A convenient synthesis of functionalised 1-aryl-1,3-alkadiynes

Article abstract of DOI:10.1002/ejoc.200400688

A two-step, one-pot synthesis of functionalised 1-arylalka-1,3-diynes is described. A key feature in this approach is exploitation of the "acetylene zipper" reaction to obtain terminal 1,3-alkadiynes 3 from internal isomers 1. Without isolation, but after

Full text of DOI:10.1002/ejoc.200400688

FULL PAPER
A Convenient Synthesis of Functionalised 1-Aryl-1,3-alkadiynes
Irina A. Balova,*[a] Victor N. Sorokoumov,[a] Svetlana N. Morozkina,[a]
Olga V. Vinogradova,[a] David W. Knight,[b] and Sergey F. Vasilevsky[c]
Keywords: 1,3-Alkadienes / Acetylene zipper / 1-Arylalka-1,3-diynes / Cross-coupling / Rearrangement
A two-step, one-pot synthesis of functionalised 1-arylalka-
1,3-diynes is described. A key feature in this approach is ex-
ploitation of the “acetylene zipper” reaction to obtain ter-
minal 1,3-alkadiynes 3 from internal isomers 1. Without isola-
tion, but after protonation, the 1,3-alkadiynes 3 are subjected
to subsequent Pd/Cu-catalyzed Sonogashira cross-couplings
with aryl iodides having both electron-withdrawing and elec-
tron-donating groups. The whole sequence takes place un-
der mild reaction conditions to afford functionalised 1-aryl-
alka-1,3-diynes 21–35 in high yields.
(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
Germany, 2005)
The Cadiot–Chodkiewicz coupling,[18] consisting of the
union of terminal alkynes with 1-bromoacetylenes in the
Introduction
Functionalized acetylene derivatives, due to their high presence of a copper(i) salt, is useful and important for the
synthetic potential, are often indispensable in pathways to synthesis of unsymmetrically substituted diynes. A variety
complicated molecules. Additional applications followed of other heterocoupling methods have also been devel-
from Castro’s original discovery[1,2] that suitably positioned oped.[19,20] However, a general problem associated with
nucleophiles can undergo intramolecular cyclizations onto these is the prevalence of homo-coupling side reactions,
acetylene groups. Many studies have shown functionalised arising by halogen-metal exchange. Dramatic increases in
aryl- and heteraryl-acetylenes to be useful precursors for a such by-product formation can occur in such reactions
wide variety of heterocyclic systems.[3–5] However, a careful when these are applied to long-chain acetylenes. It is also
review of the literature revealed that examples of similar relevant that cross-coupling methods require prior synthesis
reactions involving buta-1,3-diynyl-substituted arenes are of the alkyne and especially the 1-bromoalkyne compo-
limited[5,6–9] due to the lack of convenient preparative meth- nents. From these points of view, the development of new
ods to the necessary functionalised aryldiynes. For example, and convenient methods for the synthesis of conjugated di-
the synthesis of arylbutadiynes from the corresponding 1,3- ynes in general is clearly desirable. As a part of our program
diketones[10] is unsuitable for the preparation of function- exploring the chemistry of functionalised diynes,[21,22] we
alised derivatives. The far-reaching synthetic applications of report herein a method that allows the synthesis of func-
the Pd-Cu-catalyzed cross-coupling reaction between tionalised 1-arylalka-1,3-diynes from simple starting mate-
haloarenes and halo-heteroarenes with terminal acetylenes rials in a convenient and efficient manner.
(the Sonogashira reaction).[11] have been demonstrated in
many fields of chemistry, including polymer and supramol-
Results and Discussion
ecular synthesis.[12–15] In comparison with 1-alkynes, appli-
cations of 1,3-diynes as the acetylenic component in such
couplings is notably limited, mainly due to their lower sta-
bility and availability.[16,17]
We have previously reported the first examples of an one-
pot synthesis of 1-arylalka-1,3-diynes by sequential zipper
and Sonogashira reactions.[23] Consequently, we have car-
ried out a detailed study of the scope and limitations of this
approach and herein, we report in full the results of our
findings. The coupling reactivity of a series of iodo- and
bromoarenes, having both electron-withdrawing and elec-
tron-donating substituents, has been tested in reactions with
1,3-diynes, formed in situ by “acetylene zipper” reactions
(Scheme 1). Palladium acetate, [PdCl2(PPh3)2] and
[PdPPh3)4] in the presence of CuI, PPh3 and Et3N, have
been used as catalytic systems for these Sonogashira reac-
tions. The representative haloarene substrates 5–20 are de-
picted in Scheme 2.
[a] Saint-Petersburg State University, Chemical Faculty, Depart-
ment of Organic Chemistry,
Universitetskjj pr. 26, Saint-Petersburg, 198504, Russia
Fax: (internat.) +7-812-4286939,
E-mail: blv@rol.ru
[b] Cardiff School of Chemistry, Cardiff University,
P. O. Box 912, Cardiff, CF10 3TB, UK
Fax: (internat.) +44-2920-874210,
E-mail: knightdw@cf.ac.uk
[c] Institute of Chemical Kinetics & Combustion of Russian Acad-
emy of Sciences,
Institutskaya Str. 3, Novosibirsk, 630090, Russia
E-mail: Vasilev@ns.kinetics.nsc.ru
882
© 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
DOI: 10.1002/ejoc.200400688
Eur. J. Org. Chem. 2005, 882–888

A Convenient Synthesis of Functionalised 1-Aryl-1,3-alkadiynes
FULL PAPER
Table 2. Couplings of 1,3-diynes 3a–d with aryl iodides 5–19
(Scheme 2)
Entry ArI Product Method
Ratio
ArI:1
Yield of product
[%]
1
2
3
4
5
6
7
8
5
6
7
8
5
5
9
21b
22b
23b
24b
21b
21a
25b
A
A
A
A
A
A
B
B
A
A
A
A
B
B
A
B
A
A
B
B
B
B
A
A
B
1:1
1:1
1:1
1:1
72
86
49
69
93–95
77–87
27
99
77
72
92
77–88
99
98
63
71
93
80
1:1.25
1:1.25
1:1.5
1:2.5
1:1.25
1:1.25
1:1.25
1:1.25
1:1.25
1:1.25
1:1.25
1:1.25
1:5
1:1.25
1:1.25
1:1.5
1:2.5
1:1.5
1:1.5
1:1.5
1:1.5
10 26b
23b
9
7
10
11
12
13
14
15
16
17[b]
18
19
20[a]
21[a]
22[b]
23
24
25[b]
11 27b
12 28b
12 28a
13 29b
14 30b
15 31b
15 31b
16 32b
17 33b
19 35b
19 35b
19 35b
19 35c
18 34d
Scheme 1. i) 3 Equiv. lithium 2-aminoethylamide (LAETA), THF,
C6H6, hexane, (1:1:1), 16° C, add diyne 1, 10 min.; ii) add H2O (0.2
mL mmol–1 of diyne 1; iii) 0.8 equiv. ArI 5–20, 0.08 equiv. Pd cata-
lyst (see Table 2), Et3N (2 mL mmol–1 of diyne 1), 0.12 equiv. CuI,
0.5–12 h, 16– 40° C (see Table 1 and Table 2)
96
95
54
92
90
67
77
5
21d
11 27c
[a] [PdCl2(PPh3)2] was used as a catalyst. [b] [Pd(PPh3)4] was used
as a catalyst. In other Entries Pd(OAc)2 was used. All yields iso-
lated.
