Synthesis of conjugated dienes and polyenes via diethyl phosphite promoted carbonyl olefination

Article abstract of DOI:10.1039/c4ra06256f

A protocol has been developed for the synthesis of conjugated dienes and polyenes from unsaturated carbonyl compounds and Grignard reagents in the presence of diethyl phosphite. This reaction was conveniently carried out under mild conditions in a one-pot fashion with moderate to good yields.

Full text of DOI:10.1039/c4ra06256f

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Synthesis of conjugated dienes and polyenes via
diethyl phosphite promoted carbonyl olefination†
Cite this: RSC Adv., 2014, 4, 39497
*
Ru Wang and Songlin Zhang
Received 26th June 2014
Accepted 18th August 2014
A protocol has been developed for the synthesis of conjugated dienes and polyenes from unsaturated
carbonyl compounds and Grignard reagents in the presence of diethyl phosphite. This reaction was
conveniently carried out under mild conditions in a one-pot fashion with moderate to good yields.
DOI: 10.1039/c4ra06256f
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compounds and Grignard reagents (Scheme 2). Herein, we
report a convenient one-pot protocol involving the transfer of
Introduction
carbon–carbon double bonds to obtain conjugated dienes and
polyenes in the presence of diethyl phosphite.
Alkenes represent one of the most widely occurring and
important classes of organic compounds due to their versatility
as building blocks or starting substrates in organic synthesis.
Especially conjugated alkenes not only play an important role in
the synthesis of many compounds, but also are found in the
structure of numerous natural products and pharmaceutical
agents (Fig. 1).1 Accordingly, the practical and efficient
synthesis of conjugated alkenes has provided major challenges
to synthetic organic chemists. Carbonyl olenation has been
considered as a well-established approach for the construction
of olens. In particular, Wittig reaction,2 Julia reaction3 and
Peterson reaction,4 as well as their variants5 have been applied
as the most powerful tools of modern organic chemistry.
Whereas, the need of ylides which were generated by a stepwise
procedure under basic condition could not be avoided in these
reactions. Then, Wong6 and Hopf7 investigated that utilizing
elimination reaction affords conjugated diene under the
condition of strong base. Moreover, several reactions employing
Ni,8 Pd,9 Ru (ref. 10) complexes to synthesize conjugated alkene
have been researched, this strategy is useful but becomes less
practical with precious metal.
Results and discussion
Initially, a,b-unsaturated ketone 1a and phenyl magnesium
bromide 2a were selected as a model reaction to optimize
reaction conditions (Table 1, entries 1–13). Firstly, kinds of
organophosphorus additives were examined at room tempera-
ture with THF as the solvent and the results were summarized
in Table 1. The reaction was dramatically inuenced by the
additives. With Ph3P, (EtO)3P, (EtO)3PO and (EtO)2P(O)CH2-
COOEt as additives, no product was obtained (Table 1, entries
1–4). However, with (EtO)2P(O)H as an additive, product 3a
could be obtained in good yield (Table 1, entry 5). Subsequently,
the molar ratio of 1a/additive/2a was also investigated (Table 1,
entries 6–10). In the presence of 1.2 equiv. of (EtO)2P(O)H and 3
equiv. of Grignard reagent, a gratifying yield was obtained. To
our delight, the yield could be further improved through
increasing the temperature from room temperature to 50 ꢀC
(Taꢀble 1, entries 11–13). Thus, (EtO)2P(O)H as an additive and
50 C as the reaction temperature with a 1/1.2/3 molar ratio of
1a/additive/2a were proved to be the optimal reaction condi-
tions for the reaction.
The above widely used methods still suffer from several
drawbacks. More recently, our attentions have been focused on
the concise and elegant synthesis of olens by the application of
organometallic reagents. Several ndings involving allylsama-
rium bromide,11 Grignard reagents12 or organozinc reagents13
have been presented (Scheme 1).
These works prompted us to explore the possibility of
developing a one-pot synthesis method for the preparation of
conjugated dienes and polyenes through unsaturated carbonyl
Key Laboratory of Organic Synthesis of Jiangsu Province, College of Chemistry,
Chemical Engineering and Materials Science, Soochow University, Suzhou 215123,
P. R. China. E-mail: zhangsl@suda.edu.cn; Fax: +86 512 65880353; Tel: +86 512
65880352
† Electronic supplementary information (ESI) available: Detailed experimental
procedures, characterization data for all compounds. See DOI: 10.1039/c4ra06256f
Fig. 1 General structure and numbering of retinoid and carotenoid.
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Table 2 to obtain the corresponding conjugated dienes in good
to excellent yields (Table 2, entries 1–6). Good yields were also
afforded with other kinds of Grignard reagents, such as 4-
methyl phenyl magnesium bromide, 4-chloride phenyl magne-
sium, 4-phenyl phenyl magnesium bromide, 3,5-dimethyl
phenyl magnesium bromide, 2-naphthyl magnesium bromide
(Table 2, entries 7–24). The above results clearly showed that the
yields were not received signicant impact with a,b-unsaturated
ketones bearing electron-donating groups or electron-with-
drawing groups. When the aryl groups of a,b-unsaturated
ketones and the group of Grignard reagents were not the same,
the mixture of E/Z isomers were obtained. The ratio of E/Z (or Z/
E) could be determined from 1H NMR spectra (Table 2, entries 5,
10, 14, 23).
Scheme
reagents.
1 Olefination of carbonyl compounds with Grignard
Experiments to further explore the scope of this method were
then conducted, a number of unsaturated aldehydes were
subjected to this reaction and the results were summarized in
Table 3. As we can see, when (2E,4E)-hexa-2,4-dienal was applied
with phenyl magnesium bromide, 4-methyl phenyl magnesium
bromide or 3,5-dimethyl phenyl magnesium bromide, the
reaction could occur smoothly to afford the desired products
Scheme
Grignard reagents.
2 Olefination of unsaturated carbonyl compounds with with moderate yields (Table 3, entries 1–3). When, (2E,4E)-hexa-
2,4-dienal was treated with 2-naphthyl magnesium bromide, 4-
phenyl phenyl magnesium bromide or 9-phenanthryl magne-
sium bromide, corresponding conjugated-trienes were obtained
at an acceptable yields (Table 3, entries 4–6). Additionally, when
(2E,4E,6E)-octa-2,4,6-trienal was applied, slightly lower yields
were obtained (Table 3, entries 7–8). Fortunately, we were
pleased to nd that this type of reaction has high
In order to investigate the generality of this reaction, the
scope of the substrate with different Grignard reagent was
subsequently explored and the results were summarized in
Table 2. We found that a,b-unsaturated ketones were treated
with phenyl magnesium bromide under the conditions listed in
Table 1 Optimization of reaction conditionsa
2a
(equiv.)
Entry
Additive (equiv.)
Time (h)
Temp (oC)
Yieldb (%)
1
2
3
4
5
6
7
8
Ph3P (1.2)
(EtO)3P (1.2)
(EtO)3PO (1.2)
3
3
3
3
3
3
3
3
4
2
3
3
3
12
12
12
12
12
12
12
12
12
12
12
6
r.t.
r.t.
r.t.
r.t.
r.t.
r.t.
r.t.
r.t.
r.t.
r.t.
