Lilial: Difference between revisions

Lilial
Names
	IUPAC name 3-(4-tert-Butylphenyl)-2-methylpropanal
	Other names 4-tert-Butyl-α-methyl-benzenepropanal; 4-tert-Butyl-α-methyl-hydrocinnamaldehyde; Butylphenyl methylpropional;
Identifiers
CAS Number	80-54-6 (Racemic) ; 75166-31-3 (2R) ; 75166-30-2 (2S) ;
3D model (JSmol)	Interactive image;
ChemSpider	1266494 (2R); 1363748 (2S); 199342;
ECHA InfoCard	100.001.173
EC Number	201-289-8;
PubChem CID	1549660 (2R); 1715213 (2S); 228987;
RTECS number	MW4895000;
UNII	T7540GJV69 (Racemic) ; 14X71K3AMT (2R) ; WP1PPC4R9G (2S) ;
UN number	3082
CompTox Dashboard (EPA)	DTXSID9026500 ;
	InChI InChI=1S/C14H20O/c1-11(10-15)9-12-5-7-13(8-6-12)14(2,3)4/h5-8,10-11H,9H2,1-4H3 Key: SDQFDHOLCGWZPU-UHFFFAOYSA-N;
	SMILES CC(CC1=CC=C(C=C1)C(C)(C)C)C=O;
Properties
Chemical formula	C14H20O
Molar mass	204.313 g·mol−1
Appearance	Clear viscous liquid
Density	0.94 g/cm3
Melting point	−20 °C (−4 °F; 253 K)
Boiling point	275 °C (527 °F; 548 K)
Solubility in water	0.045 g/L at 20 °C
log P	4.36
Pharmacology
Routes of; administration	Topical
Related compounds
Related aldehydes	Bourgeonal; Isobutyraldehyde; Hexyl cinnamaldehyde; 2-Methylundecanal
	Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa). Infobox references

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Latest revision as of 10:38, 23 December 2024

Lilial (a trade name for lily aldehyde, also known as lysmeral or lilestralis) is a chemical compound commonly used as a perfume in cosmetic preparations and laundry powders, often under the name butylphenyl methylpropional. It is an aromatic aldehyde, naturally occurring in crow-dipper and tomato plants,^[2] and produced synthetically in large scale. It was banned for use in cosmetics by the EU in March 2022 after being found to be harmful to fertility.

It is also used as an intermediate in the synthesis of agrochemicals such as fenpropimorph.

Synthesis

Lilial is produced by the mixed aldol coupling of 4-tert-butylbenzaldehyde (typically as it's methanol acetal) and propionaldehyde, followed by hydrogenation.

Properties

Lilial is commonly produced and sold as a racemic mixture; however, testing has indicated that the different enantiomers of the compound do not contribute equally to its odor. The (R)-enantiomer has a strong floral odor, reminiscent of cyclamen or lily of the valley; whereas the (S)-enantiomer possesses no strong odor.^[3]

Like most aldehydes, lilial is not long term stable and tends to slowly oxidize on storage.

Safety

The Scientific Committee on Consumer Safety (SCCS, scientific committee for consumer safety of the EU Commission) concluded in May 2019 that the use of lilial in both rinse-off and leave-on cosmetics "cannot be considered as safe".^[4]

After animal studies found it to be toxic for reproduction, it was reclassified as a prohibited substance in the EU, and banned from use in cosmetics as of March 2022.^[5]

It can sometimes act as an allergen and may cause contact dermatitis in susceptible individuals.

