Agricultural and Biological Chemistry

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Novel Synthesis of (Z)-3-Hexen-1-ol and cis-

Jasmone

Akimichi Furuhata, Ken Onishi, Akira Fujita & Kunio Kogami

To cite this article: Akimichi Furuhata, Ken Onishi, Akira Fujita & Kunio Kogami (1982) Novel
Synthesis of (Z)-3-Hexen-1-ol and cis-Jasmone, Agricultural and Biological Chemistry, 46:7,
1757-1760, DOI: 10.1080/00021369.1982.10865324

To link to this article: https://doi.org/10.1080/00021369.1982.10865324

Published online: 09 Sep 2014.

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Agric. BioI. Chern., 46 (7), 1757 ~ 1760, 1982 1757

Novel Synthesis of (Z)-3-Hexen-I-ol and cis-Jasmone

Akimichi FURUHATA, Ken ONISHI, Akira FUJITA

and Kunio KOGAMI
Kawasaki Research Laboratories, T. Hasegawa Co., Ltd.,
335 Kariyado, Nakahara-ku, Kawasaki-shi 211, Japan
Received October 12, 1981

Both (Z)-3-hexen-l-ol and cis-jasmone were synthesised via 1,4-selective hydrogenation of

conjugated dienes in the presence of arene Cr(COh or Cr(CO)6 catalysts as the key step.

(Z)-3-Hexen-1-ol (1) is a key component in and confirmed to be (2E,4E)-2,4-hexadien-1-

its characteristic odor of tea leaves and cis- 01 on the basis of PMR spectral data [(CDC13)
jasmone (2) is known as a key substance in its 6: 5.3 ~6.4 (4H, m, J Z - 3 = 16 Hz, J 3 - 4 = 14 Hz,
pleasant odor of jasmine oil. Both compounds, J4 - 5 = 15 Hz)]. The other minor alcohol, how-
which occur in nature and are very useful in ever, could not be separated from the major
perfumery, have a (Z)-double bond in com- alcohol, and was supposed to be a (Z)-(E)
mon. In order to afford these (Z)-double double bond isomer from the MS data. The
bonds, many synthetic procedures, such as resulting dien alcohol (4) was employed for the
selective hydrogenation of triple bonds,!) Birch following selective hydrogenation without fur-
reduction?) Diels-Alder reaction,3) Wittig re- ther purification.
action4 ) and condensation of compounds hav- The selectivity of the l,4-selective hydrogen-
ing a (Z)-double bond,S) have been reported. ation of 4 was examined with various arene
We report here the novel synthesis of 1 and 2 ligands of Cr(COh [4: 0.1 mol, catalyse): 0.005
by 1,4-selective hydrogenation of conjugated mol, MeOH: 25ml, initial Hz: 50kg/cmz,
dienes. 6a ,6b) The synthetic routes for 1 and 2 190 ~ 200°Cj4 hr]. The results are summarized
are shown in Figs. 1 and 2. in Table I. No remarkable differences among
At first, the synthesis of 1 is described. The various arene ligands can be seen in Table I,
preparation of the starting material, 2,4-hex- the specific arene ligands did not seem to have
adienal (3), was done by simple aldol conden- any influence on this hydrogenation.
sation of acetaldehyde with croton aldehyde Thus, commercially available Cr(CO)6 cat-
(molar ratio, 5: 1) in the presence of alyst instead of arene Cr(COh catalysts6a ,6b)
morpholine-aqueous H 3P04 catalyst in a 26% gave the same results for obtaining the desired
yield. 7) We improved this condensation proc- 1 with high selectivity. Then, we examined the
ess to give 3 in a 38 % yield by changing the selectivity with various solvents, as summa-
molar ratio to 3: 2. The reduction of 3 to the rized in Table II [4: 0.1 mol, Cr(CO)6: 0.005
corresponding alcohol (4) was reported using mol, solvent: 25 ml, initial Hz: 50 kg/cmz,
Meerwein-Pondorf reduction with a 64% 190~200°C/4hr]. There were no large differ-
yield,8) but by utilizing the sodium boro- ences between the solvents, but methanol show-
hydride reduction, we obtained 4 in a 86% ed relatively good selectivity. As a result, the
yield, which was the key intermediate for 1 and key step of selective hydrogenation of 4 was
was found to be a mixture of two isomers in a effected with Cr(CO)6 catalyst in MeOH to
ca. 9 to 1 ratio by GLC (PEG 20M, 2 m x give 1 in a 90% yield, the purity of which was
3 mm). The major alcohol was purified by more than 98% as judged by GLC analysis
preparative GLC (PEG 20M, 2m x 20mm) (PEG 20M, 2 m x 3 mm). Physical data of syn-
1758 A. FURUHATA et at.

