Syntheses and properties of dichlorodimethyltetradehydro-trideca-,-pentadeca-, -heptadeca-, and -nonadeca-fulvene, and benzannelated pentadecafulvene derivatives

摘要

2997J. CHEM. SOC. PERKIN TRANS. I 1983 Syntheses and Properties of Dichlorod imet hyltetradehydro-trideca-,-pentadeca-, -heptadeca-, and -nonadeca-fulvene, and Benzannelated Pentadecaf ulvene Derivatives Jiiro Ojima," Kazunori Itagawa, Satoru Hamai, and Tetsuya Nakada Department of Chemistry, Faculty of Science, To yama University, Gofuku, To yam 930, JapanShigeyasu Kuroda Department of Industrial Chemistry, Faculty of Engineering, To yama University, Takaoka 933,Japan ~~~-~~~ ~~~~~~ ~~ ~ ~~ Syntheses of 1 3-dic hloromet hylene-4,9-dimethyl-5,6,7,8-tetradehydrocyclotridecene (18),1 5-dic hloro- methylene-4,9-dimethyl-5,6,7,8-tetradehydrocyclopentadecene (1 9) , 1 7-dichloromet hylene-6,ll -di -methyl-7,8,9,10-tetrade hydrocycloheptadecene (20), and 19-dic hloromet hylene-6,ll- dimet hyl- 7,8,9,1O-tetradehydrocyclononadecene(21) are described.Examination of the H n.m.r. spectra indicates that all of these fulvenes are atropic. Syntheses of benzannelated derivatives of (19), i.e. 7-dichloro-methylene-l3-methyl-l4,15,16,17-tetradehydrobenzocyclopentadecene (28), 9-dichloromethylene-13- methyl-14,15,16,17-tetradehydrobenzocyclopentadecene (29), and 7-dichloromethylene-16,17,18,19-tetradehydrodibenzoa,gcyclopentadecene (30) are also described. The influence of the dichloro substitution at the exocyclic bond of the fulvene, and of benzannelation on the structure of tetra- dehydropentadecafulvene, is discussed on the basis of the 'H n.m.r. and U.V. spectra of these fulvenes as well as those of the corresponding diphenyl substituted derivatives.Of the many methods available for the synthesis of the fulvene system, most involve addition of various reagents to cyclic compounds followed by an elimination or condensation reaction producing an exocyclic double bond.' In the pre- ceding paper, we reported two approaches for the synthesis of dimethyldiphenyltetradehydro-trideca-type (3; n = l), -pentadeca- type (4; n = l), -heptadeca-(3; n = 2), and -nonadeca-fulvene (4; n = 2)J. One was the direct reaction of a cyclic ketone (annulenone) with diphenylketene, and the other was the reaction of an acyclic ketone (a precursor of annulenone) with diphenylketene, followed by an intramolecu- lar oxidative coupling of the resulting cross-conjugated acyclic polyene containing two terminal acetylene group^.^ The latter method was the preferred one since the overall yields of the desired fulvenes starting from the acyclic ketones were usually better than those obtained by the former method, and the cross-conjugated acyclic polyenediynes (precursors of the desired fulvenes) served as 'open-chain ' models for an ex- amination of the tropicity of fulvenes.All of the dimethyldiphenyltetradehydrofulvenes (3 ; n = 1,2) and (4; n = 1,2) were shown to be atropic by examination of their 'H n.m.r. spectra and by comparison of the 'H n.m.r. spectra of their precursors with some benzannelated deriv- atives.' This atropicity appeared to be attributable to the absence of any contribution from a dipolar structure in the ground state of the fulvenes (3) and (4) due to the fact that the phenyl group is both electron-withdrawing and -donating and is an ambiguous substituent as far as induction is con- cerned.In contrast, halogen atoms exert an electron-with- drawing effect and are better electron attractors than the phenyl group. If an electronegative substituent were present at an exocyclic bond of the fulvenes (5) and (6), electron density would be pulled toward these substituents and the fulvene molecules would suffer an induced polarization in the ground state. If such polarization of an exocyclic bond occurs, fulvenes of type (5) are potentially paratropic and those of type (6) are potentially diatropic since the ring of the former contains (4n) x-electrons and the ring of the latter has (4n + 2) 7c-electrons, as has been shown in dehydroannulenones of types (1) and (2).394 In view of these facts, we chose chlorine as the substituent at the exocyclic bond of the fulvene system since dichloro- ketone is relatively easily obtained.This paper deals with the syntheses and properties of the title compounds (18)-(21). Also, from an examination of the 'H n.m.r. spectra, it was found that the dibenzannelated