50
None
None
None
None
75
59
63
60
66
43
95
47
85
(EtO)2P(O)CH2COEt (1.2)
(EtO)2P(O)H (1.2)
(EtO)2P(O)H (1.5)
(EtO)2P(O)H (1.0)
(EtO)2P(O)H (0.8)
(EtO)2P(O)H (1.2)
(EtO)2P(O)H (1.2)
(EtO)2P(O)H (1.2)
(EtO)2P(O)H (1.2)
(EtO)2P(O)H (1.2)
9
10
11
12
13
50
50
18
a
Unless noted, to a solution of 1a (0.5 mmol) in THF (3 mL) was added 2a (X mmol) in THF under a nitrogen atmosphere at room temperature, the
mixture was stirred for 4 h, then the additive (Y mmol) was added to this mixture and stirred at corresponding temperature. b Isolated yield based on
1a aer silica gel chromatography.
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Table 2 Olefination of a,b-unsaturated ketones with Grignard reagentsa
Entry
1
Substrate
Magnesium reagent
Product
Yieldb (%)
95
2
3
80c
65c
4
5
77c
65 (3 : 1)
6
7
55c
90c
8
9
80c
45
10
47 (5 : 1)
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Table 2 (Contd.)
Entry
11
Substrate
Magnesium reagent
Product
Yieldb (%)
43c
12
77c
13
14
15
82c
40 (6 : 1)
89c
16
17
45c
74c
18
19
50c
83c
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Table 2 (Contd.)
Entry
20
Substrate
Magnesium reagent
Product
Yieldb (%)
71c
21
66c
22
23
61c
55 (10 : 1)
24
64c
a
Unless noted, to a solution of a,b-unsaturated ketone (0.5 mmol) in THF (3 mL) was added Grignard reagent (1.5 mmol) in THF under a nitrogen
atmosphere at room temperature. The mixture was stirred for 4 h, and then diethyl phosphite (0.6 mmol) was added to this mixture and stirred at 50
ꢀC for 12 h. b Isolated yield based on a,b-unsaturated ketones aer silica gel chromatography. c The ratio of E/Z can not be determined by 1H NMR.
stereoselectivity, only (E)-selective alkene isomerization could
Experimental section
General methods and materials
be obtained.
According to our previous work,11–13 a similar mechanism
was proposed (Scheme 3). First, unsaturated carbonyl
compound 4 transforms into intermediate 5 through nucle-
ophilic addition. Then the P anion of 6 abstracts the H of the
methyl group of intermediate 5 with –MgBr of 6 as the
assistant in the cyclic transition state 7. Then elimination of
phosphite gives conjugated alkene 8 and corresponding
magnesium salts.
THF was distilled from sodium benzophenone under
nitrogen. All reactions were conducted under a nitrogen
atmosphere. Metallic magnesium and all solvents were
purchased from commercial source, without further puri-
cation before use. The ash column chromatography was
1
carried out on Merck silica gel (300–400 mesh). H and 13C
NMR spectra were recorded on a Varian-Inova-400 spec-
trometer. Solvent for NMR is CDCl3 or DMSO-d6, unless the
otherwise noted. Chemical shis are reported in delta (d)
units in parts per million (ppm) relative to the singlet (0
ppm) for tetramethylsilane (TMS). Data are reported as
follows: chemical shi, multiplicity (s ¼ single, d ¼ doublet,
t ¼ triplet, m ¼ multiplet, dd ¼ doublet of doublets),
coupling constants (Hz), and integration. 13C NMR spectra
were recorded on 100 MHz. Chemical shis are reported in
parts per million relative to the central line of the multiplet
at 77.5 ppm for CDCl3, 40.5 ppm for DMSO. High-resolution
mass spectra were obtained with a GCT-TOF instrument.
Conclusions
In summary, we have documented a promising one-pot
synthetic protocol for the preparation of conjugated dienes and
polyenes from unsaturated carbonyl compounds and Grignard
reagents in the presence of diethyl phosphite. This strategy
provides a broad scope and moderate to good yields of the
products. Efforts are in progress to elucidate the mechanistic
details of this reaction.
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Table 3 Olefination of unsaturated aldehydes with Grignard reagentsa
Entry
1
Substrate
Magnesium reagent
Product
Yieldb(%)
63
2
3
54
55
4
5
27
40
6
7
35
27
24
8
a
Unless noted, to a solution of unsaturated aldehyde (0.5 mmol) in THF (3 mL) was added Grignard reagent (1.0 mmol) in THF under a nitrogen
atmosphere at room temperature. The mixture was stirred for 4 h, and then diethyl phosphite (0.6 mmol) was added to this mixture and stirred at 50
b
ꢀC for 12 h. Isolated yield based on unsaturated aldehydes aer silica gel chromatography.
All chemicals were purchased from Aldrich, Alfa or Acros
chemical company and used thus, without further purication.
ꢀ
Petroleum ether (PE) used refers to the 60–90 C boiling point
fraction of petroleum.
General procedure for synthesis of Grignard reagents
Aryl bromide (2a, 2b, 2d and 2f, 1.6 mmol) and Mg powder
(0.0365 g, 1.5 mmol) in dry THF (3 mL) under a nitrogen
atmosphere at room temperature (5% I2 was added to trigger
the reaction.). The mixture was stirred for about 1 h.
Mg powder (0.0243 g, 1.1 mmol) in dry THF (3 mL) was
treated dropwise with a solution of aryl bromide (2c and 2e, 1.0
mmol) in dry THF (3 mL) under a nitrogen atmosphere at ice-
bath (5% I2 was added to trigger the reaction.), and the reaction
Scheme 3 Proposed mechanism for olefination of carbonyl.
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mixture was allowed to warm to room temperature. Stirring was 1H), 5.38 (d, J ¼ 9.2 Hz, 1H), 5.09 (s, 1H). 13C NMR (100 MHz,
continued for 1 h.
CDCl3): d 144.8, 144.7, 144.4, 142.9, 141.9, 139.8, 139.4, 139.3,
138.8, 134.1, 133.8, 133.6, 131.9, 130.5, 129.7, 128.8, 128.8,
128.7, 128.6, 128.6, 128.5, 128.4, 127.9, 118.9, 118.8. HRMS (EI+):
calcd. for C22H16Cl2 [M + 1]+: 351.0702, found: 351.0698.
Synthesis of conjugated dienes
To a solution of a,b-unsaturated ketone (0.5 mmol) in dry THF
(3 mL) was added Grignard reagent (1.5 mmol) in dry THF
under a nitrogen atmosphere at room temperature. The mixture
was stirred for about 4 h. Then diethyl phosphite (0.6 mmol)
was added (the reaction was monitored by TLC). The reaction
mixture was stirred at 50 ꢀC and then was quenched with dilute
hydrochloric acid. The resulting mixture was extracted with
diethyl ether (3 ꢁ 10 mL), and dried over anhydydrous Na2SO4.
The solvent was removed by evaporation under reduced pres-
sure. Purication by column chromatography on silica gel
afforded olens (300–400 mesh, petroleum ether as eluent).
4,40-(1-Phenylbuta-1,3-diene-1,3-diyl)bis(methylbenzene) (3d).
