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Mendeleev Communications Electronic Version, Issue 6, 1997 (pp. 213–252) A new, general route to 1-chloro-1-ethynylcyclopropanes via chloro(trimethylsilylethynyl)carbene Konstantin N. Shavrin, Irina V. Krylova, Inna B. Shvedova and Oleg M. Nefedov* N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, 117913 Moscow, Russian Federation. Fax: +7 095 135 5328 A new, general route to 1-chloro-1-ethynylcyclopropanes 6 has been developed via cycloaddition of previously unknown chloro(trimethylsilylethynyl)carbene 4b to olefins with formation of the corresponding cyclopropanes 5a–f in 35–65% yield and subsequent removal of the trimethylsilyl group under the action of KF·2H2O in aqueous DMF to give cyclopropanes 6 in up to 80% yield.We have previously developed a new method for the preparation of 1-chloro-1-alkynylcyclopropanes by cycloaddition of (alk-1-ynyl)halocarbenes 4 [RCºC(X) , R = Alk, cyclo-Alk, Ph; X = Cl, Br] to the double bond of olefins.1 Our attempts to obtain 1-chloro-1-ethynylcyclopropanes 6 via cyclopropanation of olefins with chloro(ethynyl)carbene 4a (R = H, X = Cl), generated from dichloromethylacetylene 3a (HCºCCHCl2) by the action of bases, have not been successful.Under the basic solvolysis conditions employed, dichloride 3a undergoes g-elimination of hydrogen chloride to give chlorovinylidenecarbene, which in the presence of alkene results in chlorovinylidenecyclopropanes. 2 In connection with this problem we attempted to prepare cyclopropanes 6 using a so-called ‘silyl protection’ of the terminal triple bond in 3a.In particular, we have previously successfully used silyl protection to synthesise 1-H- and 1,2-H-cyclopropene-3-carboxylic or 1-H- and 1,2-Hcyclopropene- 3,3-dicarboxylic acids as well as their esters.3 Starting 3,3-dichloro-1-trimethylsilylpropyne 3b† was obtained by oxidation of 3-trimethylsilylprop-2-yn-1-ol 1 with the complex CrO3·Py·HCl4 and subsequent chlorination of intermediate aldehyde 2, used directly without isolation, with PCl5. After interaction with freshly prepared and sublimed ButOK in hexane at –10 °C, the dichloride 3b a-eliminated hydrogen chloride to form chloro(trimethylsilylethynyl)carbene 4b (R = SiMe3, X = Cl), a new (alk-1-ynyl)halocarbene possessing a reactive substituent at the triple bond.In the presence of alkenes this carbene readily added to the double bond giving (35–65% yield) 1-chloro-1-(trimethylsilylethynyl)cyclopropanes 5a–f,‡ promising synthons