fulvene (9) exists in the un-likely conformation (9a) and the monobenzannelated fulvene (8) also exists in the conformation (8a) at -30 "C, although the non-benzannelated (4; n = 1) and the monobenzannelated fulvene (7) exist in the conformations indicated.The existence of these unexpected conformations of (8a) and (9a) prompted us to investigate the effect of benzannelation upon the molecu- lar skeleton of dichlorodimethylpentadecafulvene(1 9), and we attempted the preparation of its benzannelated derivatives. Results and Discussion The synthesis of compounds (18)-(21) was carried out by a reaction sequence similar to that adopted for compounds (3) and (4). Reaction of the acyclic ketones (10); (1 1),3 (12),3 and (13) with dichlor~ketene,~ formed in situ from dichloro- acetyl chloride and triethylamine, in refluxing benzene for 3-5 h afforded 7-dichloromethylene-3,1l-dimethyltrideca-3,5,8,10-tetraene-1,12-diyne(14) (1 5), 7-dichloromethylene-3,13-dimethylpentadeca-3,5,8,10,12-pentaene-l,14-diyne (1 5) (1 2), 9-dichloromethylene-3,15-dimethylheptadeca-3,5,7,10,-12,14-hexaene-1,16-diyne(16) (1 1), and 9-dichloromethyl- ene-3,17-dimethylnonadeca-3,5,7,10,12,14,16-heptaene-l,18-diyne (17) (14), respectively.All of these acyclic compounds (14)-(17) were rather unstable substances. Oxidative coupling of (14)-(17) with anhydrous copper(r1) acetate in pyridine and diethyl ether at 50 "C gave 13-dichloromethylene-4,9-dimethyl-5,6,7,8-tetradehydrocyclotridecene(1 8) (1 573, 15-dichloromet hylene4,Pdimet hyl-5,6,7,8-tetradehydrocyclo-pentadecene (19) (2079, 17-dichloromethylene-6,11-dimethyl-7,8,9,1O-tetradehydrocycloheptadecene(20) (8.7), and 19-dichloromethylene-6,11-dimethyl-7,8,9,lO-tetradehydro-cyclononadecene (21) (27), respectively.All of these di- chlorofulvene derivatives (18)--(21) were also unstable sub- stances. The overall yields of these fulvenes, starting from the acyclic ketones (10)-(13) were less than those of the corres- ponding diphenylfulvene derivatives (3) and (4). This might be attributed to instability of dichloroketene, compared with 2998 J. CHEM. SOC. PERKIN TRANS. I 1983 n= 1J2 n=1,2 (1) (2) diphenylketene,' and also of the acyclic compounds (14)- (17) and the dichlorofulvene derivatives (1 8)-(21). Variable-temperature 'H n.m.r. spectra of (1 8)-(21) were run over the range -60 to 60 "C.The spectra of all the fulvenes (1 8)-(21) proved to be essentially temperature-independent, reflecting that the conformations indicated for (1 8)-(21), respectively, remain unchanged over this temperature range.The 'H n.m.r. chemical shifts of these fulvenes (18)-(21) are listed in Table 1, together with those of the correspond- ing acyclic compounds (14)-( 17). Individual assignments were made on the basis of the multiplicities and coupling constants (Experimental section), and were assisted by use of the double resonance technique where necessary. Comparison of the chemical shifts of the various protons of the fulvene derivatives (18)-(21) with those of the corres- ponding model compounds (14)-(17) (Table l), respectively, indicates that all of these fulvenes are atropic, since no sig- nificant upfield or downfield shifts in the signals due to the outer (and methyl) and inner protons, respectively, were observed on passing from the acyclic model compounds to cyclic compounds (fulvenes) in the cases of (18) and (20), and the reverse in the cases of (19) and (21).The inner proton(s) of all of the fulvenes (18)-(21) resonate at rather low field com- pared with the outer protons in each case, reflecting the fact that the diacetylene moiety exerts a local anisotropic effect on the inner proton(s), as has been observed for the correspond- ing diphenyl series (3) and (4).2This observation also supports the supposition that these fulvenes do not possess a ring cur- rent. Therefore, it is concluded that the fulvene molecules (18)-(21) are not significantly polarized by the presence of two chlorine atoms at the exocyclic double bond in the ground state. The preparation of the fulvenes (28)-(30) was carried out similarly to that of (18)-(21).Reaction of compounds n=lJ2 n:1,2 (3) R=Ph (4)R=Ph (5)R=X (6)R=X phK (22),8 (23),8 and (24) with dichloroketene in refluxing benzene for 3-5 h gave 9-dichloromethylene-1 l-(o-ethynylphenyl)-3- methylundeca-3,5,7,1O-tetraen-l-yne (25) (22), 7-dichloro- methylene-1l-(u-ethynylphenyl)-3-methylundeca-3,5,8,10-tetraen-1-yne (26) (2173, and 3-dichloromethylene-1,7-bis(o-ethynylphenyl)hepta-1,4,6-triene (27) (23), respectively. Oxidative coupling of (25)-(27), as before, afforded 7-dichloromethylene-13-methyl-14,15,16,17-tetradehydrobenzo-cyclopentadecene (28) (16), 9-dichloromethylene-13-methyl-14,15,16,17-tetradehydrobenzocyclopentadecene (29) (36), and 7-dichloromethylene-16,17,18,19-tetradehydrodibenzo-a,gcyclopentadecene (30) (3573, respectively.The overall yields of these benzannelated dichlorofulvene derivatives (28)-(30) starting from the acyclic ketones (22)-(24), respectively, were less than those of the benzannelated di- phenylfulvene derivatives (7)-(9) presumably for the same reason as stated above for the less satisfactory yields of (18)- (21).The chemical shifts of the olefinic, aromatic, and methyl protons of these fulvenes (28)-(30) and those of the corres- ponding acyclic model compounds (25)-(27) are listed in Table 2. Ascan be seen from Table 2, comparison of the chem- ical shifts of the olefinic protons of the benzannelated fulvenes (28)-(30) with those of the corresponding acyclic compounds (25)-(27),respectively, indicates that the fulvenes (28)-(30) are atropic, since no significant upfield and downfield shifts due to the inner and outer protons of (28)-(30), respectively, are observed. The doublet (J 8 Hz) due to only one proton appears at low field in the spectra of both the monobenzan- nelated (28)and the dibenzannelated fulvene (30). This must be assigned to H4 of (28) and (30), since no similar resonance appears in the spectrum of (29) in which the corresponding proton is absent. The fact that this resonance appears so far downfield must be due to a large extent to a deshielding effect 2999J.CHEM. SOC. PERKIN TRANS. I 1983 (10) (14 1 116) 0 0 Me ' Me Me A-0 ,*-HE I HD -HF' 1 HG' -1-Me/ bsol;Me (131 (21 Table 1.'H N.m.r. parameters of compounds (14)-(21) in CDCI, at 200 MHz, determined at 21 "C (r-values) Compd. HA HA' HB HB' HC He HD HD' HE HE' HV HG' Me (14) (18) 3.51 3.49 3.01 2.55 3.58 3.35 8.05 8.13 (15) 3.52 3.48 3.03 3.36 3.53 3.55 3.18 3.59 7.99, 8.01 (19) 3.39 3.27 2.74 3.59 3.37 3.38 2.77 3.35 8.08 (16) (20) 3.54 3.70 3.19 3.26 3.52 3.55 3.42 2.97 3.6I 3.3I 8.02 8.06 (17) 3.36-3.70 3.20 3.21 3.36 3.70 8.02 (21) 3.28 3.71 2.92 3.2-3.71 2.99 3.28-3.71 8.09 8.06, arising from the proximity of the H4and HA protons in both and (30) are mobile around theCHA'-CHB'-CH"-CHD moiety (28) and (30).at room temperature, as in the case of the corresponding The spectrum of the fulvene (28) shows an apparent first- diphenyl-substituted derivative (8).* These puzzling patterns order pattern which is assignable to the protons present in in the spectra led us to question the proposed structures for (28). However, the spectra of both fulvenes (29) and (30) are compounds (29) and (30). complex, particularly the resonances of the HA', HB',HC',and In view of these observations, variable-temperature spectra HD'protons, revealing that the molecular skeletons of (29) of (28)-(30) were taken over the range -60 to 60 "C. The 3000 0 (22) (23) 0 spectrum of (28) proved to be essentially temperature-inde- pendent, as observed for the structurally closely related fulvene (7).2In contrast, the spectra of (29) and (30) were temperature- dependent.Although the HA',HB', H", and HD'resonances of (29) are complex multiplets over this temperature range, the corresponding bands of (30) were resolved on cooling, and an analysis of the first-order pattern indicates that (30) exists as the conformer (30a) at -60 "C (Experimental sec- tion). The observed temperature-dependency of the 'H n.m.r. spectra of (29) and (30), and comparison with those of the corresponding diphenyl-substituted fulvenes (8) and (9), suggests that both the phenyl groups and the chlorine atoms on the exocyclic bond exert more influence upon the structure of the molecular skeleton than the oxygen atom of the tetra- dehydro 1Sann~lenone.