April, 1954] The Condensation of Benzaldehyde with Methyl Ethyl Ketone 131

The Condensation of Benzaldehyde with Methyl Ethyl Ketone by Aqueous

Sodium Hydroxide
By Hiroshi MIDORIKAWA
(Received
November4, 1953)
Harries and Miiller1) demonstrated that, The semicarbazone melting at 218∼219° was

when aqueous sodium hydroxide was em- identified with that of 3-methyl-4-phenyl-3-
ployed as the condensing agent, benzaldehyde buten-2-one obtained by condensing ben-
condensed with methyl ethyl ketone at the zaldehyde with methyl ethyl ketone by hy-
α-methyl group of the ketone at ordinary drogen chloride. Consequently, it was con-
temperature, forming 1-phenyl-1-penten-3-one, firmed that the condensation products at the
and, when hydrogen chloride was employed reaction temperature 3∼5° were a larger

as the condensing agent, benzaldehyde re- amount of 3-methyl-4-phenyl-4-butanol-2-one

acted with methyl ethyl ketone at its α- (II) and a smaller amount of 1-phenyl-1-pen-

methylene group, giving 3-methyl-4-phenyl-3- tanol-3-one (III), and, on the dehydration with

buten-2-one. acetic anhydride, gave the corresponding un-

saturated ketones, 3-methyl-4-phenyl-3-buten-

In the preceding report2), it was indicated
2-one (IV) and 1-phenyl-1-penten-3-one (I).
that furfural condensed with methyl ethyl
Furthermore, 3-methyl-4-phenyl-3-buten-2-
ketone chiefly by aqueuos sodium hydroxide
one was oxidized by sodium hypochlorite to
at its methylene group at the lowered reac-
-methylcinnamic acid (V) ƒ¿
tion temperature 0∼5°, giving the chief prod- , while 1-phenyl-1-

penten-3-one (I) was not acted upon by this

uct 4-(2-furyl)-3-methyl-4-butanol-2-one, where-
oxidizing agent.
as furfural condensed with the ketone chiefly
The overall reactions are illustrated by the
at its α-methyl group at the elevated reac-
following formulation.
tion temperature 60∼65°, giving 1-(2-furyl)-
3-Methyl-4-phenyl-3-buten-2-one (IV) and 1-
1-penten-3-one.
phenyl-1-penten-3-one (I) obtained here gave
In the present experiment, the condensa-
respective 2,4-dinitrophenylhydrazones. It
tion of benzaldehyde with methyl ethyl ketone
was of interest that the mixture of the aldoll
by aqueous sodium hydroxide at lowered and
condensation products at the reaction tem-
elevated reaction temperatures was studied
perature 3∼5°, on the reaction with 2,4-dini-
in order to compare it with the result of
trophenylhydrazine in methanolic sulfuric
furfural in the preceding report2).
acid, gave the 2,4-dinitrophenylhydrazones of
At the elevated reaction temperature 60∼
1-phenyl-1-penten-3-one (I) and benzaldehyde,
65°,the condensation of benzaldehyde with
but no 2,4-dinitrophenylhydrazone of 3-methyl-
methyl ethyl ketone gave only 1-phenyl-1- 4-phenyl-3-buten-2-one (IV). This result ap-
penten-3-one (I) as illustrated below, since peared to indicate that, under such a reac-
this condensation product afforded an oxime tion condition, 1-phenyl-1-pent anol-3-one (III)
melting at 86∼87° which was identical with
gave 2,4-dinitrophenylhydrazone of 1-phenyl-
that of 1-phenyl-1-penten-3-one obtained by 1-penten-3-one (I) with simultaneous dehy-
Harries and Mu11er.1) The semicarbazone of dration, and 3-methyl-4-phenyl-4-butanol-2-
this ketone melted at 181∼182°.
one (II) initially dissociated to methyl ethyl
At the lowered reaction temperature 3∼5°, ketone and benzaldehyde, which subsequently
benzaldehyde and methyl ethyl ketone under- gave its 2,4-dinitrophenylhydrazone.
went aldol condensation by sodium hydroxide,
giving a mixture of 3-methyl-4-phenyl-4-but- Experimental
anol-2-one (II) and 1-phenyl-1-pentanol-3-one Condensation at Reaction Temperature 3∼

(III), as illustrated below. The mixture of 5° Into a stirred suspension of benzaldehyde

these condensation products gave no semicar- (20 g.) and methyl ethyl ketone (40 g.) in water
bazone, but, after the dehydration with acetic (300 cc.) was at once introduced 10% aqueous
sodium hydroxide(15 cc.)at 3°. The reaction
anhydride, gave a mixture of a semicarbazone
was complete after prolonged stirring for 6 hrs.
melting at 218∼219° in a larger proportion
at 3∼5°. The reaction mixture was neutralized
and the semicarbazone(m.p.181∼182°)of 1-
with dilute sulfuric acid, the oily layer separated
phenyl-1-penten-3-one in a smaller proportion. and the aqueous solution extracted twice with
1) C. Harries and G. H. Miller. Bor., 35, 966 (1902). ether. The oily layer and the ether extract were
2) H. Midorikawa. This Bulletin, 26, 460 (1953). combined and dried over anhydrous sodium sul-
132 Hiroshi MIDORIKAWA [Vol. 27, No. 3

α-methylcinnamic acid

fate. Fractionation of the ethereal solution gave ourless crystals(0.4 g.), which was recrystallised
apale yellow liquid(25 g.), b.p.122∼129°/6 mm. from methanol as plates, m.p.218∼219°, unde-