The title compound was obtained according to the general
procedure. Colourless oil; yield: 77%; IR (KBr): 3079, 3050,
3023, 2922, 2855, 1606, 1510, 1492, 1445, 895, 820, 764,
699 cmꢂ1; 1H NMR (CDCl3, 400 MHz): d 7.32–7.30 (m, 3H), 7.27
(d, J ¼ 7.6 Hz, 1H), 7.21 (d, J ¼ 8.0 Hz, 1H), 7.17 (s, 3H), 7.10 (d,
J ¼ 8.0 Hz, 1H), 7.07–7.05 (m, 3H), 7.00 (d, J ¼ 8.0 Hz, 1H), 6.99
(m, 13H), 6.67 (d, J ¼ 6.4 Hz, 1H), 5.35 (d, J ¼ 8.8 Hz, 1H), 4.95
(d, J ¼ 13.2 Hz, 1H), 2.34–2.30 (m, 3H), 2.30–2.29 (m, 3H). 13
C
NMR (100 MHz, CDCl3): d 145.4, 144.9, 143.8, 140.8, 138.4,
137.8, 137.6, 137.1, 130.5, 130.4, 129.4, 129.3, 129.1, 128.7,
128.6, 128.4, 128.4, 128.3, 128.2, 127.9, 127.4, 126.9, 116.6,
30.2, 21.7, 21.6. HRMS (EI+): calcd. for C24H22 [M + 1]+:
Synthesis of conjugated polyenes
To a solution of unsaturated aldehyde (0.5 mmol) in dry THF (3 311.1794, found: 311.1795.
mL) was added Grignard reagent (1.0 mmol) in dry THF under a
2,20-(1-Phenylbuta-1,3-diene-1,3-diyl)bis(methylbenzene) (3e).
nitrogen atmosphere at room temperature. The mixture was The title compound was obtained according to the general
stirred for about 4 h. Then diethyl phosphite (0.6 mmol) was procedure. Colourless oil; yield: 65%; IR (KBr): 3059, 3018,
added (the reaction was monitored by TLC). The reaction 2952, 2924, 2854, 1600, 1489, 1457, 1378, 902, 762, 696 cmꢂ1
;
mixture was stirred at 50 ꢀC and then was quenched with dilute 1H NMR (CDCl3, 400 MHz): d 7.27–7.09 (m, 5H), 7.04–6.99 (m,
hydrochloric acid. The resulting mixture was extracted with 1H), 6.97–6.91 (m, 5H), 6.88 (d, J ¼ 8.0 Hz, 2H), 6.88–6.85 (m,
diethyl ether (3 ꢁ 10 mL), and dried over anhydydrous Na2SO4. 1H), 5.22 (s, 1H), 5.01 (d, J ¼ 1.6 Hz, 1H), 2.25 (s, 3H), 1.96 (s,
The solvent was removed by evaporation under reduced pres- 3H). 13C NMR (100 MHz, CDCl3): d 147.0, 144.7, 143.7, 142.7,
sure. Purication by column chromatography on silica gel 142.5, 142.3, 141.4, 139.6, 139.3, 136.8, 136.7, 135.3, 135.1,
afforded olens (300–400 mesh, petroleum ether as eluent).
131.6, 130.9, 130.5, 130.3, 130.2, 130.2, 130.1, 130.0, 129.9,
Buta-1,3-diene-1,1,3-triyltribenzene (3a). The title compound 129.5, 129.1, 128.8, 127.8, 127.7, 127.4, 127.3, 127.1, 127.0,
was obtained according to the general procedure. Colourless 126.0, 125.8, 125.6, 125.6, 122.2, 120.3, 21.0, 20.8, 20.2. HRMS
oil; yield: 95%; IR (KBr): 3080, 3055, 3025, 2952, 2929, 2855, (EI+): calcd. for C24H22 [M + 1]+: 311.1794, found: 311.1802.
1660, 1597, 1491, 1444, 905, 734, 698 cmꢂ1; 1H NMR (CDCl3, 400
4,40-(1-Phenylbuta-1,3-diene-1,3-diyl)bis(methoxybenzene) (3f).
MHz): d 7.38 (d, J ¼ 6.8 Hz, 2H), 7.31–7.28 (m, 5H), 7.22–7.15 (m, The title compound was obtained according to the general
8H), 6.73 (s, 1H), 5.38 (s, 1H), 5.03 (s, 1H). 13C NMR (100 MHz, procedure. Colourless oil; yield: 55%; IR (KBr): 3031, 3000,
CDCl3): d 145.7, 145.2, 143.6, 141.1, 140.5, 130.6, 128.8, 128.6, 2956, 2931, 2835, 1713, 1605, 1509, 1461, 1416, 891, 823, 740,
128.6, 128.4, 128.4, 128.1, 127.9, 127.5, 127.1, 117.8. HRMS 700 cmꢂ1; 1H NMR (CDCl3, 400 MHz): d 7.33 (d, J ¼ 8.4 Hz, 3H),
(EI+): calcd. for C22H18 [M + 1]+: 283.1481, found: 283.1489.
7.27 (d, J ¼ 7.6 Hz, 1H), 7.24 (d, J ¼ 8.4 Hz, 1H), 7.19–7.14 (m,
4,40-(1-Phenylbuta-1,3-diene-1,3-diyl)bis(uorobenzene) (3b). 3H), 7.06 (d, J ¼ 8.4 Hz, 1H), 6.84 (d, J ¼ 8.8 Hz, 1H), 6.77 (d, J ¼
The title compound was obtained according to the general 8.4 Hz, 2H), 6.72 (d, J ¼ 8.4 Hz, 1H), 6.64 (d, J ¼ 5.6 Hz, 1H),
procedure. Colourless oil; yield: 80%; IR (KBr): 3055, 3023, 2958, 5.32–5.27 (m, 1H), 4.96–4.89 (m, 1H), 3.80–3.75 (m, 6H). 13C
2926, 2844, 1660, 1506, 1445, 1402, 835, 766, 699 cmꢂ1; 1H NMR NMR (100 MHz, CDCl3): d 159.7, 159.5, 159.1, 145.3, 145.1,
(CDCl3, 400 MHz): d 7.29–7.26 (m, 6H), 7.15 (s, 1H), 7.06–7.02 (m, 144.6, 144.5, 144.0, 140.8, 136.2, 134.4, 134.0, 133.8, 132.9,
2H), 6.98 (t, J ¼ 7.2 Hz, 1H), 6.88–6.81 (m, 3H), 6.74–6.66 (m, 1H), 131.8, 130.5, 129.9, 129.6, 129.2, 128.6, 128.6, 128.5, 128.3,
5.33 (d, J ¼ 10.4 Hz, 1H), 5.08 (d, J ¼ 11.6 Hz, 1H). 13C NMR (100 128.2, 128.2, 128.0, 127.7, 127.6, 127.5, 127.4, 115.8, 115.7,
MHz, CDCl3): d 164.2, 163.9, 163.7, 161.8, 161.5, 161.2, 145.1, 114.0, 113.9, 113.8, 55.7, 55.6. HRMS (EI+): calcd. for C24H22O2
145.0, 144.3, 144.2, 143.3, 140.2, 139.6, 139.6, 137.2, 137.1, 137.1, [M + 1]+: 343.1693, found: 343.1700.
137.0, 136.3, 136.2, 132.3, 132.2, 130.5, 130.1, 130.0, 128.9, 128.9,
(1-(p-Tolyl)buta-1,3-diene-1,3-diyl)dibenzene (3g). The title
128.9, 128.8, 128.8, 128.7, 128.4, 128.3, 127.8, 118.3, 118.1, 115.6, compound was obtained according to the general procedure.
