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DOI: 10.1055/s-2006-947337
Reactions of Arylvinylidenecyclopropanes with Bromine and Iodine
Publikationsverlauf
Publikationsdatum:
24. Juli 2006 (online)
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Abstract
Reactions of arylvinylidenecyclopropanes 1 with equimolar amount of bromine or iodine at low temperature produced the corresponding addition products 2, 3 and 5, 6 in moderate to good yields at -40 °C and -100 °C, respectively. On the other hand, the reactions of 1 with equimolar amount of iodine gave the corresponding iodinated naphthalene derivatives 4 via the corresponding addition products 3 under similar conditions at 25 °C. The further transformation of the addition product 6a has been presented.
Key words
arylvinylidenecyclopropanes - bromine - iodine - addition reaction - iodinated naphthalene derivatives
-
1a
Poutsma ML.Ibarbia PA. J. Am. Chem. Soc. 1971, 93: 440 -
1b
Smadja W. Chem. Rev. 1983, 83: 263 -
1c
Paulson DR.Crandall JK.Bunnell CA. J. Org. Chem. 1970, 35: 3708 -
1d
Hendrick ME.Hardie JA.Jones M. J. Org. Chem. 1971, 36: 3061 -
1e
Patrick TB.Haynie EC.Probst WJ. J. Org. Chem. 1972, 37: 1553 -
1f
Aue DH.Meshishnek MJ. J. Am. Chem. Soc. 1977, 99: 223 -
1g
Sasaki T.Eguchi S.Ogawa T. J. Am. Chem. Soc. 1975, 97: 4413 -
1h
Sadler IH.Stewart JAG. J. Chem. Soc., Perkin Trans. 2 1973, 3: 278 -
1i
Sugita H.Mizuno K.Saito T.Isagawa K.Otsuji Y. Tetrahedron Lett. 1992, 33: 2539 -
1j
Mizuno K.Sugita H.Kamada T.Otsuji Y. Chem. Lett. 1994, 449 -
1k
Akasaka T.Misawa Y.Ando W. Tetrahedron Lett. 1990, 31: 1173 -
1l
Mizuno K.Sugita H.Isagawa K.Goto M.Otsuji Y. Tetrahedron Lett. 1993, 34: 5737 -
1m
Mizuno K.Nire K.Sugita H.Otsuji Y. Tetrahedron Lett. 1993, 34: 6563 -
1n
Mizuno K.Sugita H.Hirai T.Maeda H. Chem. Lett. 2000, 1144 -
1o
Mizuno K.Nire K.Sugita H.Maeda H. Tetrahedron Lett. 2001, 42: 2689 -
1p
Mizuno K.Maeda H.Sugita H.Nishioka S.Hirai T.Sugimoto A. Org. Lett. 2001, 3: 581 -
1q
Mizuno K.Sugita H.Hirai T.Maeda H.Otsuji Y.Yasuda M.Hashiguchi M.Shima K. Tetrahedron Lett. 2001, 42: 3363 -
1r
Maeda H.Zhen L.Hirai T.Mizuno K. ITE Lett. Batteries, New Technol. Med. 2002, 3: 485 -
1s
Sydnes LK. Chem. Rev. 2003, 103: 1133 - For the synthesis of vinylidenecyclopropanes, please see:
-
2a
Isagawa K.Mizuno K.Sugita H.Otsuji Y. J. Chem. Soc., Perkin Trans. 1 1991, 2283 ; and references cited therein -
2b
Sasaki T.Eguchi S.Ohno M.Nakata F. J. Org. Chem. 1976, 41: 2408 -
2c
Sasaki T.Eguchi S.Ogawa T. J. Org. Chem. 1974, 39: 1927 -
2d
Sasaki T.Eguchi S.Ogawa T. Heterocycles 1975, 3: 193 -
2e
Eguchi S.Arasaki M. J. Chem. Soc., Perkin Trans. 1 1988, 1047 -