thetic 1 were entirely identical with those of an

~o+ ~O~ ~O
authentic sample from 3-hexyn-I-ol.
(3)
Next, the synthesis of 2 was examined. By
the usual method, a mixture of two isomers (4)
was treated with PBr3 in the presence of
~OH ~OH pyridine at - 10 ~ O°C to give diene bromide
(4) (1)
(5) as a sole product in a 60% yield, which was
FIG. I. Synthetic Route for (Z)-3-Hexen-I-ol.
confirmed to be a (2E,4E)-isomer by the PMR
spectral data [(CCI4 ) b: 4.9~6.7 (4H, m,
J 2 _ 3 =16Hz, J 3 _ 4 =14Hz, J 4 _ s =15Hz)].
Compound 5 was employed to introduce the
(4) (5 ) side chain to the Cs-position of 2-methylfuran.
Thus the condensation of 5 with 2-lithio-5-
methylfuran, derived from 2-methylturan and
BuLi at - 20°C, gave (2E,4E)-hexadienyl-
(6) (7) furan (6) in a 64 % yield, which was the key
intermediate for our synthesis of 2.
The structure of 6 was supported by physi-
cal data. The selective hydrogenation of 6 with
Cr(CO)6 in MeOH (initial H 2 : 50kg/cm2 ,
(8 ) (2)
190~200°C;2hr) gave (Z)-hexenylfuran (7) in

FIG. 2. Synthetic Route for cis-Jasmone. a 76% yield, which was contaminated with 2%

TABLE I. HYDROGENATION OF 2,4-HEXADIEN-I-OL WITH

ARENE Cr(CO)3 OR Cr(CO)6 CATALYSTS

Prod\lct composItIOn (%)

Arene ligand in
catalyst 2,4-Hexadlen- (Z)-3-Hexen- (E)-3-Hexen- 4-Hexen-I-ol Hexanol
1-01 1-01 1-01

Methyl benzoate 0.0 92.5 4.6 2.3 0.6

Anisole 0.0 95.0 3.3 1.4 0.3
Cydoheptatriene 0.0 95.7 2.4 1.9 0.0
Durene 0.0 96.0 2.4 1.6 0.0
Cr(CO)6 3.6 95.1 1.1 0.0 0.1

TABLE II. HYDROGENATION OF 2,4-HEXADIEN-I-OL WITH

Cr(CO)6 CATALYST IN DIFFERENT SOLVENTS

Product composItion (%)

Solvent
2,4-Hexadien- (Z)-3-Hexen- (E)-3-Hexen- 4-Hexen-I-ol Hexanol
1-01 1-01 1-01