This fraction was considered to consist of 3- pressed on admixture with the semicarbazone of
methyl-4-phenyl-4-butanol-2-one (II) in a larger 3-methyl-4-phenyl-3-buten-2-one (IV) indicated
proportion and 1-phenyl-1-pentanol-3-one (III) in a below. The filtrate on standing overnight gave
smaller proportion. Calcd. for C11H14O2: C, 74.11 colourless crystals (0.1 g.), which were recry-
H, 7.92; Found : C, 72.22, H, 7.67%. stallised twice from methanol in needles, m.p.
This analysis appeared to show that this frac- 181∼182°. This specimen was identical with the
tion contains a small quantity of the , dehydrated semicarbazone of 1-phenyl-1-penten-3-one (I).
ketones C11H12O, but the fraction gave no semi- The oil (1 g.), above mentioned was suspended
carbazone. From this fraction were obtained two in an aqueous sodium hypochlorite solution2) (8 cc.)
2,4-dinitrophenylhydrazones in equal proportions, at ordinary temperature with occasional shaking
which were readily separable from each other for 2 days. The reaction mixture was freed of
by the difference of the solubility in nitrobenzene. oily matter by extraction with ether, and acidified
The more soluble one crystallised in red needles, with dilute hydrochloric acid to yield crystals
m.p.212.213°, undepressed on admixture with (0.3 g.) on cooling, which were recrystallised from
2,4-dinitrophenylhydrazone of 1-phenyl-1-penten- water as colourless prisms, m.p.77∼78°. This

3-one (I) as indicated below. The less soluble specimen was identified with α-methylcinnamic
one formed orange prisms melting at 235∼236°, acid (V);lit3)., m.p.78°. Calcd. for C10H10O2:
undepressed on admixture with benzaldehyde 2,4- C, 74.04, H, 6.22%; Found : C, 73.96, H, 6.11%.
dinitrophenylhydrazone.
Cndensation at the Reaction Temperature
Dehydration of the Condensation Product at 60∼65° Into a stirred suspension of benzalde-
the Reaction Temperature 3∼5C° The forego- hyde (15 g.) and methyl ethyl ketone (30 g.) in
ing aldol condensation product(5 g.)at the reac- water (200 cc.) was at once introduced 10% aqueous
tion temperature 3∼5° was refluxed with acetic sodium hydroxide (7 cc.)at about 60°.After
anhydride (15 g.) for 16 hrs. Fractionation of the proloneed stirring for 3 hrs. at 60∼65°, the reac-
reaction mixture gave a pale yellow oil (4 g.), b.p. tion was over. The reaction mixture was worked
112∼114°/6mm. up as described above. Fractionation of the ether
This oil (0.5 g.) was suspended in an aqueous solution, after drying over calcium chloride, gave
semicarbazide-sodium acetate solution, and meth- apale yellow oil(19 g.), b.p.117∼118°/6 mm.,
anol added until a clear solution was obtained. which solidified at ordinary temperature. This
The solution, after heating on the water-bath for fraction was composed of 1-phenyl-1-penten-3-one
a short time and standing for 3 hrs., gave col- (I). Calcd. for C11H12O : C, 82.45 H, 7.55%; Found :
133
April, 1954]

C,82.29H,7.70%. Summary
This fraction gave the oxime melting at 86∼87°,
In the condensation of benzaldehyde with.
which was identical with the oxime(m.p.85∼86°)
methyl ethyl ketone by aqueous sodium hy-
of 1-phenyl-1-penten-3-one (I) obtained by Harries droxide, the lowered reaction temperature-
and Muller1). Its semicarbazone formed colourless
(3∼5°) favored the aldol condensation at the
needle crystals melting at 181∼182°(litg)., m.p.
α-methylene group of the ketone as in the
173°),and its 2,4-dinitrophenylhydrazone, carmine
condensation of furfural with the ketone2).
rhombic crystals, melting at 212∼213° on crys-
tallisation from pyridine. Calcd. for C17H16O4N4: On the other hand, the elevated reaction
C, 59.97, H, 4.74, N, 16.46 % ; Found: C, 59.78, H, temperature (60∼65°) conducted exclusively

4.59, N, 16.50 %. the condensation at the α-methyl group of

3-Methyl-4-phenyl-3-buten-2-one (IV) was synthe- the ketone, giving 1-phenyl-1-penten-3-one (I)_

sised from benzaldehyde and methyl ethyl ketone 3-Methyl-4-phenyl-4-butanol-2-one (II), ob-
by the use of hydrogen chloride as the condens- tained by the aldol condensation at the low-
ing agent, as reported by Harries and Miiller1). ered reaction temperature(3∼5°), was dehy-
This ketone gave the oxime melting at 105∼ drated with acetic anhydride to 3-methyl-4-
106°(lit1)., m.p.103∼104°), the semicarbazone
phenyl-3-buten-2-one (IV), which was oxidized.
melting at 218∼219°(lit4., m.p.204°) and a 2,4-
by sodium hypochlorite to afford α-methyl-
dinitrophenylhydrazone, red needles, melting
cinnamic acid (V).
at 199∼200°. Calcd. for C17H16O4N4: C,59.97,
H,4.74, N,16.46% ; Found : C,59.52, H, 4.56, The author expresses his sincere thanks,
N,16.51%. for Dr. T. Hayashi for his kind advice.
3) R. Stoermer and R. Wehlu: Ber., 35, 3552 (1902). Scientific Research Institute, Komqgome,
4) C. V. Gheroghiu and B. Arwentiew : Bull. Soc. Chim.,
47, 195 (1930). Bunkyo-ku, Tokgo