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Synlett 2007(12): 1909-1912  
DOI: 10.1055/s-2007-984532
LETTER
© Georg Thieme Verlag Stuttgart · New York

Convenient Synthesis of (1-Propynyl)arenes through a One-Pot Double Elimination Reaction, and Their Conversion to Enynes

De-Lie An*a, Zhiyang Zhanga,b, Akihiro Orita*b, Hidetaka Mineyamab, Junzo Otera*a,b
a Department of Chemistry, College of Chemistry and Chemical Engineering, Hunan University, Changsha 410082, P. R. of China
Fax: +86(731)8827944; e-Mail: deliean@sina.com;
b Department of Applied Chemistry, Okayama University of Science, Ridai-cho, Okayama 700-0005, Japan
Fax: +81(86)2564292; e-Mail: orita@high.ous.ac.jp; e-Mail: otera@high.ous.ac.jp;
Further Information

Publication History

Received 2 May 2007
Publication Date:
27 June 2007 (online)

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Abstract

A series of (1-propynyl)arenes were prepared by one-pot double elimination reaction of ethyl sulfone, aromatic aldehyde and chloro diethylphosphate in THF with a base such as BuLi and t-BuOK. A propargyllithium which was prepared by treatment of (1-propynyl)arene with BuLi in the presence of 1,3-dimethyl-3,4,5,6-tetrahydro-2(1H)-pyrimidinone (DMPU) reacted with aromatic aldehyde, chloro diethylphosphate and t-BuOK to afford (4-arylbut-3-en-1-ynyl)arene. Photoluminescence of the enynes thus prepared was recorded both in solution and in the solid state.