~-~ The electronic absorption maxima of the fulvenes (1 8)-(21) in dichloromethane are given in Table 3.Although the main maxima of the fulvenes exhibit a bathochromic shift as the ring size increases, this shift is larger between the trideca- fulvene (18) (A,,,,, 287 nm) and the pentadecafulvene (19) (XmaX. 308 nm) and between the heptadecafulvene (20) 315 nm) and the nonadecafulvene (21) (Amax. 338 nm) than that between the pentadeca- (19) and the heptadeca-fulvene (20). Although they are not illustrated, the electronic spectra of (18) and (20) type (5) are similar, while those of (19) and J. CHEM. SOC. PERKIN TRANS. I 1983 H' A'(26) (29) H3/ H2' 1' (21) type (6)) differ only in the bathochromic shift of each band.This might be again considered to be due to the occur- rence of the same sort of alternation in the wavelengths of the main maxima between 4n + 2) and 4nsystems,'O as has been observed for the corresponding diphenyl series.2 Also, the longest wavelength bands of the fulvenes (1 8)-(21) appear at shorter wavelength than those of the corresponding diphenyl-substituted fulvenes (3) and (4), of the same ring size, reflecting the fact that the degree of extended conjugation is smaller in the dichloro series than in the diphenyl series. Also, the longest wavelength bands of the fulvenes show a shift in absorption towards longer wavelength in the sequence (19) (28) 21 (29) (30), i.e.with increasing number of fused benzene rings on the macrocyclic system, reflecting the degree of extended conjugation of the n-electron system in these fulvenes, as has been observed for the corresponding diphenyl series (4; n = l)), (7)-(9).2 However, the longest wavelength bands of these fulvenes (28)-(30) are at shorter wavelength than those of the corresponding diphenyl fulvenes (7)-(9), and this difference is also observed between the diphenylful- vene (4; n = l) and the dichlorofulvene (19). Experimental M.p.s were determined with a hot-stage apparatus and are uncorrected. 1.r. spectra were taken on a Hitachi 260-50 J. CHEM. SOC. PERKIN TRANS. I 1983 3001 Table 2. 'H N.m.r. parameters of compounds (25)-(30) in CDCIJat 200 MHz, determined at 21 "C(r-values) Compound HA HA' HB HE' HC H" HD' HE' (28) (25) 2.76 3.03 3.38 3.39 2.52 2.64 3.46 3.23 3.22 3.56 2.91 3.19 3.33 3.60 (26) (29) 3.38 3.25 3.48 3.58-3.72 2.96 2.87 2.98 3.363.46 3.5 1 3.35 3.23 3.363.46 2.76 2.92-2.97 (27)(30) 2.98 2.74 3.28 3.50-3.63 2.56 2.53 2.96 3.1 8-3.37 3.08 3.18-3.3 7 2.98 2.90-3.03 HL H2 H3 H4 HI' H2' H" H" Me (25)(28) 2.45 2.60 2.66 2.78 2.58 2.68 2.32 2.25 8.13 8.08 (26)(29) 2.46 2.56 2.76 2.65 2.32 2.80 7.99 8.08 (27)(30) 2.44 2.56 2.55- 2.80 2.77 2.30 2.25 2.48 2.56 2.55- 2.80 2.32 2.77 Table 3.Electronic absorption maxima of fulvenes in dichloromethane La*,.(nm) (Ernax.) (1 8) (1 9) 269sh (1 6 900) 268sh (16 100) 287 (22600) 282sh (21 100) 355 (8 170) 308 (30100)378sh (5 100) spectrophotometer as KBr discs.U.V. spectra were measured for solutions in dichloromethane and run with a Hitachi 220A spectrophotometer. Mass spectra were recorded with a JEOL JMS-200 spectrometer operating at 75 eV using a direct-inlet system. 'H N.m.r. spectra were run with a Varian XL-200 (200 MHz), JEOL FX-200 (200 MHz), or FX-90Q (90 MHz) spectrometer (CDC13 solutions). Merck alumina (activity II- 111) was used for column chromatography. Most of the reac- tions were followed by t.1.c. using Merck pre-coated alumina. Sodium sulphate was used as the drying agent, and solvents were evaporated under water-pump pressure. Ether refers to diethyl ether.7- Dichloromethylenc-3,11 -dimethyltrideca-3,5,8,1O-tetraene-1,12-diyne (14).-A solution of dichloroacetyl chloride (4.0 ml) in dry benzene (30 ml) was added dropwise during 2 h to a stirred, refluxing solution of the acyclic ketone (10) (1.30 g, 6.18 mmol) and triethylamine (8.0 ml) in dry benzene (45 ml) under nitrogen, and the mixture was stirred under reflux for a further 2.5 h. It was then chilled and poured onto water. The organic layer, combined with the benzene extracts from the aqueous layer, was washed successively with 7 hydrochloric acid, water, aqueous sodium hydrogen carbonate, and brine. Drying followed by solvent removal gave a red liquid which was passed through a short column of alumina (2 x 3 cm) and eluted with 20 ether in hexane.The liquid obtained by concentrating the eluates was chromatographed on alumina (4 x 11 cm). Fractions, eluted with 2 ether in hexane, gave the acyclic compound (14) (260 mg, 15) as a solid. It formed yellow plates from hexane, m.p. 105-106 "C; ni/z 278 (M+, 30), 276 (M+, 50), and 191 (100);M, 277.1; vnmx. 3 300 (C-CH), 2 090 (C-C), and 960 cm-' (trans-C=C); A,,,. 