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

De-Lie An; Zhiyang Zhang; Akihiro Orita; Hidetaka Mineyama; Junzo Otera

doi:10.1055/s-2007-984532

LETTER

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

De-Lie An*^a, Zhiyang Zhang^a,b, Akihiro Orita*^b, Hidetaka Mineyama^b, 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;

Abstract

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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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Referenzen

References and Notes

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8

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.