References

^ ^a ^b Haefliger, Olivier P.; Jeckelmann, Nicolas; Ouali, Lahoussine; León, Géraldine (2010). "Real-Time Monitoring of Fragrance Release from Cotton Towels by Low Thermal Mass Gas Chromatography Using a Longitudinally Modulating Cryogenic System for Headspace Sampling and Injection". Analytical Chemistry. 82 (2): 729–737. doi:10.1021/ac902460d. ISSN 0003-2700. PMID 20025230.
^ "Lilial".
^ Bartschat, Dietmar; Bürner, Susanne; Mosandl, A.; Bats, Jan W. (1997). "Stereoisomeric flavour compounds LXXVI: direct enantioseparation, structure elucidation and structure-function relationship of 4-tert-butyl-α-methyldihydrocinnamaldehyde". Zeitschrift für Lebensmittel-Untersuchung und -Forschung A. 205 (1): 76–79. doi:10.1007/s002170050127. ISSN 1431-4649. S2CID 97399242.
^ Scientific Committee on Consumer Safety (2019-05-10). "OPINION ON the safety of Butylphenyl methylpropional (p-BMHCA) in cosmetic products" (PDF). Retrieved 2020-05-28. On individual product basis, Butylphenyl methylpropional (p-BMHCA) (CAS 80-54-6) with alpha-tocopherol at 200 ppm, can be considered safe when used as fragrance ingredient in different cosmetic leave-on and rinse-off type products. However, considering the first-tier deterministic aggregate exposure, arising from the use of different product types together, Butylphenyl methylpropional at the proposed concentrations cannot be considered as safe.
^ "COMMISSION REGULATION (EU) 2021/1902 OF 29 October 2021 amending Annexes II, III and V to Regulation (EC) No 1223/2009 of the European Parliament and of the Council as regards the use of cosmetic products of certain substances classified as carcinogenic, mutagenic or toxic for reproduction". Retrieved 2022-01-03. CAS No. 80-54-6

[HaefligerJeckelmann2010-1] Haefliger, Olivier P.; Jeckelmann, Nicolas; Ouali, Lahoussine; León, Géraldine (2010). "Real-Time Monitoring of Fragrance Release from Cotton Towels by Low Thermal Mass Gas Chromatography Using a Longitudinally Modulating Cryogenic System for Headspace Sampling and Injection". Analytical Chemistry. 82 (2): 729–737. doi:10.1021/ac902460d. ISSN 0003-2700. PMID 20025230.

[2] "Lilial".

[BartschatBürner1997-3] Bartschat, Dietmar; Bürner, Susanne; Mosandl, A.; Bats, Jan W. (1997). "Stereoisomeric flavour compounds LXXVI: direct enantioseparation, structure elucidation and structure-function relationship of 4-tert-butyl-α-methyldihydrocinnamaldehyde". Zeitschrift für Lebensmittel-Untersuchung und -Forschung A. 205 (1): 76–79. doi:10.1007/s002170050127. ISSN 1431-4649. S2CID 97399242.

[4] Scientific Committee on Consumer Safety (2019-05-10). "OPINION ON the safety of Butylphenyl methylpropional (p-BMHCA) in cosmetic products" (PDF). Retrieved 2020-05-28. On individual product basis, Butylphenyl methylpropional (p-BMHCA) (CAS 80-54-6) with alpha-tocopherol at 200 ppm, can be considered safe when used as fragrance ingredient in different cosmetic leave-on and rinse-off type products. However, considering the first-tier deterministic aggregate exposure, arising from the use of different product types together, Butylphenyl methylpropional at the proposed concentrations cannot be considered as safe.

[5] "COMMISSION REGULATION (EU) 2021/1902 OF 29 October 2021 amending Annexes II, III and V to Regulation (EC) No 1223/2009 of the European Parliament and of the Council as regards the use of cosmetic products of certain substances classified as carcinogenic, mutagenic or toxic for reproduction". Retrieved 2022-01-03. CAS No. 80-54-6

[1]

[2]

[3]

[4]

[5]