247sh (E 10 loo), 256 (15 100), 265 (15 300), 299sh (21 500), 317 (29 900), and 331 nm (24 800); T 3.01 (2 H, dd, J 16 and 11.5 (20) (21) 291sh (29 800) 303sh (27 200) 315 (39000) 338 (49400)390 (llO00) 391sh (11 700)423sh (5980) Hz, HB),3.51 (2 H, d, J 16 Hz, HA), 3.58 (2 H, d, J 11.5 Hz, HC), 6.70 (2 H, s, C-CH), and 8.05 (6 H, s, Me) (Found: C, 69.2; H, 5.0.Cl6HI4Cl2 requires C, 69.3; H, 5.1). 13-Dichloromethylene-4,9-dimethyl-5,6,7,8-tetradehydro-cyclotridecene (1 8).-A solution of the acyclic compound (1 4) (233 mg, 0.84 mmol) in pyridine (20 ml) and dry ether (6 ml) was added dropwise to a stirred solution of anhydrous copper- (11) acetate (1.88 g) in pyridine (50 ml) and dry ether (17 ml) during 2 h at 50-52 "Cand the solution was stirred for a fur- ther l h at the same temperature, and then poured onto water. The organic layer, combined with the benzene extracts from the aqueous layer, was washed with 5 hydrochloric acid until it turned acidic, then with water, aqueous sodium hydro- gen carbonate, and brine. Drying followed by solvent removal gave a red liquid which was chromatographed on alumina (4 x 9 cm).Fractions, eluted with hexane, gave the trideca- fulvene (18) (35 mg, 15) as a solid. It formed pale yellow needles from hexane, m.p. 162 "C (decornp.); m/z 276 (M+, 3573, 774 (M+, 48), and 189 (100); M, 275.1; vnms.2 150 C-C) and 970 cm-' (trans-C=C); for U.V. data see Table 3; 5 2.55 (2 H, dd, J 16 and 10 Hz, HB), 3.35 (2 H, d, J 10 Hz, HC), 3.49 (2 H, d, J 16 Hz, HA), and 8.13 (6 H, s, Me) (Found: C, 70.0; H, 4.2. CI6Hl2Cl2 requires C, 69.85; H, 4.4). 7-Dichloromethylene-3,13-dimethylpentacieca-3,5,8,10,12-pentaene-1,14-diyne (15).-A solution of dichloroacetyl chloride (3.0 ml) in dry benzene (20 ml) was added dropwise during 3 h to a stirred, refluxing solution of the acyclic ketone (1 1) (1.00 g, 4.23 mmol) and triethylamine (4.0 ml) in dry benzene (30 ml) under nitrogen, and the mixture was stirred under reflux for a further 1 h.After work-up as for the isol- ation of (14), the product was chromatographed on alumina (4 x 10 cm). Fractions, eluted with 3 ether in hexane, gave the acyclic compound (15) (162mg, 12) as a solid. It formed yellow plates from hexane, m.p. 77-78 "C;m/z 304 (M+, 42), 302 (M+,64), and 153 (100);M, 303.2;v,,,. 3 300 (CXH), 2 100 (C-C),1 015, and 990cm-' (trans-CZC); h,,,. 263sh (E 19 900), 273 (24 900) 282sh (22 800), 328 (49 500), 343 (51 700), and 362 nm (39 100); '1: 3.03 (1 H, dd, J 16.5 and 11 Hz, HB), 3.18 (1 H, dd, J 15.5 and 11 Hz, HD'), 3.36 (1 H,dd, J 15.5 and 11 Hz, HE'),3.48(1 H, d, J 15.5 Hz, HA'), 3.52(1 H,d, J 16.5 Hz, HA),3.53 (1 H, d, J 11 Hz, Hc), 3.55 (1 H,dd, J 15.5 and 11 Hz, H"),3.59 (1 H, d, J 11 Hz, HE'), 6.61 (1 H, s, CZCH),6.65(1 H, s, CECH),7.99 (3 H, s, Me), and 8.01 (3 H, s, Me) (Found: C,71.4;H,5.4.C,,H,,CI,re-quires C,71.3;H, 5.3).1 5-Dichloromethylene-4,9-dimethyl-5,6,7,8-tetradehydro-cyclopentadecene (1 9).-A solution of the acyclic compound (15) (176 mg, 0.58 mmol) in pyridine (14 ml) and dry ether (4 ml) was added dropwise during 1.5 h to a stirred solution of anhydrous copper(r1) acetate (1.29 g) in pyridine (40 ml) and dry ether (15 ml) at 50-52 "C, and the solution was stirred for a further 1 h at the same temperature. After work-up as for the isolation of (18), the product was chromatographed on alumina (4 x 10 cm).Fractions, eluted with 3 ether in hexane, gave the pentzdecafulvene (19)(35 mg, 20) as a solid. It formed orange cubes from hexane, m.p. 87-89 "C;ntlz 302 (M+, 779, 300 (M+, lo), and 215 (100); M, 301.2;vmax. 2 160 (CX),1 605 (C=C),and 970cm-' (trans-C=C);for U.V. data see Table 3 ;r 2.74(1 H, dd, J 15.5 and 1 1.5 Hz, HB), 2.77 (1 H, dd, J 15.5 and 11.5 Hz, HD'),3.27(1 H, d, J 16 Hz, HA'),3.35 (1 H,d, J 10 Hz, HE'),3.37 (1 H, d, J 10 Hz, HC),3.38 (1 H, dd, J 15.5 and 4 Hz,Hc'), 3.39 (1 H,d, J 16 Hz, HA), 3.59 (1 H, dd, J 15.5 and 4 Hz, HB'),and 8.08 (6 H, s, Me) (Found: C, 71.6;H,4.8.Cl,H,4Cl,requires C, 71.8;H, 4.7). J. CHEM. SOC. PERKIN TRANS. I 1983 224 "C(decomp.); m/z 328 (M', 25), 326 (M+,40), and 239(10); M,327.2;vnlax.2 180 (CGC)and 990cm-' (trans-C=C); U.V.data see Table 3; r 2.97 (2 H, dd, J 15 and 1 1 Hz, HD), 3.26(2 H, dd, J 16 and 10.5 Hz, HE),3.31 (2 H, d, J 11 Hz, HE),3.55 (2 H, dd, J 15 and 10.5Hz, Hc), 3.70 (2 H,d, J 16 Hz, HA), and 8.06 (6 H, s, Me) (Found: C,73.1;H,5.0.C20H16C12requires C,73.4;H, 4.9). 9-Dichlorornethylene-3,17-dimethyfnonadeca-3,S,7,10,12,14,-16-heptaene-l,18-diyne(17).