Acetaldoxime

Acetaldoxime
Names
IUPAC name
N-ethylidenehydroxylamine
Other names
aldoxime, acetaldehyde oxime, ethanal oxime, ethylidenehydroxylamine
Identifiers
107-29-9
3D model (Jmol) Interactive image
1209252
ChEBI CHEBI:28465
ChemSpider 4481813
ECHA InfoCard 100.003.164
EC Number 203-479-6
PubChem 5324279
RTECS number AB2975000
UNII ME6U10SD7D YesY
Properties
C2H5NO
Molar mass 59.067 g mol−1
Appearance clear, colorless to yellow liquid
Density 0.97 g cm−3
Melting point 25 °C (77 °F; 298 K) (average of the α and β forms)
Boiling point 115.24 °C (239.43 °F; 388.39 K)
299 g L−1
Solubility in ethanol miscible
log P -0.13
Vapor pressure 13 mmHg
Acidity (pKa) 11.82
Hazards
Main hazards Flammable, harmful by ingestion, irritant
Safety data sheet External MSDS
NFPA 704
Flammability code 2: Must be moderately heated or exposed to relatively high ambient temperature before ignition can occur. Flash point between 38 and 93 °C (100 and 200 °F). E.g., diesel fuel Health code 2: Intense or continued but not chronic exposure could cause temporary incapacitation or possible residual injury. E.g., chloroform Reactivity code 0: Normally stable, even under fire exposure conditions, and is not reactive with water. E.g., liquid nitrogen Special hazards (white): no codeNFPA 704 four-colored diamond
2
2
0
Flash point 40 °C (104 °F; 313 K)
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
Infobox references

Acetaldoxime is the chemical compound with formula C2H5NO. It is one of the simplest oxime-containing compounds, and has a wide variety of uses in chemical synthesis.

Properties

Acetaldoxime will often appear as a colorless liquid, or a white solid. Its solid can form two different crystallize modifications with needle-like structures, one melting at approximately 44°C-47°C for the alpha form, and 12°C for the beta form. The liquid is known to have a pungent odor, and is highly flammable. The compound can act as both an acid or a base, due to its acidic proton on the hydroxyl group and the basic nitrogen atom. The compound exists as a mixture of its Z and E stereoisomers (i.e. syn and anti, or cis and trans) in its normal form. The E stereoisomer can be isolated by slow crystallization of a distilled E/Z mixture.[1][2]

Production

Acetaldoxime can be prepared by combining pure acetaldehyde and hydroxylamine under heating in the presence of a base.[3]

The use of CaO for preparation of oximes has also been examined. It has been found that CaO react with various types of ketones and aldehydes under mild condition to give the corresponding oximes in a quantitative yield. CaO as an efficient reagent for the production of oximes from ketones and aldehydes in solid rate.[4]

Reactions

A. Alkylation of Acetaldoxime

Deprotonation of acetaldoxime with 2 equiv of n-Butyllithium at -78 °C generates the dianion which reacts with Benzyl Bromide or 1-iodopropane to give excellent yields of a-alkylated (Z)-oximes.[5] a,a-Dialkylation by further alkylation in similar way has been achieved.[5] It is generally known that ketone oximes can be deprotonated and alkylated regiospecifically syn to the oxime hydroxy group.[6][7] It is essential to perform the deprotonation and alkylation at -78 °C as otherwise no a-alkylated oximes are isolated, the major byproducts being nitriles.[6]

B. Rearrangement into Acetamide

Heating of acetaldoxime in xylene in the presence of 0.2 mol % nickel(II) acetate[1] or silica gel[8] as catalyst caused isomerization into acetamide.

C. Synthesis of Heterocycles

Chlorination of acetaldoxime with N-chlorosuccinimide[9] or chlorine gas[7][10] in chloroform affords acetohydroxamic acid chloride, which suffers dehydrochlorination with Triethylamine to give acetonitrile N-oxide. The latter 1,3-dipole undergoes 1,3-dipolar cycloaddition to alkenes giving 2-isoxazolines in a one-pot procedure.[9] This reaction is also suitable for the construction of more complex molecules such as the conversion of a 6-ethylideneolivanic acid derivative into the corresponding spiroisoxazoline.[10]

Uses

Aldoximes such as acetylaldoxime are using during chemical synthesis processes as intermediates for chemical reactions. It is especially notable for its commercial application as an intermediate for the production of pesticides.[11]

References

  1. 1 2 Field, L.; Hughmark, P. B.; Shumaker, S. H.; Marshall, W. S. J. Am. Chem. Soc. 1961, 83, 1983.
  2. ↑ http://www.theodora.com/encyclopedia/o/oximes.html
  3. ↑ http://www.wiley.com/legacy/wileychi/eros/a004.html
  4. ↑ Sharghi, H., & Sarvari, M. H.. A mild and versatile method for the preparation of pximes by use of calcium oxide. J. Chem. Research, 2000, pp. 24—25.
  5. 1 2 Gawley, R. E.; Nagy, T. TL. 1984, 25, 263.
  6. 1 2 Kofron, W. G.; Yeh, M. K. J. Org. Chem. 1976, 41, 439.
  7. 1 2 Mukerji, S. K.; Sharma, K. K.; Torssell, K. B. G. T. 1983, 39, 2231.
  8. ↑ Chattopadhyaya, J. B.; Rama Rao, A. V. T. 1974, 30, 2899.
  9. 1 2 Larsen, K. E.; Torssell, K. B. G. T. 1984, 40, 2985.
  10. 1 2 Corbett, D. F. J. Chem. Soc. 1986, 421.
  11. ↑ http://www.google.com/patents?hl=en&lr=&vid=USPAT4323706&id=Bs84AAAAEBAJ&oi=fnd&dq=production+of+acetaldoxime+production+OR+of+OR+acetaldoxime&printsec=abstract#v=onepage&q=production%20of%20acetaldoxime%20production%20OR%20of%20OR%20acetaldoxime&f=false
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