Dibenzylideneacetone

Chemical compound From Wikipedia, the free encyclopedia

Dibenzylideneacetone or dibenzalacetone, often abbreviated dba, is an organic compound with the formula C₁₇H₁₄O. It is a pale-yellow solid insoluble in water, but soluble in ethanol.

Quick facts Names, Identifiers ...

Dibenzylideneacetone
Names



Preferred IUPAC name (1E,4E)-1,5-Diphenylpenta-1,4-dien-3-one
Other names Dibenzalacetone
Identifiers
CAS Number	538-58-9 non-specific^Y 35225-79-7 (E,E)^Y 115587-57-0 (E,Z)^Y 58321-78-1 (Z,Z)^Y
3D model (JSmol)	undefined: Interactive image (E,E): Interactive image (E,Z): Interactive image (Z,Z): Interactive image
ChEMBL	ChEMBL17201 (E,E)^N
ChemSpider	86113 undefined^N 555548 (E,E)^N 1266463 (E,Z)^N 1266462 (Z,Z)^N
ECHA InfoCard	100.126.050
PubChem CID	95417 undefined 640180 (E,E) 1549622 (E,Z) 1549621 (Z,Z)
UNII	9QXO7BCY9L (E,E)^Y N4SH2VDI6Y (E,Z)^Y 5L4OCE3E5U (Z,Z)^Y
CompTox Dashboard (EPA)	DTXSID401274418
InChI undefined: InChI=1S/C17H14O/c18-17(13-11-15-7-3-1-4-8-15)14-12-16-9-5-2-6-10-16/h1-14H Key: WMKGGPCROCCUDY-UHFFFAOYSA-N (E,E): InChI=1S/C17H14O/c18-17(13-11-15-7-3-1-4-8-15)14-12-16-9-5-2-6-10-16/h1-14H/b13-11+,14-12+ Key: WMKGGPCROCCUDY-PHEQNACWSA-N (E,Z): InChI=1S/C17H14O/c18-17(13-11-15-7-3-1-4-8-15)14-12-16-9-5-2-6-10-16/h1-14H/b13-11-,14-12+ Key: WMKGGPCROCCUDY-HEEUSZRZSA-N (Z,Z): InChI=1S/C17H14O/c18-17(13-11-15-7-3-1-4-8-15)14-12-16-9-5-2-6-10-16/h1-14H/b13-11-,14-12- Key: WMKGGPCROCCUDY-XSYHWHKQSA-N
SMILES undefined: O=C(C=Cc1ccccc1)C=Cc2ccccc2 (E,E): O=C(/C=C/c1ccccc1)/C=C/c2ccccc2 (E,Z): O=C(\C=C\c1ccccc1)/C=C\c2ccccc2 (Z,Z): O=C(/C=C\c1ccccc1)/C=C\c2ccccc2
Properties
Chemical formula	C₁₇H₁₄O
Molar mass	234.29 g/mol
Appearance	Yellow solid
Melting point	111 Â°C (232 Â°F; 384 K) (trans, trans isomer)^[1] 60 Â°C (140 Â°F; 333 K) (cis, trans isomer)^[1]
Boiling point	130 Â°C (266 Â°F; 403 K) (cis, cis isomer)^[1]
Solubility in water	Insoluble
Solubility in other solvents	Soluble in acetone and chloroform, slightly soluble in ethanol.
Hazards
Occupational safety and health (OHS/OSH):
Main hazards	Irritant
Except where otherwise noted, data are given for materials in their standard state (at 25 Â°C [77 Â°F], 100 kPa). N verify (what is ^YN ?) Infobox references

It was first prepared in 1881 by the German chemist Rainer Ludwig Claisen (1851â1930) and the Swiss chemist Charles-Claude-Alexandre ClaparÃ¨de (14 April 1858 â 1 November 1913).^[2]^[3]^[4]

Preparation

The trans,trans isomer can be prepared in high yield and purity by condensation of benzaldehyde and acetone with sodium hydroxide in a water/ethanol medium followed by recrystallization.^[5]

This reaction, which proceeds via the intermediacy of benzylideneacetone, is often performed in organic chemistry classes,^[6] and is called Claisen-Schmidt condensation.

Reactions and derivatives

Prolonged exposure to sunlight initiates [2+2] cycloadditions, converting it to a mixture of dimeric and trimeric cyclobutane cycloadducts.^[7]

Uses

Dibenzylideneacetone is used as a component in sunscreens and as a ligand in organometallic chemistry.

For example, it is a component of the catalyst tris(dibenzylideneacetone)dipalladium(0). It is a labile ligand that is easily displaced by triphenylphosphine, hence it serves a useful entry point into palladium(0) chemistry.

