Concise synthesis of (8Z,11Z,14Z)-8,11,14-heptadecatrienal, (7Z,10Z,13Z)-7,10,13-hexadecatrienal, and (8Z,11Z)-8,11-heptadecadienal, components of the essential oil of marine green alga Ulva pertusa

Article abstract of DOI:10.1271/bbb.69.1348

The long-chain aldehydes, (8Z,11Z,14Z)-8,11,14-heptadecatrienal, (7Z,10Z,13Z)-7,10,13-hexadecatrienal, and (8Z,11Z)-8,11-heptadecadienal, were concisely synthesized by using Grignard coupling, catalytic hydrogenation with the Lindlar catalyst, and oxidation with Dess-Martin periodinane as the key steps. Particularly, (8Z,11Z,14Z)-8,11,14-heptadecatrienal and (7Z,10Z, 13Z)-7,10,13-hexadecatrienal both possessed a seaweed-like odor.

Full text of DOI:10.1271/bbb.69.1348

Biosci. Biotechnol. Biochem., 69 (7), 1348–1352, 2005
Concise Synthesis of (8Z,11Z,14Z)-8,11,14-Heptadecatrienal,
(7Z,10Z,13Z)-7,10,13-Hexadecatrienal, and (8Z,11Z)-8,11-Heptadecadienal,
Components of the Essential Oil of Marine Green Alga Ulva pertusa
Yoshihiko AKAKABE,y Kensuke WASHIZU, Kenji MATSUI, and Tadahiko KAJIWARA
Department of Biological Chemistry, Faculty of Agriculture, Yamaguchi University,
1677-1 Yoshida, Yamaguchi 753-8515, Japan
Received March 7, 2005; Accepted April 6, 2005
The long-chain aldehydes, (8Z,11Z,14Z)-8,11,14-
heptadecatrienal, (7Z,10Z,13Z)-7,10,13-hexadecatrienal,
and (8Z,11Z)-8,11-heptadecadienal, were concisely syn-
thesized by using Grignard coupling, catalytic hydro-
genation with the Lindlar catalyst, and oxidation with
Dess–Martin periodinane as the key steps. Particularly,
(8Z,11Z,14Z)-8,11,14-heptadecatrienal and (7Z,10Z,
extraction with boiled toluene to exclusively afford 7-
bromoheptan-1-ol, and the remaining hydroxy group
was then protected as a THP ether with DHP. The
bromide was coupled with lithium acetylide in DMSO to
give nonynyloxy-THP ether 6a. Coupling THP ether 6a
with bromide 4 and subsequently deprotection of the
THP group gave triyn-1-ol 7a. Catalytic hydrogenation
of 7a with the Lindlar catalyst5) afforded (8Z,11Z,14Z)-
8,11,14-heptadecatrien-1-ol (8a). Alcohol 8a was oxi-
dized with Dess–Martin periodinane6) in CH2Cl2 to give
(8Z,11Z,14Z)-8,11,14-heptadecatrienal (1a). The overall
yield was 5.6% based on 2 (10 steps).
13Z)-7,10,13-hexadecatrienal both possessed
weed-like odor.
a sea-
Key words: long-chain aldehyde; Grignard coupling;
Dess-Martin periodinane
Aldehyde 1b was synthesized from 1,6-hexanediol
(5b) by the same procedure as that used for obtaining 1a
from 2. After selectively monobrominating diol 5b with
48% HBr and protecting the remaining hydroxy group as
a THP ether, the resulting THP ether was coupled with
lithium acetylide in DMSO to give octynyloxy-THP
ether 6b. Triyn-1-ol 7b was obtained by coupling 6b
with 4 and subsequently deprotecting the THP group.
After the catalytic hydrogenation of 7b, resulting trien-
1-ol 8b was oxidized with Dess–Martin periodinane to
give (7Z,10Z,13Z)-7,10,13-hexadecatrienal (1b). The
overall yield was 14% based on 5b (7 steps).