in organic synthesis.5,6 As expected, the endo(Cl)- and exo(Cl)-isomers of cyclopropane 5c as well as the cis- and trans-isomers of cyclopropanes 5d–f were obtained in the reactions with cyclohexene, trimethylethylene, vinyl ethyl ether and styrene, respectively.Removal of the trimethylsilyl group from the cyclopropanes 5a–f by treatment with KF·2H2O in DMF at room temperature yielded unsubstituted 1-chloro-1-ethynylcyclopropanes 6a–f§ in 70–80% yield. 1H NMR, 13C NMR and IR spectra of cyclopropanes 6a–d are identical to those given in the literature.7 † Characterization data for 3b: 51% yield, bp 73–74 °C (20 Torr). 1HNMR (250 MHz, CDCl3) d: 6.23 (s, 1H, CHCl2), 0.23 (s, 9H, 3CH3). 13C NMR (50 MHz, CDCl3) d: 98.9 (s, ºCCHCl2), 96.09 (Me3SiCº), 55.07 (d, CHCl2, J 185.6 Hz), –0.57 (q, CH3, J 119.6 Hz). IR (thin film, n/cm–1): 2174 (CºC). MS [electron impact, 70 eV, m/z (Irel,%)]: 180 (0.17), 169/167/165 (3.4/24/3.51) [M–CH3]+, 141 (5.4), 139 (30.8), 138 (8.3), 137 (55.3), 132 (5.2), 130 (15.5), 129 (10.2), 119 (11.2), 117 (51), 115 (80.4), 113 (100), 103 (8.2), 95 (13.1), 93 (29.3), 79 (6.7), 78 (5.5), 67 (10.5), 65 (21.1), 63 (24), 53 (20.3), 52 (22), 51 (8.3), 43 (17). Thus, silyl protection of the terminal triple bond in chloride 3a allows us to propose a new simple route to the 1-chloro- 1-ethynylcyclopropanes 6, which are versatile polyfunctional synthons.5,8 These cyclopropanes had previously been obtained by interaction of a three-fold molar excess of BuLi with ‡ All new compounds 5a–f gave satisfactory analytical and spectral data.For 5a: 64% yield, mp 76–77 °C (from EtOH) (lit.,6 68 °C). 1H NMR (250 MHz, CDCl3) d: 1.16 (s, 6H, 2CH3), 1.14 (s, 6H, 2CH3), 0.19 (s, 9H, Me3Si). IR (KBr, n/cm–1): 2164 (CºC), 1250, 837 (Me3Si).MS [electron impact, 70 eV, m/z (Irel,%)]: 230/228 [M]+ (1/3). For 5b: 50% yield, bp 91 °C (42 Torr). 1H NMR (250 MHz, CDCl3) d: 1.37 (s, 3H, CH3), 1.32 (s, 3H, CH3), 1.18 (d, 1H, J 5.9 Hz), 1.08 (d, 1H, J 5.9 Hz), 0.204 (s, 9H, Me3Si). IR (KBr, n/cm–1): 2178 (CºC). MS [electron impact, 70 eV, m/z (Irel,%)]: 202/200 [M]+ (1/3). For 5c: mixture of endo(Cl)- and exo(Cl)-isomers in the ratio 1:4.5, 43% yield, bp 150 °C (bath temperature, 20 Torr). 1H NMR (90 MHz, CDCl3) d: 1.55–2.0 (m, 6H, 2CH and 2CH2), 1.1–1.4 (m, 4H, 2CH2), 0.108 and 0.165 (s, 9H, Me3Si for the endo-, exo-isomers). 