Dibenzylideneacetone

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Dibenzylideneacetone
(1E,4E)-1,5-diphenylpenta-1,4-dien-3-one 200.svg
Dibenzylideneacetone-3D-balls.png
Dibenzylideneacetone Crystals.jpg
Names
Preferred IUPAC name
(1E,4E)-1,5-Diphenylpenta-1,4-dien-3-one
Other names
Dibenzalacetone
Identifiers
3D model (JSmol)
ChEMBL
ChemSpider
ECHA InfoCard 100.126.050 OOjs UI icon edit-ltr-progressive.svg
PubChem CID
UNII
  • 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
  • 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
C17H14O
Molar mass 234.29 g/mol
AppearanceYellow solid
Melting point
  • 111 °C (232 °F; 384 K) (trans, trans isomer) [1]
  • 60 °C (140 °F; 333 K) (cis, trans isomer) [1]
Boiling point 130 °C (266 °F; 403 K) (cis, cis isomer) [1]
Insoluble
Solubility in other solventsSoluble 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 °C [77 °F], 100 kPa).
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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.

Contents

It was first prepared in 1881 by the German chemist Rainer Ludwig Claisen (1851–1930) and the Swiss chemist Charles-Claude-Alexandre Claparède (14 April 1858 – 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]

Synthesis Dibenzylideneaceton.svg

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.

Related Research Articles

<span class="mw-page-title-main">Ester</span> Compound derived from an acid

In chemistry, an ester is a compound derived from an acid in which the hydrogen atom (H) of at least one acidic hydroxyl group of that acid is replaced by an organyl group. These compounds contain a distinctive functional group. Analogues derived from oxygen replaced by other chalcogens belong to the ester category as well. According to some authors, organyl derivatives of acidic hydrogen of other acids are esters as well, but not according to the IUPAC.

Mesitylene or 1,3,5-trimethylbenzene is a derivative of benzene with three methyl substituents positioned symmetrically around the ring. The other two isomeric trimethylbenzenes are 1,2,4-trimethylbenzene (pseudocumene) and 1,2,3-trimethylbenzene (hemimellitene). All three compounds have the formula C6H3(CH3)3, which is commonly abbreviated C6H3Me3. Mesitylene is a colorless liquid with sweet aromatic odor. It is a component of coal tar, which is its traditional source. It is a precursor to diverse fine chemicals. The mesityl group (Mes) is a substituent with the formula C6H2Me3 and is found in various other compounds.

<span class="mw-page-title-main">Acetone peroxide</span> Chemical compound

Acetone peroxide is an organic peroxide and a primary explosive. It is produced by the reaction of acetone and hydrogen peroxide to yield a mixture of linear monomer and cyclic dimer, trimer, and tetramer forms. The monomer is dimethyldioxirane. The dimer is known as diacetone diperoxide (DADP). The trimer is known as triacetone triperoxide (TATP) or tri-cyclic acetone peroxide (TCAP). Acetone peroxide takes the form of a white crystalline powder with a distinctive bleach-like odor when impure, or a fruit-like smell when pure, and can explode powerfully if subjected to heat, friction, static electricity, concentrated sulfuric acid, strong UV radiation, or shock. Until about 2015, explosives detectors were not set to detect non-nitrogenous explosives, as most explosives used preceding 2015 were nitrogen-based. TATP, being nitrogen-free, has been used as the explosive of choice in several terrorist bomb attacks since 2001.

<span class="mw-page-title-main">Cinnamic acid</span> Chemical compound

Cinnamic acid is an organic compound with the formula C6H5-CH=CH-COOH. It is a white crystalline compound that is slightly soluble in water, and freely soluble in many organic solvents. Classified as an unsaturated carboxylic acid, it occurs naturally in a number of plants. It exists as both a cis and a trans isomer, although the latter is more common.

The Perkin reaction is an organic reaction developed by English chemist William Henry Perkin in 1868 that is used to make cinnamic acids. It gives an α,β-unsaturated aromatic acid or α-substituted β-aryl acrylic acid by the aldol condensation of an aromatic aldehyde and an acid anhydride, in the presence of an alkali salt of the acid. The alkali salt acts as a base catalyst, and other bases can be used instead.

Barbituric acid or malonylurea or 6-hydroxyuracil is an organic compound based on a pyrimidine heterocyclic skeleton. It is an odorless powder soluble in water. Barbituric acid is the parent compound of barbiturate drugs, although barbituric acid itself is not pharmacologically active. The compound was first synthesised by Adolf von Baeyer.

The Claisen condensation is a carbon–carbon bond forming reaction that occurs between two esters or one ester and another carbonyl compound in the presence of a strong base. The reaction produces a β-keto ester or a β-diketone. It is named after Rainer Ludwig Claisen, who first published his work on the reaction in 1887. The reaction has often been displaced by diketene-based chemistry, which affords acetoacetic esters.

In organic chemistry, a cyanohydrin reaction is an organic reaction in which an aldehyde or ketone reacts with a cyanide anion or a nitrile to form a cyanohydrin. For example:

Chloral, also known as trichloroacetaldehyde or trichloroethanal, is the organic compound with the formula Cl3CCHO. This aldehyde is a colourless liquid that is soluble in a wide range of solvents. It reacts with water to form chloral hydrate, a once widely used sedative and hypnotic substance.

