Diketene

Diketene is an organic compound with the molecular formula C₄H₄O₂, and which is sometimes written as (CH₂CO)₂. It is formed by dimerization of ketene, H₂C=C=O. Diketene is a member of the oxetane family. It is used as a reagent in organic chemistry.[1] It is a colorless liquid.

Diketene

Names
IUPAC name 4-Methylideneoxetan-2-one
Other names γ-Methylenepropiolactone
Identifiers
CAS Number	674-82-8^Y
3D model (JSmol)	Interactive image
ChemSpider	12140^Y
ECHA InfoCard	100.010.562
EC Number	211-617-1
PubChem CID	12661
RTECS number	RQ8225000
UNII	0DZ97C3Z7D
UN number	2521
CompTox Dashboard (EPA)	DTXSID9027289
InChI InChI=1S/C4H4O2/c1-3-2-4(5)6-3/h1-2H2^Y Key: WASQWSOJHCZDFK-UHFFFAOYSA-N^Y InChI=1/C4H4O2/c1-3-2-4(5)6-3/h1-2H2 Key: WASQWSOJHCZDFK-UHFFFAOYAM
SMILES O=C1OC(=C)C1
Properties
Chemical formula	C4H4O2
Molar mass	84.074 g·mol^−1
Density	1.09 g cm^−3
Melting point	−7 °C (19 °F; 266 K)
Boiling point	127 °C (261 °F; 400 K)
Viscosity	0.88 mPa.s
Hazards
GHS pictograms
GHS Signal word	Danger
GHS hazard statements	H226, H301, H302, H315, H318, H330, H331, H332, H335
GHS precautionary statements	P210, P233, P240, P241, P242, P243, P260, P261, P264, P270, P271, P280, P284, P301+310, P301+312, P302+352, P303+361+353, P304+312, P304+340, P305+351+338, P310, P311, P312, P320, P321
Flash point	33 °C (91 °F; 306 K)
Autoignition temperature	275
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
Y verify (what is ^YN ?)
Infobox references

Production

Ketene is generated by dehydrating acetic acid at 700–750 °C in the presence of triethyl phosphate as a catalyst or by the thermolysis of acetone at 600–700 °C in the presence of carbon disulfide as a catalyst.[2]

${\displaystyle {\begin{array}{lclrr}\\{\ce {CH3CO2H}}&{\ce {->[{\overset {\text{triethyl phosphate}}{\ce {(CH3CH2O)3PO}}}][{\text{700–750 °C}}]}}&{\ce {{\underset {ketene}{H2C=C=O}}+H2O}}&&\Delta H=+147{\text{ kJ mol}}^{-1}\\{}\\{\ce {CH3COCH3}}&{\ce {->[{\overset {\text{carbon disulfide}}{\ce {CS2}}}][{\text{600–700 °C}}]}}&{\ce {{H2C=C=O}+CH4}}\\{}\end{array}}}$

The dimerization to diketene proceeds spontaneously at room temperature:

2 H₂C=C=O → C₄H₄O₂

Reactions

Heating or irradiation with UV light[3] regenerates the ketene monomer:

(C₂H₂O)₂   ⇌   2 CH₂CO

Alkylated ketenes also dimerize with ease and form substituted diketenes.

Diketene readily hydrolyzes in water forming acetoacetic acid. Its half-life in water is approximately 45 min. a 25 °C at 2 < pH < 7.[4]

Certain diketenes with two aliphatic chains, such as alkyl ketene dimers (AKDs), are used industrially to improve hydrophobicity in paper.

At one time acetic anhydride was prepared by the reaction of ketene with acetic acid:[2]

H₂C=C=O   +   CH₃COOH   →   (CH₃CO)₂O     ΔH = −63 kJ mol⁻¹

Acetoacetylation

Diketene also reacts with alcohols and amines to the corresponding acetoacetic acid derivatives. The process is sometimes called acetoacetylation. An example is the reaction with 2-aminoindane:[5]

Diketene is an important industrial intermediate used for the production of acetoacetate esters and amides as well as substituted 1-phenyl-3-methylpyrazolones. The latter are used in the manufacture of dyestuffs and pigments.[6] A typical reaction is:

ArNH₂   +   (CH₂CO)₂   →   ArNHC(O)CH₂C(O)CH₃

These acetoacetamides are precursors to arylide yellow and diarylide pigments.[7]

Use

Diketenes with two alkyl chains are used in the manufacture of paper for sizing of paper in order to improve their printability (by hydrophobization). Besides the rosin resins with about 60% share of world consumption, long chain diketenes called alkylketene dimers (AKD) are with 16% share the most important synthetic paper sizes, they are usually used in concentrations of 0.15%, meaning 1.5 kg solid AKD/t paper.

