Structure ·elucidation

• Fonnallon of an oxime of cffral indicated the presence of an oxo group in citral.

! ~CHO 1
r~ rn = \ - OH

+ NH.,OH

Ciral (a)
Geanial (tmns)
i
Oxim

• Clnll when heated with potassium hydrogen sulphate afforded the known aromatic
hyctocarbon, p-cymene, which fixed the position of methyl and isoJM"opyl groups In cHral.
\

I
,.~
,

.
-.. _(
'-
~

r'
.
'T ;·
,.
i. .

' ·' .

I I
Al , C .. ... Olnl , - eylltl t

Sho , ~~~-®'Jifl8!.i••i••·· ..
 Structure elucidation
° Clral formed both mono- and di- bisulphites
by the addition of sodium bisulfite to reveal + ~

the presence of a conJugcited aldehyde

group. Its UV spectrum displayed a band at
238 nm to confirm this.

° CBral on reducfion with sodium-amalgam ....•

gave an alcohol, geraniol, C10H180.
~

- - - --.---- - ----
 .•
• • • I • ~• ti J

; : ~. ~ ~ 1 ,_,· ' • ,

f . • ••

. ··~...,.............__..,,oi.ll"'l!I'... .
 NaO H
~Br N" , H l LV M eJ,

x~r·"
r

-I
¢C0
-... .

-
2

( ~-:- ~->~
2
: ~: ·: _
1

:-a
(_:·- ~--~-~;-
2
~ CHO

I) Q A ,._,.i
~_u) .. A more recent synthesis of citral is that of Arens et al. ( 1948). ·~ ·-

}__ + C2H2 ; :J::: liqNH, HO>( z:~iu HOX~ PBr _,

i
B (i) Na EAA
(ii) OH · : (iii) H +

(i) EtOC::= CMgBr

(ii) H +
Pd-BaS0 4
OEt CHO
OEt

(IV)

abould be noted that an allylic rearrangement occurs in both parts of this synthesis (see also §8).
acetylenemagnesiwn bromide ma OilYenientLv b e...,_nren!;lrQ_d £....~~ "t... l ...... - --~ - - ~ - ...l - L_ . ..J _