<span class="mw-page-title-main">Wilhelm Rudolph Fittig</span> German chemist (1835–1910)

Wilhelm Rudolph Fittig was a German chemist. He discovered the pinacol coupling reaction, mesitylene, diacetyl and biphenyl. Fittig studied the action of sodium on ketones and hydrocarbons. He discovered the Fittig reaction or Wurtz–Fittig reaction for the synthesis of alkylbenzenes, he proposed a diketone structure for benzoquinone and isolated phenanthrene from coal tar. He discovered and synthesized the first lactones and investigated structures of piperine, naphthalene, and fluorene.

<span class="mw-page-title-main">Benzylideneacetone</span> Chemical compound

Benzylideneacetone is the organic compound described by the formula C6H5CH=CHC(O)CH3. Although both cis- and trans-isomers are possible for the α,β-unsaturated ketone, only the trans isomer is observed. Its original preparation demonstrated the scope of condensation reactions to construct new, complex organic compounds. Benzylideneacetone is used as a flavouring ingredient in food and perfumes.

Picoline refers to any of three isomers of methylpyridine (CH3C5H4N). They are all colorless liquids with a characteristic smell similar to that of pyridine. They are miscible with water and most organic solvents.

In organic chemistry, the Claisen–Schmidt condensation is the reaction between an aldehyde or ketone having an α-hydrogen with an aromatic carbonyl compound lacking an α-hydrogen. It can be considered as a specific variation of the aldol condensation. This reaction is named after two of its pioneering investigators Rainer Ludwig Claisen and J. Gustav Schmidt, who independently published on this topic in 1880 and 1881. An example is the synthesis of dibenzylideneacetone ( -1,5-diphenylpenta-1,4-dien-3-one).

<span class="mw-page-title-main">Stobbe condensation</span>

The Stobbe condensation entails the reaction of an aldehyde or ketone with an ester of succinic acid to generate alkylidene succinic acid or related derivatives. The reaction consumes one equivalent of metal alkoxide. Commonly, diethylsuccinate is a component of the reaction. The usual product is salt of the half-ester. The Stobbe condensation is named after its discoverer, Hans Stobbe, whose work involved the sodium ethoxide-induced condensation of acetone and diethyl succinate.

Benzaldehyde (C6H5CHO) is an organic compound consisting of a benzene ring with a formyl substituent. It is among the simplest aromatic aldehydes and one of the most industrially useful.

<span class="mw-page-title-main">2-Nitrobenzaldehyde</span> Chemical compound

2-Nitrobenzaldehyde is an organic compound with the formula O2NC6H4CHO. It is one of three isomers of nitrobenzaldehyde. It contains a nitro group adjacent to the formyl group.

α-Phenylcinnamic acid Chemical compound

α-Phenylcinnamic acid is a phenylpropanoid, or, more specifically, a derivative of cinnamic acid. It has the formula C15H12O2 and appears as an off-white crystalline solid.

<span class="mw-page-title-main">Acetone oxime</span> Chemical compound

Acetone oxime (acetoxime) is the organic compound with the formula (CH3)2CNOH. It is the simplest example of a ketoxime. It is a white crystalline solid that is soluble in water, ethanol, ether, chloroform, and ligroin. It is used as a reagent in organic synthesis.

<span class="mw-page-title-main">Georg Städeler</span> German chemist (1821–1871)

Georg Andreas Karl Städeler was a German chemist.

References

  1. 1 2 3 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): 327–328. doi:10.1021/jo01048a529. ISSN   0022-3263.
  2. Claisen, L.; Claparède, A. (1881). "Ueber Verbindungen des Acetons und Mesityloxds mit Benzaldehyd und über 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: 349–353. doi:10.1002/cber.18810140182. ; see pp. 350–351.
  3. Claisen wrote that the German chemist Adolf Baeyer might have synthesized dibenzylideneacetone as early as 1866, although the evidence wasn't clear.
    • (Claisen & Claparède, 1881), p. 350: "Die Einwirkung wasserentziehender Mittel auf ein solches Gemenge ist schon von Baeyer1) flüchtig untersucht worden. Nach ihm entsteht als Endprodukt ein gelbes, in Alkohol unlösliches Harz, als Zwischenprodukt ein ölförmiger, unzersetzt siedender und cumarinartig riechender Körper, der, wie er meint, das Methylketon der Zimmtsäure 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): 79–95. ; see p. 82. From p. 82: "Um für diese Ansicht noch einen weiteren Beweis beizubringen, habe ich ein Gemenge von Bittermandelöl und Aceton mit wasserentziehenden Mitteln, Salzsäure, Schwefelsäure, 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 löslich und durch Alkohol daraus als gelbes Pulver gefällt wird, welches schwach nach Rhabarber riecht. Die Analyse gab keine verständlichen Zahlen, daher ist die Substanz wahrscheinlich ein Gemenge. Zuerst bildet sich aber ein öliger, unzersetzt flüchtiger Körper, der einen an Cumarin erinnernden Geruch besitzt, und der höchst wahrscheinlich das Methylaceton der Zimmtsäure ist: … ." (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: … .)
  4. For biographical information about Charles-Claude-Alexandre Claparède (with photograph), see: Reverdin, Frédéric (1914) "Dr. Alexandre Claparède. 1858–1913," Verhandlungen der Schweizerischen Naturforschenden Gesellschaft: Nekrologe und Biographien verstorbener Mitglieder … (Proceedings of the Swiss Society of Natural Sciences: Obituaries and biographies of deceased members … ), 96 : 22–27. (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.