The resulting lithium acetylides 2 were then quenched by
the addition of water. With no further work-up, the subse-
quent Sonogashira couplings with iodoarenes 5–19 in the
presence of the Pd-Cu catalyst system led to the desired
products 21–35 in good to excellent yields. All reactions
were carried out under argon at ambient temperature or
with slight heating (40 °C) until TLC indicated complete
conversion of the starting iodides. In general, iodoarenes
having either electron-withdrawing or electron-donating
groups readily reacted with the 1,3-diynes 3 to afford the
expected cross-coupling products. The results are summa-
rized and hence the scope of the method indicated in
Table 2. Evidently, the presence of a small amount of water
Scheme 2
1,3-Decadiyne (3a), 1,3-dodecadiyne (3b), 1,3-tetradeca- has no deleterious effect on the Sonogashira coupling step.
diyne (3c) and 1,3-hexadecadiyne (3d) were obtained in situ Homo-coupled products, the tetraynes 4, were also iso-
from the internal diynes 1a–d respectively, by treatment lated from the reaction mixtures, initially in yields of 8–
with three equivalents of lithium 2-aminoethylamide LA- 14 %, with respect to the starting alkynes 1. The formation
ETA). This step is remarkably rapid, reaching completion of such products during Sonogashira reactions has been ob-
within a few minutes at ambient temperature 16–18 °C). served earlier and a mechanism which accounts for this has
Table 1. Influence of reaction conditions and temperature on the yield of products 21b and 31b (ratio ArI:diyne 1 = 1:1.25)
Entry
ArI
Time
T [°C]
Method
Yield of 4 [%]
Yield of product [%]
1, 2
3
4
5
6
5
5
5
5
7
7
12 h
10 h
6 h
30 min
12 h
room temp.
40 °C
room temp.
40 °C
40 °C
room temp.
A
A
B
B
A
B
2–4
4
3
2
6
93–95
77
81
92
63
7
10 min
2
71
Eur. J. Org. Chem. 2005, 882–888
www.eurjoc.org
© 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
883

I. A. Balova et al.
FULL PAPER
been proposed.[15] In an attempt to increase the yields of acid has also been reported, together with formation of the
the target products 3 and reduce this homo-coupling, the corresponding isocoumarins, as minor products;[26] no
molar ratio of the starting diynes 1, relative to the iodoar- traces of isocoumarin or non-cyclized cross-coupling pro-
enes, was varied. We established that a 1.25 fold excess of ducts were detected in the present case. It should be noted
diynes 1a–c with respect to the iodoarene was necessary to that similar cyclizations did not occur in reactions with or-
complete the conversion. Fortunately, this molar ratio also tho-amino derivatives.
led to a decrease in the yield of the tetrayne by-products 4
to 1–4 %. In contrast, reactions involving 1,3-hexadeca-
diyne (3d) and aryl iodides were completed only when a 1.5
fold excess of hexadeca-7,9-diyne (1d) was used initially.
Because the syntheses were carried out in a one-pot pro-
cess (Procedure A, see Exp. Sect.), the resulting mixture of
solvents contained ethylenediamine (EDA), benzene, hex-
Scheme 3
ane and THF. It is known that PdII can form stable com-
plexes with EDA.[24] To elucidate the influence of EDA on
the present Pd-catalyzed couplings, some experiments in
which this component had been removed were conducted
(Procedure B) in couplings with 1,3-dodecadiyne (3b). 2-
Iodoaniline (5) and 4-iodobenzaldehyde (7) were chosen as
model substrates. From the results presented in Table 1, it
can be seen that, in the examples where EDA had been
removed, the coupling reactions required significantly
shorter reaction times and/or a lower reaction temperature.
Removing the EDA also led to slightly increased yields. De-
spite this finding, the simplicity of the one-pot procedure
(A) can make this preferable. Crucially, however, procedure
B had to be used in reactions with less reactive iodoarenes,
having several electron-donating groups [13, 14], along with
couplings to 2-iodobenzoic acid (9) and the polyhalogen-
ated substrates 10, 16 and 19.
In an effort to extend this method to the synthesis of
poly(butadiynes), we examined the reactions of 1,3-dodeca-
diyne 3b with 2,5-diiodothiophene and 1,2,4,5-tetraiodob-
enzene (Table 2; Entries 8 and 17). This idea was successful:
the reactions occurred rapidly at ambient temperature and
2,5-bis(dodeca-1,3-diynyl)thiophene (26b) and 1,2,4,5-
tetrakis(dodeca-1,3-diynyl)benzene (32b) were obtained in
high yields.
According to our results, the nature of the substituents
(i. e. electron-withdrawing or -donating) on the iodoarenes
did not have a great influence on the course of the cross-
coupling Sonogashira reactions. One exception was in the
case of an ortho-carboxylic acid group. Thus, reaction of 2-
iodobenzoic acid (9) with 1,3-dodecadiyne (3b), in the pres-
ence of the [Pd(PPh3)2Cl2] – CuI – Et3N catalyst system
using procedure B, was complete in 10 min at ambient tem-
perature. However, there was an unexpected increase in the
yield of the tetrayne by-product 4b and a low yield of a
cross–coupled product. This turned out to be the ylideneph-
thalide 25b, due to a subsequent and additional cyclisation
(Scheme 3). The phthalide 25b and tetrayne 4b were sepa-
rated from the reaction mixture in yields of 27 % and 15 %
respectively (Table 2, Entry 7). The Castro reaction of cop-
per acetylides with 2-iodobenzoic acid can afford either or
both isocoumarins or phthalides, depending upon the exact
conditions and nature of the acetylenes.[2,5,25] The synthesis
of phthalides by [Pd(PPh3)2Cl2] – CuI – Et3N catalysed
We also tested the reactivity of bromoarenes in this pro-
cess. In contrast to iodoarenes, which reacted readily in the
presence of either Pd(OAc)2 or [PdCl2(PPh3)2], 1,3-dodeca-
diyne (3b) did not react with bromoarenes using procedure
A or B. This result is not surprising, given the established
lower reactivity of bromides in comparison with iodoarenes.