Likewise, 1c was synthesized from THP ether 2. After
the Grignard coupling of 2 with pentylbromide and
subsequently removing the THP group, the resulting
alcohol was brominated with PBr3 to give bromide 9.
Coupling 6a with 9 and removing the THP group gave
diynol 10. After the catalytic hydrogenation of 10 and
oxidation of 11 in the same manner, (8Z,11Z)-8,11-
heptadecadienal (1c) was obtained in a 12% overall
yield based on 2 (7 steps).
The long-chain aldehydes, (8Z,11Z,14Z)-8,11,14-
heptadecatrienal, (7Z,10Z,13Z)-7,10,13-hexadecatrie-
nal, and (8Z,11Z)-8,11-heptadecadienal, have been
identified in the essential oil of Ulva pertusa by
simultaneous distillation and extraction.1) It has been
suggested that the biosynthesis of these aldehydes was
due to oxygenation by an ꢀ-oxygenase of long-chain
fatty acids into 2-hydroperoxy fatty acids, with subse-
quent decarboxylation and the loss of one carbon atom.
As expected, long-chain fatty acids such as linolenic,
linoleic, oleic, and palmitic acid were converted to
the corresponding (R)-2-hydroperoxy acids with
>99%ee.2,3) In order to further investigate the metabo-
lism of fatty acids and the relationship between their
structure and odor, it was necessary to effectively
synthesize these aldehydes.
Results and Discussion
Synthesis of the long-chain aldehydes (1a–c) is
summarized in Scheme. Coupling THP ether 2 with 2-
pentynyl bromide by employing the Grignard reagent
gave diynyloxy-THP 3.4) After removing the THP group
with 5% PTS in MeOH, the resulting alcohol was treated
with PBr3 with a catalytic amount of pyridine in ether to
afford bromide 4. On the other hand, 1,7-heptanediol
(5a) was treated with 47% HBr under continuous
Although the geometrical purity of long-chain alde-
hydes 1a–c was rather difficult to estimate, because the
internal double bonds in these aldehydes could not be
1
separated by H-NMR, the 13C-NMR spectra and GC–
MS data showed no isomers of 1a–c. We had thus
synthesized aldehydes 1a–c in a sufficiently pure form.
Furthermore, it was suggested that aldehydes 1a–c and
y
To whom correspondence should be addressed. Fax: +81-83-933-5820; E-mail: akakabe@yamaguchi-u.ac.jp

Concise Synthesis of Trienals and Dienal
1349
Scheme 1. Synthesis of Long-Chain Aldehydes 1a–c.
Reagents: (a) 2-pentynyl bromide, Mg, EtBr, I2, CuCN, THF; (b) PTS, MeOH; (c) PBr3, pyridine, ether; (d) 48% HBr, toluene; (e) DHP, Hþ;
(f) lithium acetylide ethylenediamine complex, DMSO; (g) Mg, EtBr, I2, CuCN, THF; (h) H2, 5% Pd/BaSO4, quinoline, MeOH; (i) Dess–Martin
periodinane, CH2Cl2; (j) pentyl bromide, Mg, EtBr, I2, CuCN, THF; (k) 6a, Mg, EtBr, I2, CuCN, THF.
corresponding alcohols 8a, 8b and 11 would be valuable
for investigating the metabolite profile for ꢀ-oxidation
of fatty acids. Interestingly, the odor of aldehydes 1a
and 1b was seaweed-, Ulva-, or green-like, whereas
aldehyde 1c had an oily or fatty odor. The odors of
alcohols 8a, 8b and 11 were similar to those of the
corresponding aldehydes. However, these odors could
not be evaluated correctly, because of the weaker odor
intensities than those of the aldehydes. Variation of the
odor was found in the position of the double bonds and
the functional groups.
