New application of n-halosuccinimide/PPh3 for the halogenation of propargyl alcohols to haloallenes

Article abstract of DOI:10.1080/00397910902883587

An efficient and convenient new method has been developed for the preparation of haloallenes from propargyl alcohols by a reagent combination of N-halosuccinimide and triphenylphosphine. Chloroallenes 2 and bromoallenes 3 were obtained exclusively in mode

Full text of DOI:10.1080/00397910902883587

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New Application of N-
Halosuccinimide/PPh3 for the
Halogenation of Propargyl
Alcohols to Haloallenes
Xin Du a , Yao Dai a , Ren He a , Shirong Lu a & Ming
Bao a
a State Key Laboratory of Fine Chemicals , Dalian
University of Technology , Dalian, China
Published online: 07 Oct 2009.
To cite this article: Xin Du , Yao Dai , Ren He , Shirong Lu & Ming Bao (2009)
New Application of N-Halosuccinimide/PPh3 for the Halogenation of Propargyl
Alcohols to Haloallenes, Synthetic Communications: An International Journal for
Rapid Communication of Synthetic Organic Chemistry, 39:21, 3940-3949, DOI:
10.1080/00397910902883587
To link to this article: http://dx.doi.org/10.1080/00397910902883587
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Synthetic Communications1, 39: 3940–3949, 2009
Copyright # Taylor & Francis Group, LLC
ISSN: 0039-7911 print=1532-2432 online
DOI: 10.1080/00397910902883587
New Application of N-Halosuccinimide/PPh3
for the Halogenation of Propargyl Alcohols
to Haloallenes
Xin Du, Yao Dai, Ren He, Shirong Lu, and Ming Bao
State Key Laboratory of Fine Chemicals, Dalian University
of Technology, Dalian, China
Abstract: An efficient and convenient new method has been developed for the
preparation of haloallenes from propargyl alcohols by a reagent combination
of N-halosuccinimide and triphenylphosphine. Chloroallenes 2 and bromoallenes
3 were obtained exclusively in moderate to good yields with regioselectivity.
Keywords: Haloallene, N-halosuccinimide, preparation, propargyl alcohol,
triphenylphisphine
INTRODUCTION
Haloallenes can be used as synthetic intermediates in organic synthesis,[1–3]
and the haloallene moieties have been found in many molecules of
natural products.[4] Over the past few years, several synthetic methods,
including the isomerization of 3-bromo- and 3-chloropropyne in the
presence of cuprous halide;[5] the conversion of propargyl alcohols by
halogenating reagents such as thionyl chloride,[6] TiCl4=tertiary alkyl-
amine,[7] and hydrochloric acid;[8] and the conversion of propargylic
methanesulfonate by a halocuprate[9] have been reported for the purpose
of preparing haloallenes. However, using these methods to synthesize
haloallenes often has drawbacks: (i) poor yield, (ii) frequent obtaining
Received October 5, 2008.
Address correspondence to Ming Bao, State Key Laboratory of Fine
Chemicals, Dalian University of Technology, Dalian 116012, China. E-mail:
mingbao@dlut.edu.cn
3940