Usually, cross-couplings of terminal alkynes with bromo
derivatives requires significantly higher temperatures and
prolonged reaction times (12–72h). Even 2-bromo-4-nitro-
aniline did not react with 1,3-dodecadiyne 3b in the pres-
ence of Pd(OAc)2 at 40 °C. Increasing the temperature to
80 °C resulted in decomposition of the unstable 1,3-diyne
3b and only homocoupled product 4b and starting material
20 were detected by TLC monitoring. Of course, this lack
of reactivity can be utilised in a positive sense. Thus, 1-
bromo-4-iodobenzene (19) afforded only 1-(4-bromophe-
nyl)dodeca-1,3-diyne (35b) in the presence of Pd(OAc)2 or
[PdCl2(PPh3)2] (Table 2; Entries 19, 20). Using a 2.5 molar
excess of starting diyne and [PdCl2(PPh3)2] as catalyst, at
80 °C also led to the bromophenyl derivative 35b, which
was obtained in 54 % yield (Table 2, Entry 21). The yield
decrease was a consequence of decomposition of the un-
stable terminal diyne 1b under these conditions. A similar
product 35c was separated from the reaction of 1,3-tetrade-
cadiyne 2c with 1-bromo-4-iodobenzene in the presence the
more active catalyst [Pd(PPh3)4] (Table 2, Entry 22), but
now in excellent yield.
Conclusions
A novel and synthetically convenient approach to func-
tionalised 1-aryl-1,3-alka-diynes has been developed which
can be applied to a wide range of electronically diverse aryl
iodides.
Experimental Section
General Remarks: All reactions were performed under dry argon
and all solvents were dried according to standard methods. Deca-
4,6-diyne (1a), dodeca-5,7-diyne (1b), tetradeca-6,8-diyne (1c) and
hexadeca-7,9-dyne (1d) were prepared by an oxidative coupling
method.[27] [PdCl2(PPh3)2], Pd(OAc)2, [Pd(PPh3)4], CuI and Et3N
were used as purchased. IR spectra were recorded using a Specord-
1
M80. H and 13C NMR spectra were recorded with a Bruker AX-
cross coupling of terminal acetylenes with 2-iodobenzoic 300 spectrometer at 300 and 75 MHz, respectively. Solvent reso-
884 © 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim www.eurjoc.org
Eur. J. Org. Chem. 2005, 882–888

A Convenient Synthesis of Functionalised 1-Aryl-1,3-alkadiynes
FULL PAPER
nances were used as internal standards. Thin layer chromatography
was performed on glass plates, pre-coated with Merck Kieselgel 60
to 0.5 mm thickness. CHN analyses were performed in the analyti-
cal laboratory of the Saint-Petersburg State University using a Per-
kin–Elmer B18 instrument. GC/MS analysis was performed an Ag-
ilent 68–90, MS detector Agilent 5973 (ionization voltage 70eV).
Tetraynes 4 have been characterized earlier.[28] Starting iodides 5–
7, 10, 11, 17 and 19 are commercially available. Other iodides were
prepared by known methods.[29–32]
80.0, 86.4, 107.1, 114.9, 118.4, 130.6, 133.5, 149.6 ppm. IR (CCl4):
ν = 3500, 3400, 3080, 2925, 2850, 2240, 2150, 1610, 1470, 1400,
˜
1255, 840 cm–1. MS (EI): m/z (%) = 253 (100) [M+], 224 (23), 210
(34), 196 (22), 184 (56), 160 (17), 146 (28), 130 (53), 106 (35).
C18H23N (253.4): calcd. C 85.32, H 9.15, N 5.53; found C 85.24,
H 9.13, N 5.63.
The separation of 2-(dodeca-1,3-diynyl)aniline (21b) was also
modified: upon completion, the reaction mixture was concentrated
in vacuo. The dark residue was re-dissolved in dry hexane and dry
hydrogen chloride gas was passed through the solution for 30 min.
The resulting hydrochloric salt of 21b was filtered and dried. This
separation has the advantage of removing the requirement for puri-
fication by chromatography. The yield of the salt was 74 %; how-
ever, it is more stable when compared with aniline 21b and could
be stored for a longer time.
General Acetylene Zipper Procedure: LAETA was obtained by the
reaction of lithium metal (53 mg, 7.5 mmol) with absolute ethylene
diamine (0.6 mL, 7.5 mmol) in dry THF (1.8 mL). After lithium
dissolution, benzene (1.8 mL) and hexane (1.8 mL) were added to
the resulting straw-coloured suspension of LAETA. The resulting
mixture was cooled to 16 °C, the diyne 1 (2.5 mmol) added by sy-
ringe and the final mixture stirred at 16–18 °C for 10 min.
2-(Hexadeca-1,3-diynyl)aniline (21d): Hexadeca-7,9-diyne (1d,
654 mg, 3 mmol) was used to obtain 1,3-hexadecadiyne (3d) which
was reacted with 2-iodoaniline (5, 438 mg, 2 mmol) using pro-
cedure A. Chromatography on silica gel (hexanes/CH2Cl2, 2:1) af-
General in situ 1,3-Diyne Coupling. Procedure A: When the “acety-
lene zipper” reaction was complete, water (0.5 mL) was added to
the dark-brown reaction mixture. An aryl iodide (2 mmol), the pal-
ladium catalyst (0.2 mmol, see Table 2), triphenylphosphane
(52.5 mg, 0.2 mmol), triethylamine (5 mL) and copper(i) iodide
(57 mg, 0.3 mmol) were then added sequentially, in this order, to
the stirred reaction mixture. TLC was used to monitor the progress
of the reaction. Upon completion, the reaction mixture was poured
into ice-water and the resulting mixture extracted with dichloro-
methane (4 × 25 mL). The combined organic extracts were washed
with water and dried with MgSO4. After solvent evaporation, the
product was isolated by flash chromatography on silica gel, eluting
with hexane, then hexane/CH2Cl2 mixtures. The reactions are scal-
able: only a slight decrease in yields were observed using 5 g of the
diynes 1.
forded the diyne 21d (409 mg, 67 %) as a light yellow oil, R
=
f
0.24 (hexanes/CH2Cl2, 4:1), which slowly crystallised, m. p. 31 °C.
1H NMR (300 MHz, CDCl3): δ = 0.91 (t, J = 7 Hz, 3 H), 1.21–
1.67 (m, 20 H), 2.39 (t, J = 7 Hz, 2 H), 4.28 (s, 2 H, NH2), 6.65–
6.69 (m, 2 H), 7.14 (t, J = 7 Hz, 1 H), 7.28 (t, J = 7 Hz, 1 H) ppm.
