In the intermediate organic chemistry laboratory course at

the University of Wisconsin, we wish to acquaint the students,

predominately chemistry majors, with the strategies and
techniques involved in carrying out a multistep synthesis. This
paper describes a synthesis of chrysanthemic acid (I), which
has been used successfully in our laboratory course. The
overall synthetic route is outlined in eqn. (1) and is based on
a synthesis originally reported by Martel and Huynh 11) at
Roussel-Uclaf.
Paul F. Schatz
University of Wisconsin
Madison, Wisconsin 53706
(111) ( N l
I
1; : &o,
48% HBr
kBr g
S O ~ @N ~ @
(11
(VI) (W)
Synthesis of Chrysanthemic Acid
A multistep organic synthesis
for undergraduate students
There are several aspects of the experiment which make it
especially suitable for the intermediate or advanced under-
graduate chemistrv student. The student's interest in the
"~ ~
exprrimtmt is stimulated by the fact rhvt the s\mth<:tic goal,
chrysanthemic mid, cnn beobtained f r m pyrethrin flower%.
which are a naturally wcurring, eflcctive, and ecologically dafr
insectieidr (2-121. In discussinr rent:ral svnthetic strateries
such as synthons(l3), strategic ionds (121, and converGnt
and linear syntheses (15), the numerous published syntheses
(1, 16-36) of chrysanthemic acid can serve as examples for
critical analvsis.
Presented at the 173rd National Meeting of the American Chemical
Society, Chemical Education Division, New Orleans, Louisiana,
March, 1977.
Dimethyl formamide dried over molecular sieves is sufficient.
The starting materials, 3-methyl-2-butenoic acid (II), and
2-methyl-3-huten-2-01 (III), are readily available and inex-
pensive. Moreover, it can be shown that these starting mate-
rials can be easily synthesized from acetylene and acetone
(eqn. (2)).
1. KOCl
& hCOgH (1,
Thus all the carbon atoms of chrysanthemic acid can he traced
hack to com~ounds containine two or three carbon atoms. and
this synthesis is an excellentexample of how a struct&ally
complicated natural product can he assembled from very
simple starting materials.
The synthetic plan is convergent which offers advantages
other than just thwarting the "arithmetic demon" of linear
synthesis ( 15~) . The first steps of the synthesis review ex-
perimental techniques, such as refluxing, distillation, and
recrvstallization, ~reviously used in the introductory organic
. -
lah&atory course. The new, more advanced techniques, such
as working under an inert atmosphere and high vacuum dis-
tillation, are introduced in the later steps. Also,the convergent
scheme allows for error (i.e., poor yield or accidental loss of
intermediates) without total disaster, since the starting point
of any branch of the synthesis is no more than one or two steps
away. Finally, the intermediates and products are compatible
Summary of Student Results
Reactiond Student Yieldsb Time Required (Hr)
79.81.81.86,88.93
(72 * 14)
(111) - (VI) - (VIII) 42,42.53,57.64.66.66, 6
68.74,74,75,79.81.86
(66 * 14)
(Vlll) + (V) - (IX) 26.34.35.38.46.51,55 8
57.58.58.71.72.77
( 52* 16)=
(Ix) - (1) 10,33.43.47,49.59.59. 8
62,69.70,79,87,90
(58 * 22)
T h e numbers comespodto cCmpovnds in sqn. (1).
Percent of thewetical yield, me numbers in parenmesessremeaverage a d sfadard
deviation
s a d on t eal yield of cyclopropanated produnn.
468 / Journal of Chemical Education
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