Key word

alkynes - sulfones - aldehydes - eliminations - enynes

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Typical Procedure of Preparation for 2-(1-Propynyl)naphthalene (3i): To a THF solution (15 mL) of ethyl phenyl sulfone (1, 204.3 mg, 1.2 mmol) was added BuLi (1.6 M, 0.75 mL, 1.2 mmol) at -78 °C, and the mixture was stirred for 30 min. A THF solution (2 mL) of 2-naph-thaldehyde (156.2 mg, 1.0 mmol) was added at -78 °C, and the mixture was stirred for 30 min. Diethyl chlorophosphate (207.1 mg, 1.2 mmol) was added at -78 °C, and the mixture was stirred at r.t. for 3 h. t-BuOK (561.1 mg, 5.0 mmol) was added at -78 °C, and the mixture was stirred at r.t. for 15 h. After usual workup with EtOAc and aq NH4Cl solution, the organic layer was evaporated, and the residue was subjected to column chromatography on silica gel to give 2-(1-prop-ynyl)naphthalene (3i) as a white powder (123.0 mg, 74%).
2-(1-Propynyl)naphthalene (3i): mp 30-31 °C. 1H NMR (500 MHz, CDCl3): δ = 2.10 (s, 3 H), 7.44-7.49 (m, 3 H), 7.74-7.80 (m, 3 H), 7.90 (s, 1 H). 13C NMR (125 MHz, CDCl3): δ = 4.4, 80.1, 86.2, 121.3, 126.2, 126.3, 127.5, 127.6, 127.8, 128.6, 131.0, 132.4, 133.0.
(1-Propynyl)benzene (3a): colorless oil. 1H NMR (500 MHz, CDCl3): δ = 2.06 (s, 3 H), 7.27-7.29 (m, 3 H), 7.38-7.40 (m, 2 H). 13C NMR (125 MHz, CDCl3): δ = 4.3, 79.7, 85.8, 124.0, 127.5, 128.2, 131.5.
1-Methoxy-3-(1-propynyl)benzene (3b): yellow oil. 1H NMR (500 MHz, CDCl3): δ = 2.04 (s, 3 H), 3.77 (s, 3 H), 6.82 (d, J = 8.2 Hz, 1 H), 6.92 (s, 1 H), 6.98 (d, J = 7.7 Hz, 1 H), 7.18 (t, J = 7.9 Hz, 1 H). 13C NMR (125 MHz, CDCl3): δ = 4.2, 55.1, 79.6, 85.7, 114.0, 116.3, 124.0, 125.0, 129.2, 159.2.
1-Methoxy-4-(1-propynyl)benzene (3c): colorless oil. 1H NMR (500 MHz, CDCl3): δ = 2.03 (s, 3 H), 3.78 (s, 3 H), 6.81 (d, J = 8.9 Hz, 2 H), 7.32 (d, J = 8.9 Hz, 2 H). 13C NMR (125 MHz, CDCl3): δ = 4.3, 55.2, 79.4, 84.1, 113.8, 116.1, 132.7, 158.9.
1,4-Dimethoxy-2-(1-propynyl)benzene (3d): white powder; mp 61-62 °C. 1H NMR (500 MHz, CDCl3): δ = 2.12 (s, 3 H), 3.75 (s, 3 H), 3.84 (s, 3 H), 6.77-6.81 (m, 2 H), 6.94 (d, J = 7.5 Hz, 1 H). 13C NMR (125 MHz, CDCl3): δ = 4.8, 55.7, 56.3, 75.7, 90.1, 111.6, 113.4, 114.7, 118.3, 153.1, 154.2.
1-Phenylmethyloxy-2-(1-propynyl)benzene (3e): colorless oil. 1H NMR (500 MHz, CDCl3): δ = 2.12 (s, 3 H), 5.18 (s, 2 H), 6.87 (d, J = 8.3 Hz, 1 H), 6.89 (t, J = 7.5 Hz, 1 H), 7.18 (t, J = 8.0 Hz, 1 H), 7.30 (t, J = 7.2 Hz, 1 H), 7.36-7.40 (m, 3 H), 7.47 (d, J = 7.6 Hz, 2 H). 13C NMR (125 MHz, CDCl3): δ = 4.7, 70.3, 75.8, 90.1, 112.8, 113.9, 120.8, 126.8, 127.6, 128.4, 128.7, 133.1, 159.0.