115.4, 115.4, 115.4, 115.2, 115.2, 115.2. HRMS (EI+): calcd. for Colourless oil; yield: 90%; IR (KBr): 3079, 3054, 3024; 2921,
C22H16F2 [M + 1]+: 319.1293, found: 319.1295.
2866, 1714, 1660, 1598, 1492, 1444, 907, 818, 758, 699 cmꢂ1; 1H
4,40-(1-Phenylbuta-1,3-diene-1,3-diyl)bis(chlorobenzene) (3c). NMR (CDCl3, 400 MHz): d 7.38 (t, J ¼ 6.8 Hz, 2H), 7.32–7.31 (m,
The title compound was obtained according to the general 1H), 7.26 (d, J ¼ 6.0 Hz, 1H), 7.21–7.20 (m, 4H), 7.14 (s, 3H), 7.10
procedure. Colourless oil; yield: 65%; IR (KBr): 3058, 3030, 2925, (d, J ¼ 7.6 Hz, 1H), 7.04 (d, J ¼ 7.6 Hz, 1H), 7.00 (d, J ¼ 7.6 Hz,
2852, 1659, 1593, 1489, 1445, 907, 759, 699 cmꢂ1
;
1H NMR 1H), 6.69 (d, J ¼ 8.0 Hz, 1H), 5.37 (d, J ¼ 8.0 Hz, 1H), 5.01 (d, J ¼
(CDCl3, 400 MHz): d 7.30–7.28 (m, 3H), 7.26–7.22 (m, 4H), 7.16 7.6 Hz, 1H), 2.33–2.27 (m, 3H). 13C NMR (100 MHz, CDCl3): d
(t, J ¼ 11.6 Hz, 4H), 7.03 (t, J ¼ 12.8 Hz, 2H), 6.70 (d, J ¼ 11.6 Hz, 145.8, 145.2, 145.0, 143.8, 141.3, 140.8, 140.7, 137.9, 137.6,
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137.1, 130.6, 130.5, 129.4, 129.1, 128.6, 128.6, 128.5, 128.5, 113.7, 55.7, 55.6, 21.7, 21.6. HRMS (EI+): calcd. for C25H24O2
128.4, 128.3, 128.3, 128.0, 127.8, 127.4, 127.1, 127.1, 117.6, [M + 1]+: 357.1849, found: 357.1848.
117.5, 21.7, 21.6. HRMS (EI+): calcd. for C23H20 [M + 1]+:
297.1638, found: 297.1635.
4-(1,3-Diphenylbuta-1,3-dien-1-yl)-1,10-biphenyl (3l). The title
compound was obtained according to the general procedure.
4,40-(1-(p-Tolyl)buta-1,3-diene-1,3-diyl)bis(uorobenzene) (3h). Colourless oil; yield: 77%; IR (KBr): 3077, 3055, 3027, 2958,
The title compound was obtained according to the general 2929, 1754, 1599, 1488, 1444, 1403, 905, 839, 765, 698 cmꢂ1; 1H
procedure. Colourless oil; yield: 80%; IR (KBr): 3045, 3026, NMR (CDCl3, 400 MHz): d 7.43–7.38 (m, 3H), 7.24 (s, 7H), 7.14 (s,
2952, 2922, 2867, 1688, 1657, 1601, 1507, 1451, 1409, 908, 3H), 7.05 (s, 6H), 6.65 (d, J ¼ 14.0 Hz, 1H), 5.27 (s, 1H), 4.99–4.92
835, 733, 606 cmꢂ1; 1H NMR (CDCl3, 400 MHz): d 7.26 (s, 3H), (m, 1H). 13C NMR (100 MHz, CDCl3): d 145.9, 145.7, 144.7, 143.6,
7.18 (d, J ¼ 7.6 Hz, 1H), 7.11 (d, J ¼ 8.0 Hz, 1H), 7.03-7.02 (m, 142.5, 141.3, 141.2, 141.1, 140.8, 140.4, 140.2, 139.5, 131.1,
1H), 6.96 (s, 3H), 6.86–6.80 (m, 3H), 6.70–6.61 (m, 1H), 5.32 (s, 130.6, 129.2, 129.2, 129.1, 128.8, 128.7, 128.7, 128.6, 128.5,
1H), 5.06 (s, 1H), 2.34–2.27 (m, 3H). 13C NMR (100 MHz, 128.4, 128.1, 127.9, 127.8, 127.6, 127.5, 127.4, 127.4, 127.3,
CDCl3): d 145.1, 145.0, 144.1, 140.5, 138.2, 137.5, 137.2, 132.3, 127.2, 127.1, 127.0, 118.1, 117.9. HRMS (EI+): calcd. for C28H22
132.2, 130.4, 130.1, 129.5, 129.1, 128.9, 128.8, 128.8, 128.3, [M + 1]+: 359.1794, found: 359.1793.
128.1, 128.1, 118.1, 117.8, 115.6, 115.4, 115.1, 21.7, 21.6.
HRMS (EI+): calcd. for C23H18F2 [M + 1]+: 333.1449, found: title compound was obtained according to the general proce-
333.1452. dure. Colourless oil; yield: 82%; IR (KBr): 3057, 3026, 2923,
4-(1,3-Di-p-tolylbuta-1,3-dien-1-yl)-1,10-biphenyl (3m). The
4,40,400-(Buta-1,3-diene-1,1,3-triyl)tris(methylbenzene) (3i). 2854, 1654, 1602, 1510, 1485, 1450, 1404, 1380, 895, 821, 763,
The title compound was obtained according to the general 696 cmꢂ1; 1H NMR (CDCl3, 400 MHz): d 7.56 (d, J ¼ 8.0 Hz, 1H),
procedure. Colourless oil; yield: 45%; IR (KBr): 3083, 3040, 7.52 (t, J ¼ 6.4 Hz, 2H), 7.38–7.35 (m, 4H), 7.32–7.23 (m, 4H),
3022, 2944, 2919, 2864, 1607, 1510, 1448, 1407, 895, 785, 732 7.19 (d, J ¼ 7.2 Hz, 1H), 7.09 (d, J ¼ 8.0 Hz, 2H), 7.02 (dd, J ¼
1
cmꢂ1; H NMR (CDCl3, 400 MHz): d 7.31 (d, J ¼ 8.4 Hz, 2H), 15.6, J ¼ 8.0 Hz, 2H), 6.71 (d, J ¼ 6.0 Hz, 2H), 5.36 (s, 1H), 5.02–
7.19 (d, J ¼ 8.0 Hz, 2H), 7.10 (d, J ¼ 8.0 Hz, 2H), 7.05 (dd, J ¼ 4.97 (m, 1H), 2.28 (t, J ¼ 15.2 Hz, 6H). 13C NMR (100 MHz,
8.4, J ¼ 2.4 Hz, 4H), 6.99 (d, J ¼ 8.0 Hz, 2H), 6.62 (s, 1H), 5.34 CDCl3): d 145.6, 145.4, 144.5, 144.5, 142.7, 141.3, 141.1, 140.8,
(d, J ¼ 1.6 Hz, 1H), 4.93 (s, 1H), 2.34 (s, 3H), 2.30 (d, J ¼ 7.6 Hz, 140.7, 140.1, 139.8, 138.4, 138.3, 137.9, 137.6, 137.5, 137.1,
6H). 13C NMR (100 MHz, CDCl3): d 145.5, 144.9, 141.0, 138.5, 131.0, 130.4, 129.4, 129.3, 129.2, 129.2, 129.2, 129.1, 128.8,
137.8, 137.6, 137.0, 130.4, 129.3, 129.3, 129.1, 128.3, 127.9, 128.7, 128.5, 128.4, 127.7, 127.6, 127.4, 127.4, 127.3, 127.1,
126.9, 116.4, 21.7, 21.6, 21.6. HRMS (EI+): calcd. for C25H24 [M 126.9, 117.1, 116.7, 21.6. HRMS (EI+): calcd. for C30H26 [M + 1]+:
+ 1]+: 325.1951, found: 325.1959.