13C NMR (50 MHz, C6D6) d, for the exo-isomer: 102.49 (ºC), 94.32 (Me3SiCº), 38.45 (C–Cl); 27.53 (CH), 20.52 and 19.59 (CH2), –0.37 (Me3Si); for the endo-isomer: 108.52 (ºC), 84.59 (Me3SiCº), 41.68 (C–Cl); 24.31 (CH), 20.76 and 18.69 (CH2), –0.28 (Me3Si).IR (KBr, n/cm–1): 2168 (CºC). MS [electron impact, 70 eV, m/z (Irel,%)]: 226/228 [M]+ (1/3). For 5d: mixture of cis(Cl,H)- and trans(Cl,H)-isomers in the ratio 1.13:1, 60% yield, bp 80 °C (8 Torr). 1H NMR (90 MHz, CDCl3) d: 1.24 and 1.21 (s, 3H, Me), 1.13–1.0 (m, CH and CH3), 1.05 and 1.03 (s, 3H, CH3), 0.1 and 0.09 (s, 9H, Me3Si). 13C NMR (50 MHz, CDCl3) d, for cis-isomer: 105.73 (ºC), 90.54 (Me3SiCº), 44.83 (C–Cl), 33.91, 23.76 and 17.09 (CH3), 9.78 (CH); –0.02 (Me3Si); for trans-isomer: 102.34 (ºC), 86.93 (Me3SiCº), 44.83 (C–Cl), 31.93, 24.81 and 16.10 (CH3), 27.15 (CH); –0.02 (Me3Si). IR (thin film, n/cm–1): 2164 (CºC). MS [electron impact, 70 eV, m/z (Irel,%)]: 216/214 [M]+ (1/3) for cis- and trans-isomers.For 5e: mixture of cis(Cl,OEt)- and trans(Cl,OEt)-isomers in the ratio 1:2, 35% yield, bp 84 °C (26 Torr). 1H NMR (200 MHz, CDCl3) d, for cis-isomer: 3.6–3.95 (m, 2H, CH2), 3.44 (dd, H, J 5.3 and 7.5 Hz), 1.54 (dd, H, J 7.5 and 7.5 Hz), 1.35 (dd, H, J 5.3 and 7.5 Hz), 1.27 (t, 3H, Me, J 7.0 Hz), 0.15 (s, 9H, Me3Si); for trans-isomer: 3.6–3.95 (m, 2H, CH2), 3.58 (dd, H, J 5.3 and 7.5 Hz), 1.57 (dd, H, J 5.0 and 7.4 Hz), 1.48 (dd, H, J 7.4 and 7.4 Hz), 1.25 (t, 3H, Me, J 7.0 Hz), 0.17 (s, 9H, Me3Si). 13C NMR (50 MHz, CDCl3) d, for cis-isomer: 104.6 (ºC), 87.3 (Me3SiCº), 67.2 (OCH2), 62.8 (OCH), 31.3 (C–Cl), 26.3 (CH2), 15.0 (CH3), –0.02 (Me3Si); for trans-isomer: 101.9 (ºC), 89.5 (Me3SiCº), 66.8 (OCH2), 65.4 (OCH), 33.2 (C–Cl), 27.3 (CH2), 15.1 (CH3), –0.02 (Me3Si).IR (thin film, n/cm–1): 2165 (CºC). MS [electron impact, 70 eV, m/z (Irel,%)]: 218/216 [M]+ (1/3) for cis- and trans-isomers. For 5f: mixture of cis(Cl,Ph)- and trans(Cl,Ph)-isomers in the ratio 1:2.5, 40% yield. 1H NMR (200 MHz, CDCl3) d, for cis-isomer: 7.35 (m, 5H, Ph), 2.82 (dd, H, PhCH, J 8.5 and 9.8 Hz), 1.89 (dd, H, J 6.4 and 9.8 Hz), 1.75 (dd, H, J 6.4 and 8.5 Hz), 0.26 (s, 9H, Me3Si), for trans-isomer: 7.35 (m, 5H, Ph), 2.85 (dd, H, J 8.8 and 8.8 Hz), 1.8–1.91 (m, 2H, CH2), 0.04 (s, 9H, Me3Si). 13C NMR (50 MHz, CDCl3) d, for cis-isomer: 134.8 (1-C in Ph), 129.3, 128.1 and 127.4 (CH in Ph); 106.1 (ºC), 86.3 (Me3SiCº), 35.7 (PhCH), 29.7 (C–Cl), 24.1 (CH2), –0.1 (Me3Si); for trans-isomer: 135.6 (1-C in Ph), 128.3, 127.9 and 127.1 (CH in Ph), 102.4 (ºC), 90.7 (Me3SiCº), 35.8 (PhCH), 33.8 (C–Cl), 25.5 (CH2), –0.4 (Me3Si).IR (thin film, n/cm–1): 2170 (CºC). MS [electron impact, 70 eV, m/z (Irel,%)]: 250/248 [M]+ (1/3) for cis- and trans-isomers. C: Me3SiCºCCH2OH Me3SiCºCCHO Me3SiCºCCHCl2 i ii Scheme 1 Reagents and conditions: i, CrO3–Py–HCl, CH2Cl2, room temperature, 2 h; ii, PCl5, pyridine (cat.), CH2Cl2, 0 °C, 30 min. 1 2 3bMendeleev Communications Electronic Version, Issue 6, 1997 (pp. 213–252) chloro(trichloroethenyl)cyclopropanes,7 prepared by lengthy thermolysis of tetrachlorocyclopropene (12–72 h at 150–180 °C in a special apparatus9) in the presence of alkenes.However, the high temperature and long duration of these processes limited any practical application of this process.§ Characterization data for 6e: mixture of cis(Cl,OEt)- and trans- (Cl,OEt)-isomers in the ratio 1:2, 70% yield. 1H NMR (200 MHz, CDCl3) d, for cis-isomer: 3.6–4.0 (m, 2H, CH2), 3.44 (dd, H, J 5.3 and 7.4 Hz), 2.42 (s, H, ºCH), 1.54 (dd, H, J 7.4 and 7.4 Hz), 1.35 (dd, H, J 5.3 and 7.4 Hz), 1.26 (t, 3H, Me, J 7.0 Hz), for trans-isomer: 3.6–3.95 (m, 2H, CH2), 3.58 (dd, H, J 5.1 and 7.3 Hz), 2.51 (s, H, ºCH), 1.56 (dd, H, J 5.1 and 7.3 Hz), 1.48 (dd, H, J 7.3 and 7.3 Hz), 1.25 (t, 3H, Me, J 7.0 Hz). 13C NMR (50 MHz, CDCl3) d, for cis-isomer: 83.5 (ºC), 70.8 (HCº), 67.3 (OCH2), 62.5 (OCH), 31.3 (C–Cl), 25.7 (CH2), 15.0 (CH3); for trans-isomer: 80.8 (ºC), 72.9 (HCº), 67.1 (OCH2), 65.0 (OCH), 32.5 (C–Cl), 26.8 (CH2), 15.1 (CH3). MS [electron impact, 70 eV, m/z (Irel,%)]: 146/144 [M]+ (1/3) for cis- and trans-isomers.For 6f: mixture of cis(Cl,Ph)- and trans(Cl,Ph)-isomers in the ratio 1:2.5, 70% yield. 1H NMR (200 MHz, CDCl3) d, for cis-isomer: 7.35 (m, 5H, Ph), 2.83 (dd, H, PhCH, J 8.4 and 9.8 Hz), 2.5 (s, H, ºCH), 1.90 (dd, H, J 6.4 and 9.8 Hz), 1.76 (dd, H, J 6.4 and 8.5 Hz); for trans-isomer: 7.35 (m, 5H, Ph), 2.86 (dd, H, J 8.8 and 8.8 Hz), 2.4 (s, H, ºCH), 1.8–1.91 (m, 2H, CH2). 13C NMR (50 MHz, CDCl3) d, for cis-isomer: 134.6 (1-C in Ph), 127.9, 127.5 and 127.4 (CH in Ph); 85.1 (ºC), 69.9 (HCº), 33.7 (PhCH), 29.7 (C–Cl), 24.1 (CH2); for trans-isomer: 135.6 (1-C in Ph), 129.3, 128.9 and 128.0 (CH in Ph), 81.0 (ºC), 74.1 (HCº), 35.8 (PhCH), 35.0 (C–Cl), 24.8 (CH2). MS [electron impact, 70 eV, m/z (Irel,%)]: 178/176 [M]+ (1/3) for cis- and trans-isomers. The research described in this publication was made possible in part by grants no.NGR300 from the International Science Foundation and Russian Government and no. 96-03-32907a from Russian Foundation for Basic Research. References 1 (a) K. N. Shavrin, I. V. Krylova, I. B. Shvedova, G. P. Okonnishnikova, I. E. Dolgy and O. M. Nefedov, J.Chem. Soc., Perkin Trans. 