Cydohexane 4.8 87.2 3.6 2.5 1.9

Benzene 4.3 90.4 3.6 1.4 0.3
Tetrahydrofuran 4.0 90.3 1.8 1.8 3.1
Acetone 2.9 88.9 2.0 4.7 1.5
Methanol 3.6 95.1 1.1 0.0 0.1
Butylamine 12.4 82.6 2.8 2.2 0.0
Acetonitrile 2.3 93.8 1.5 1.4 1.0
 Novel Synthesis of (Z)-3-Hexen-I-ol and cis-Jasmone
of 2-hexyl-5-methylfuran. Physical data of the
resulting 7 were completely identical with
those reported. 5 ) Finally, cis-jasmone (2) was
synthesized from 7 via a dione (8) in a 70%
overall yield in the same manner as reported. 5 )
EXPERIMENTAL
All bps were uncorrected. IR spectra were determined
on a JASCO IRA-2 spectrometer. PMR spectra were
, recorded at 60 MHz with TMS as an internal standard on
a Hitachi R-24A spectrometer. MS spectra were obtained
on a Hitachi RMU 6E spectrometer. GLC analyses were
performed on a Hitachi 063 gas chromatograph.
2,4-Hexadienal (3). A mixture of 80% aq. acetaldehyde
(495 g) and 90% aq. crotonaldehyde (467 g) in the presence
of 50% morpholine--aq.H3 P04 (molar ratio 3: 1, 24 g) was
heated at 90 ",95°C for I hr in an autoclave (2 liters). The
reaction mixture was cooled and saturated with NaCI. The
organic layer was separated and dried over MgS04. After
the recovery of crotonaldehyde (408 g), the residue was
distilled to give 3 (114 g, 38% based on the recovery of
crotonaldehyde): bp 75~76°CJ30 mmHg; IR v:!~~ cm- I :
1680, 1640, 1600; PMR (CDCI3 ) c5: 1.89 (3H, d, J=
4.2 Hz), 5.8~7.3 (4H, m), 9.46 (lH, d, J=7.8Hz); MS
m/z: 96 (M+, 31%), 81 (100),67 (41), 53 (46), 41 (63),39
(76).
2,4-Hexadien-I-ol (4). To a stirred suspension of
NaB~ (11.0g) in water (3OOml) was added dropwise 3
(96.0 g) over I hr at room temperature and then the
stirring was continued for 2hr. The mixture was extracted
with ether and the extract was washed with brine and dried
over MgS04. After removal of the solvent, the residue was
distilled to give a mixture of (2E,4E)-4 and (2Z,4E) or
(2E,4Z)-4 (84.0g, 86%, bp 76~77°Cj12 mmHg) in a ca.
9: 1 ratio by GLC (PEG 20M; 2 m x 3 mm; column tem-
perature, 150°C; carrier gas, N 2, 40mljmin; tR: 13 min 30
sec and 14 min 10 sec). Pure (2E,4E)-4 was isolated by
preparative GLC (pEG 20M, 2m x 20mm).
(2E,4E)-4: IR vf~~~ cm- I : 3350, 1660, 990; PMR
(CDCI 3) c5: 1.83 (3H, d, J= 5.2 Hz), 3.19 (2H, d, J=
5.4 Hz), 5.3~6.4 (4H, m, J 2 _ 3=16Hz, J 3_4 =14Hz,
J4 - 5 = 15 Hz); MS m/z: 98 (M+, 47%), 83 (43), 69 (37),55
(70),41 (100), 39 (67).
(2Z,4E) or (2E,4Z)-4: MS m/z: 98 (M+, 38%), 83 (43),
69 (34), 55 (71), 41 (100), 39 (62).
(Z)-3-Hexen-I-ol (1).
a) A mixture of 4 (49.0 g) and Cr(CO)6 (5.5 g) in MeOH
(125 ml) was stirred under H2 (initial, 50 kgjcm2) at
190~200°C for 1 hr in an autoclave (300ml). The cooled
mixture was filtered to remove the catalyst and con-
centrated. The residue was distilled to give 1 (45.0 g, 90%)
containing a small amount of (E)-3-hexen-l-01 (1.2%) by
1759
GLC (PEG 20M, 2mx3mm): bp 95~96°Cj80 mmHg;
IR v:!~~ cm- I : 3350, 1660; PMR (CDCI3) c5: 0.95 (3H, t,
J=7.6Hz), 1.80~2.45 (4H, in), 3.58 (2H, t, J=6.8Hz),
5.08~5.73 (2H, m); MS m/z: 100 (M+, 3%), 82 (32),69
(27), 67 (64), 55 (37), 41 (100), 31 (35). These data of
synthetic 1 are completely identical with those of an
authentic sample.
b) In the same manner, a solution of 4 (9.8 g) in MeOH
(25ml) was hydrogenated in the presence of (Durene)
Cr(CO)3' prepared9 ) from durene (50 g) and Cr(CO)6
(5.0 g), under H2 (initial, 50kgjcm2) at 190~200°C for4hr
in an autoclave (lOOml). The cooled mixture was filtered
and concentrated. The residue was shown to be a mixture
of 1 (96.0%), (E)-3-hexen-l-01 (2.4%) and 4-hexen-l-01
(1.6%) by GLC (PEG 20M, 2m x 3mm; column tempera-
ture, 150°C; carrier gas, N 2, 40mljmin; tR: 5 min 50 sec,.5