13C NMR (75 MHz, CDCl3): δ = 14.6, 20.1, 23.1, 28.7, 29.3, 29.5,
29.8, 29.9, 30.0, 30.1, 30.2, 32.3, 65.5, 72.1, 80.0, 86.3, 106.9, 114.7,
118.3, 130.6, 133.5, 149.9 ppm. IR (CCl ): ν = 3505, 3405, 3080,
˜
4
3030, 2950, 2850, 2230, 2150, 1600, 1480, 1455, 1300, 900 cm–1.
MS (EI): m/z (%) = 309 (100) [M+], 224 (11), 196 (26), 182 (23),
168 (23), 167 (22), 156 (57), 154 (51), 130 (34), 117 (26), 106 (37).
C22H31N (309.5): calcd. C 85.38, H 10.10, N 4.53; found C 85.23,
H 10.02, N 4.57.
1,3-Diyne Coupling after Removal of Ethylene Diamine. Procedure
B: When the “acetylene zipper” reaction was complete, the dark-
brown reaction mixture was poured into ice-water and the mixture
shaken. The organic layer was separated, returned to the flask, then
the coupling reaction was carried out as described in Procedure A.
4-(Dodeca-1,3-diynyl)acetophenone (22b): Dodeca-5,7-diyne (1b,
405 mg, 2.5 mmol) was used to obtain 1,3-dodecadiyne (3b) which
was reacted with 4-iodoacetophenone (6, 492 mg, 2 mmol) (Pro-
cedure A). Chromatography on silica gel (hexanes/CH2Cl2, 4:1) af-
forded the diyne 22b (482 mg, 86 %) as a light yellow oil. R
=
2-(Deca-1,3-diynyl)aniline (21a): Deca-4,6-diyne (1a, 335 mg,
2.5 mmol) was used to obtain 1,3-decadiyne (3a) which was reacted
with 2-iodoaniline (5, 438 mg, 2 mmol) (Procedure A). Chromatog-
raphy on silica gel (hexane/CH2Cl2, 2:1) afforded the diyne 21a
f
0.37 (hexanes/CH2Cl2, 4:1). 1H NMR (300 MHz, CDCl3): δ = 0.89
(t, J = 7 Hz, 3 H), 1.09–1.55 (m, 10 H), 1.60 (quint., J = 7 Hz, 2
H), 2.37 (t, J = 7 Hz, 2 H), 2.58 (s, 3 H), 7.53 (d, J = 9 Hz, 2 H),
7.65 (d, J = 9 Hz, 2 H) ppm. 13C NMR (75 MHz, CDCl3): δ =
14.5, 20.0, 23.0, 28.6, 29.3, 29.4, 29.5, 32.2, 27.0, 65.3, 74.1, 78.1,
(435 mg, 87 %) as a light yellow oil. R = 0.27 (hexanes/CH2Cl2,
f
4:1). 1HNMR (300 MHz, CDCl3): δ = 0.90 (t, J = 7 Hz, 3 H), 1.18–
1.32 (m, 8 H), 2.35 (t, J = 7 Hz, 2 H), 4.44 (s, 2 H, NH2), 6.65–
6.72 (m, 2 H), 7.11 (t, J = 7 Hz, 1 H), 7.27 (t, J = 7 Hz, 1 H) ppm.
13C NMR (75 MHz, CDCl3): δ = 14.3, 20.0, 23.1, 28.7, 29.5, 32.3
65.7, 71.7, 80.0, 86.3, 107.2, 114.5, 118,0, 130.4, 133.3, 149.3 ppm.
87.2, 127.5, 128.6, 133.0, 136.9, 197.4 ppm. IR (CCl ): ν = 3090,
˜
4
2245, 1680, 1600, 1470, 1430, 1400, 1250 cm–1. MS (EI): m/z (%)
= 280 (48) [M+], 251 (21), 237 (42), 223 (37), 199 (54), 185 (44),
171 (17), 167 (100), 139 (19). C20H24O (280.4): calcd. C 85.67, H
8.63; found C 85.66, H 8.57.
IR (CCl ): ν = 3495, 3390 (NH ), 3070, 2960, 2230, 2140, 1620,
˜
4
2
1560, 1470, 1400, 1255, 840 cm–1. MS (EI): m/z (%) = 225 (100)
[M+], 196 (30), 186 (40), 182 (30), 154 (70), 144 (10), 130 (33), 117
(33). C16H19N (225.3): calcd. C 85.28, H 8.50, N 6.22; found C
85.29, H 8.45, N 6.03.
4-(Dodeca-1,3-diynyl)benzaldehyde (23b): Dodeca-5,7-diyne (1b,
405 mg, 2.5 mmol) was used to obtain 1,3-dodecadiyne (3b) which
was reacted with 4-iodobenzaldehyde (7, 464 mg, 2 mmol) (Pro-
cedure A). Chromatography on silica gel (hexanes/CH2Cl2, 4:1) af-
forded the diyne 23b (410 mg, 77 %), m. p. 34–36 °C. 1H NMR
(300 MHz, CDCl3): δ = 0.89 (t, J = 7 Hz, 3 H), 1.29–1.44 (m, 10
H), 1.59 (quint., J = 7 Hz, 2 H), 2.38 (t, J = 7 Hz, 2 H), 7.61 (d, J
= 9 Hz, 2 H), 7.82 (d, J = 9 Hz, 2 H), 10.00 (s, 1 H) ppm. 13C
NMR (75 MHz, CDCl3): δ = 14.5, 20.0, 23.0, 28.5, 29.3, 29.4, 29.5,
32.2, 65.2, 73.9, 78.8, 87.8, 128.9, 129.9, 133.4, 136.1, 191.6 ppm.
2-(Dodeca-1,3-diynyl)aniline (21b): Dodeca-5,7-diyne (1b, 405 mg,
2.5 mmol) was used to obtain 1,3-dodecadiyne (3b) which was re-
acted with 2-iodoaniline (5, 438 mg, 2 mmol) (Procedure A). Chro-
matography on silica gel (hexane/CH2Cl2, 2:1 ) afforded the diyne
21b (481 mg, 95 %) as an oil. Using Procedure B, the product 21b
was obtained in 92 % yield (466 mg, 1.84 mmol). R = 0.22 (hex-
f
1
anes/CH2Cl2, 4:1). H NMR (300 MHz, CDCl3): δ = 0.89 (t, J =
IR (CCl ): ν = 3090, 2950, 2930, 2850, 2245, 1680, 1600, 1470,
˜
4
7 Hz, 3 H), 1.21–1.42 (m, 10 H), 1.57 (quint., J = 7 Hz, 2 H), 2.39
1430, 1400, 1250 cm–1. MS [EI]: m/z (%) = 266 (31) [M+], 239 (29),
(t, J = 7 Hz, 2 H), 4.29 (s, 2 H, NH2), 6.66–6.71 (m, 2 H), 7.14 (t, 225 (100), 211 (44), 209 (46, 181 (98), 165 (78), 155 (50), 139 (99),
J = 7 Hz, 1 H), 7.31 (t, J = 7, 1 H) ppm. 13C NMR (75 MHz,
107 (45), 104 (79), 77 (71). C19H22O (266.4): calcd. C 85.67, H 8.32;
CDCl3): δ = 14.5, 20.1, 23.1, 28.7, 29.3, 29.5, 29.6, 32.3, 65.4, 72.0, found C 85.39, H 8.25.