387.2107, found: 387.2109.
(E)-2,20-(1-(p-Tolyl)buta-1,3-diene-1,3-diyl)bis(methylbenzene)
4-(1,3-Di-o-tolylbuta-1,3-dien-1-yl)-1,10-biphenyl (3n). The
(3j). The title compound was obtained according to the title compound was obtained according to the general proce-
general procedure. Colourless oil; yield: 47%; IR (KBr): 3058, dure. Colourless oil; yield: 40%; IR (KBr): 3058, 3026, 2951,
3018, 2949, 2921, 2861, 1734, 1601, 1509, 1453, 1381, 903, 2921, 2858, 1731, 1666, 1599, 1486, 1452, 1380, 905, 840, 764,
1
820, 761, 701 cmꢂ1; H NMR (CDCl3, 400 MHz): d 7.25–7.10 730, 696 cmꢂ1; 1H NMR (CDCl3, 400 MHz): d 7.54 (d, J ¼ 7.6 Hz,
(m, 3H), 7.04 (d, J ¼ 8.0 Hz, 2H), 7.02–7.00 (m, 1H), 6.96–6.93 2H), 7.46 (d, J ¼ 8.0 Hz, 2H), 7.40–7.33 (m, 3H), 7.28 (d, J ¼ 8.0
(m, 4H), 6.88–6.87 (m, 1H), 6.85 (s, 1H), 6.83–6.72 (m, 1H), Hz, 2H), 7.19–7.09 (m, 1H), 7.05–7.00 (m, 1H), 6.98 (d, J ¼ 4.4
5.19 (s, 1H), 4.98 (d, J ¼ 1.6 Hz, 1H), 2.30 (s, 3H), 2.24 (s, 3H), Hz, 2H), 6.94 (d, J ¼ 4.4 Hz, 2H), 6.92–6.89 (m, 2H), 6.88–6.74
1.96 (s, 3H). 13C NMR (100 MHz, CDCl3): d 147.0, 144.8, 143.6, (m, 1H), 5.23 (s, 1H), 5.02 (d, J ¼ 1.2 Hz, 1H), 2.26 (s, 3H), 2.00 (s,
142.6, 142.5, 141.6, 139.5, 139.5, 137.6, 136.8, 136.7, 136.6, 3H). 13C NMR (100 MHz, CDCl3): d 147.0, 142.7, 142.6, 139.7,
135.3, 135.1, 131.2, 130.8, 130.5, 130.2, 130.1, 130.1, 130.0, 139.3, 136.9, 135.1, 133.9, 133.2, 130.4, 130.3, 130.0, 130.0,
129.7, 129.5, 129.1, 128.6, 128.2, 127.7, 127.6, 127.0, 127.0, 129.2, 128.8, 128.3, 128.0, 127.8, 127.1, 126.5, 126.4, 126.3,
125.9, 125.8, 125.6, 125.5, 121.7, 119.9, 30.2, 21.6, 21.0, 20.8, 126.3, 125.9, 125.6, 125.0, 120.4, 20.9, 20.3. HRMS (EI+): calcd.
20.2. HRMS (EI+): calcd. for C25H24 [M + 1]+: 325.1951, found: for C30H26 [M + 1]+: 387.2107, found: 387.2114.
325.1949.
4,40-(1-(p-Tolyl)buta-1,3-diene-1,3-diyl)bis(methox-
4-(1,3-Bis(4-uorophenyl)buta-1,3-dien-1-yl)-1,10-biphenyl (3o).
The title compound was obtained according to the general
ybenzene) (3k). The title compound was obtained according to procedure. Colourless oil; yield: 89%; IR (KBr): 3080, 3048,
the general procedure. Colourless oil; yield: 43%; IR (KBr): 3030, 2960, 2929, 2847, 1652, 1600, 1506, 1486, 1404, 907, 877,
3034, 2999, 2953, 2931, 2835, 1606, 1510, 1461, 1413, 1380, 733, 696 cmꢂ1; 1H NMR (CDCl3, 400 MHz): d 7.58 (d, J ¼ 6.8 Hz,
1359, 891, 831, 726 cmꢂ1; 1H NMR (CDCl3, 400 MHz): d 7.33 (t, 1H), 7.52 (t, J ¼ 8.4 Hz, 2H), 7.40–7.34 (m, 4H), 7.32–7.26 (m,
J ¼ 7.6 Hz, 2H), 7.23 (t, J ¼ 9.6 Hz, 2H), 7.11 (d, J ¼ 8.0 Hz, 1H), 3H), 7.12–7.05 (m, 2H), 7.00 (t, J ¼ 11.2 Hz, 1H), 6.86–6.79 (m,
7.06–7.03 (m, 2H), 6.99 (d, J ¼ 8.0 Hz, 1H), 6.82 (d, J ¼ 8.4 Hz, 4H), 6.68 (s, 1H), 5.34 (s, 1H), 5.12 (d, J ¼ 12.4 Hz, 1H). 13C
1H), 6.78–6.75 (m, 2H), 6.71 (d, J ¼ 8.0 Hz, 1H), 5.29 (d, J ¼ 11.2 NMR (100 MHz, CDCl3): d 163.9, 161.5, 145.1, 143.9, 143.8,
Hz, 1H), 4.91 (d, J ¼ 18.8 Hz, 1H), 3.76 (t, J ¼ 10.6 Hz, 6H), 142.2, 141.2, 141.1, 141.0, 140.6, 139.6, 139.1, 137.1, 136.2,
3.37–3.29 (m, 3H). 13C NMR (100 MHz, CDCl3): d 159.7, 159.5, 132.3, 132.3, 131.0, 130.2, 130.1, 129.3, 129.2, 129.0, 128.9,
159.5, 159.1, 145.3, 145.2, 144.4, 141.2, 137.8, 137.8, 137.0, 128.9, 128.8, 128.7, 127.9, 127.8, 127.4, 127.1, 118.4, 115.7,
136.4, 134.0, 133.9, 133.0, 131.7, 130.4, 129.6, 129.3, 129.1, 115.5, 115.4, 115.2, 115.2. HRMS (EI+): calcd. for C28H20F2 [M +
128.4, 128.2, 128.2, 127.8, 127.2, 115.6, 115.5, 113.9, 113.9, 1]+: 395.1606, found: 395.1600.
39504 | RSC Adv., 2014, 4, 39497–39507
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(1-(4-Chlorophenyl)buta-1,3-diene-1,3-diyl)dibenzene (3p).
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1-(1,3-Bis(4-uorophenyl)buta-1,3-dien-1-yl)naphthalene(3t).
