Di-n-propyl ketone

Small quantities of the sjunmetrical ketones (CHjjjCO and (CHjCHjCHjjjCO (di-n-propyl ketone) are formed as by-products these can easily be removed by fractional distillation through an efficient column. An excess of the cheaper reagent, acetic acid, is employed the resulting acetone is readily removed by washing with water and little di-n-propyl ketone is formed under these conditions. 

Di-n-propyl ketone [123-19-3] M 114.2, b 143.5 , d 0.8143, n 1.40732. Dried with CaS04, then distd from P2O5 under nitrogen. 

Fig. 1. The effect of sodium oxide on the conversion of n-butyraldehyde to di-n-propyl ketone.

Attempts to trap other di-alkyl ketyl radicals from methyl-ethyl, di-ethyl, di-n-propyl and di-isopropyl ketones were unsuccessful. The observed spectrum was not that expected from the ketyl radical but in each case it could be identified as that of a radical formed by a hydrogen abstraction from the parent ketone. The structurally similar radicals, CH3—CH—CO—CHg and CH3—CH—CO—CHa—CHg, were formed from methyl-ethyl and di-ethyl ketone respectively and the radical (0113)2—C—CO—CH—(0113)2 was formed by abstraction of the tertiary hydrogen from di-isopropyl ketone. The reaction of di-n-propyl ketone was somewhat unexpected as the spectrum obtained was typical of that for an allyl radical rather than an alkyl radical. It is possible that the allyl radical was formed by abstraction of a hydrogen adjacent to the carboxyl group in a parent molecule followed by an intramolecular rearrangement. Thus... 

In general, the yields in aluminum isopropoxide reductions range from 80 to 100%. With a few low-boiling ketones difficulty may be experienced in separating the resulting alcohol from isopropyl alcohol thus the yields of reduction products from diethyl ketone and methoxyacetone are reported to be 60% and 40%, respectively. Di-n-propyl ketone, on the other hand, gives a 92% yield of the carbinol. As would be expected, side reactions are more significant and the yields are consequently lower when extremely sensitive compounds, such as unsaturated aldehydes and the carotenoids, are reduced. 

CO, CH4, CO2, acetone, ketene. ethene. propene. 1-butene, benzene, toluene, xylene, cydopentene, methyl ethyl ketone, diethyl ketone, methyl-n-propyl ketone, di-n-propyl ketone, methyl vinyl ketone, methyl Isopropenyl ketone, methyl isopropyl ketone, ethyl vinyl ketone, trace amounts of methyl-n-bulyl ketone, cyclopentanone, cydohexanone. acrolein, ethanal. butanal. chain fragments, some monomer CO. CH4, COj, ketene, 1-butene, propene, acetone, methyl ethyl ketone, methyl n-propyl ketone, 1,4-cyclohexadiene. toluene, l-methy. l.3-cydohexadlene, 2-hexanone, cydopentene, 1-methyl cydopentene. mesityl oxide, xylenes, benzene, ethene, cyclopentanone, 1.3-cyclopentad iene, diethyl ketone, short chain fragments, traces of monomer CO, CH4, COi, ketene, 1-butene, propene, acetone, methyl ethyl ketone, methyl isopropyl ketone, methyl-n-propyl ketone, diethyl ketone, methyl propenyl ketone, 3-hexanone. toluene, 2-hexanone. 1,3-cydopentadiene, cyclopentanone, 2-melhylcydopenlanone, mesityl oxide, xylenes, benzene, propionaldehyde, acrolein, acetaldehyde ethene, short chain fragments, traces of monomer CO, COj, H2O, CH4. acetone, ketene, ethene, propylene, 1-butene, methyl vinyl ketone, benzene, acrylic add, toluene, xylene, short chain fragments such as dimer to octamer with unsaturated and anhydride functionalities... 

---