was stirred for 18 hr at room temperature. The reaction
mixture was carefully poured into a cooled saturated
aqueous NH4Cl solution. The mixture was extracted
with ether and successively washed with 2 N HCl, a
saturated aqueous NaHCO3 solution, and brine. After
drying over Na2SO4, the extract was concentrated in
vacuo to give THP ether 3 (8.60 g, 49%) as a colorless
oil. IR ꢁmax (film) cmꢁ1: 2950, 2890, 2250, 1320, 1200,
1120, 1020; NMR (250 MHz, CDCl3) ꢂH: 1.12 (3H, t,
J ¼ 7:3 Hz), 1.49–1.87 (6H, m), 2.17 (2H, qt, J ¼ 7:9,
2.5 Hz), 3.17–3.20 (2H, m), 3.49–3.57 (1H, m), 3.79–
3.89 (1H, m), 4.26 (2H, qt, J ¼ 11:6, 1.8 Hz), 4.80 (1H,
t, J ¼ 3:1 Hz); NMR (62.5 MHz, CDCl3) ꢂC: 9.67,
12.17, 13.64, 18.85, 25.20, 30.05, 54.24, 61.65, 72.58,
75.58, 80.63, 82.00, 95.56. Anal. Found: C, 75.72; H,
8.68%. Calcd. for C13H18O2: C, 75.69; H, 8.80%. 3 was
employed for the next step without further purification.
Experimental
All boiling point (bp) data are uncorrected. IR spectra
were measured as films for oil with a Hitachi R-260-10
1
spectrometer and a Nicolet 410 spectrometer. H- and
13C-NMR spectra were measured with a Hitachi R-250
spectrometer and a Bruker Avance 400 spectrometer.
Silica gel 60 (spherical, 60–230 mm) from Kanto Chemi-
cal Co. was used for column chromatography.
2,5-Octadiynyl bromide (4). THP ether 3 (22.1 g,
107.3 mmol) was added to a 5% (w/w) PTS-MeOH
solution (500 ml), and the mixture was stirred for 20 hr
at room temperature. After adding brine, MeOH was
removed in vacuo. The mixture was extracted with ether
and successively washed with a saturated aqueous
NaHCO3 solution and brine. After drying over Na2SO4,
the extract was concentrated in vacuo and purified by
distillation to give 2,5-octadiyn-1-ol as a colorless oil.
PBr3 (13.8 g 50.9 mmol) was added to a solution of this
octadiyn-1-ol (6.20 g, 51.2 mmol) in ether (100 ml)
containing a catalytic amount of pyridine at ꢁ10 ꢀC.
2-(2,5-Octadiynyloxy)tetrahydropyran (3). THP ether
2 (10.2 g, 72.4 mmol) was added to a solution of EtMgBr
at 0–5 ꢀC, which had been prepared from ethyl bromide
(8.7 g, 80.0 mmol) and Mg (2.0 g, 80.0 mmol) in THF
(100 ml) with a catalytic amount of I2. After stirring for
3 hr at 40 ꢀC, a catalytic amount of CuCN was added to
the suspension at room temperature. Then, 2-pentynyl
bromide (11.7 g, 79.6 mmol) was added, and the mixture

1350
Y. AKAKABE et al.
After stirring for 6 hr at room temperature, the reaction
mixture was poured into an ice–water mixture. The
mixture was extracted with ether and successively
washed with 2 N HCl, a saturated aqueous NaHCO3
solution, and brine. After drying over Na2SO4, the
extract was concentrated in vacuo and purified by
distillation to give bromide 4 (3.3 g, 39%) as a colorless
oil, bp 72 ꢀC at 1.5–2 Torr. IR ꢁmax (film) cmꢁ1: 2980,
2940, 2890, 2260, 2240, 1320, 1210; NMR (250 MHz,
CDCl3) ꢂH: 1.13 (3H, t, J ¼ 7:9 Hz), 2.18 (2H, qt,
J ¼ 7:9, 5.5 Hz), 3.20–3.23 (2H, m), 3.92 (2H, t,
J ¼ 2:4 Hz); NMR (62.5 MHz, CDCl3) ꢂC: 9.52, 11.77,
13.24, 14.34, 71.60, 74.68, 81.45, 82.06. Anal. Found:
C, 52.08; H, 4.76%. Calcd. for C8H9Br: C, 51.92; H,
4.90%.