-A solution of dichloroacetyl chloride (6.5ml) in dry benzene (40 ml) was added dropwise during 1.5 h to a stirred, refluxing solution of the acyclic ketone (1 3) (1.95g, 6.76 mmol) and triethylamine (1 3 ml) in dry benzene (70 ml) under nitrogen, and the mixture was stirred under reflux for a further 2 h.After work-up as for the isolation of (14), the product was passed through a short column of alumina (4 x 6cm) and eluted with hexane-ether (1 : I). The red liquid obtained by concentrating the eluates was chromatographed on alumina (4 x 12 cm). The fractions eluted with 8 ether in hexane gave the acyclic compound (17) (342 mg, 14) as a solid. It formed orange cubes from hexane, m.p. 120-122 "C;m/z 356 (M+,50), 354(M+,75), and 179 (100); M, 355.3;vmaXu.3 290 (CECH),2090 (CX), 1 005,and 990 cm-I (trans-C=C);A,,,,,. 297sh (E 25 600), 31 1 (31 500), 330sh (38 600), 347 (55000), 366 (58900), 389 (38OOO), 423sh (5 070), and 447sh nm (2 800); r 3.20 (1 H, dd, J 15.5 and 11.5 Hz, HE),3.21 (1 H, dd, J 15.5 and 11.5 Hz, HB'),3.36-3.70 (10H, m, HA, HA', HC, HC', HD, HD', HE, HE', HF',and HG'), 6.62 (2 H, s, CXH),and 8.02(6 H, s, Me) (Found: C,74.2;H,5.7.CzzH2,Clrrequires C, 74.4; H, 5.7).19-Dichlororriethylene-6,ll-dirnethyl-7,8,9,1O-tetradehydro-cyclononadecene (21).-A solution of the acyclic compound 9-Dichloromethylene-3,15-dimethylheptadeca-3,5,7,10,12,14-(17) (191 mg, 0.54 mmol) in pyridine (14 ml) and dry ether (10 ml) was added dropwise during 1 h to a stirred solution of hexaene- 1,16-diyne (1 6).-A solution of dichloroacetyl chlor- ide (4.6 ml) in dry benzene (35 ml) was added dropwise to a stirred, refluxing solution of the acyclic ketone (1 2) (1.88 g,7.17mmol) and triethylamine (9.3ml) in dry benzene (52 ml) during 2 h under nitrogen, and the mixture was stirred under reflux for a further 3 h. After work-up as for the isolation of (14), the product was passed through a short column of alumina (4 x 5 cm) and eluted with 30 ether in hexane.The red liquid obtained by concentrating the eluates was chro- matographed on alumina (4 x 12 cm). The fractions eluted with 8 ether in hexane gave the acyclic compound (16) (269 mg, 11) as a solid. It formed yellow needles from hexane, m.p. 106-108 "C;mlz 330 (M+,55), 328 (M+,73, and 179 (100);M, 329.2;vnla,. 3 290 (CSCH),2 090 (CX),995, and 960cm-' (trans-C=C); h,,,. 273sh (E 15 loo), 284 (25 loo), 296 (30300), 329 (45 100), 344 (60300), 362 (50 400), and 425sh nm (1 570); T 3.19 (2 H, dd, J 15 and 11 Hz, HB),3.42 (2 H, dd, J 15 and 11 Hz, HD),3.52 (2 H, dd, J 15 and 11 Hz,Hc),3.54 (2 H, d, J 15 Hz, HA),3.61 (2 H, d, J I1 Hz, HE), 6.62(2H, s, C-CH),and 8.02 (6 H, s, Me) (Found: C, 72.8; H, 5.5.C20HlaC12 requires C, 72.95; H, 5.5). 17- Dichlorornethylene-6,ll -dimethyl-7,8,9,1O-tetradehydro-cycfoheptadecene (20).-A solution of the acyclic compound (16) (501 mg, 1.51 mmol) in pyridine (37 ml) and dry ether (11 ml) was added dropwise to a stirred solution of anhydrous copper(r1) acetate (3.4g) in pyridine (105 ml) and dry ether (39 ml) during 2 h at 51-53 "C,and the mixture was stirred for a further 1 h at the same temperature. After work-up as for the isolation of (18),the product was chromatographed on alumina (4 x 9 cm). The fractions eluted with 5 ether in hexane gave the heptadecafulvene (20) (43 mg, 8.7) as a solid. It formed orange needles from hexane, m.p.222-anhydrous copper(r1) acetate (1.3 g) in pyridine (39 ml) and dry ether (15 ml) at 51-52 "C,and the solution was stirred for a further 1 h at the same temperature. After work-up as for the isolation of (18), the product was chromatographed on alumina (4 x 10 cm). Fractions, eluted with 5 ether in hexane, gave the nonadecafulvene (21) (51 mg, 27) as a solid. It formed orange microcrystals from hexane, m.p. 135-136 "C;rn/z 354 (M+,30), 352 (M+,42), and 267 (100);M, 353.2;vnIax.2 180 (C-C)and 995 cm-' (trans-C=C); U.V. data see Table 3;T 2.92(1 H,dd, J 15 and 1 I .5 Mz, HD),2.99(1 H, dd, J 15 and 11.5 Hz, HF'), 3.28-3.71 (10 H, m, HA,HA',HB, HE, HE',and HG'),8.06(3 H,HB', HC, HC',HD', s, Me), and 8.09(3 H,s, Me) (Found: C,74.8;H, 5.3.C22HiB-C12 requires C,74.8;H, 5.1). 9- Dichlorornethylene- 1 l-(o-ethynylphenyf)-3-methylundeca-3,5,7,1O-tetraen-l-yne(25).