Ultrasonics Sonochemistry 9 (2002) 205–207

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Ultrasonic acceleration of iodination of unactivated

aliphatic hydrocarbons
Takahide Kimura, Mitsue Fujita, Hajime Sohmiya, Takashi Ando *

Department of Chemistry, Shiga University of Medical Science, Seta, Otsu, Shiga 520-2192, Japan
Received 19 November 2001; received in revised form 10 December 2001; accepted 10 December 2001

Abstract

Iodination of unactivated aliphatic hydrocarbons with iodoform (CHI3 ) and solid NaOH were greatly accelerated under ul-
trasonic irradiation. The mechanism of the sonochemical acceleration was studied.
Ó 2002 Elsevier Science B.V. All rights reserved.

PACS: 43.35.Vz
Keywords: Iodination; Sonochemistry; Ultrasound; Iodoform

1. Introduction posed of reaction steps involving an electron transfer

reaction on the surface of solid NaOH and homo-
Functionalization of unactivated aliphatic hydrocar- geneous atom abstraction by radicals (Scheme 1), irra-
bons is one of the important targets for synthetic or- diation of ultrasound was expected to improve this
ganic chemists. In spite of the accumulation of the iodination reaction.
results of long years of study [1–3], modern methods of
activation introduced in organic synthesis have always
2. Experimental
been examined for the target [4–7]. Ultrasound has re-
cently been introduced in organic synthesis as a novel
Ultrasound was irradiated in an ultrasonic cleaning
type of energy to control the reactivity and selectivity,
bath, Elmer Transonic T490DH, at 40 kHz and 240 W
but, as far as we know, never been successfully applied
under circulation of thermostated water. In a flat bot-
to the functionalization of alkanes. Ultrasound is known
tom reaction flask held at the same position in the bath
to accelerate heterogeneous reactions and switch the
at the maximum ultrasound intensity, 0.35 g (0.89
course of the reactions from ionic to radical [8–10].
mmol) of CHI3 and 0.5 g (12.5 mmol) of NaOH beads
Halogenation is one of the simplest and most classi-
(20–40 mesh) were mixed in 5 ml of an alkane or
cal ways of functionalization of alkanes. In contrast to
cycloalkane (10–54 mmol depending on the molecular
the very reactive and often less selective chlorination, the
weight) and irradiated under Ar. Runs under magnetic
direct iodination of alkanes had been known to be dif-
stirring were also carried out in a same reaction flask for
ficult and unpractical. Recently, Schreiner and his co-
comparison. Reaction mixtures were washed with 5%
workers reported an interesting method of iodination of
sodium thiosulfate solution and analyzed by VPC using
simple aliphatic hydrocarbons with iodoform (CHI3 )
the internal standard method. Identification of products
and solid sodium hydroxide (NaOH) [11]. The reaction
was carried out by NMR after separation by preparative
was carried out at 25 °C for a long reaction time (24–96
LC.
h) or at a higher reaction temperature (105 °C) to in-
crease the yield. As the mechanism proposed is com-
3. Results and discussion
*
Corresponding author. Tel.: +81-77-548-2108; fax: +81-77-548-
2405. Results at 56 °C are summarized in Table 1. Yields
E-mail address: ando@belle.shiga-med.ac.jp (T. Ando). were based on the amount of CHI3 used. Positive effect

1350-4177/02/$ - see front matter Ó 2002 Elsevier Science B.V. All rights reserved.
PII: S 1 3 5 0 - 4 1 7 7 ( 0 2 ) 0 0 0 7 3 - 1
206 T. Kimura et al. / Ultrasonics Sonochemistry 9 (2002) 205–207