3.14 (4H, s), 3.64 (2H, t, J ¼ 6:6 Hz); NMR (100 MHz,
CDCl3) ꢂC: 10.14, 10.18, 12.75, 14.24, 19.05, 25.99,
28.98, 29.17, 29.29, 33.08, 63.38, 73.51, 74.18, 75.18,
75.24 81.16, 82.53. Anal. Found: C, 83.73; H, 9.60%.
Calcd. for C17H24O: C, 83.55; H, 9.90%.
(8Z,11Z,14Z)-8,11,14-Heptadecatrien-1-ol (8a). Triyn-
1-ol 7a (210 mg, 0.86 mmol) was hydrogenated in
ethanol (1.5 ml) at 0 ꢀC over a Lindlar catalyst (60 mg)
poisoned with quinoline (6.0 mg) until the theoretical
amount of H2 gas (50 ml) had been absorbed. The
catalyst was then removed by filtration, the filtrate was
extracted with ether, and the extract washed with brine.
After drying over Na2SO4, the extract was concentrated
in vacuo and purified by column chromatography to give
trienol 8a (198 mg, 92%) as a colorless oil. IR ꢁmax
(film) cmꢁ1: 3360, 3007, 2930, 2860, 1464, 1053, 914,
735; NMR (400 MHz, CDCl3) ꢂH: 0.98 (3H, t,
J ¼ 7:5 Hz), 1.27–1.39 (9H, m), 1.53–1.58 (2H, m),
2.02–2.10 (4H, m), 2.81 (4H, t, J ¼ 6:2 Hz), 3.64 (2H, t,
J ¼ 6:7 Hz), 5.33–5.43 (6H, m); NMR (100 MHz,
CDCl3) ꢂC: 14.66, 20.91, 25.88, 25.97, 26.07, 27.57,
29.62, 29.70, 29.95, 32.97, 63.27, 127.46, 128.06,
128:60 ꢂ 2, 130.64, 132.31. Anal. Found: C, 81.63; H,
11.98%. Calcd. for C17H30O: C, 81.54; H, 12.08%.
2-(8-Nonynyloxy)tetrahydropyran (6a). 1,7-Heptane-
diol (5a, 22.6 g, 170.7 mmol) was heated with a 47%
HBr solution for 40 hr at 80 ꢀC under continuous
extraction with toluene (600 ml). After removing the
solvent, the residue was extracted with ether and washed
with brine. After drying over Na2SO4, the extract was
concentrated in vacuo and purified by distillation to give
7-bromoheptan-1-ol (24.5 g, 75%). To this alcohol
(2.78 g, 16.5 mmol) was added DHP (1.44 g, 177.1
mmol) containing a catalytic amount of concentrated
HCl at 10 ꢀC. After stirring for 16 hr at room temper-
ature, the mixture was extracted with ether and washed
with a saturated aqueous NaHCO3 solution. After drying
over Na2SO4, the extract was concentrated in vacuo to
give 2-(7-bromoheptanyloxy)tetrahydropyran (4.3 g, qu-
nat.). This bromide (72.5 g, 259.8 mmol) was added to a
suspension of lithium acetylide ethylenediamine com-
plex (29.3 g, 309.9 mmol) in DMSO (200 ml) at 10 ꢀC.
After stirring for 12 hr at 10 ꢀC, brine was added to the
reaction mixture, the mixture was extracted with
petroleum ether, and the extract washed with brine.