-A solution of dichloroacetyl chloride (4.0ml) in dry benzene (26 ml) was added dropwise during 1 h to a stirred, refluxing solution of the acyclic ketone (22) (1.25 g, 4.57mmol) and triethylamine (7.0ml) in drybenzene (35 ml) under nitrogen, and the mixture was stirred under reflux for a further 5.5 h.After work-up as for the isol- ation of (14), the product was chromatographed on alumina (4 x I1 cm). Fractions, eluted with 3 ether in hexane, gave the acyclic compound (25) (337 mg, 22) as a solid.It formed pale yellow needles from hexane, m.p. 119-120 "C; m/z 340 (M+,30), 338 (M+,49,and 252 (100);M, 339.2;vnlaX. 3 300, 3 290 (CECH),2 110,2 100(C-C),1 000,985,and 980 cm-' (trans-C=C); h,,,,. 237 (E 26 700), 264 (22 600), 312sh (34 loo), 327 (46 400),343 (54 ZOO), 362 (43 500), 396 (4 OOO), and 421 nm (3 100); r 2.32(1 H, d, J8 Hz, H4), 2.45(1 H,d, J8 Hz, H'),2.58(1 H, d, J8 Hz, H3),2.64(1 H,d, J 16.5 Hz, J. CHEM. SOC. PERKIN TRANS. I 1983 HB), 2.66 (1 H, d, J 8 Hz, H'), 3.03 (1 H, d, J 16.5 Hz, HA), 3.19 (1 H, dd, J 15.5 and 10.5 Hz, HD'), 3.23 (1 H, dd, J 15.5 and 10.5 Hz, HB), 3.39 (1 H, d, J 15.5 Hz, HA'), 3.56 (1 H, dd, J 15.5 and 10.5 Hz, H"), 3.60 (1 H, d, J 10.5 Hz, HE'), 6.62 (1 H, s, C-CH), 6.64 (1 H, s, CECH), and 8.13 (3 H, s, Me) (Found: C, 74.2; H, 4.5.CZ1H16C12requires C, 74.35; H, 4.75). 7-Dichloromethylene-l3-methyl-14,15,16,17-tetradehydro-benzocyclopentadecene (28).-A solution of the acyclic com- pound (25) (507 mg, 1.49 mmol) in pyridine (37 ml) and dry ether (11 ml) was added dropwise during 2 h to a stirred solution of anhydrous copper(@ acetate (3.4 g) in pyridine (106 ml) and dry ether (40ml) at 50-52 "C, and the solution was stirred for a further 1 h at the same temperature. After work-up as for the isolation of (18), the product was chro- matographed on alumina (4 x 11 cm). The fractions eluted with 2 ether in hexane gave the monobenzannelated fulvene (28) (79 mg, 16) as a solid. It formed orange needles from hexane-benzene, m.p.176-177 "C; m/z 338 (M+,873, 336 (M+, lo), and 255 (100); M, 337.2; vmx. 2190 (CEC) and 965 cm-' (trans-C=C); h,,,,. 231 (E 20200), 293 (37 300), 318sh (30 400), and 371sh nm (13 900); r 2.25 (1 H, d, J 8 Hz, H4), 2.52 (1 H, d, J 16 Hz, HB), 2.60 (1 H, d, J 8 Hz, H'), 2.68 (1 H, d, J 8 Hz, H3), 2.76 (1 H, d, J 16 Hz, HA), 2.78 (1 H, d, J 8 Hz, H2), 2.91 (1 H, dd, J 15.5 and 9.5 Hz, HD'), 3.22 (1 H, dd, J 15.5 and 6 Hz, H"), 3.33 (1 H, d, J 9.5 Hz, HE'), 3.38 (1 H, d, J 15.5 Hz, HA'), 3.46 (1 H, dd, J 15.5 and 6 Hz, HB'), and 8.08 (3 H, s, Me) (Found: C, 75.0; H, 4.1. C2,H14C12 requires C, 74.8; H, 4.2). 7- Dichloronrethylene- 1 1-(o-ethynylpheny1)-3-methylundeca-3,5,8,10-tetraen-I -yne (26).-A solution of dichloroacetyl chloride (7.0 ml) in dry benzene (45 ml) was added dropwise during 2 h to a stirred, refluxing solution of the acyclic ketone (23) (1.91 g, 6.99 mmol) and triethylamine (14.0 ml) in dry benzene (67 ml) under nitrogen, and the mixture was stirred under reflux for a further 4 h.After work-up as for the isol- ation of (14), the product was chromatographed on alumina (4 x 10 cm). The fractions eluted with 2 ether in hexane gave the acyclic compound (26) (499 mg, 21) as a solid. It formed pale yellow needles from hexane, m.p. 98-99 "C; m/z 340 (M+, 12), 338 (M+, 19), and 252 (100); M, 339.2; vmas. 3 290 (C-CH), 2 090 (C-C), 995, 990, and 970 cm-' (trans- C=C); A,,,. 235 (E 16500), 262 (21 700), 271 (21 900), 317sh (38 loo), 329 (40 400), 343sh (34 500), and 372sh nm (19 900); r 2.32 (1 H, d, J 7.5 Hz, H4), 2.46 (1 H, d, J 8 Hz, HI), 2.65 (1 H, d, J 8 Hz, H3), 2.76 (1 H, d, J 7.5 Hz, H2), 2.76 (1 H, d, J 15.5 Hz, HD'), 2.96 (1 H, dd, J 16 and 11.5 Hz, HB), 2.98 (1 H, dd, J 15.5 and 9.5 Hz, HB'),3.23 (1 H, dd, J 15.5 and 9.5 Hz, H"), 3.38 (1 H, d, J 16 Hz, HA), 3.48 (1 H, d, J 16 Hz, HA'), 3.51 (1 H, d, J 11 Hz, HC), 6.62 (1 H, s, C-CH), 6.65 (1 H, s, C-CH), and 7.99 (3 H, s, Me) (Found: C, 74.4; H, 4.8.C2,Hi6CIZ requires C, 74.4; H, 4.8). 9-Dichloromethylene-l3-methyl-14,15,16,17-tetradehydro-benzocyclopentadecene (29).-A solution of the acyclic com- pound (26) (216 mg, 0.64 mmol) in pyridine (15 ml) and dry ether (5 ml) was added dropwise to a stirred solution of an- hydrous copper(r1) acetate (1.4 g) in pyridine (44ml) and dry ether (17 ml) during 2 h at 50-52 "C, and the solution was stirred for a further 1 h at the same temperature.After work-up as for the isolation of (18), the product was chro- matographed on alumina (4 x 8 cm). The fractions eluted with 2 ether in hexane gave the monobenzannelated fulvene (29) (77 mg, 36) as a solid. It formed yellow needles from hexane-benzene, m.p. 134-136 "C;m/z 338 (M+,2079, 336 (M+,25), and 265 (100); M, 337.2; v,,,,,~. 