1-Bromo-2-(1-propynyl)benzene (3f): yellow oil. 1H NMR (500 MHz, CDCl3): δ = 2.11 (s, 3 H), 7.11 (t, J = 7.7 Hz, 1 H), 7.22 (t, J = 8.0 Hz, 1 H), 7.42 (d, J = 7.7 Hz, 1 H), 7.55 (d, J = 8.0 Hz, 1 H). 13C NMR (125 MHz, CDCl3): δ = 4.4, 78.4, 90.8, 125.1, 125.8, 126.7, 128.6, 132.1, 133.2.
4-Bromo-1-(1-propynyl)benzene (3g): yellow oil. 1H NMR (500 MHz, CDCl3): δ = 2.02 (s, 3 H), 7.23 (d, J = 8.4 Hz, 2 H), 7.40 (d, J = 8.4 Hz, 2 H). 13C NMR (125 MHz, CDCl3): δ = 4.3, 78.7, 87.1, 121.6, 122.9, 131.4, 132.9.
1-Iodo-2-(1-propynyl)benzene (3h): yellow oil. 1H NMR (500 MHz, CDCl3): δ = 2.11 (s, 3 H), 6.94 (t, J = 8.0 Hz, 1 H), 7.25 (t, J = 7.6 Hz, 1 H), 7.39 (d, J = 7.6 Hz, 1 H), 7.81 (d, J = 8.0 Hz, 1 H). 13C NMR (125 MHz, CDCl3): δ = 4.5, 82.0, 90.2, 100.8, 127.7, 128.7, 130.4, 132.5, 138.5.
(1-Propynyl)ferrocene (3j): red powder; mp 79-80 °C. 1H NMR (500 MHz, CDCl3): δ = 1.94 (s, 3 H), 4.13 (t, J = 1.8 Hz, 2 H), 4.19 (s, 5 H), 4.35 (t, J = 1.8 Hz, 2 H). 13C NMR (125 MHz, CDCl3): δ = 4.4, 66.0, 68.0, 69.6, 70.9, 77.2, 81.7.
2-Bromo-5-(1-propynyl)thiophene (3k): red oil. 1H NMR (500 MHz, CDCl3): δ = 2.06 (s, 3 H), 6.84 (d, J = 3.7 Hz, 1 H), 6.88 (d, J = 3.9 Hz, 1 H). 13C NMR (125 MHz, CDCl3): δ = 4.7, 72.2, 91.3, 111.4, 125.9, 129.7, 131.2.
1-(Phenylethynyl)-2-(1-propynyl)benzene (3l): yellow oil. 1H NMR (500 MHz, CDCl3): δ = 2.15 (s, 3 H), 7.23-7.26 (m, 2 H), 7.33-7.38 (m, 3 H), 7.42-7.44 (m, 1 H), 7.50-7.52 (m, 1 H), 7.54-7.57 (m, 2 H). 13C NMR (125 MHz, CDCl3): δ = 4.5, 78.5, 88.5, 90.3, 92.9, 123.3, 125.5, 126.5, 127.2, 127.9, 128.2, 128.3, 131.5, 131.6, 131.1.
1-(Phenylethynyl)-3-(1-propynyl)benzene (3m): colorless oil. 1H NMR (500 MHz, CDCl3): δ = 2.03 (s, 3 H), 7.23 (t, J = 7.9 Hz, 1 H), 7.31-7.34 (m, 4 H), 7.41 (d, J = 7.6 Hz, 1 H), 7.50-7.52 (m, 2 H), 7.57 (s, 1 H). 13C NMR (125 MHz, CDCl3): δ = 4.3, 78.9, 86.6, 88.6, 89.7, 123.0, 123.3, 124.3, 128.2, 128.3, 130.6, 131.2, 131.6, 134.5.
1-(Phenylethynyl)-4-(1-propynyl)benzene (3n): white powder; mp 99-101 °C. 1H NMR (500 MHz, CDCl3): δ = 2.06 (s, 3 H), 7.32-7.34 (m, 3 H), 7.35 (d, J = 8.6 Hz, 2 H), 7.44 (d, J = 8.2 Hz, 2 H), 7.51-7.53 (m, 2 H). 13C NMR (125 MHz, CDCl3): δ = 4.4, 79.5, 87.9, 89.1, 90.7, 122.3, 123.0, 123.9, 128.3, 131.3, 131.4, 131.5.
1,2-Bis[2-(1-propynyl)phenyloxymethyl]benzene (3o): white powder; mp 99-100 °C. 1H NMR (500 MHz, CDCl3): δ = 2.04 (s, 6 H), 5.33 (s, 4 H), 6.89 (t, J = 7.5 Hz, 2 H), 6.97 (d, J = 8.3 Hz, 2 H), 7.21 (t, J = 7.8 Hz, 2 H), 7.34-7.36 (m, 2 H), 7.38 (d, J = 7.6 Hz, 2 H), 7.61 (s, 2 H). 13C NMR (125 MHz, CDCl3): δ = 4.6, 68.7, 75.9, 90.1, 112.4, 113.7, 120.8, 128.0, 128.2, 128.8, 133.4, 134.9, 158.8.