Preparation of Haloallenes
3941
of a mixture, (iii) use of toxic halogenating reagent, and (iv) difficulty of
operation. During the course of our research on the preparation of halo-
allene, we found that propargyl alcohols can be converted effectively to
corresponding haloallenes by a reagent combination of N-halosuccinimide
and triphenylphosphine under mild conditions. Herein, we report this
efficient and convenient new method.
RESULTS AND DISCUSSION
To the best of our knowledge, there is no report of the use of N-
halosuccinimide as a halogenating reagent for the conversion of propar-
gyl alcohols to haloallenes. It is easier to handle than other halogenating
reagents, and it is also readily available. We first examined the reaction
of 1-phenylhept-2-yn-1-ol (1a) with N-chlorosuccinimide (NCS) and
triphenylphosphine in dichloromethane at room temperature to give
the corresponding chloroallene (2a) in 83% yield (Table 1, entry 1).
The success of the reaction encouraged us to perform reactions of various
propargyl alcohols with NCS in the presence of triphenylphosphine, and
the results are shown in Table 1. Neither the electron-donating group nor
the electron-withdrawing group located at the para position of aromatic
ring significantly influenced the chlorination, except for the phenyl
group, and the yields of the chloroallenes 2b–d were in the range of
80–88% (entries 2–4); a lesser yield was obtained from the reaction of
para phenyl-substituted substrate (1e) (entry 5). In comparison with the
para chlorine-substituted substrate (1b), a lesser reactivity of ortho
chlorine-substituted substrate (1f) was found, which is perhaps due to
the steric hindrance of ortho-chlorine atom (61%, entry 6). When the
n-butyl group on 1a was changed to n-hexyl group, the chlorination also
proceeded smoothly to give the desired chloroallene (2g) in good yield
(83%, entry 7). The naphthyl propargyl alcohols (1h and 1i) were also
employed to attempt this type of chlorination reaction but failed to
obtain chloroallene (2h and 2i) in satisfactory yields, even if the reaction
time was prolonged (entries 8 and 9).
We then examined the bromination of propargyl alcohols 1b–d and
1f with N-bromosuccinimide (NBS) and triphenylphosphine, the results
of which are summarized in Table 2. When the reaction of 1b was
performed under these conditions, the desired bromoallene 3b was
obtained in 86% yield (entry 1). Good yields of bromoallenes 3c and d
were obtained from the reactions of 1c and 1d (85% and 81%, respec-
tively; entries 2 and 3). As with the previously described chlorination,
the bromination of 1f gave bromoallene 3f in relatively lesser yield
(62%, entry 4).

3942
X. Du et al.
Table 1. Preparation of chloroallenes 2 from propargyl alcohols 1 using
a
NCS=PPh3
Entry
1
Substrate 1
Time (h)
1
Product 2
Yield (%)b
83
2
1
88
3
4
5
1
3
1
86
80
55
6
7
1
1
61
82
8
8
Trace
(Continued )

Preparation of Haloallenes
3943
Table 1. Continued
Entry
Substrate 1
Time (h)
Product 2
Yield (%)b
9
8
Trace
1
aAll products are unknown compounds and were characterized by IR, H and
13C NMR, and HRMS.
bIsolated yields.
Table 2. Preparation of bromoallenes 3 from propargyl alcohols 1 using
a
NBS=PPh3
Entry
Substrate 1
Time (h)
Product 2
Yield (%)b
1
1
86
2
1
85
81
3
4
1
3
62
1
aAll products are unknown compounds and were characterized by IR, H and
13C NMR, and HRMS.
bIsolated yields.

3944
X. Du et al.
Scheme 1. Proposed mechanism for the preparation of chloroallenes 2 from
propargyl alcohols 1 using NCS=PPh3.
The formation of haloallenes from propargyl alcohols is most likely
to proceed through a halodeoxosubstitution and can be rationalized as
follows (Scheme 1): NCS reacted with PPh3 to produce phosphonium salt
4,[10] which then reacted with propargyl alcohol 1a to generate inter-
mediate 5 and succinimide. Intermediate 5 underwent intramolecular
halodeoxosubstitution to form chloroallene 2a and generated triphenyl-
phosphine oxide. The formation of succinimide and triphenylphosphine
oxide in the halogenation of propargyl alcohols 1 was confirmed through
isolation and NMR (1H and 13C or 31P) determination of these by-products.
In summary, we have demonstrated an efficient and convenient
method for the preparation of haloallenes. In this method, for the first
time, the reagent combination of N-halosuccinimide and triphenyl-
phosphine was utilized to convert propargyl alcohols to haloallenes. This
type of formation of haloallenes from propargyl alcohols was achieved
through intramolecular halodeoxosubstitution, and consequently the
haloallenes were obtained exclusively with regioselectivity. An aryl sub-
stituent in the propargyl alcohol is essential for this reaction.
EXPERIMENTAL
1H and 13C NMR spectra were recorded in CDCl3 solution on a
Varian Inova-400 spectrometer (400 MHz for 1H, 100 MHz for 13C).
The chemical shifts are reported in parts per million (ppm) downfield
(d) from tetramethylsilane (TMS). Infrared (IR) spectra were recorded
on a Nexus Fourier transform (FT)–IR spectrometer. High-resolution
mass spectra (HRMS) were recorded on a Q-TOF mass spectrometer