After drying over Na2SO4, the extract was concentrated
in vacuo and purified by distillation to give nonynyloxy-
THP 6a (44.8 g, 72%) as a colorless oil, bp 86 ꢀC at
0.1 Torr. IR ꢁmax (film) cmꢁ1: 3330, 2950, 2870, 2140,
1210, 1140, 1120, 1080, 1040; NMR (250 MHz, CDCl3)
ꢂH: 1.28–1.60 (16H, m), 1.92–1.95 (1H, m), 2.15–2.21
(2H, m), 3.34–3.54 (2H, m), 3.68–3.91 (2H, m), 4.56–
4.59 (1H, m); NMR (62.5 MHz, CDCl3) ꢂC: 18.39,
19.71, 25.50, 26.11, 28.43, 28.68, 28.95, 29.68, 30.78,
62.33, 67.60, 68.06, 98.81, 98.90. Anal. Found: C,
74.72; H, 10.96%. Calcd. for C14H24O2: C, 74.95; H,
10.78%.
(8Z,11Z,14Z)-8,11,14-Heptadecatrienal (1a). Trien-
1-ol 8a (373 mg, 1.50 mmol) in CH2Cl2 (5 ml) was
added to a solution of Dess–Martin periodinane (3.64 g,
8.59 mmol) in CH2Cl2 (10 ml) at room temperature.
After stirring for 3 hr, the reaction mixture was diluted
with ether (50 ml), and the resulting mixture was poured
into a saturated aqueous NaHCO3 solution. The mixture
was extracted with ether and washed with water. After
drying over Na2SO4, the extract was concentrated in
vacuo and purified by column chromatography on silica
gel to give trienal 1a (268 mg, 73%) as a colorless oil. IR
ꢁmax (film) cmꢁ1: 3011, 2930, 2860, 2720, 1732, 1464,
914, 731; NMR (400 MHz, CDCl3) ꢂH: 0.98 (3H, t,
J ¼ 7:5 Hz), 1.11–1.38 (6H, m), 1.61–1.65 (2H, m),
2.03–2.10 (4H, m), 2.43 (2H, td, J ¼ 7:3, 1.8 Hz), 2.81
(4H, t, J ¼ 6:5 Hz), 5.30–5.41 (6H, m), 9.77 (1H, t,
J ¼ 1:8 Hz); NMR (100 MHz, CDCl3) ꢂC: 14.70, 20.95,
22.43, 25.92, 26.00, 27.52, 29.39, 29.45, 29.79, 44.29,
127.47, 128.26, 128.59, 128.71, 130.48, 132.37, 203.31.
Anal. Found: C, 82.24; H, 11.34%. Calcd. for C17H28O:
C, 82.20; H, 11.36%.
2-(7-Octynyloxy)tetrahydropyran (6b). According to
essentially the same procedure as that used for the
preparation of 6a from 5a, octynyloxy-THP 6b (6.40 g,
54%) was synthesized as a colorless oil. IR ꢁmax (film)
cmꢁ1: 3300, 2940, 2860, 2210, 1140, 1120, 1080, 1030;
NMR (250 MHz, CDCl3) ꢂH: 1.11 (3H, t, J ¼ 7:3 Hz),
1.33–1.59 (11H, m), 2.12–2.21 (4H, m), 3.13 (4H, s),
3.64 (2H, t, J ¼ 6:4 Hz); NMR (62.5 MHz, CDCl3) ꢂC:
18.27, 19.62, 25.47, 25.69, 28.37, 28.49, 29.53, 30.72,
62.17, 67.39, 68.03, 84.47, 98.75. Anal. Found: C,
8,11,14-Heptadecatriyn-1-ol (7a). According to es-
sentially the same procedure as that used for the
preparation of 4 from 2, except for the deprotection of
3, triyn-1-ol 7a (0.94 g, 82%) was prepared as a light
yellow amorphous liquid. IR ꢁmax (film) cmꢁ1: 3349,
3046, 2972, 2930, 2852, 2259, 2309, 2220, 2140, 1460,
1320, 1061, 735; NMR (400 MHz, CDCl3) ꢂH: 1.12 (3H,
t, J ¼ 7:5 Hz), 1.34–1.57 (11H, m), 2.15–2.18 (4H, m),

Concise Synthesis of Trienals and Dienal
1351
74.33; H, 10.68%. Calcd. for C13H22O2: C, 74.24; H,
10.54%.