2f
Sugita H.Mizuno K.Mori T.Isagawa K.Otsuji Y. Angew. Chem., Int. Ed. Engl. 1991, 30: 984 -
2g
Patrick TB. Tetrahedron Lett. 1974, 15: 1407 -
2h
Al-Dulayymi JR.Baird MS. J. Chem. Soc., Perkin Trans. 1 1994, 1547 -
2i
Patrick TB.Schmidt DJ. J. Org. Chem. 1977, 42: 3354 -
2j
Hartzler HD. J. Am. Chem. Soc. 1971, 93: 4527 - The other papers related to vinylidenecyclopropanes. For the reactions of vinylidenecyclopropanes with carbenes and carbene complexes, see:
-
3a
Crandall JK.Paulson DR.Bunnell CA. Tetrahedron Lett. 1969, 48: 4217 -
3b
Hwu C.-C.Wang F.-C.Yeh M.-CP. J. Organomet. Chem. 1994, 474: 123 -
3c
Billups WE.Haley MM.Boese R.Blaser D. Tetrahedron 1994, 50: 10693 -
3d
Maeda H.Hirai T.Sugimoto A.Mizuno K. J. Org. Chem. 2003, 68: 7700 -
3e
Bloch R.Perchec PL.Conia J.-M. Angew. Chem., Int. Ed. Engl. 1970, 9: 798 -
3f
Pasto DJ.Yang SH. J. Org. Chem. 1986, 51: 1676 - For the addition reactions to vinylidenecyclopropanes, see:
-
3g
Pasto DJ.Miles MF. J. Org. Chem. 1976, 41: 2068 -
3h
Pasto DJ.Chen AF.-T.Binsch G. J. Am. Chem. Soc. 1973, 95: 1553 -
3i
Pasto DJ.Chen A. J. Am. Chem. Soc. 1971, 93: 2562 -
3j
Pasto DJ.Borchardt JK.Fehlner TP.Baney HF.Schwartz ME. J. Am. Chem. Soc. 1976, 98: 526 -
3k
Pasto DJ.Fehlner TP.Schwartz ME.Baney HF. J. Am. Chem. Soc. 1976, 98: 530 -
3l
Pasto DJ.Miles MF. J. Org. Chem. 1976, 41: 425 -
3m
Pasto DJ.Chen AF.-T.Cuirdaru G.Paquette LA. J. Org. Chem. 1973, 38: 1015 -
3n
Gompper R.Lach D. Tetrahedron Lett. 1973, 29: 2683 -
3o
Poutsma ML.Ibarbia PA. J. Am. Chem. Soc. 1971, 93: 440 -
3p
Gompper R.Lach D. Tetrahedron Lett. 1973, 29: 2687 -
3q
Pasto DJ.Wampfler D. Tetrahedron Lett. 1974, 22: 1933 -
3r
Sasaki T.Eguchi S.Ogawa T. J. Am. Chem. Soc. 1975, 97: 4413 -
3s
Pasto DJ.Whitmer JL. J. Org. Chem. 1980, 45: 1987 -
3t
Pasto DJ.Brophy JE. J. Org. Chem. 1991, 56: 4554 -
3u
Cairns PM.Combie L.Pattenden G. Tetrahedron Lett. 1982, 23: 1405 -
3v
Crombie L.Maddocks PJ.Pattenden G. Tetrahedron Lett. 1978, 19: 3483 -
4a
Shi M.Wang B.-Y.Li J. Eur. J. Org. Chem. 2005, 759 -
4b
Shi M.Lu J.-M. Synlett 2005, 2352 -
4c
Shi M.Ma M.Shao L.-X. Tetrahedron Lett. 2005, 46: 7609 - For the addition of olefinic compounds with halogen, see:
-
5a
de la Mare DP.Bolton R. In Electrophilic Additions to Unsaturated System 2nd ed.: Elsevier; New York: 1982. p.136-197 -
5b
Schmidt GH.Garratt DG. In The Chemistry of Double Bonded Functional Groups Supplement A, Part 2:Patai S. Wiley-Interscience; New York: 1977. Chap. 9. -
8a
Siehl H.-U.Aue DH. Dicoordinated CarbocationsRappoport Z.Stang PJ. John Wiley and Sons; New York: 1997. p.137-138 - The stabilizing effect of cyclopropyl substituents in carbocations is well documented. See:
-
8b
Olah GA.Reddy VP.Prakash GKS. Chem. Rev. 1992, 92: 69 -
8c
Carey FA.Sundberg RJ. Advanced Organic Chemistry 5th ed.: Plenum Press; New York: 1998. p.221 -
8d
Carey FA.Sundberg RJ. Advanced Organic Chemistry 5th ed.: Plenum Press; New York: 1998. p.419 -
8e
Carey FA.Tremper HS. J. Am. Chem. Soc. 1969, 91: 2967 -
9a
Miyaura N.Yanagi T.Suzuki A. Synth. Commun. 1981, 11: 513 -
9b
Miyaura N.Suzuki A. Chem. Rev. 1995, 95: 2457 -
10a
Larock RC.Campo MA. J. Am. Chem. Soc. 2002, 124: 14326 -
10b
Huang Q.Campo MA.Yao T.Tian Q.Larock RC. J. Org. Chem. 2004, 69: 8251
References and Notes
The crystal data of 2c has been deposited in CCDC with number 273885. Empirical formula: C24H20Br2; formula weight: 468.22; crystal color, habit: colorless, prismatic; crystal dimensions: 0.506 × 0.367 × 0.331 mm; crystal system: triclinic; lattice type: primitive; lattice parameters: a = 8.721 (3)Å, b = 11.157 (3)Å, c = 11.857 (3)Å, α = 109.253 (5)°, β = 106.367 (5)°, γ = 95.731 (5)°, V = 1021.1 (5)Å3; space group: P-1; Z = 2; D calcd = 1.523 g/cm3; F 000 = 468; diffractometer: Rigaku AFC7R; residuals: R1 = 0.0739, wR2 = 0.1669. A colorless solid, mp 175.1-176.3 °C. IR (CH2Cl2): 3052, 3018, 2960, 2920, 2851, 1613, 1591, 1513, 1488, 1442, 1381, 1261, 1030, 813, 699, 745 cm-1. 1H NMR (300 MHz, CDCl3, TMS): δ = 1.22 (1 H, dd, J 1 = 8.1 Hz, J 2 = 8.1 Hz, CH), 1.70 (1 H, dd, J 1 = 8.7 Hz, J 2 = 8.7 Hz, CH), 2.40 (3 H, s, Me), 2.90 (1 H, dd, J 1 = 8.1 Hz, J 2 = 8.1 Hz, CH), 6.94-7.08 (4 H, m, Ar), 7.16-7.26 (5 H, m, Ar), 7.33-7.43 (5 H, m, Ar). MS (EI): m/z (%) = 468 (1.75) [M+], 389 (13.50), 388 (21.71), 387 (14.75), 309 (15.26), 308 (67.40), 307 (100), 293 (26.93), 292 (32.96), 229 (55.53), 215 (85.84), 189 (18.23), 105 (13.53). HRMS (EI): m/z calcd for C24H20Br2 [M+]: 465.9916; found: 465.9932.
7The spectroscopic data (1H NMR and 13C NMR spectral data) and analytic data of the compounds shown in Tables [1 ] - [4] , Scheme [1] and the detailed description of experimental procedures are available free of charge via the Internet.
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General Reaction Procedure.
A solution of iodine (88 mg, 0.3 mmol) in DCE (5.0 mL) was added dropwise into a solution of diphenylvinylidene-cyclopropane (1a, 76 mg, 0.3 mmol) in DCE (2.0 mL). The reaction mixture was stirred for 6 h at -40 °C (monitored by TLC). After the starting materials 1a were consumed. The solvent in filtration was removed under reduced pressure and the residue was subjected to a flash column chromatography to give the desired product 3a (133 mg, 81%) as a yellow solid.