The title compound was obtained according to the general The title compound was obtained according to the general
procedure. Colourless oil; yield: 45%; IR (KBr): 3080, 3048, 3030, procedure. Colourless oil; yield: 71%; IR (KBr): 3054, 3020, 2955,
2960, 2929, 2847, 1652, 1600, 1506, 1486, 1404, 907, 877, 733, 2925, 2854, 1771, 1600, 1506, 1440, 900, 837, 748. cmꢂ1 1H
;
696 cmꢂ1; 1H NMR (CDCl3, 400 MHz): d 7.36–7.33 (m, 2H), 7.29 NMR (CDCl3, 400 MHz): d 7.82–7.74 (m, 2H), 7.69–7.62 (m, 1H),
(s, 3H), 7.24 (d, J ¼ 4.0 Hz, 2H), 7.22–7.19 (m, 3H), 7.17 (dd, J ¼ 7.54 (s, 1H), 7.46–7.40 (m, 2H), 7.31–7.27 (m, 3H), 7.20 (t, J ¼ 7.6
4.4, J ¼ 1.2 Hz, 1H), 7.13–7.10 (m, 2H), 7.05 (d, J ¼ 8.4 Hz, 1H), Hz, 1H), 7.10–7.07 (m, 1H), 6.99 (t, J ¼ 8.4 Hz, 1H), 6.89–6.84 (m,
6.73 (d, J ¼ 16.8 Hz, 1H), 5.40 (d, J ¼ 8.8 Hz, 1H), 5.04 (d, J ¼ 10.8 2H), 6.81 (d, J ¼ 8.4 Hz, 1H), 6.78–6.73 (m, 1H), 5.38–5.30 (m,
Hz, 1H). 13C NMR (100 MHz, CDCl3): d 145.7, 145.6, 144.0, 143.9, 1H), 5.14–5.07 (m, 1H). 13C NMR (100 MHz, CDCl3): d 164.2,
143.1, 142.1, 141.0, 140.9, 140.1, 139.0, 133.9, 133.4, 132.0, 163.9, 163.8, 163.7, 161.8, 161.5, 161.4, 161.3, 145.1, 144.7,
130.5, 129.7, 129.5, 129.2, 128.8, 128.7, 128.6, 128.6, 128.5, 144.2, 144.2, 140.6, 139.6, 139.5, 137.7, 137.1, 137.1, 137.0,
128.4, 128.3, 128.0, 127.9, 127.7, 127.1, 127.1, 118.3, 118.2. 137.0, 136.2, 136.2, 133.7, 133.5, 133.4, 133.0, 132.4, 132.3,
HRMS (EI+): calcd. for C22H17Cl [M + 1]+: 317.1092, found: 130.2, 130.1, 129.8, 129.5, 128.9, 128.8, 128.7, 128.7, 128.7,
317.1093.
128.5, 128.3, 128.3, 128.0, 127.7, 126.8, 126.7, 126.5, 126.4,
4,40-(1-(4-Chlorophenyl)buta-1,3-diene-1,3-diyl)bis(methylbenzene) 126.3, 126.3, 118.4, 118.4, 115.7, 115.5, 115.4, 115.4, 115.3,
(3q). The title compound was obtained according to the general 115.2, 115.1. HRMS (EI+): calcd. for C26H19F2 [M + 1]+: 369.1449,
procedure. Colourless oil; yield: 74%; IR (KBr): 3084, 3051, found: 369.1456.
3024, 2949, 2920, 2865, 1654, 1608, 1510, 1487, 1449, 1400, 906,
(1-(3,5-Dimethylphenyl)buta-1,3-diene-1,3-diyl)dibenzene (3u).
822, 766, 731 cmꢂ1; 1H NMR (CDCl3, 400 MHz): d 7.29–7.22 (m, The title compound was obtained according to the general
4H), 7.17 (d, J ¼ 8.0 Hz, 1H), 7.10 (t, J ¼ 8.4 Hz, 3H), 7.05 (d, J ¼ procedure. Colourless oil; yield: 66%; IR (KBr): 3078, 3054,
9.2 Hz, 2H), 7.01–6.99 (m, 2H), 6.69–6.62 (m, 1H), 5.35 (s, 1H), 3025, 2949, 2917, 2861, 1751, 1598, 1492, 1440, 1382, 900, 848,
4.96 (s, 1H), 2.33–2.27 (m, 6H). 13C NMR (100 MHz, CDCl3): d 772, 699 cmꢂ1; 1H NMR (CDCl3, 400 MHz): d 7.37 (d, J ¼ 6.8 Hz,
145.4, 145.3, 143.8, 143.6, 142.3, 140.4, 139.2, 138.2, 138.1, 1H), 7.32 (d, J ¼ 7.2 Hz, 2H), 7.26 (d, J ¼ 10.4 Hz, 1H), 7.21–7.15
138.0, 137.8, 137.7, 137.4, 137.2, 133.8, 133.3, 131.9, 130.4, (m, 6H), 6.93 (d, J ¼ 8.0 Hz, 2H), 6.75–6.72 (m, 1H), 6.70 (d, J ¼
129.7, 129.4, 129.3, 129.2, 129.0, 128.9, 128.7, 128.5, 128.3, 10.4 Hz, 1H), 5.36 (s, 1H), 5.09–5.00 (m, 1H), 2.26 (s, 3H), 2.15
127.0, 126.9, 117.1, 116.9, 21.7, 21.6, 21.6. HRMS (EI+): calcd. (s, 3H). 13C NMR (100 MHz, CDCl3): d 146.1, 145.8, 145.4, 143.8,
for C24H21Cl [M + 1]+: 345.1405, found: 345.1402.
143.7, 141.3, 140.3, 138.1, 137.6, 130.6, 129.8, 129.0, 128.6,
1-(1,3-Diphenylbuta-1,3-dien-1-yl)naphthalene (3r). The title 128.5, 128.4, 128.3, 127.9, 127.8, 127.6, 127.4, 127.2, 127.2,
compound was obtained according to the general procedure. 126.4, 118.1, 117.6, 21.8, 21.6. HRMS (EI+): calcd. for C24H22 [M
Colourless oil; yield: 50%; IR (KBr): 3080, 3054, 3024, 2960, + 1]+: 311.1794, found: 311.1797.
2926, 2847, 1597, 1573, 1492, 1443, 1383, 904, 857, 748, 699
4,40-(1-(3,5-Dimethylphenyl)buta-1,3-diene-1,3-diyl)bis(me-
cmꢂ1; 1H NMR (CDCl3, 400 MHz): d 7.66–7.62 (m, 2H), 7.51 (d, J thylbenzene) (3v). The title compound was obtained according
¼ 10.0 Hz, 1H), 7.37 (d, J ¼ 8.4 Hz, 1H), 7.28 (s, 5H), 7.16 (d, J ¼ to the general procedure. Colourless oil; yield: 61%; IR (KBr):
5.6 Hz, 2H), 7.12–6.99 (m, 6H), 6.70–6.60 (m, 1H), 4.95 (d, J ¼ 3083, 3022, 2949, 2921, 2856, 1788, 1652, 1600, 1510, 1455,
10.8 Hz, 1H). 13C NMR (100 MHz, CDCl3): d 145.8, 145.7, 145.2, 1378, 895, 820, 731, 708 cmꢂ1; 1H NMR (CDCl3, 400 MHz): d 7.31
145.1, 143.6, 141.2, 141.0, 140.5, 138.1, 133.8, 133.6, 133.4, (d, J ¼ 7.6 Hz, 1H), 7.23 (q, J ¼ 7.6 Hz, 2H), 7.09–6.91 (m, 7H),
133.0, 130.7, 129.7, 129.4, 129.3, 128.8, 128.7, 128.6, 128.5, 6.75 (d, J ¼ 12.4 Hz, 1H), 6.63 (d, J ¼ 7.6 Hz, 1H), 5.31 (d, J ¼ 12.8
128.5, 128.2, 128.0, 127.9, 127.8, 127.6, 127.2, 127.1, 126.6, Hz, 1H), 4.98–4.92 (m, 1H), 2.31 (d, J ¼ 12.4 Hz, 3H), 2.28 (s, 3H),
126.5, 126.4, 126.3, 118.2, 118.0. HRMS (EI+): calcd. for C26H20 2.26 (s, 3H), 2.17 (s, 3H). 13C NMR (100 MHz, CDCl3): d 145.7,
[M + 1]+: 333.1638, found: 333.1635.
