https://web.archive.org/web/20230803143925/https://www.in.gov.br/en/web/dou/-/resolucao-rdc-n-784-de-31-de-marco-de-2023-474904992 |archive-date=2023-08-03 |access-date=2023-08-15 |publisher=] |language=pt-BR |publication-date=2023-04-04}}</ref> |
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| legal_US = |
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| legal_UK = |
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| legal_UN = |
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'''Piperonal''', also known as '''heliotropin''', is an ] which is commonly found in fragrances and flavors.<ref name=Ullmann>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}}</ref> The molecule is structurally related to other ] ]s such as ] and ]. |
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'''Piperonal''', also known as '''heliotropin''', is an aromatic ] that comes as transparent crystals, C<sub>8</sub>H<sub>6</sub>O<sub>3</sub>, and has a floral odor commonly described as being similar to that of ] and ]. It is used as flavoring and in ]. It can be obtained by oxidation of ] or the reduction of ]. It is also a minor natural component of the extract of ]. It is a common additive in inexpensive synthetic vanilla flavor and candies. |
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== Natural occurrence == |
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Piperonal has powerful aromatherapeutic qualities which appear to elevate mood and general well-being. Tests performed by the Memorial Sloan-Kettering Cancer Center in New York demonstrated a reduction in the anxiety of patients receiving an ] by as much as 63 percent.<ref>, Polarized Light Microscopy Digital Image Gallery</ref> |
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Piperonal naturally occurs in various plants. Examples include ], ], ], and ]. |
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==Chemistry== |
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==Preparation== |
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Piperonal can be prepared by the oxidative cleavage of ] or by using a multistep sequence from ] or ]. Synthesis from the latter chemical is accomplished through a ] with ] followed by ] the resulting ] with an ].<ref name=Ullmann /><ref name = syn>{{cite journal|author1=Fatiadi, Alexander |author2=Schaffer, Robert |name-list-style=amp |title=An Improved Procedure for Synthesis of DL-4-Hydroxy-3-methoxymandelic Acid (DL-"Vanillyl"-mandelic Acid, VMA)|journal=Journal of Research of the National Bureau of Standards Section A|year=1974|volume=78A|issue=3|pages=411–412|doi=10.6028/jres.078A.024|pmid=32189791 |pmc=6742820 |doi-access=free}}</ref><ref>{{cite journal|last1=Nwaukwa|first1=Stephen|last2=Keehn|first2=Philip|title=Oxidative cleavage of α-diols, α-diones, α-hydroxy-ketones and α-hydroxy- and α-keto acids with calcium hypochlorite |journal=Tetrahedron Letters|date=1982|volume=23|issue=31|pages=3135–3138|doi=10.1016/S0040-4039(00)88578-0}}</ref> Synthesis from catechol requires an additional step, ] using ].<ref>{{cite journal|author1=Bonthrone, W. |author2=Cornforth, J. |name-list-style=amp |title=The methylenation of catechols|journal=Journal of the Chemical Society|issue=9 |year=1969|pages=1202–1204|doi=10.1039/J39690001202}}</ref> |
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==Reactions== |
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Piperonal may be used in the synthesis of ] (MDA). In one synthetic path, ] in a ] solution with an ] catalyst yields a substituted ] via a ]. This intermediate can then be reduced by a strong reducing agent such as ] (LiAlH<sub>4</sub>) to yield MDA. |
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Piperonal, like all ]s, can be ] to its ] (]) or oxidized to give its ] (]). |
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<ref> </ref> |