min 20 sec and 6 min 20 sec) and MS analysis.
(2E,4E)-I-Bromo-2,4-hexadiene (5). To a stirred so-
lution of 4 (19.6 g) and pyridine (16.6 g) in hexane (40ml)
was added dropwise PBr3 (19.0 g) over 1 hr at -10 ~O°C
and the mixture was stirred at O°C for 2 hr. The reaction
mixture was. poured into ice-water and extracted with
hexane. The extract was washed with brine, dried .over
MgS04 and concentrated. The residue was distilled to give
5 (19.7g, 60%): bp 37~39°Cj5 mmHg; IR v:!~~ cm- I :
1660, 1600, 1440, 1200,990,580; PMR (CCI4 ) c5: 1.80 (3H,
d, J=6.0Hz), 3.98 (2H, d, J=7.2Hz), 4.9~6.7 (4H, m,
J2~3=16Hz, J 3 _4 =14Hz, J 4 _ 5 =15Hz); MS m/z: 162
(M+, 6%), 160 (M+, 6), 81 (100),79 (35), 66 (13),53 (35),
41 (49), 39 (31).
2[ (2E,4E)-2,4-HexadienyIJ-5-methylfuran (6). To a so-
lution of 2-methylfuran (10.1 g) in dry THF (50ml) was
added dropwise a 15% solution of BuLi in hexane (77 ml)
over 30 min at -20°C under Ar. and the mixture was
stirred for 1 hr. To this was added dropwise a solution of 5
(19.4 g) in dry THF (20 ml) over 30 min at - 20 ~ - 10°C
and then the stirring was continued for 2 hI. After stirring
at room temperature for a further 15hr, the mixture was
poured i1) t o NH4Cl solution and extracted with ether. The
extract was washed with brine, dried over MgS04 and
concentrated. The residue was distilled to give 6 (12.4 g,
64%); bp 71 ~73°CJ4 mmHg; IR v~~ cm- I : 1650, 1570,
1220, 990, 780; PMR (CCI4) c5: 1.72 (m, d, J=6.0Hz),
2.20 (3H, s), 3.26 (2H, d, J= 6.4 Hz), 5.74 (2H, s), 4.6~6.8
(4H, m); MS m/z: 162 (M+, 37%),147 (27),129 (17),119
(29), 95 (34), 91 (34), 43 (100), 41 (37).
2[(Z)-3-HexenyIJ-5-methylfuran (7). A solution of 6
(l1.4g) in MeOH (30ml) was hydrogenated in the pres-
ence of Cr(CO)6 (0.8 g) under H2 (initial, 50 kgjcm2) at
190~200°C for 2hr in an autoclave (lOOml). The cooled
mixture was filtered and concentrated. The residue was
distilled to give 7 (8.7 g, 76%) containing 2-hexyl-5-
methylfuran (2.0%) by GC-MS analysis: bp 66~68°CJ4
mmHg; IR v:!~~ cm- I : 3100,3000,2950,2910,2860,1650,
1760 A. FURUHATA
1620, 1570, 1450, 1385, 1370, 1220, 1020,960,935; PMR
(CDCI 3 ) <5: 0.92 (3H, t, J = 7.0 Hz), 2.20 (3H, s), 1.9 ~ 2.6
(6H, m), 5.2 ~ 5.5 (2H, m), 5.72 (2H, s); MS rn/z: 164 (M+,
7%), 96 (8), 95 (100), 43 (21), 41 (20). These data of 2)
synthetic 7 are identical with those reported. S ) 3)
cis-Jasrnone (2). By the same procedure as described by
Buchi et al.,S) 7 (8.2 g) was converted to 2 (5.7 g, 70%): bp 4)
74~ 75°C;2 mmHg; IR v~~~ cm -1: 1700, 1645, 1440, 1385,
1340,1300,1180, 1070. PMR (CCI4 ) <5: 0.98 (3H, t, J= 5)
7.0 Hz), 2.06 (3H, s), 2.85 (2H, d, J = 5.5 Hz), 4.92 ~ 5.52
(2H, m). MS rn/z: 164 (M+, 60%), 149 (42), 135 (39), 122 6)
(44), 110 (58), 93 (46), 91 (46), 79 (77), 55 (84), 41 (100), 39
(79). These data of synthetic 2 are completely identical
with those' of an authentic sample.
7)
Acknowledgments. We are indebted to Messrs. T.
Yanai and T. Habu in our laboratory for MS and PMR 8)
analyses.
9)
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1) F. Sondheimer, J. Chern. Soc., 1950, 877; A.
et al.
Hatanaka and M. Ohno, Bull. Agric. Chern. Soc.
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R. T. Dahill, Jr., J. Chern. Eng. Data, 17, 399 (1972).
T. Kobayashi and H. Turuta, The 23rd Symposium
on the Chemistry of Terpenes, Essential Oils and
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A. J. Birch, K. S. Keogh and V. R. Mamdapur, Aust.
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H. C. Chitwood and B. T. Freure, Brit. Patent,
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Chirn. Acta, 15, 261 (1932).
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