Eur. J. Org. Chem. 2005, 882–888
www.eurjoc.org
© 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
885

I. A. Balova et al.
FULL PAPER
Methyl 4-(Dodeca-1,3-diynyl)benzoate (24b): Dodeca-5,7-diyne (1b,
405 mg, 2.5 mmol) was used to obtain 1,3-dodecadiyne (3b) which
was reacted with methyl 4-iodobenzoate (8, 524 mg, 2 mmol) (Pro-
cedure A). Chromatography on silica gel (hexanes/CH2Cl2, 4:1) af-
which was reacted with 1-iodo-4-nitrobenzene 11 (498 mg, 2 mmol)
(Procedure B). Chromatography on silica gel (hexanes/CH2Cl2, 4:1)
afforded the diyne 27c (480 mg, 77 %) as an oil. R f = 0.43 (hexanes/
1
CH2Cl2, 4:1). H NMR (300 MHz, CDCl3): δ = 0.89 (t, J = 7 Hz,
forded the diyne 24b (408 mg, 69 %) as an oil. R f = 0.43 (hexanes/
3 H), 1.30–1.43 (m, 14 H), 1.60 (quint., J = 7 Hz, 2 H), 2.37 (t, J
1
CH2Cl2, 4:1). H NMR (300 MHz, CDCl3): δ = 0.93 (t, J = 7 Hz, = 7 Hz, 2 H), 7.34 (d, J = 8 Hz, 2 H), 7.46 (d, J = 8 Hz, 2 H) ppm.
3 H), 1.30–1.62 (m, 12 H), 2.48 (t, J = 7 Hz, 2 H), 4.02 (s, 3 H), 13C NMR (75 MHz, CDCl3): δ = 14.5, 20.0, 23.1, 28.4, 28.6, 29.3,
7.53 (d, J = 8 Hz, 2 H), 7.71 (d, J = 8 Hz, 2 H) ppm. 13C NMR
(75 MHz, CDCl3): δ = 14.5, 21.0, 23.0, 28.5, 29.4, 29.5, 29.6, 32.3,
51.5, 65.6, 74.5, 78.5, 89.3, 125.0, 130.5, 130.6, 133.7, 177.1 ppm.
29.5, 29.7, 29.9, 30.0, 32.3, 65.4, 73.9, 76.1, 86.0, 121.6, 123.6,
132.1, 134.2 ppm. IR (CCl ): ν = 3120, 2230, 1585, 1475, 1450,
˜
4
1260, 850 cm–1. MS (EI): m/z (%) = 311 (25) [M+], 207 (19), 283
IR (CCl ): ν = 3095, 2955, 2920, 2850, 2245, 1730, 1600, 1470, (24), 269 (54), 255 (29), 241 (37), 227 (53), 213 (51), 199 (100), 123
˜
4
1430, 1400, 1240 cm–1. MS (EI): m/z (%) = 298 (15) [M+], 239 (68),
(77). C20H25NO2 (311.4): calcd. C 77.13, H 8.09, N 4.50; found C
186 (100), 181 (95), 91 (10). C20H24O2 (296.4): calcd. C 81.04, H 77.05, H 8.22, N 4.37.
8.16; found C 81.15, H 8.31.
2-(Deca-1,3-diynyl)-4-nitro-1-naphthylamine (28a): Deca-4,6-diyne
3-(Undec-2-ynylidene)phthalide (25b): Dodeca-5,7-diyne (1b,
405 mg, 2.5 mmol) was used to obtain 1,3-dodecadiyne (3b) which
was reacted with 2-iodobenzoic acid (9, 496 mg, 2 mmol) according
to Procedure B. Chromatography on silica gel (hexane/CH2Cl2, 1:1)
separated the ylidenephthalide 25b as a light brown oil (149 mg,
(1a, 335 mg, 2.5 mmol) was used to obtain 1,3-decadiyne (3a)
which was reacted with 2-iodo-4-nitro-1-naphthylamine (12,
628 mg, 2 mmol) (Procedure A). Chromatography on silica gel
(hexanes/CH2Cl2, 2:1) afforded the amine 28a (563 mg, 88 %) as a
solid, m. p. 134–136 °C. R f = 0.56 (hexane/CH2Cl2, 1:1). 1H NMR
27 %). R = 0.48 (hexanes/CH2Cl2, 1:1). 1H NMR (300 MHz, (300 MHz, CDCl3): δ = 0.89 (t, J = 7 Hz, 3 H), 1.22–1.38 (m, 6
f
CDCl3): δ = 0.88 (t, J = 7 Hz, 3 H), 1.23–1.49 (m, 10 H), 1.60
(quint., J = 7 Hz, 2 H), 2.45 (td, J = 7 and 2.8 Hz, 2 H), 5.68 (t, J NH2), 7.62 (t, J = 8 Hz, 1 H), 7.77 (t, J = 8 Hz, 1 H), 7.89 (d, J =
= 2.8 Hz, 1 H), 7.55 (t, J = 7 Hz, 1 H), 7.64–7.74 (m, 2 H), 7.90
8 Hz, 1 H), 8.39 (s, 1 H), 8.89 (d, J = 8 Hz, 1 H) ppm. 13C NMR
(d, J = 8 Hz, 1 H) ppm. 13C NMR (75 MHz, CDCl3): δ = 14.5, (75 MHz, CDCl3): δ = 14.1, 20.1, 23.1, 29.3, 29.5, 32.2, 66.1, 70.0,
20.5, 23.1, 29.0, 29.4, 29.5, 29.6, 32.2, 74.3, 89.0, 102.2, 120.2, 81.3, 87.9, 116.9, 121.3, 122.2, 124.8, 126.9, 127.4, 130.1, 130.9,
H), 1.57 (quint., J = 7 Hz, 2 H), 2.47 (t, J 7 Hz, 2 H), 5.86 (s, 2 H,
124.6, 126.0, 130.8, 134.9, 139.0, 152.9, 166.4 ppm. IR (CCl ): ν =
136.1, 153.1. IR (CCl ): ν = 3535, 3480, 3425, 2290, 2260, 2150,
˜
˜
4
4
3115, 3065, 2975, 2940, 2870, 2220, 2065, 1990, 1950, 1850, 1800,
1765, 1660, 1625, 1475, 1360, 1280, 1210, 1180, 1100, 980, 770,
1630, 1370. MS (EI): m/z (%) = 320 (28) [M+], 303 (10), 188 (14), 97
(100). C20H20N2O2 (320.4): calcd. C 74.98, H 6.29, N 8.74; found C
695 cm–1. MS (EI): m/z (%) = 282 (17) [M+], 267 (7), 253 (9), 239 74.72, H 6.33, N 8.69.