1,3-Bis[2-(1-propynyl)phenyloxymethyl]benzene (3p): pale yellow oil. 1H NMR (500 MHz, CDCl3): δ = 2.10 (s, 6 H), 5.18 (s, 4 H), 6.85 (d, J = 8.3 Hz, 2 H), 6.89 (t, J = 7.5 Hz, 2 H), 7.17 (t, J = 7.9 Hz, 2 H), 7.36-7.42 (m, 5 H), 7.59 (s, 1 H). 13C NMR (125 MHz, CDCl3): δ = 4.7, 70.4, 75.8, 90.2, 113.0, 114.0, 120.9, 125.4, 126.2, 128.6, 128.7, 133.5, 137.4, 159.0.
1,4-Bis[2-(1-propynyl)phenyloxymethyl]benzene (3q): white powder; mp 112-114 °C. 1H NMR (500 MHz, CDCl3): δ = 2.10 (s, 6 H), 5.15 (s, 4 H), 6.84-6.89 (m, 2 H), 7.17 (t, J = 7.8 Hz, 2 H), 7.38 (d, J = 7.6 Hz, 4 H), 7.46 (s, 4 H). 13C NMR (125 MHz, CDCl3): δ = 4.7, 70.2, 75.8, 90.1, 112.8, 113.9, 120.8, 127.0, 128.7, 133.5, 136.5, 159.0.
Typical Procedure of Preparation for 2-(4-Phenylbut-3-en-1-ynyl)naphthalene (4a): To a THF solution (10 mL) of 2-(1-propynyl)naphthalene (83.1 mg, 0.5 mmol) and DMPU (64.1 mg, 0.5 mmol) was added BuLi (1.6 M, 0.31 mL, 0.5 mmol) at -78 °C, and the mixture was stirred for 30 min. A THF solution (2 mL) of benzaldehyde (53.1 mg, 0.5 mmol) was added at -78 °C, and the mixture was stirred for 30 min. Diethyl chlorophosphate (103.5 mg, 0.6 mmol) was added at -78 °C, and the mixture was stirred at r.t. for 2 h. t-BuOK (140.3 mg, 1.25 mmol) was added at -78 °C, and the mixture was stirred at r.t. for 2 h. After usual workup with EtOAc and aq NH4Cl solution, the organic layer was evaporated, and the residue was subjected to column chromatography on silica gel and recrystallization (from hexane) to afford (E)-2-(4-phenylbut-3-en-1-ynyl)naphthalene (4a) as a white powder (59.0 mg, 46%). Recrystallization of the second crop from hexane gave a 3:5 mixture of E- and Z-isomers (21.1 mg, 17%). ( E ) - 2-(4-Phenylbut-3-en-1-ynyl)naphthalene (4a): white powder; mp 135-136 °C (hexane). 1H NMR (500 MHz, CDCl3): δ = 6.44 (d, J = 16.2 Hz, 1 H), 7.09 (d, J = 16.2 Hz, 1 H), 7.30 (t, J = 7.4 Hz, 1 H), 7.35 (d, J = 7.6 Hz, 1 H), 7.36 (d, J = 8.6 Hz, 1 H), 7.44-7.50 (m, 4 H), 7.53 (d, J = 8.2 Hz, 1 H), 7.78-7.82 (m, 3 H), 8.00 (s, 1 H). 13C NMR (125 MHz, CDCl3): δ = 89.3, 92.2, 108.1, 120.7, 126.3, 126.5, 126.6, 127.7, 127.8, 128.0, 128.3, 128.6, 128.7, 131.3, 132.7, 133.0, 136.3, 141.4. ESI-MS: m/z [M+] calcd for C20H14: 254.1; found: 254.8.