The preparation of AKD is carried out by chlorination of long chain fatty acids (such as stearic acid, using chlorinating agents such as thionyl chloride) to give the corresponding acid chlorides and subsequent elimination of HCl by amines (for example triethylamine) in toluene or other solvents:[8]

Furthermore, diketenes are used as intermediates in the manufacture of pharmaceuticals, insecticides and dyes. For example pyrazolones are formed from substituted phenylhydrazines, they were used as analgetics but are now largely obsolete. With methylamine diketenes reacts to N,N'-dimethylacetoacetamide which is chlorinated with sulfuryl chloride and reacted with trimethyl phosphite to the highly toxic insecticide monocrotophos (especially toxic to bees). Diketenes react with substituted aromatic amines to acetoacetanilides, which are important precursors for mostly yellow, orange or red azo dyes and azo pigments.

Exemplary for the synthesis of arylides by the reaction of diketenes with aromatic amines is:

Aromatic diazonium coupling with arylides to form azo dyes, such as Pigment Yellow 74:

The industrial synthesis of the sweetener acesulfam-K is based on the reaction of diketene with sulfamic acid and cyclization by sulfur trioxide (SO₃).[9]

Safety

Despite its high reactivity as an alkylating agent, and unlike analogue β-lactones propiolactone and β-butyrolactone, diketene is inactive as a carcinogen, possibly due to the instability of its DNA adducts.[10]

References

1. Beilstein E III/IV 17: 4297.
2. Arpe, Hans-Jürgen (2007), Industrielle organische Chemie: Bedeutende vor- und Zwischenprodukte (in German) (6th ed.), Weinheim: Wiley-VCH, pp. 200–1, ISBN 3-527-31540-3
3. Susana Breda; Igor Reva; Rui Fausto (2012). "UV Induced Unimolecular Photochemistry of Diketene Isolated in Cryogenic Inert Matrices". J. Phys. Chem. A. 116 (9): 2131–2140. doi:10.1021/jp211249k.
4. Rafael Gómez-Bombarelli; Marina González-Pérez; María Teresa Pérez-Prior; José A. Manso; Emilio Calle; Julio Casado (2008). "Kinetic Study of the Neutral and Base Hydrolysis of Diketene". J. Phys. Org. Chem. 22 (5): 438–442. doi:10.1002/poc.1483.
5. Kiran Kumar Solingapuram Sai; Thomas M. Gilbert; Douglas A. Klumpp (2007). "Knorr Cyclizations and Distonic Superelectrophiles". J. Org. Chem. 72 (25): 9761–9764. doi:10.1021/jo7013092. PMID 17999519.
6. Ashford's Dictionary of Industrial Chemicals, Third Edition, 2011, pages 3241-2.
7. Hunger, K.; Herbst, W. (2012). "Pigments, Organic". Ullmann's Encyclopedia of Industrial Chemistry. Weinheim: Wiley-VCH. doi:10.1002/14356007.a20_371.
8. Wolf S. Schultz: Sizing Agents in Fine Paper Abgerufen am 1. März 2012.
9. EP 0218076 Process for the preparation of the non-toxic salts of 6-methyl-3,4-dihydro-1,2,3-oxathiazin-4-on-2,2-dioxide.
10. Rafael Gómez-Bombarelli; Marina González-Pérez; María Teresa Pérez-Prior; José A. Manso; Emilio Calle; Julio Casado (2008). "Chemical Reactivity and Biological Activity of Diketene". Chem. Res. Toxicol. 21 (10): 1964–1969. doi:10.1021/tx800153j. PMID 18759502.