(8), 225 (8), 211 (11), 197 (100), 183 (22), 170 (40), 146 (43), 91
(56). C19H22O2 (282.4): calcd. C 80.82, H 7.85; found C 80.57; H
7.88.
2-(Dodeca-1,3-diynyl)-4-nitro-1-naphthylamine (28b): Dodeca-5,7-
diyne (1b, 405 mg, 2.5 mmol) was used to obtain 1,3-dodecadiyne
(3b) which was reacted with 2-iodo-4-nitro-1-naphthylamine (12,
628 mg, 2 mmol) (Procedure A). Chromatography on silica gel
(hexanes/CH2Cl2, 2:1) afforded the amine 28b (640 mg, 92 %) as a
solid, m. p. 112–114 °C. R f = 0.59 (hexanes/CH2Cl2, 1:1). 1H NMR
(300 MHz, CD2Cl2): δ = 0.92 (t, J = 7 Hz, 3 H), 1.21–1.46 (m, 10
H), 1.63 (quint., J = 7 Hz, 2 H), 2.45 (t, J = 7 Hz, 2 H), 5.90 (s, 2
2,5-Bis(dodeca-1,3-diynyl)thiophene (26b): Dodeca-5,7-diyne (1b,
810 mg, 5 mmol) was used to obtain 1,3-dodecadiyne (3b) which
was reacted with 2,5-diiodothiophene (10, 772 mg, 2 mmol) (Pro-
cedure B). Chromatography on silica gel (hexane) afforded the
bis(diynylthiophene) 26b (801 mg, 99 %) as a light yellow oil. R
f
= 0.8 (hexane). 1H NMR (300 MHz, CDCl3): δ = 0.89 (t, J = 6 Hz, H, NH2) 7.61(t, J = 8 Hz, 1 H), 7.76 (t, J = 8 Hz, 1 H), 7.91 (d, J
6 H), 1.22–1.61 (m, 24 H), 2.39 (t, J = 7 Hz, 4 H), 7.09 (s, 2 H)
ppm. 13C NMR (75 MHz, CDCl3): δ = 14.5, 20.2, 23.1, 28.6, 29.3,
29.5, 29.6, 32.3, 65.4, 67.4, 80,1, 88.5, 124.8, 133.8 ppm. IR (CCl4):
= 8 Hz, 1 H), 8.42 (s, 1 H), 8.83 (d, J = 8 Hz, 1 H) ppm. 13C NMR
(75 MHz, [D6]DMSO): δ = 14.8, 19.7, 22.9, 28.5, 29.2, 29.3, 29.4,
32.1, 66.4, 71.7, 87.8, 96.5, 113.0, 121.6, 124.4, 124.7, 127.0, 127.8,
ν = 3100, 2245, 1515, 1410, 1280, 740 cm–1. MS (EI): m/z (%) =
131.9, 132.9, 142.8, 155.8 ppm. IR (CCl ): ν = 3540, 3430, 2995,
˜
˜
4
404 (100) [M+], 370 (95), 336 (70), 313 (32), 273 (50), 219 (46, 91
(30), 82 (98). C28H36S (404.7): calcd. C 83.11, H 8.97; found C
83.31, H 9.13.
2895, 2300, 2150, 1640, 1475, 1375, 710 cm–1. MS (EI): m/z (%) =
348 (5) [M+], 314 (7), 168 (8), 97 (100). C22H24N2O2 (348.4): calcd.
C 75.84, H 6.94, N 8.04; found C 75.65, H 7.16, N 7.91.
1-(4-Nitrophenyl)dodeca-1,3-diyne (27b): Dodeca-5,7-diyne (1b, 1-(2,4,5-Trimethylphenyl)dodeca-1,3-diyne (29b): Dodeca-5,7-diyne
405 mg, 2.5 mmol) was used to obtain 1,3-dodecadiyne (3b) which
was reacted with 1-iodo-4-nitrobenzene (11, 498 mg, 2 mmol) (Pro-
cedure A). Chromatography on silica gel (hexanes/CH2Cl2, 4:1) af-
(1b, 405 mg, 2.5 mmol) was used to obtain a 1,3-dodecadiyne (3b)
which was reacted with 1-iodo-2,4,5-trimethylbenzene (13, 492 mg,
2 mmol) (Procedure B). Chromatography on silica gel (hexane) af-
forded the diyne 29b as an oil (555 mg, 99 %), R f = 0.83 (hexane).
forded the diyne 27b (408 mg, 72 %) as an oil. R f = 0.43 (hexanes/
1
CH2Cl2, 4:1). H NMR (300 MHz, CDCl3): δ = 0.92 (t, J = 7 Hz, 1H NMR (300 MHz, CDCl3): δ = 0.92 (t, J = 7 Hz, 3 H), 1.22–
3 H), 1.31–1.51 (m, 10 H), 1.59 (quint., J = 7 Hz, 2 H), 2.46 (t, J
= 7 Hz, 2 H), 7.73 (d, J = 8 Hz, 2 H), 8.23 (d, J = 8 Hz, 2 H) ppm.