ol 10 (0.93 g, 62%) was prepared from 9 as a light
yellow amorphous liquid. IR ꢁmax (film) cmꢁ1: 3368,
2930, 2860, 2220, 1464, 1313, 1061, 914, 735; NMR
(400 MHz, CDCl3) ꢂH: 0.89 (3H, t, J ¼ 7:3 Hz), 1.32–
1.51 (17H, m), 2.13–2.17 (4H, m), 3.11–3.13 (2H, m),
3.64 (2H, t, J ¼ 6:6 Hz); NMR (100 MHz, CDCl3) ꢂC:
10.10, 14.38, 18.55, 19.09, 22.61, 26.00, 28.84, 29.03,
29.18, 29.30, 31.46, 33.09, 63.36, 74.81, 74.93, 80.78,
80.93. Anal. Found: C, 82.03; H, 11.45%. Calcd. for
C17H28O: C, 82.20; H, 11.36%.
7,10,13-Hexadecatriyn-1-ol (7b). According to essen-
tially the same procedure as that used for the preparation
of 7a from 4 and 6a, triyn-1-ol 7b (0.65 g, 52%)
was prepared from 6b as a light yellow amorphous
liquid. IR ꢁmax (film) cmꢁ1: 3375, 3046, 2976, 2934,
2864, 2309, 2216, 1460, 1418, 1317, 1270, 1057, 739;
NMR (400 MHz, CDCl3) ꢂH: 1.12 (3H, t, J ¼ 7:4 Hz),
1.38–1.60 (9H, m), 2.15–2.18 (4H, m), 3.14 (4H, s), 3.65
(2H, t, J ¼ 6:6 Hz); NMR (100 MHz, CDCl3) ꢂC: 10.14,
10.18, 12.76, 14.24, 19.02, 25.63, 28:98 ꢂ 2, 32.99,
63.31, 73.51, 74.26, 75.20, 75.23, 81.08, 82.54. Anal.
Found: C, 83.22; H, 9.81%. Calcd. for C16H22O: C,
83.43; H, 9.63%.
(8Z,11Z)-8,11-Heptadecadien-1-ol (11). According to
essentially the same procedure as that just described,
dien-1-ol 11 (374 mg, 88%) was synthesized from 10 as
a colorless oil. IR ꢁmax (film) cmꢁ1: 3340, 3007, 2922,
2856, 1654, 1464, 1061, 914, 739; NMR (400 MHz,
CDCl3) ꢂH: 0.89 (3H, t, J ¼ 6:8 Hz), 1.26–1.41 (15H,
m), 1.53–1.58 (2H, m), 2.12–2.21 (4H, dt, J ¼ 7:0,
7.0 Hz), 2.77 (2H, t, J ¼ 6:8 Hz), 3.64 (2H, t, J ¼
6:6 Hz), 5.31–5.40 (4H, m); NMR (100 MHz, CDCl3)
ꢂC: 14.49, 22.98, 26.02, 26.11, 27:60 ꢂ 2, 29.65, 29.73,
29.75, 29.99, 31.93, 33.17, 63.44, 128.30, 128.42,
130.46, 130.61. Anal. Found: C, 80.96; H, 12.70%.
Calcd. for C17H32O: C, 80.88; H, 12.78%.
(7Z,10Z,13Z)-7,10,13-Hexadecatrien-1-ol (8b). Ac-
cording to essentially the same procedure as that used
for the preparation of 8a from 7a, trien-1-ol 8b (374 mg,
97%) was synthesized as a colorless oil. IR ꢁmax (film)
cmꢁ1: 3340, 3007, 2957, 2930, 2856, 1460, 1057, 913,
735; NMR (400 MHz, CDCl3) ꢂH: 0.98 (3H, t, J ¼
7:5 Hz), 1.27–1.39 (7H, m), 1.53–1.58 (2H, m), 2.02–
2.12 (4H, m), 2.81 (4H, t, J ¼ 6:0 Hz), 3.62 (2H, t,
J ¼ 6:6 Hz), 5.30–5.42 (6H, m); NMR (100 MHz,
CDCl3) ꢂC: 14.67, 20.94, 25.91, 26.00, 26.05, 27.55,
29.47, 29.99, 33.11, 63.29, 127.48, 128.16, 128.61,
128.67, 130.58, 132.34. Anal. Found: C, 81.20; H,
11.98%. Calcd. for C16H28O: C, 81.29; H, 11.94%.