145.5, 145.2, 145.0, 143.9, 141.1, 140.5, 138.8, 138.5, 138.0,
1-(1,3-Di-p-tolylbuta-1,3-dien-1-yl)naphthalene (3s). The 137.8, 137.7, 137.6, 137.3, 137.0, 130.4, 129.7, 129.3, 129.3,
title compound was obtained according to the general proce- 129.1, 129.1, 128.9, 128.5, 128.3, 128.3, 127.8, 127.0, 126.9,
dure. Colourless oil; yield: 83%; IR (KBr): 3053, 3023, 2955, 126.4, 116.8, 116.3, 30.2, 21.8, 21.6. HRMS (EI+): calcd. for
2923, 2853, 1606, 1510, 1461, 1377, 895, 854, 818, 745, 723
C
26H27 [M + 1]+: 339.2107, found: 339.2111.
2,20-(1-(3,5-Dimethylphenyl)buta-1,3-diene-1,3-diyl)bis(me-
cmꢂ1; 1H NMR (CDCl3, 400 MHz): d 7.73–7.68 (m, 2H), 7.62 (d,
J ¼ 8.0 Hz, 2H), 7.47 (dd, J ¼ 8.4, J ¼ 1.6 Hz, 1H), 7.38–7.29 (m, thylbenzene) (3w). The title compound was obtained accord-
4H), 7.23 (d, J ¼ 8.0 Hz, 1H), 7.10 (d, J ¼ 8.4 Hz, 1H), 7.01 (td, J ing to the general procedure. Colourless oil; yield: 55%; IR
¼ 15.6, J ¼ 8.0 Hz, 4H), 6.78 (d, J ¼ 16.4 Hz, 1H), 5.38–5.30 (m, (KBr): 3063, 3016, 2955, 2918, 2861, 1597, 1486, 1453, 1380,
1H), 4.98 (m, 1H), 2.31–2.20 (m, 6H). 13C NMR (100 MHz, 904, 848, 763, 730, 702, 658 cm-1; 1H NMR (CDCl3, 400 MHz): d
CDCl3): d 145.5, 145.4, 145.0, 144.8, 141.2, 140.9, 138.4, 138.4, 7.15–7.00 (m, 2H), 6.94 (d, J ¼ 7.6 Hz, 4H), 6.86 (d, J ¼ 15.2 Hz,
138.3, 137.9, 137.6, 137.6, 137.6, 137.2, 133.8, 133.7, 133.3, 5H), 6.75–6.41 (m, 1H), 5.17 (s, 1H), 4.98 (s, 1H), 2.25 (s, 3H),
133.0, 130.5, 129.6, 129.4, 129.3, 129.3, 129.3, 129.2, 128.9, 2.22 (s, 6H), 1.98 (s, 3H). 13C NMR (100 MHz, CDCl3): d 147.1,
128.7, 128.7, 128.5, 128.4, 128.1, 128.0, 127.8, 127.6, 127.0, 142.9, 142.7, 142.5, 139.5, 138.1, 136.8, 135.1, 130.2, 130.1,
126.9, 126.6, 126.5, 126.4, 126.2, 117.1, 116.7, 21.7, 21.6, 21.6, 130.0, 129.6, 129.3, 129.1, 127.5, 127.0, 125.8, 125.5, 125.0,
21.5. HRMS (EI+): calcd. for C28H24 [M + 1]+: 361.1951, found: 120.0, 21.8, 20.9, 20.3. HRMS (EI+): calcd. for C26H26 [M + 1]+:
361.1950.
339.2107, found: 339.2105.
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124.5, 119.1. HRMS (EI+): calcd. for C14H16 [M + 1]+: 185.1325,
found: 185.1328.
4,40-(1-(3,5-Dimethylphenyl)buta-1,3-diene-1,3-diyl)bis-
(uorobenzene) (3x). The title compound was obtained
according to the general procedure. Colourless oil; yield: 64%;
IR (KBr): 3041, 3009, 2955, 2923, 2855, 1649, 1601, 1507, 1462,
1380, 1228, 901, 838, 734, 707 cmꢂ1; 1H NMR (CDCl3, 400 MHz):
d 7.28–7.19 (m, 3H), 7.05–7.01 (m, 1H), 6.97 (d, J ¼ 8.8 Hz, 1H),
6.92 (d, J ¼ 12.4 Hz, 2H), 6.84–6.79 (m, 3H), 6.72 (d, J ¼ 14.4 Hz,
1H), 6.63 (d, J ¼ 3.2 Hz, 1H), 5.30 (d, J ¼ 12.4 Hz, 1H), 5.13–5.06
(m, 1H), 2.27 (s, 3H), 2.14 (s, 3H). 13C NMR (100 MHz, CDCl3): d
164.1, 163.9, 163.7, 163.6, 161.7, 161.4, 161.3, 161.2, 145.4,
145.1, 144.5, 144.3, 143.4, 139.9, 138.2, 137.7, 137.4, 137.3,
137.1, 137.1, 136.5, 136.4, 132.3, 132.2, 130.1, 130.1, 130.0,
129.3, 128.9, 128.9, 128.8, 128.8, 128.7, 128.4, 128.1, 126.4,
124.6, 118.4, 118.0, 115.5, 115.4, 115.3, 115.3, 115.2, 115.1,
115.0, 114.8, 21.8. HRMS (EI+): calcd. for C24H20F2 [M + 1]+:
347.1606, found: 347.1606.
4-((1E,3E)-Hexa-1,3,5-trien-1-yl)-1,10-biphenyl (5e). The title
compound was obtained according to the general procedure.
White solid; yield: 40%; IR (KBr): 3060, 3025, 2918, 1720, 1675,
1618, 1492, 1449, 989, 910, 748, 693 cmꢂ1; 1H NMR (DMSO, 400
MHz): d 7.67 (dd, J ¼ 10.8, J ¼ 7.6 Hz, 4H), 7.57 (d, J ¼ 8.0 Hz,
2H), 7.46 (t, J ¼ 7.6 Hz, 2H), 7.36 (t, J ¼ 7.2 Hz, 1H), 7.06–7.00 (m,
1H), 6.70 (d, J ¼ 15.6 Hz, 1H), 6.54-6.44 (m, 2H), 5.31 (d, J ¼ 15.2
Hz, 1H), 5.16 (d, J ¼ 10.0 Hz, 1H). 13C NMR (100 MHz, DMSO): d
140.5, 140.2, 138.1, 137.1, 134.9, 134.7, 133.3, 130.05, 129.9,
128.5, 127.9, 127.9, 127.4, 119.0. HRMS (EI+): calcd. for C14H16
[M + 1]+: 185.1325, found: 185.1328.