Preparation of Haloallenes
3945
(Micromass, England) equipped with Z-spray ionization source.
Thin-layer chromatography (TLC) was carried out on SiO2 (silica gel
60 F254, Merck). Flash chromatography was carried out on SiO2 (silica
gel 60, 200–300 meth). Aldehydes, 1-hexyne, and 1-octyne were all
commercial products and were used without further purification.
General Procedure for the Preparation of Propargyl Alcohols
A mixture of metal sodium (2.30 g, 10.0 mmol) and alkyne (10.0 mmol) in
40 mL of diethyl ether was stirred at room temperature under a nitrogen
atmosphere until the sodium was completely consumed. Then the mixture
was cooled to ꢀ10ꢁC, and a solution of aldehyde (5.0 mmol) in 20 mL of
diethyl ether was added dropwise slowly through a dropping funnel at the
same temperature. After the reaction mixture was stirred at ꢀ10ꢁC for
2–5 h, dilute hydrochloric acid (0.5 M, 10 mL) was added to quench the
reaction. The product was extracted with diethyl ether (3 ꢂ 15 mL), and
the combined organic layer was dried over magnesium sulfate. The sol-
vent was removed under reduced pressure, and the crude product was
purified by silica-gel column chromatography (eluent: petroleum ether
(60–90ꢁC)–ethyl acetate ¼ 10:1) to afford pure propargyl alcohols in
50–70% yields.
General Procedure for the Preparation of Haloallenes
A mixture of propargyl alcohol (1.00 mmol), N-halosuccinimide (1.55 mmol),
and triphenylphosphine (1.50 mmol) in 10 mL of dichloromethane was
stirred magnetically at room temperature for 1–3 h. The solvent was
removed under reduced pressure, and then the crude product was purified
by flash-column chromatography on silica gel (eluent: hexane) to give
pure haloallenes in 55–88% yields (Tables 1 and 2).
Spectral Data for New Compounds
1-Biphenyl-4-ylhept-2-yn-1-ol (1e)
White solid; 1H NMR (400 MHz, CDCl3) d 7.60–7.62 (m, 6H), 7.43–7.47
(m, 2H), 7.36–7.38 (m, 1H), 5.51 (m, 1H), 2.31 (dt, J ¼ 2.0, 6.8 Hz, 2H),
2.14 (bs, 1H), 1.52–1.58 (m, 2H), 1.42–1.48 (m, 2H), 0.94 (t, J ¼ 7.2 Hz,
3H); 13C NMR (100 MHz, CDCl3) d 141.2, 140.7, 140.3, 128.8, 128.8,
127.4, 127.3, 127.3, 127.1, 127.1, 127.0, 127.0, 87.8, 79.9, 64.6, 30.7,