References

[1]
Dinwiddie, J. G. Jr.; White, H. M.; Day, W. J. (1 January 1962). "The Geometrical Isomers of 1,5-Diphenylpentadiene-3-one". The Journal of Organic Chemistry. 27 (1): 327â328. doi:10.1021/jo01048a529. ISSN 0022-3263.
[2]
Claisen, L.; ClaparÃ¨de, A. (1881). "Ueber Verbindungen des Acetons und Mesityloxds mit Benzaldehyd und Ã¼ber die Constitution des Acetophorons" [On compounds of acetone and mesityl oxide with benzaldehyde and on the composition of phorone]. Berichte der Deutschen Chemischen Gesellschaft (in German). 14: 349â353. doi:10.1002/cber.18810140182. ; see pp. 350â351.
[3]
Claisen wrote that the German chemist Adolf Baeyer might have synthesized dibenzylideneacetone as early as 1866, although the evidence wasn't clear.
(Claisen & ClaparÃ¨de, 1881), p. 350: "Die Einwirkung wasserentziehender Mittel auf ein solches Gemenge ist schon von Baeyer¹) flÃ¼chtig untersucht worden. Nach ihm entsteht als Endprodukt ein gelbes, in Alkohol unlÃ¶sliches Harz, als Zwischenprodukt ein Ã¶lfÃ¶rmiger, unzersetzt siedender und cumarinartig riechender KÃ¶rper, der, wie er meint, das Methylketon der ZimmtsÃ¤ure darstellt." (The effect of a dehydrating agent on such a mixture has already been briefly investigated by Baeyer¹). According to him, a yellow resin [that's] insoluble in alcohol arises as a final product, [and] as an intermediate, [there arises] an oily substance [which] boils without decomposing and smells like coumarin [and] which, he thinks, represents the methyl ketone of cinnamic acid.)

Baeyer, Adolf (1866). "Ueber Condensation und Polymerie" [On condensation and polymerism]. Annalen der Chemie und Pharmacie (in German). 5 (Supplement): 79â95. ; see p. 82. From p. 82: "Um fÃ¼r diese Ansicht noch einen weiteren Beweis beizubringen, habe ich ein Gemenge von BittermandelÃ¶l und Aceton mit wasserentziehenden Mitteln, SalzsÃ¤ure, SchwefelsÃ¤ure, Kali behandelt. Die Condensation erfolgt ausserordentlich schnell, schon nach wenigen Minuten, und nach einiger Zeit verharzt die ganze Masse. Das Endproduct ist ein gelbes Harz, das in Aether lÃ¶slich und durch Alkohol daraus als gelbes Pulver gefÃ¤llt wird, welches schwach nach Rhabarber riecht. Die Analyse gab keine verstÃ¤ndlichen Zahlen, daher ist die Substanz wahrscheinlich ein Gemenge. Zuerst bildet sich aber ein Ã¶liger, unzersetzt flÃ¼chtiger KÃ¶rper, der einen an Cumarin erinnernden Geruch besitzt, und der hÃ¶chst wahrscheinlich das Methylaceton der ZimmtsÃ¤ure ist: â¦ ." (In order to provide further proof for this view, I have treated a mixture of benzaldehyde and acetone with dehydrating agents [e.g.,] hydrochloric acid, sulfuric acid, potash. The condensation occurs extraordinarily quickly, after just a few minutes, and after some time the whole mass becomes resinous. The final product is a yellow resin, which [is] soluble in ether and is precipitated therefrom by alcohol as a yellow powder, which smells faintly of rhubarb. Analysis [to determine its empirical formula] produced no intelligible numbers, so the substance is probably a mixture. Initially, however, an oily, stable, volatile substance is formed, which has a smell recalling coumarin, and which is very likely the methyl acetone of cinnamic acid: â¦ .)
[4]
For biographical information about Charles-Claude-Alexandre ClaparÃ¨de (with photograph), see: Reverdin, FrÃ©dÃ©ric (1914) "Dr. Alexandre ClaparÃ¨de. 1858â1913," Verhandlungen der Schweizerischen Naturforschenden Gesellschaft: Nekrologe und Biographien verstorbener Mitglieder â¦ (Proceedings of the Swiss Society of Natural Sciences: Obituaries and biographies of deceased members â¦ ), 96 : 22â27. (in French)
[5]
Conard, C. R.; Dolliver, M. A. (1943). "Dibenzalacetone". Organic Syntheses; Collected Volumes, vol. 2, p. 167.
[6]
Hull, L. A. (February 2001). "The Dibenzalacetone Reaction Revisited". J. Chem. Educ. 78 (2): 226. Bibcode:2001JChEd..78..226H. doi:10.1021/ed078p226.
[7]
Rao, G. N.; Janardhana, C.; Ramanathan, V.; Rajesh, T.; Kumar, P. H. (November 2006). "Photochemical Dimerization of Dibenzylideneacetone. A Convenient Exercise in [2+2] Cycloaddition Using Chemical Ionization Mass Spectrometry". J. Chem. Educ. 83 (11): 1667. Bibcode:2006JChEd..83.1667R. doi:10.1021/ed083p1667.

Related Articles