@@ Line 7: / Line 7: @@
 | CASNo_Ref = {{cascite|correct|CAS}}
 | CASNo_Comment = ([[Racemic]])
 | CASNo1 = 75166-31-3
 | CASNo1_Ref = {{cascite|correct|CAS}}
 | CASNo1_Comment = (2''R'')
 | CASNo2 = 75166-30-2
 | CASNo2_Ref = {{cascite|correct|CAS}}
 | CASNo2_Comment = (2''S'')
@@ Line 40: / Line 40: @@
 }}
 |Section2={{Chembox Properties
-| C=14 | H=20 | O=1
+| C=14|H=20|O=1
 | Appearance = Clear viscous liquid
-| Density = 0.94 g/ml
+| Density = 0.94 g/cm<sup>3</sup>
 | MeltingPtC = -20
 | BoilingPtC = 275
 | BoilingPt_ref = <ref name="HaefligerJeckelmann2010">{{cite journal|last1=Haefliger|first1=Olivier P.|last2=Jeckelmann|first2=Nicolas|last3=Ouali|first3=Lahoussine|last4=León|first4=Géraldine|title=Real-Time Monitoring of Fragrance Release from Cotton Towels by Low Thermal Mass Gas Chromatography Using a Longitudinally Modulating Cryogenic System for Headspace Sampling and Injection|journal=Analytical Chemistry|volume=82|issue=2|year=2010|pages=729–737|issn=0003-2700|doi=10.1021/ac902460d|pmid=20025230}}</ref>
-| Solubility =0.045 g/l at 20 °C
+| Solubility =0.045 g/L at 20 °C
 | LogP = 4.36 <ref name="HaefligerJeckelmann2010" />
 }}
 |Section3={{Chembox Pharmacology
@@ Line 61: / Line 60: @@
 }}
-'''Lilial''' (a trade name for '''lily aldehyde''', also known as '''lysmeral''') is a [[chemical compound]] commonly used as a [[perfume]] in [[cosmetics|cosmetic preparations]] and laundry powders, often under the name ''butylphenyl methylpropional''. It is a synthetic [[Aromaticity|aromatic]] [[aldehyde]].
+'''Lilial''' (a trade name for '''lily aldehyde''', also known as '''lysmeral''' or '''lilestralis''') is a [[chemical compound]] commonly used as a [[perfume]] in [[cosmetics|cosmetic preparations]] and laundry powders, often under the name ''butylphenyl methylpropional''. It is an [[Aromaticity|aromatic]] [[aldehyde]], naturally occurring in [[Pinellia ternata|crow-dipper]] and [[Solanum lycopersicum|tomato]] plants,<ref>{{cite web | url=https://pubchem.ncbi.nlm.nih.gov/compound/Lilial | title=Lilial }}</ref> and produced synthetically in large scale. It was banned for use in cosmetics by the EU in March 2022 after being found to be harmful to fertility.
+It is also used as an intermediate in the synthesis of agrochemicals such as [[fenpropimorph]].
 ==Synthesis==
+Lilial is produced by the mixed aldol coupling of [[4-tert-butylbenzaldehyde]] (typically as it's methanol [[acetal]]) and [[propionaldehyde]], followed by [[hydrogenation]].
-Lilial is produced at BASF through a double anodic oxidation of 4-tert-butyl toluene on >10,000 ton per year scale.<ref>Möhle, S.; Zirbes, M.; Rodrigo, E.; Gieshoff, T.; Wiebe, A.;
-Waldvogel, S. R. Modern Electrochemical Aspects for the Synthesis of Value-Added Organic Products. Angew. Chem., Int. Ed. 2018, 57, 6018−6041</ref>
+:[[File:Lysmeral Industriell.svg|600px]]
 ==Properties==
-Lilial is commonly produced and sold as a [[racemic mixture]]; however, testing has indicated that the different [[enantiomer]]s of the compound do not contribute equally to its odor. The (''R'')-enantiomer has a strong floral odor, reminiscent of [[cyclamen]] or [[lily of the valley]]; whereas the (''S'')-enantiomer possesses no strong odor.<ref name="BartschatBürner1997">{{cite journal|last1=Bartschat|first1=Dietmar|last2=Bürner|first2=Susanne|last3=Mosandl|first3=A.|last4=Bats|first4=Jan W.|title=Stereoisomeric flavour compounds LXXVI: direct enantioseparation, structure elucidation and structure-function relationship of 4-tert-butyl-α-methyldihydrocinnamaldehyde|journal=Zeitschrift für Lebensmitteluntersuchung und -Forschung A|volume=205|issue=1|year=1997|pages=76–79|issn=1431-4649|doi=10.1007/s002170050127}}</ref>