3946
X. Du et al.
22.0, 18.5, 13.6; IR (neat) n: 3334, 2956, 2933, 2859, 2222, 1487, 1465,
1405, 1028, 1014, 1006, 988, 857, 757, 738, 693 cmꢀ1; HRMS (EI) calcd.
for C19H20O: 264.1514 [M]þ; found: 264.1517.
Naphthalen-1-ylhept-2-yn-1-ol (1i)
1
Yellow oil; H NMR (400 MHz, CDCl3) d 7.94 (m, 1H), 7.79–7.83 (m,
3H), 7.63 (dd, J ¼ 1.6, 8.4 Hz, 1H), 7.44–7.47 (m, 2H), 5.57 (s, 1H),
2.48 (bs, 1H), 2.26–2.30 (m, 2H), 1.47–1.50 (m, 2H), 1.38–1.42 (m, 2H),
0.91 (t, J ¼ 7.2 Hz, 3H); 13C NMR (100 MHz, CDCl3) d 138.6, 133.2,
133.1, 128.4, 128.2, 127.6, 126.2, 126.1, 125.3, 124.7, 87.9, 80.0, 64.9,
30.6, 22.0, 18.5, 13.6.
(3-Chlorohepta-1,2-dienyl)-benzene (2a)
1
Colorless oil; H NMR (400 MHz, CDCl3) d 7.33–7.35 (m, 4H), 7.26–7.27
(m, 1H), 6.42 (t, J¼ 2.8 Hz, 1H), 2.44–2.50 (m, 2H), 1.53–1.59 (m, 2H),
1.37–1.42 (m, 2H), 0.91 (t, J¼ 7.2 Hz, 3H); 13C NMR (100 MHz, CDCl3) d
200.5, 133.5, 128.9, 128.9, 128.3, 127.9, 127.9, 109.0, 101.9, 36.5, 29.9, 22.0,
14.0; IR (neat) n: 3064, 3033, 2960, 2933, 2873, 1955, 1453, 1265, 1176,
697 cmꢀ1. HRMS (EI) calcd. for C13H15Cl: 206.0862 [M]þ; found: 206.0871.
1-Chloro-4-(3-chlorohepta-1,2-dienyl)-benzene (2b)
Colorless oil; 1H NMR (400 MHz, CDCl3) d 7.31 (d, J ¼ 8.4 Hz, 2H), 7.25
(d, J ¼ 8.4 Hz, 2H), 6.38 (t, J ¼ 2.8 Hz, 1H), 2.44–2.48 (m, 2H), 1.54–1.57
(m, 2H), 1.38–1.41 (m, 2H), 0.91 (t, J ¼ 7.2 Hz, 3H); 13C NMR (100 MHz,
CDCl3) d 200.6, 133.9, 131.9, 129.0, 129.0, 128.9, 128.9, 109.2, 100.6,
36.2, 29.2, 21.8, 13.8; IR (neat) n: 2958, 2930, 2872, 1955, 1491, 1091,
1014, 852, 506 cmꢀ1. HRMS (EI) calcd. for C13H14Cl2: 240.0473 [M]þ;
found: 240.0484.
1-Bromo-4-(3-chlorohepta-1,2-dienyl)-benzene (2c)
Colorless oil; 1H NMR (400 MHz, CDCl3) d 7.46 (d, J ¼ 8.4 Hz, 2H), 7.19
(d, J ¼ 8.4 Hz, 2H), 6.36 (t, J ¼ 2.8 Hz, 1H), 2.44–2.46 (m, 2H), 1.54–1.57
(m, 2H), 1.35–1.45 (m, 2H), 0.91 (t, J ¼ 7.2 Hz, 3H); 13C NMR
(100MHz, CDCl3) d 200.6, 132.3, 131.9, 131.9, 131.4, 129.2, 129.2, 109.3,
100.7, 36.2, 29.2, 21.9, 13.8; IR(neat) n: 2957, 2927, 2858, 1955, 1487,
1464, 1379, 1071, 1011, 851 cmꢀ1. HRMS (EI) calcd. for C13H14ClBr:
283.9967 [M]þ; found: 283.9974.