13C NMR (75 MHz, CDCl3): δ = 13.8, 19.4, 22.8, 28.1, 28.7, 29.1,
1.51 (m, 10 H), 1.60 (quint., J = 7 Hz, 2 H), 2.20 (s, 3 H), 2.24 (s,
3 H), 2.39 (s, 3 H), 2.38 (t, J = 7 Hz, 2 H), 6.97 (s, 1 H), 7.24 (s, 1
H) ppm. 13C NMR (75 MHz, CDCl3): δ = 14.5, 19.4, 20.06, 20.09,
29.3, 32.0, 64.5, 65.7, 72.8, 88.9, 125.2, 128.9, 132.5, 139.2 ppm. IR 20.11, 20.4, 23.1, 28.7, 29.3, 29.5, 32.2, 65.7, 74.5, 77.4, 85.2, 119.4,
(CCl ): ν = 3100, 2960, 2930, 2860, 2240, 1590, 1470, 1400, 1255, 131.3, 134.2, 134.3, 138.2, 139.3 ppm. IR (CCl ): ν = 3070, 2240,
˜
˜
4
4
840 cm–1. MS (EI): m/z (%) = 283 (15) [M+], 254 (13), 240 (22), 1690, 1590, 1470, 1430, 1400, 1255, 900 cm–1. MS (EI): m/z (%) =
226 (74), 212 (32), 201 (29), 179 (45), 173 (52), 165 (100), 152 (61),
281 (24) [M + 1], 280 (100) [M+], 223 (50), 209 (31), 195 (31), 183
139 (57), 126 (38). C18H21NO2 (283.4): calcd. C 76.29, H 7.47, N (72), 179 (41), 165 (98), 152 (31), 133(34), 91 (20), 67 (28), 55 (21).
7.94; found C 76.20, H 7.55, N 4.91.
C21H28 (280.5): calcd. C 89.93, H 10.06; found C 89.49, H 10.43.
1-(4-Nitrophenyl)tetradeca-1,3-diyne (27c): Tetradeca-6,8-diyne (1c,
476 mg, 2.5 mmol) was used to obtain 1,3-tetradecadiyne (3c)
1-(3,4-Dimethoxyphenyl)dodeca-1,3-diyne (30b): Dodeca-5,7-diyne
(1b, 405 mg, 2.5 mmol) was used to obtain 1,3-dodecadiyne (3b)
886
© 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
Eur. J. Org. Chem. 2005, 882–888

A Convenient Synthesis of Functionalised 1-Aryl-1,3-alkadiynes
FULL PAPER
which was reacted with 4-iodo-1,2-dimethoxybenzene (14) (528 mg,
2 mmol) (Procedure B). Chromatography on silica gel (hexanes/
slowly crystallised, m. p. 34.5 °C. R f = 0.21 (hexanes/CH2Cl2, 4:1).
1H NMR (300 MHz, CDCl3): δ = 0.90 (t, J = 7 Hz, 3 H), 1.23–
1.64 (m, 20 H), 2.38 (t, J = 7 Hz, 2 H), 7.43 (t, J = 7 Hz, 1 H),
7.51–7.59 (m, 2 H), 7.28 (d, J 7 Hz, 1 H) ppm. 13C NMR (75 MHz,
CDCl3): δ = 13.8, 19.3, 27.7, 28.6, 28.7, 29.0, 29.1, 29.27, 29.29,
CH2Cl2, 2:1) afforded the diyne 30b (584 mg, 98 %) as an oil. R
f
= 0.45 (hexanes/CH2Cl2, 2:1). 1H NMR (300 MHz, CDCl3): δ =
0.90 (t, J = 7 Hz, 3 H), 1.25–1.49 (m, 10 H), 1.57 (quint., J = 7 Hz,
2 H), 2.36 (t, J = 7 Hz, 2 H), 3.82 (s, 3 H), 3.86 (s, 3 H), 6.42 (s, 1 29.31, 29.32, 31.6, 65.1, 70.6, 81.2, 88.6, 116.3, 117.6, 126.6, 129.1,
H), 6.45 (d, J = 8 Hz, 1 H), 7.37 (d, J = 8 Hz, 1 H) ppm. 13C NMR
(75 MHz, CDCl3): δ = 14.5, 20.1, 23.1, 28.7, 29.3, 29.5, 29.6, 32.2,
55.8, 56.2, 65.8, 71.7, 77.3, 85.2, 98.7, 104.2, 105.4, 135.7, 162.0,
132.7, 133.2, 133.8 ppm. IR (CCl ): ν = 3075, 2930, 2855, 2240
˜
4
(strong; alkyne and CN), 1470, 1460 cm–1. MS (EI): m/z (%) = 319
(6) [M+], 248 (10), 234 (19), 220 (35), 207 (64), 206 (100), 193 (35),
192 (35), 179 (52), 167 (40), 164 (43), 153 (27). C23H29N (319.5):
calcd. C 86.46, H 9.15, N 4.38; found C 86.62, H 9.22, N 4.15.
163.1 ppm. IR (CCl ): ν = 3075, 2955, 2875, 2250, 1680, 1585,
˜
4
1475, 1420, 1400, 1265, 1110, 890 cm–1. MS (EI): m/z (%) = 298
(22) [M+], 255 (32), 213 (15), 186 (100), 138 (24), 91 (32). C20H26O2
(298.5): calcd. C 80.50, H 8.78; found C 80.48, H 8.77.
1-(4-Bromophenyl)dodeca-1,3-diyne (35b): Dodeca-5,7-diyne 1b
(405 mg, 2.5 mmol) was used to obtain 1,3-dodecadiyne (3b) which
was reacted with 1-bromo-4-iodobenzene (19, 566 mg, 2 mmol)
2-(Dodeca-1,3-diynyl)benzaldehyde (31b): Dodeca-5,7-diyne (1b,
405 mg, 2.5 mmol) was used to obtain 1,3-dodecadiyne (3b) which
was reacted with 2-iodobenzaldehyde (15, 464 mg, 2 mmol) (Pro-
cedure A). Chromatography on silica gel (hexanes/CH2Cl2, 2:1) af-
forded the diyne 31b (335 mg, 63 %). Using Procedure B, the same
product 31b was obtained in 71 % isolated yield (378 mg,
(Procedure B). Chromatography on silica gel (hexane) afforded the
1
diyne 35b (533 mg, 84 %) as an oil. R = 0.8 (hexane). H NMR
f
(300 MHz, CDCl3): δ = 0.91 (t, J = 6 Hz, 3 H), 1.23–1.61 (m, 12
H), 2.37 (t, J = 7 Hz, 2 H), 7.34 (d, J = 5 Hz, 2 H), 7.45 (d, J =
5 Hz 2 H) ppm. 13C NMR (75 MHz, CDCl3): δ = 14.5, 20.0, 23.1,
28.6, 29.3, 29.5, 29.6, 32.2, 65.3, 73.9, 76.0, 86.1, 121.5, 123.6,
1
1.42 mmol). H NMR (300 MHz, CDCl3): δ = 0.89 (t, J = 7 Hz, 3
H), 1.27–1.66 (m, 12 H), 2.40 (t, J = 7 Hz, 2 H), 7.46 (t, J = 7 Hz,
1 H), 7.52–7.62 (m, 2 H), 7.92 (d, J = 8 Hz, 1 H), 10.50 (app. s, 1
H) ppm. 13C NMR (75 MHz, CDCl3): δ = 14.5, 20.1, 23.0, 28.5,
29.3, 29.4, 29.5, 32.2, 65.1, 70.4, 81.7, 87.9, 126.2, 127.7, 129.4,
132.1, 134.3 ppm. IR (CCl ): ν = 2955, 2935, 2240, 1475, 1100,
˜
4
1055 cm–1. MS (EI): m/z (%) = 318 (13) [M+ (81Br)], 316 (10) [M+
(79Br)], 290 (21), 288 (22), 261 (33), 259 (31), 219 (57), 217 (49),
206 (26), 165 (100), 152 (55), 137 (32), 125 (31), 84 (65). C18H21Br
(317.3): calcd. C 68.14, H 6.67; found C 68.05, H 6.74.