pressure of the substrate–solvent must decrease the effect

of cavitation [12]. Products were always monosubsti-
tuted iodoalkanes among which 2- and 3-isomers were
main components. Isomer ratios were similar to those
obtained under stirring [11].
In order to elucidate the mechanism of ultrasonic
activation, solid NaOH was presonicated in alkanes for
1 h before the addition of CHI3 and then the reaction
mixture was magnetically stirred for 2 h. The improve-
ment in the yields compared to those under magnetic
stirring shown in Table 2 exhibits the effect of the
presonication and becomes the evidence that activation
of the solid surface is at least a part of the origin of
ultrasonic activation. Cleaning of the deposited NaI on
the surface of NaOH during the reaction must also
Scheme 1. Proposed reaction mechanisms of iodination. be considered as an additional effect. However, preso-
nication was not effective enough at least for two hy-
drocarbons, cycloheptane and cyclooctane. The fact
of ultrasonic irradiation was apparent for alkanes and indicates that the ultrasonic acceleration for these two
cycloalkanes having boiling points higher than 80 °C. compounds is not solely due to the activation of the
Much higher yields were obtained than magnetic stirring solid surface (see below). Presonication of CHI3 was in-
and a much shorter reaction time was attained than effective at all.
those reported in the literature [11]. For example, iod- The effect of the presence of radical scavengers was
ocycloheptane was obtained in 95% yield after 3 h at studied by adding tert-butylcatechol and DPPH in order
56 °C under ultrasonic irradiation, while only 4% under to confirm the radical mechanism of the reaction. As
magnetic stirring. According to the literature [11], the shown in Table 3, DPPH could stop the reaction effec-
yield was 39% after 96 h at 25 °C or 73% after 36 h at tively even under ultrasonic irradiation. However, tert-
105 °C. The difference in the yield may be attributed to butylcatechol could quench the reaction only partially
the inefficient magnetic stirring, but the fact that alkane under ultrasonic irradiation especially for cycloheptane
and cycloalkane with lower boiling points showed lower and cyclooctane. The steric hindrance present in me-
ultrasonic effect indicates the importance of ultrasonic dium ring compounds must favor the production of rad-
irradiation for the increase in reactivity. Higher vapor icals with a less hindered sp2 carbon [13]. The fact,
together with the result of the presonication experiment,
suggests that the mechanism of ultrasonic acceleration
Table 1 of the reaction can be attributed to the activation of
Iodination of alkanes with CHI3
solid surface as well as the sonochemical acceleration of
Alkane Bp (°C) Time (h) GC yields of iodoalkanes the radical reaction step in Scheme 1.
(%)a
Ultrasoundb Stirringc
Cyclopentane 50 2 18 38
Hexane 69 2 20 (93:7) 18
5 25 (93:7) Table 2
Cyclohexane 81 2 98 Activation of solid reagents
Heptane 98 2 70 (82:18) 35 Alkane GC yields of iodoalkanes (%)a
3 73 (83:17)
Cycloheptane 118 2 72 Ultrasoundb Ultrasound þ Stirringd
3 95 4 Stirringc
Octane 126 2 76 (69:31) 27 (68:32) Cyclohexane 98 56  7 35
3 81 (68:32) Cycloheptane 72 16  1 4
Cyclooctane 149 2 70 15 Octane 76 60  2 27
3 86 Cyclooctane 70 22  6 15
Dodecane 216 2 62 (42:58) Tetradecane 54 42  8 9
3 71 (42:58) a
Yields were based on CHI3 used.
Tetradecane 253 3 54 (35:65) 9 (34:66) b
CHI3 (0.89 mmol) and NaOH beads (12.5 mmol) in alkane (5 ml;
a
Yields were based on CHI3 used. Ratios of 2- and 3-isomers were 10–54 mmol) were sonicated at 56 °C for 2 h under an Ar atmosphere.
c
presented in parentheses. NaOH beads was presonicated in alkane for 1 h before the addi-
b
CHI3 (0.89 mmol) and NaOH beads (12.5 mmol) in alkane (5 ml; tion of CHI3 and then the reaction mixture was magnetically stirred for
10–54 mmol) were sonicated at 56 ° C under an Ar atmosphere. 2 h.
c d
Reaction mixture was magnetically stirred. Reaction mixture was magnetically stirred for 2 h.
 T. Kimura et al. / Ultrasonics Sonochemistry 9 (2002) 205–207 207

Table 3
Effect of radical scavengersa
Alkane GC yields of iodoalkanes (%)b
Without scavenger With tert-butylcatechol With DPPH
Ultrasound Stirring Ultrasound Stirring Ultrasound
Cycloheptane 72 4 25 6 4
Octane 76 27 5 2 1
Cyclooctane 70 15 18 2 2
Tetradecane 54 9 6 1 1
a
CHI3 (0.89 mmol) and NaOH beads (12.5 mmol) in alkane (5 ml; 10–54 mmol) were sonicated or magnetically stirred at 56 °C for 2 h under an
Ar atmosphere. tert-Butylcatechol and DPPH were added 0.9 and 0.1 mmol, respectively.
b
Yields were based on CHI3 used.

Acknowledgements [4] P.A. Frey, Chem. Rev. 90 (1990) 1343–1357.

This work was supported by Grants-in-Aid for Sci-
entific Research no. 1160531 from the Ministry of Ed-
ucation, Culture, Sports, Science and Technology.
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