+Lilial is commonly produced and sold as a [[racemic mixture]]; however, testing has indicated that the different [[enantiomer]]s of the compound do not contribute equally to its odor. The (''R'')-enantiomer has a strong floral odor, reminiscent of [[cyclamen]] or [[lily of the valley]]; whereas the (''S'')-enantiomer possesses no strong odor.<ref name="BartschatBürner1997">{{cite journal|last1=Bartschat|first1=Dietmar|last2=Bürner|first2=Susanne|last3=Mosandl|first3=A.|last4=Bats|first4=Jan W.|title=Stereoisomeric flavour compounds LXXVI: direct enantioseparation, structure elucidation and structure-function relationship of 4-tert-butyl-α-methyldihydrocinnamaldehyde|journal=Zeitschrift für Lebensmittel-Untersuchung und -Forschung A|volume=205|issue=1|year=1997|pages=76–79|issn=1431-4649|doi=10.1007/s002170050127|s2cid=97399242}}</ref>
 :[[File:2-(4-tert-Butylbenzyl)propionaldehyd Formulae V.1.svg|thumb|left|(''R'')-Lilial (top) and (''S'')-lilial]]{{clear-left}}
@@ Line 75: / Line 77: @@
 ==Safety==
-The [[Scientific Committee on Consumer Safety]] (SCCS, scientific committee for consumer safety of the EU Commission) concluded in May 2019 that the use of lilial in both rinse-off and leave-on cosmetics "cannot be considered as safe". <ref>
+The [[Scientific Committee on Consumer Safety]] (SCCS, scientific committee for consumer safety of the EU Commission) concluded in May 2019 that the use of lilial in both rinse-off and leave-on cosmetics "cannot be considered as safe".<ref>
-{{cite web |url=https://ec.europa.eu/health/sites/health/files/scientific_committees/consumer_safety/docs/sccs_o_213.pdf |title=OPINION ON the safety of Butylphenyl methylpropional (p-BMHCA) in cosmetic products  |date=2019-05-10 |language=en |author=[[Scientific Committee on Consumer Safety]] |access-date=2020-05-28 |format=PDF | quote=On individual product basis, Butylphenyl methylpropional (p-BMHCA) (CAS 80-54-6) with alpha-tocopherol at 200 ppm, can be considered safe when used as fragrance ingredient in different cosmetic leave-on and rinse-off type products. However, considering the first-tier deterministic aggregate exposure, arising from the use of different product types together, Butylphenyl methylpropional at the proposed concentrations cannot be considered as safe. }}</ref>
+{{cite web |url=https://ec.europa.eu/health/sites/health/files/scientific_committees/consumer_safety/docs/sccs_o_213.pdf |title=OPINION ON the safety of Butylphenyl methylpropional (p-BMHCA) in cosmetic products |date=2019-05-10 |language=en |author=[[Scientific Committee on Consumer Safety]] |access-date=2020-05-28 | quote=On individual product basis, Butylphenyl methylpropional (p-BMHCA) (CAS 80-54-6) with alpha-tocopherol at 200 ppm, can be considered safe when used as fragrance ingredient in different cosmetic leave-on and rinse-off type products. However, considering the first-tier deterministic aggregate exposure, arising from the use of different product types together, Butylphenyl methylpropional at the proposed concentrations cannot be considered as safe. }}</ref>
+After animal studies found it to be [[Reproductive toxicity|toxic for reproduction]], it was reclassified as a prohibited substance in the EU, and banned from use in cosmetics as of March 2022.<ref>{{cite web |url=https://eur-lex.europa.eu/legal-content/EN/TXT/PDF/?uri=CELEX:32021R1902&from=EN |title=COMMISSION REGULATION (EU) 2021/1902 OF 29 October 2021 amending Annexes II, III and V to Regulation (EC) No 1223/2009 of the European Parliament and of the Council as regards the use of cosmetic products of certain substances classified as carcinogenic, mutagenic or toxic for reproduction |access-date=2022-01-03 | quote= CAS No. 80-54-6}}</ref>
 It can sometimes act as an [[allergen]] and may cause [[contact dermatitis]] in susceptible individuals.

Latest revision as of 10:38, 23 December 2024

Synthesis

Properties

Safety

See also

References