9-((1E,3E)-Hexa-1,3,5-trien-1-yl)phenanthrene (5f). The title
compound was obtained according to the general procedure.
White solid; yield: 35%; IR (KBr): 3025, 2923, 2858, 1720, 1677,
1615, 1493, 1449, 1383, 990, 905, 748, 692 cmꢂ1 1H NMR
;
(1E,3E)-Hexa-1,3,5-trien-1-ylbenzene
(5a).
The
title
(CDCl3, 400 MHz): d 8.71 (d, J ¼ 8.0 Hz, 1H), 8.63 (d, J ¼ 8.0 Hz,
1H), 8.18 (d, J ¼ 7.6 Hz, 1H), 7.89–7.86 (m, 2H), 7.69–7.55 (m,
4H), 7.36–7.24 (m, 1H), 6.96 (dd, J ¼ 15.2, J ¼ 10.8 Hz, 1H), 6.61–
6.41 (m, 3H), 5.32 (d, J ¼ 17.2 Hz, 1H), 5.18 (d, J ¼ 9.6 Hz, 1H).
13C NMR (100 MHz, CDCl3): d 137.5, 134.7, 134.1, 134.0, 132.5,
132.2, 130.9, 130.7, 130.5, 129.2, 127.3, 127.1, 127.0, 127.0,
124.9, 124.7, 123.6, 123.0, 118.4. HRMS (EI+): calcd. for C20H16
[M + 1]+: 257.1325, found: 257.1319.
(1E,3E,5E)-Octa-1,3,5,7-tetraen-1-ylbenzene (5g). The title
compound was obtained according to the general procedure.
White solid; yield: 27%; IR (KBr): 3023, 2923, 2852, 1720, 1675,
1595, 1444, 1383, 989, 904, 748, 691 cmꢂ1; 1H NMR (CDCl3, 400
MHz): d 7.40 (d, J ¼ 7.6 Hz, 2H), 7.31 (t, J ¼ 7.2 Hz, 2H), 7.22 (dd,
J ¼ 15.2, J ¼ 8.0 Hz, 1H), 6.84 (dd, J ¼ 15.6, J ¼ 10.0 Hz, 1H), 6.56
(d, J ¼ 15.6 Hz, 1H), 6.46–6.28 (m, 5H), 5.25 (d, J ¼ 17.6 Hz, 1H),
5.12 (d, J ¼ 11.2 Hz, 1H). 13C NMR (100 MHz, CDCl3): d 137.8,
137.6, 134.2, 134.2, 133.9, 133.6, 133.2, 129.5, 129.1, 128.0,
126.8, 118.0. HRMS (EI+): calcd. for C14H14 [M + 1]+: 183.1168,
found: 183.1166.
compound was obtained according to the general procedure.
White solid; yield: 63%; IR (KBr): 3060, 3025, 2918, 1675, 1618,
1
1492, 1449, 989, 750, 693 cmꢂ1; H NMR (CDCl3, 400 MHz): d
7.38 (d, J ¼ 7.6 Hz, 2H), 7.30 (t, J ¼ 7.2 Hz, 2H), 7.20 (t, J ¼ 7.2 Hz,
1H), 6.80 (dd, J ¼ 15.6, J ¼ 9.6 Hz, 1H), 6.56 (d, J ¼ 15.6 Hz, 1H),
6.47–6.31 (m, 3H), 5.26 (dd, J ¼ 16.8, J ¼ 1.2 Hz, 1H), 5.13–5.11
(m, 1H). 13C NMR (100 MHz, CDCl3): d 137.8, 137.5, 134.2, 133.9,
133.4, 129.3, 129.1, 128.0, 126.9, 118.0. HRMS (EI+): calcd. for
C
12H12 [M + 1]+: 157.1012, found: 157.1021.
1-((1E,3E)-Hexa-1,3,5-trien-1-yl)-4-methylbenzene (5b). The
title compound was obtained according to the general proce-
dure. White solid; yield: 54%; IR (KBr): 3021, 2918, 2861, 1725,
1
1679, 1606, 1511, 1450, 1383, 987, 802, cmꢂ1; H NMR (CDCl3,
400 MHz): d 7.29 (d, J ¼ 8.0 Hz, 2H), 7.11 (d, J ¼ 8.0 Hz, 2H), 6.76
(dd, J ¼ 15.2, J ¼ 9.6 Hz, 1H), 6.53 (d, J ¼ 15.6 Hz, 1H), 6.47–6.29
(m, 3H), 5.24 (dd, J ¼ 16.8, J ¼ 1.6 Hz, 1H), 5.10 (dd, J ¼ 10.0, J ¼
1.6 Hz, 1H), 2.33 (s, 3H). 13C NMR (400 MHz, CDCl3): d 138.0,
137.6, 135.0, 134.1, 133.7, 133.4, 129.8, 128.4, 126.8, 117.6, 21.7.
HRMS (EI+): calcd. for C13H14 [M + 1]+: 171.1168, found:
171.1170.
1-((1E,3E)-Hexa-1,3,5-trien-1-yl)-3,5-dimethylbenzene (5c).
The title compound was obtained according to the general
procedure. White solid; yield: 55%; IR (KBr): 3014, 2914, 2855,
1805, 1720, 1671, 1597, 1458, 1380, 976, 898, 824, 689 cmꢂ1; 1H
NMR (CDCl3, 400 MHz): d 7.01 (s, 2H), 6.86 (s, 1H), 6.78 (dd, J ¼
15.6, J ¼ 9.6 Hz, 1H), 6.50 (d, J ¼ 15.2 Hz, 1H), 6.46–6.32 (m, 3H),
5.25 (d, J ¼ 16.4 Hz, 1H), 5.11 (d, J ¼ 10.0 Hz, 1H), 2.29 (s, 6H).
13C NMR (100 MHz, CDCl3): d 138.5, 137.7, 137.6, 134.2, 133.9,
133.7, 129.9, 129.0, 124.8, 117.7, 21.7. HRMS (EI+): calcd. for
Acknowledgements
We gratefully acknowledge A Project Funded by the Priority
Academic Program Development of Jiangsu Higher Education
Institutions, the Project of Scientic and Technologic Infra-
structure of Suzhou (SZS201207) and the National Natural
Science Foundation of China (no. 21072143) for nancial
support.
C
14H16 [M + 1]+: 185.1325, found: 185.1328.
Notes and references
1-((1E,3E)-Hexa-1,3,5-trien-1-yl)naphthalene (5d). The title
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compound was obtained according to the general procedure.
White solid; yield: 27%; IR (KBr): 3060, 3025, 2918, 1720, 1675,
1618, 1492, 1449, 989, 910, 748, 693 cmꢂ1; 1H NMR (DMSO, 400
MHz): d 7.87 (d, J ¼ 8.8 Hz, 4H), 7.74 (d, J ¼ 8.4 Hz, 1H), 7.51–
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6.45 (m, 3H), 5.32 (d, J ¼ 15.6 Hz, 1H), 5.17 (d, J ¼ 9.2 Hz, 1H).
13C NMR (100 MHz, DMSO): d 138.2, 135.6, 135.0, 134.8, 134.3,
133.9, 133.6, 130.5, 129.2, 128.9, 128.6, 127.5, 127.3, 127.1,
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