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Piperonal can be used in the synthesis of some pharmaceutical drugs including ],<ref>{{cite journal|author1=Gilla, G.|author2=Anumula, R.R.|author3=Aalla, S.|author4=Vurimidi, H.|author5=Ghanta, M.R.|name-list-style=amp|title=Synthesis and characterization of related substances and metabolite of tadalafil, a PDE-5 inhibitor|journal=Organic Communications|year=2013|volume=6|issue=1|pages=12–22|url=http://www.acgpubs.org/OC/2013/Volume%206/Issue%201/2-OC-1204-256.pdf|access-date=2015-01-21|archive-date=2018-10-24|archive-url=https://web.archive.org/web/20181024112519/http://www.acgpubs.org/OC/2013/Volume%206/Issue%201/2-OC-1204-256.pdf|url-status=live}}</ref> ],<ref>{{cite journal | doi = 10.1248/cpb.10.680| title = Studies on Optically Active Amino Acids. I. Preparation of 3-(3, 4-Methylenedioxyphenyl)-D-, and -L-alanine| journal = Chemical & Pharmaceutical Bulletin| volume = 10| issue = 8| pages = 680–688| year = 1962| last1 = Yamada| first1 = Shun-Ichi| last2 = Fujii| first2 = Tozo| last3 = Shioiri| first3 = Takayuki| pmid = 14002245| doi-access = free}}</ref> and ].<ref name="Winnvon Geldern1996">{{cite journal|last1=Winn|first1=Martin|last2=von Geldern|first2=Thomas W.|last3=Opgenorth|first3=Terry J.|last4=Jae|first4=Hwan-Soo|last5=Tasker|first5=Andrew S.|last6=Boyd|first6=Steven A.|last7=Kester|first7=Jeffrey A.|last8=Mantei|first8=Robert A.|last9=Bal|first9=Radhika|last10=Sorensen|first10=Bryan K.|last11=Wu-Wong|first11=Jinshyun R.|last12=Chiou|first12=William J.|last13=Dixon|first13=Douglas B.|last14=Novosad|first14=Eugene I.|last15=Hernandez|first15=Lisa|last16=Marsh|first16=Kennan C.|title=2,4-Diarylpyrrolidine-3-carboxylic AcidsPotent ETASelective Endothelin Receptor Antagonists. 1. Discovery of A-127722|journal=Journal of Medicinal Chemistry|volume=39|issue=5|year=1996|pages=1039–1048|issn=0022-2623|doi=10.1021/jm9505369|pmid=8676339}}</ref> |
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==References== |
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== Fragrance == |
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Piperonal has a floral odor which is commonly described as being similar to that of vanillin or ]. For this reason it is commonly used in fragrances and ].<ref name=Ullmann /> The compound was named heliotropin after the 'cherry pie' notes found in the ]'s fragrance (even though the chemical is not present in the flower's true aroma).<ref>{{Cite web|url=http://www.bojensen.net/EssentialOilsEng/EssentialOils13A/EssentialOils13A.htm|title=Essential oils|access-date=2012-09-02|archive-date=2019-12-23|archive-url=https://web.archive.org/web/20191223140607/http://www.bojensen.net/EssentialOilsEng/EssentialOils13A/EssentialOils13A.htm|url-status=live}}</ref> Perfumers began to use the fragrance for the first time by the early 1880s.<ref name=fashion>: Global Perspectives from Early Modern to Contemporary Times By Beverly Lemire {{ISBN|9781409404927}}</ref> It is commonly used to add vanilla or almond nuances, generally imparting balsamic, powdery, and floral aspects to a scent's character.<ref>The Good Scents Company database entry for {{Webarchive|url=https://web.archive.org/web/20200801012954/http://www.thegoodscentscompany.com/data/rw1005891.html |date=2020-08-01 }}</ref> |
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] is a synthetic cherry flavoring.<ref>Fenaroli's Handbook of Flavor Ingredients.</ref> |
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== Use in MDMA manufacture == |
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Due to their role in the manufacture of ], ], ], and piperonal are Category I precursors under regulation no. 273/2004 of the ].<ref>{{CELEX|32004R0273|text=Regulation (EC) No 273/2004 of the European Parliament and of the Council of 11 February 2004 on drug precursors}}</ref> |
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== References == |
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{{reflist}} |
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{{reflist}} |
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==External links== |
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== External links == |
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{{Wikisource1911Enc Citation|Piperonal}} |
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{{EB1911 poster|Piperonal}} |
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