134.0, 134.7, 137.8, 191.5 ppm. IR (CCl ): ν = 3070, 2950, 2930,
˜
4
2850, 2230, 1690, 1590, 1470, 1430, 1400, 1255, 900 cm–1. MS (EI):
m/z (%) = 266 (17) [M+], 237 (9), 223 (100), 209 (40), 200 (25), 181
(73), 161 (39), 141 (22), 133 (19), 105 (41), 91 (38). C19H22O (266.4):
calcd. C 85.67, H 8.32; found C 85.61, H 8.40.
1-(4-Bromophenyl)tetradeca-1,3-diyne (35c): Tetradeca-6,8-diyne
(1c, 476 mg, 2.5 mmol) was used to obtain 1,3-dodecadiyne (3c)
which was reacted with 1-bromo-4-iodobenzene (19, 566 mg,
2 mmol) (Procedure B). Chromatography on silica gel (hexane) af-
1
1,2,4,5-Tetrakis(dodeca-1,3-diynyl)benzene (32b): Dodeca-5,7-diyne
(1b, 1.62 g, 10 mmol) was used to obtain 1,3-dodecadiyne (3b)
which was reacted with 1,2,4,5-tetraiodobenzene (16, 1.163 g,
2 mmol) by Procedure A. Chromatography on silica gel (hexane)
forded the diyne 35c (635 mg, 92 %). R = 0.8 (hexane). H NMR
f
(300 MHz, CDCl3): δ = 0.90 (t, J = 6 Hz, 3 H), 1.29–1.54 (m, 14
H), 1.60 (quint., J = 7 Hz, 2 H), 2.37 (t, J = 7 Hz, 2 H), 7.34 (d, J
= 5 Hz, 2 H), 7.46 (d, J = 5 Hz, 2 H) ppm. 13C NMR (75 MHz,
CDCl3): δ = 14.5, 20.0, 23.1, 28.6, 29.3, 29.5, 29.7, 29.9, 30.0, 32.3,
afforded the tetrayne 32b (1,337 g, 93 %) as a solid, m. p. 45–46 °C.
1
R
= 0.5 (hexane). H NMR (300 MHz, CDCl3): δ = 0.90 (t, J =
65.3, 73.9, 76.5, 86.1, 121.5, 123.6, 132.1, 134.3 ppm. IR (CCl ): ν
f
˜
4
= 2955, 2935, 2250, 1470, 1130, 1075 cm–1. MS (EI): m/z (%) = 346
(23) [M+ (81Br)], 344 (20) [M+ (79Br)], 316 (24), 302 (31), 288 (30),
274 (21), 260 (15), 232 (18), 156 (100), 137 (32), 125 (31), 84 (65).
C20H25Br (345.3): calcd. C 69.56, H 7.30; found C 69.55, H 7.28.
6 Hz, 12 H), 1.20–1.49 (m, 40 H), 1.60 (quint., J = 7 Hz, 8 H), 2.39
(t, J = 7 Hz, 8 H), 7.51 (s, 2 H) ppm. 13C NMR (75 MHz, CDCl3):
δ = 14.5, 20.2, 23.1, 28.6, 29.3, 29.4, 29.5, 32.2, 65.5, 71.9, 81.3,
88.4 125.8, 137.8 ppm. IR (CCl ): ν = 2950, 2850, 2260, 1475, 1455,
˜
4
900, 710 cm–1. C54H70 (719.1): calcd. C 90.19, H 9.81; found C
90.09, H 9.82.
Acknowledgments
1-(2-Nitrophenyl)dodeca-1,3-diyne (33b): Dodeca-5,7-diyne (1b,
405 mg, 2.5 mmol) was used to obtain 1,3-dodecadiyne (3b) which
was reacted with 1-iodo-2-nitrobenzene (17, 498 mg, 2 mmol) (Pro-
cedure A). Chromatography on silica gel (hexanes/CH2Cl2, 4:1) af-
forded the diyne 33b (453 mg, 80 %) as a solid, m. p. 14–16 °C. R
We gratefully acknowledge financial support from RFBR Grant
02–03–32229. We also thank E. G. Rumyantceva and N. U. Sipkina
for obtaining the CHN microanalytical data.
= 0.5 (hexanes/CH2Cl2, 4:1). 1H NMR (300 MHz, CDCl3): δ =
f
0.88 (t, J = 6 Hz, 3 H), 1.18–1.47 (m, 10 H), 1.58 (quint., J = 7 Hz,
2 H), 2.39 (t, J = 7 Hz, 2 H), 7.48 (t, J = 7 Hz, 1 H), 7.58 (t, J =
7 Hz, 1 H), 7.67 (d, J = 7 Hz, 1 H), 8.06 (d, J = 7 Hz, 1 H) ppm.
13C NMR (75 MHz, CDCl3): δ = 14.5, 20.1, 23.1, 28.5, 29.3, 29.4,
29.5, 32.2, 65.4, 69.7, 82.7, 89.1, 118.4, 125.2, 129.4, 133.3, 136.3,
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150.6 ppm. IR (CCl ): ν = 2950, 2850, 2235, 1600, 1560, 1525 cm–1.
˜
4
MS (EI): m/z (%) = 283 (5) [M+], 238 (10), 223 (26), 210 (40), 196
(40), 172 (33), 160 (100), 148 (30), 140 (26), 132 (36), 115 (40), 104
(43), 95 (30), 91 (26). C18H21NO2 (283.4): calcd. C 76.30, H 7.47,
N 4.94; found C 76.28, H 7.63, N 4.82.
2-(Hexadeca-1,3-diynyl)benzonitrile (34d): Hexadeca-7,9-diyne (1c,
654 mg, 3 mmol) was used to obtain 1,3-hexadecadiyne (3d) which
was reacted with 2-iodobenzonitrile (18, 458 mg, 2 mmol) (Pro-
cedure A). Chromatography on silica gel (hexanes/CH2Cl2, 2:1) af-
forded the diyne 34d (283 mg, 90 %) as a light yellow oil which
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887

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Received September 29, 2004
888
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Eur. J. Org. Chem. 2005, 882–888