( E ) - 2-[4-(4-Methoxyphenyl)but-3-en-1-ynyl]naph-thalene (4b): pale yellow powder; mp 145-147 °C (hexane). 1H NMR (500 MHz, CDCl3): δ = 3.83 (s, 3 H), 6.29 (d, J = 16.2 Hz, 1 H), 6.89 (d, J = 8.5 Hz, 2 H), 7.05 (d, J = 16.2 Hz, 1 H), 7.40 (d, J = 8.5 Hz, 2 H), 7.47-7.55 (m, 3 H), 7.78-7.82 (m, 3 H), 7.98 (s, 1 H). 13C NMR (125 MHz, CDCl3): δ = 55.3, 89.7, 91.4, 105.7, 114.2, 120.9, 126.5, 126.6, 127.6, 127.7, 127.8, 127.9, 128.3, 129.2, 131.1, 132.6, 133.0, 141.0, 160.1. ESI-MS: m/z [M+] calcd for C21H16O: 284.1; found: 284.8.
( E )-1-(4-Phenylbut-3-en-1-ynyl)-4-phenyl-ethynylbenzene (4c): white powder; mp 171-173 °C (hexane). 1H NMR (500 MHz, CDCl3): δ = 6.40 (d, J = 16.5 Hz, 1 H), 7.06 (d, J = 16.5 Hz, 1 H), 7.30 (t, J = 7.4 Hz, 1 H), 7.34-7.37 (m, 5 H), 7.44 (d, J = 8.3 Hz, 2 H), 7.45 (d, J = 8.5 Hz, 2 H), 7.51 (d, J = 8.6 Hz, 2 H), 7.53-7.55 (m, 2 H). 13C NMR (125 MHz, CDCl3): δ = 89.1, 90.8, 91.3, 91.5, 107.9, 122.9, 123.0, 123.2, 126.4, 128.4, 128.5, 128.8, 131.4, 131.5, 131.6, 136.2. ESI-MS: m/z [M+] calcd for C24H16: 304.1; found: 304.8.
( E )-2-[4-(2-Naphthyl)but-3-en-1-ynyl]naphthalene (4d): yellow powder; mp 157-158 °C (hexane). 1H NMR (300 MHz, CDCl3): δ = 6.56 (d, J = 16.3 Hz, 1 H), 7.26 (d, J = 16.3 Hz, 1 H), 7.47-7.52 (m, 4 H), 7.55 (d, J = 8.6 Hz, 1 H), 7.65 (d, J = 8.6 Hz, 1 H), 7.80-7.86 (m, 7 H), 8.02 (s, 1 H). 13C NMR (125 MHz, CDCl3): δ = 89.5, 92.6, 108.4, 120.7, 122.7, 126.4, 126.5, 126.6, 126.7, 127.0, 127.7, 127.8, 127.9, 128.0, 128.2, 128.3, 128.5, 131.3, 132.8, 133.0, 133.5, 133.8, 141.5. ESI-MS: m/z [M+] calcd for C24H16: 304.1; found: 304.8.
( E ) - 1-(Phenylethynyl)-4-{4-[4-(phenyl-ethynyl)phen-yl]but-3-en-1-ynyl}benzene (4e): yellow powder; mp 263-266 °C (CH2Cl2). 1H NMR (500 MHz, CDCl3): δ = 6.43 (d, J = 16.4 Hz, 1 H), 7.04 (d, J = 16.4 Hz, 1 H), 7.35-7.37 (m, 7 H), 7.43 (d, J = 8.3 Hz, 2 H), 7.45 (d, J = 8.6 Hz, 2 H), 7.50 (d, J = 8.3 Hz, 2 H), 7.51 (d, J = 8.3 Hz, 2 H), 7.53-7.55 (m, 3 H). ESI-MS: m/z [M+] calcd for C32H20: 404.2; found: 404.9. 13C NMR could not be measured because of poor solubility.
( E ) - 1-(4-Methoxyphenylethynyl)-3-(4-phenylbut-3-en-1-ynyl)benzene (4f): mp 104-106 °C (hexane). 1H NMR (300 MHz, CDCl3): δ = 3.84 (s, 3 H), 6.39 (d, J = 16.2 Hz, 1 H), 6.89 (d, J = 8.8 Hz, 2 H), 7.06 (d, J = 16.2 Hz, 1 H), 7.28 (d, J = 8.0 Hz, 1 H), 7.30 (d, J = 7.7 Hz, 1 H), 7.35 (d, J = 8.0 Hz, 1 H), 7.37 (d, J = 7.6 Hz, 1 H), 7.40-7.46 (m, 4 H), 7.48 (d, J = 8.9 Hz, 2 H), 7.63 (s, 1 H). 13C NMR (125 MHz, CDCl3): δ = 55.3, 87.3, 89.4, 90.0, 90.9, 107.9, 114.0, 123.7, 123.9, 126.3, 128.3, 128.4, 128.7, 128.8, 130.8, 131.0, 133.1, 134.3, 136.2, 141.6, 159.7. ESI-MS: m/z [M+] calcd for C25H18O: 334.1; found: 334.9.