(8Z,11Z)-8,11-Heptadecadienal (1c). According to
essentially the same procedure as that just described,
dienal 1c (36 mg, 65%) was synthesized from 11 as a
colorless oil. IR ꢁmax (film) cmꢁ1: 3007, 2926, 2860,
2712, 1731, 1464, 918, 735; NMR (400 MHz, CDCl3)
ꢂH: 0.89 (3H, t, J ¼ 6:8 Hz), 1.28–1.37 (12H, m), 1.62–
1.65 (2H, m), 2.02–2.08 (4H, m), 2.43 (2H, td, J ¼ 7:3,
1.8 Hz), 2.77 (2H, t, J ¼ 6:1 Hz), 5.29–5.42 (4H, m),
9.77 (1H, t, J ¼ 1:8 Hz); NMR (100 MHz, CDCl3) ꢂC:
14.49, 22.43, 22.98, 26.01, 27.51, 27.60, 29.39, 29.45,
29.75, 29.81, 31.93, 44.30, 128.24, 128.58, 130.26,
130.65, 203.33. Anal. Found: C, 81.36; H, 12.11%.
Calcd. for C17H30O: C, 81.54; H, 12.08%.
(7Z,10Z,13Z)-7,10,13-Hexadecatrienal (1b). Accord-
ing to essentially the same procedure as that used for the
preparation of 1a from 8a, trienal 1b (97 mg, 60%) was
synthesized as a colorless oil. IR ꢁmax (film) cmꢁ1: 3011,
2965, 2929, 2860, 2724, 1728, 1464, 914, 735; NMR
(400 MHz, CDCl3) ꢂH: 0.98 (3H, t, J ¼ 7:5 Hz), 1.32–
1.39 (4H, m), 1.62–1.68 (2H, m), 2.04–2.10 (4H, m),
2.43 (2H, td, J ¼ 7:3, 1.8 Hz), 2.82 (4H, t, J ¼ 6:6 Hz),
5.32–5.41 (6H, m), 9.77 (1H, t, J ¼ 1:8 Hz); NMR
(100 MHz, CDCl3) ꢂC: 14.70, 20.96, 22.38, 25.93, 26.01,
27.39, 29.18, 29.75, 44.28, 127.46, 128.43, 128.53,
128.76, 130.28, 132.40, 203.27. Anal. Found: C, 81.78;
H, 11.28%. Calcd. for C16H26O: C, 81.99; H, 11.18%.
Acknowledgments
This work was supported in part by a Grant-in-Aid for
scientific research from the Ministry of Education,
Culture, Sports, Science and Technology of Japan (No-
14760134).
2-Octynyl bromide (9). According to essentially the
same procedure as that just described, bromide 9 (8.84 g,
62%) was prepared from 2 as a colorless oil. IR ꢁmax
(film) cmꢁ1: 2960, 2930, 2850, 2230, 1200; NMR
(250 MHz, CDCl3) ꢂH: 0.89 (3H, t, J ¼ 7:3 Hz), 1.24–
1.38 (4H, m), 2.12–2.21 (2H, m), 1.40–1.56 (2H, m),
3.93 (2H, t, J ¼ 2:4 Hz); NMR (62.5 MHz, CDCl3) ꢂC:
13.88, 15.65, 18.91, 22.15, 27.61, 30.99, 75.26, 88.26.
Anal. Found: C, 50.92; H, 6.73%. Calcd. for C8H13Br:
C, 50.81; H, 6.93%.
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