2, 1991, 1875; (b) K. N. Shavrin, I. B. Shvedova and O. M. Nefedov, Izv. Akad. Nauk SSSR, Ser. Khim., 1991, 2559 (Bull. Acad. Sci. USSR, Div. Chem. Sci., 1991, 40, 2235); (c) K. N. Shavrin, I. V. Krylova, I. E. Dolgy and O. M. Nefedov, Izv. Akad. Nauk, Ser. Khim., 1992, 1128 (Bull. Russ. Acad. Sci., Div. Chem. Sci., 1992, 41, 885). 2 (a) K. N. Shavrin, I.B. Shvedova and O. M. Nefedov, Mendeleev Commun., 1993, 50; (b) K. N. Shavrin, I. B. Shvedova and O. M. Nefedov, Izv. Akad. Nauk, Ser. Khim, 1993, 1242 (Russ. Chem. Bull., 1993, 42, 1185). 3 (a) O. M. Nefedov, I. E. Dolgij, G. P. Okonnishnikova and I. B. Shvedova, Angew. Chem., 1972, 84, 946; (b) I. E. Dolgy, G. P. Okonnishnikova and O. M. Nefedov, Izv. Akad. Nauk SSSR, Ser.Khim., 1986, 2803 (Bull. Acad. Sci. USSR, Div. Chem. Sci., 1986, 35, 2571). 4 E. J. Corey and J. W. Suggs, Tetrahedron Lett., 1975, 2647. 5 A. de Meijere, in Proceedings of the 5th International Kyoto Conference on New Aspects in Organic Chemistry II, eds. Yoshida Zen-ichi, Ohshiro Yoshiki, Kodansha, Tokyo, Japan, 1992, p. 181. 6 (a) L. T. Scott, G. J. DeCicco, J. L. Hyun and G.Reinhardt, J. Am. Chem. Soc., 1985, 107, 6546; (b) I. Kuwajima, E. Nakamura and K. Hashimoto, Tetrahedron, 1983, 39, 975; (c) G. Capozzi, G. Romeo and F. Marcuzzi, J. Chem. Soc., Chem. Commun., 1982, 959; (d) R. Yamaguchi, H. Kawasaki, T. Yoshitome and M. Kawanisi, Chem. Lett., 1982, 1485; (e) V. Jäger, Alkine, in Methoden der Organishe Chemie (Houben–Weyl), Georg Thieme, Stuttgart, 1977, B. V/2a, p. 404 (in German). 7 Th. Liese and A. de Meijere, Chem. Ber., 1986, 119, 2995. 8 U. Misslitz and A. de Meijere, (1-Alkenyl)carbenes, in Methoden der Organishe Chemie (Houben–Weyl), Georg Thieme, Stuttgart, 1989, B. E19b, Teil 1, p. 746. 9 U. Misslitz and A. de Meijere, (1-Alkenyl)carbenes, in Methoden der Organishe Chemie (Houben–Weyl), Georg Thieme, Stuttgart, 1989, B. E19b, Teil 1, p. 741. Me3SiCºCCHCl2 Me3SiCºCCCl i –HCl R4 R2 R3 R1 R3 Cl C R1 Me3SiC R2 R4 ii R3 Cl C R1 HC R2 R4 : 3b 4b 5a–f 6a–f 5,6a R1 = R2 = R3 = R4 = Me b R1 = R3 = Me, R2 = R4 = H c R1 + R2 = (CH2)4, R3 = R4 = H d R1 = R2 = R3 =Me, R4 = H e R1 = R2 = R3 =H, R4 = OEt f R1 = R2 = R3 = H, R4 = Ph Scheme 2 Reagents and conditions: i, ButOK, hexane, –10 °C to 20 °C, 75 min (35–65%); ii, KF·2H2O, DMF, room temperature, 90 min (70–80%). Received: Moscow, 5th January 1997 Cambridge, 28th January 1997; Com. 7/00340D

ISSN:0959-9436     

出版商:RSC    

年代:1997

数据来源: RSC