Preparation of Haloallenes
3947
1-(3-Chlorohepta-1,2-dienyl)-4-methyl-benzene (2d)
1
Colorless oil; H NMR (400 MHz, CDCl3) d 7.22 (d, J ¼ 8 Hz, 2H), 7.14
(d, J ¼ 8 Hz, 2H), 6.40 (bs, 1H), 2.43–2.47 (m, 2H), 2.35 (s, 3H), 1.52–1.60
(m, 2H), 1.36–1.42 (m, 2H), 0.91 (t, J ¼ 7.2 Hz, 3H); 13C NMR (100 MHz,
CDCl3) d 199.9, 138.2, 130.4, 129.5, 129.5, 127.7, 127.7, 108.6, 101.7,
36.4, 29.3, 21.9, 21.2, 13.8; IR (neat) n: 2959, 2929, 2872, 1957, 1606,
1513, 1457, 812, 751 cmꢀ1. HRMS (EI) calcd. for C14H17Cl:220.1019
[M]þ; found: 220.1015.
4-(3-Chlorohepta-1,2-dienyl)-biphenyl (2e)
White solid; 1H NMR (400 MHz, CDCl3) d 7.56–7.59 (m, 4H), 7.39–7.45
(m, 4H), 7.32–7.36 (m, 1H), 6.46 (bs, 1H), 2.46–2.50 (m, 2H), 1.55–1.62
(m, 2H), 1.38–1.45 (m, 2H), 0.92 (t, J ¼ 7.2 Hz, 3H); 13C NMR
(100 MHz, CDCl3) d 200.6, 141.0, 140.5, 132.3, 128.8, 128.8, 128.2,
128.2, 127.5, 127.5, 127.5, 127.0, 127.0, 108.9, 101.4, 36.4, 29.3, 21.9,
13.8; IR (neat) n: 3433, 2955, 2931, 2870, 1951, 1487, 1465, 1456, 1378,
1328, 1107, 1007, 939, 866, 762, 723, 708, 695 cmꢀ1. HRMS (EI) calcd.
for C19H19Cl: 282.1175[M]þ; found: 282.1185.
1-Chloro-2-(3-chlorohepta-1,2-dienyl)-benzene (2f)
1
Colorless oil; H NMR (400 MHz, CDCl3) d 7.44 (dd, J ¼ 1.6, 7.6 Hz,
1H), 7.36 (dd, J ¼ 1.6, 7.6 Hz, 1H), 7.16–7.26 (m, 2H), 6.87 (t, J ¼ 3.2 Hz,
1H), 2.44–2.49 (m, 2H), 1.53–1.61 (m, 2H), 1.34–1.44 (m, 2H), 0.91 (t,
J ¼ 7.2 Hz, 3H); 13C NMR (100 MHz, CDCl3) d 201.7, 133.1, 131.1,
129.9, 129.1, 129.1, 127.0, 109.3, 97.9, 36.2, 29.2, 21.9, 13.8; IR(neat) n:
2958, 2930, 2872, 1957, 1477, 1444, 1050, 1032, 834, 751 cmꢀ1. HRMS
(EI) calcd. for C13H14Cl2: 240.0473 [M]þ; found: 240.0471.
(3-Chloronona-1,2-dienyl)-benzene (2g)
Colorless oil; 1H NMR (400 MHz, CDCl3) d 7.33–7.34 (m, 4H), 7.26–7.27
(m, 1H), 6.42 (t, J ¼ 2.8 Hz, 1H), 2.43–2.46 (m, 2H), 1.53–1.58 (m, 2H),
1.25–1.29 (m, 6H), 0.87 (t, J ¼ 7.2 Hz, 3H); 13C NMR (100 MHz, CDCl3)
d 200.4, 133.3, 128.7, 128.7, 128.2, 127.8, 127.8, 109.0, 101.7, 36.6, 31.5,
28.4, 27.1, 22.6, 14.0; IR (neat) n: 2955, 2928, 2857, 1954, 1496, 1459,
746, 651 cmꢀ1. HRMS (EI) calcd. for C15H19Cl: 234.1175[M]þ; found:
234.1180.

3948
X. Du et al.
1-(3-Bromohepta-1,2-dienyl)-4-chloro-benzene (3b)
Colorless oil; 1H NMR (400 MHz, CDCl3) d 7.29–7.33 (m, 2H), 7.22–7.26
(m, 2H), 6.14 (t, J ¼ 2.8 Hz, 1H), 2.50–2.55 (m, 2H), 1.50–1.59 (m, 2H),
1.34–1.41 (m, 2H), 0.88 (m, 3H); 13C NMR (100 MHz, CDCl3) d 200.0,
133.9, 131.6, 129.0, 129.0, 128.9, 128.9, 99.3, 96.4, 37.7, 29.7, 21.8,
13.8; IR (neat) n: 2924, 2853, 1952, 1491, 1464, 1378, 1093, 1014,
850 cmꢀ1. HRMS (EI) calcd. for C13H14ClBr: 283.9967 [M ꢀ Br]þ; found:
205.0786.
1-Bromo-4-(3-bromohepta-1,2-dienyl)-benzene (3c)
Colorless oil; 1H NMR (400 MHz, CDCl3) d 7.45 (d, J ¼ 8.4 Hz, 2H), 7.18
(d, J ¼ 8.4 Hz, 2H), 6.13 (t, J ¼ 2.8 Hz, 1H), 2.50–2.54 (m, 2H), 1.51–1.59
(m, 2H), 1.35–1.42 (m, 2H), 0.90 (m, 3H); 13C NMR (100 MHz, CDCl3) d
200.0, 132.0, 131.9, 131.9, 129.2, 129.2, 122.1, 99.4, 96.4, 37.7, 31.6, 22.7,
14.1; IR (neat) n: 2957, 2929, 2871, 1952, 1587, 1487, 1464, 1379, 1109,
1071, 1010, 953, 850, 818 cmꢀ1. HRMS (EI) calcd. for C13H14Br2:
327.9462 [M]þ; found: 327.9466.
1-(3-Bromohepta-1,2-dienyl)-4-methyl-benzene (3d)
1
Colorless oil; H NMR (400 MHz, CDCl3) d 7.22 (d, J ¼ 8 Hz, 2H), 7.14
(d, J ¼ 8 Hz, 2H), 6.18 (t, J ¼ 2.8 Hz, 1H), 2.50–2.54 (m, 2H), 2.35 (s, 3H),
1.52–1.60 (m, 2H), 1.36–1.43 (m, 2H), 0.90 (t, J ¼ 7.2 Hz, 3H); 13C NMR
(100 MHz, CDCl3) d 199.4, 138.2, 130.1, 129.5, 129.5, 127.7, 127.7, 100.4,
98.9, 37.9, 30.1, 21.9, 21.3, 13.8; IR (neat) n: 2957, 2929, 2860, 1952, 1514,
1458, 1176, 1108, 849, 800, 752 cmꢀ1. HRMS (EI) calcd. for C14H17Br:
264.0514 [M ꢀ Br]þ; found: 185.1332.
1-(3-Bromohepta-1,2-dienyl)-2-chloro-benzene (3f)
1
Colorless oil; H NMR (400 MHz, CDCl3) d 7.45 (dd, J ¼ 1.6, 8.0 Hz,
1H), 7.35 (dd, J ¼ 1.6, 8.0 Hz, 1H), 7.22–7.26 (m, 1H), 7.15–7.19 (m,
1H), 6.65 (t, J ¼ 2.8 Hz, 1H), 2.51–2.55 (m, 2H), 1.53–1.60 (m, 2H),
1.34–1.43 (m, 2H), 0.91 (t, J ¼ 7.2 Hz, 3H); 13C NMR (100 MHz, CDCl3)
d 200.9, 133.1, 130.8, 129.9, 129.9, 129.1, 127.0, 96.5, 96.4, 37.6, 30.0,
21.8, 13.7; IR (neat) n: 2957, 2928, 2860, 1953, 1477, 1465, 1444, 1380,
1050, 831, 751 cmꢀ1; HRMS (EI) calcd. for C13H14ClBr: 283.9967
[M ꢀ Br]þ; found: 205.0798.

Preparation of Haloallenes
3949
ACKNOWLEDGMENTS
We are grateful to the National Natural Science Foundation of China
(20572010) for financial support. This work was partly supported by
the Program for Changjiang Scholars and Innovative Research Teams
in Universities (IRT0711).
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