2 190, 2 150 (CX) and 970 cm-* (trans-GC); kmx. 232 (E 30 lOO), 273sh (34 700), 285 (42 OOO), 305 (35 8OO), 368sh (14 OOO), and 394sh (10400); r 2.56-2.80 (4 H, m, Ar-H), 2.87 (1 H, dd, J 15.5 and 10.5 Hz, HB), 2.92-2.97 (1 H, m, HD'), 3.25 (1 H, d,J15.5Hz,HA),3.35(1H,d,J10.5Hz,HC),3.34-3.46(2H, m, HB' and Hc'), 3.58-3.72 (1 H, m, HA'),and 8.08 (3 H, s, Me) (Found: C, 75.0;H, 4.4.C21H14C12 requires C, 74.8; H, 4.2). 3- Dichloromethylene- 1,7-bis(o-ethynylphenyl)hepta-1,4,6-triene (27).-A solution of dichloroacetyl chloride (7.5 ml) in dry benzene (46 ml) was added dropwise during 1.5 h to a stirred, refluxing solution of the acyclic ketone (24) (2.24 g, 7.25 mmol) and triethylamine (15 ml) in dry benzene (73 ml) under nitrogen, and the mixture was stirred under reflux for a further 2.5 h. After work-up as for the isolation of (14), the product was chromatographed on alumina (4 x 10 cm). The fractions eluted with 3 ether in hexane gave the acyclic com- pound (27) (554 mg, 23) as a solid.It formed pale yellow needles from hexane-benzene, m.p. 159-160 "C;m/z 376 (M+, 14), 374 (M+, 22), and 303 (100); M, 375.2; vmx. 3 290 (CECH), 2 110 (CX), 1 OOO, 985, and 980 cm-' (frans- C=C); A,,,,. 235 (E 40 300), 255 (33 800), 262 (33 800), 270sh (28 600), 326 (55 700), 341 (54 800), and 359sh nm (33 800); T 2.30 (1 H, d,J 8 Hz, H4), 2.32 (1 H, d,J 8 Hz, H4'), 2.44 (1 H, d, J 8 Hz, HI), 2.48 (1 H, d, J 8 Hz, H"), 2.56 (1 H, d, J 15.5 Hz, HB),2.55-2.80 (4 H, m, H2, H2', H3, and H3'), 2.96 (1 H, dd, J 15 and 10 Hz, HB'), 2.98 (2 H, d, J 15.5 Hz, HA and HD'), 3.08 (1 H, dd, J 15 and 10 Hz, H"), 3.28 (1 H, d, J 15 Hz, HA'), 6.58 (1 H, s, CCH), and 6.64 (1 H, s, CECH) (Found: C, 77.1 ;H, 4.2. CZ4Hl6Cl2 requires C, 76.8; H, 4.3).7-Dichloromethylene-l6,17,18,19-tetradehydrodibenzoa,g-cyclopentadecene (30).-A solution of the acyclic compound (27) (98 mg, 0.26 mmol) in pyridine (7 ml) and dry ether (2 ml) was added dropwise during 2 h to a stirred solution of an- hydrous copper(i1) acetate (0.6 g) in pyridine (19 ml) and dry ether (7 ml) at 50-52 "C, and the solution was stirred for a further 1 h at the same temperature. After work-up as for the isolation of (18), the product was chromatographed on alumi- na (4 x 9 cm). Fractions, eluted with 2 ether in hexane, gave the dibenzannelated fulvene (30) (34 mg, 35) as a solid. It formed pale yellow needles from hexane-benzene, map. 192-193 "C; m/z 374 (M+,15), 372 (M+,25), and 302 (100); M, 373.2; vmax.2 200 (CEC), 1 OOO, and 980 cm-' (trans-CX); A,,,.231 (E 39 OOO), 303 (56 loo), and 371sh nm (13 700); r (27 "C) 2.25 (1 H, d, J8 Hz, H4), 2.53 (1 H, d, J 16 Hz, HB), 2.56-2.77 (7 H, m, Hi, H2, H3, HI', H2', H3', and H4'), 2.74 (1 H, d, J 16 Hz, HA), 2.90-3.03 (1 H, m, HD'), 3.18-3.37 (2 H, m, HB'and Hc'), and 3.50-3.63 (1 H, m, HA'); T (-60 "C) 2.24 (1 H, d, J 8 Hz, H4), 2.54 (1 H, d, J 16 Hz, HB), 2.55-2.72 (7 H, m, H', H2, H3, HI', HZ', H3', and H4'), 2.77 (1 H, d, J 16 Hz, HA), 3.04 (1 H, d, J 16 Hz, HD'), 3.19 (1 H, dd, J 16 and 11 Hz, H"), 3.31 (1 H, dd, J 16 and 11 Hz, HB'), and 3.58 (1 H, d, J 16 Hz, HA') (Found: C, 77.0; H, 4.0. CZ4Hl4Clz requires C, 77.2; H, 3.8). Acknowledgements This work was financially supported by grants from the Minis- try of Education, Japan (554141), and the It6 Science Found- ation.References I For reviews, see E. D. Bergmann, Chem. Rev., 1968, 68, 41 and F. Pietra, ibid.,1973, 73,293. 2 S. Kuroda, J. Ojirna, K. Kitatani, M. Kirita, and T. Nakada, J. Chern. SOC.,Perkin Trans. 1, preceding paper; S. Kuroda, K. Kitatani, and J. Ojima, Tetrahedron Lett., 1982, 2657; J. Ojima, S. Kuroda, and M. Kirita, Chem. Lett., 1982, 1371. 3 J. Ojima, Y. Shiroishi, K. Wada, and F. Sondheimer, J. Org. Chem., 1980,45, 3564. 4 T. M. Cresp, J. Ojima, and F. Sondheimer, J. Org. Chem., 1977, 42,2 130. 5 H. C. Stevens, D. A. Reich, D. R. Brandt, K. R. Fountain, and E. C. Gaughan, J. Am. Chem. SOC.,1963, 87, 5257; L. Ghosez, R. Montaigne, and P. Moller, Tetrahedron Lett., 1966, 135. 6 N. Darby, T. M. Cresp, and F. Sondheimer, J. Org. Chem., 1977,42, 1960. J. CHEM. SOC. PERKIN TRANS. I 1983 7 R. S. Ward, in lsquo;The Chemistry of Ketenes, Allenes, and Related Compounds,rsquo; ed. S. Patai, Wiley Interscience, Chichester, 1980, part 1, p. 249. 8 J. Ojima and Y. Shiroishi, Bull. Chem. SOC.Jpn., 1978, 51, 1204. 9 J. Ojima, K. Wada, K. Kanazawa, and Y. Nakagawa, J. Chem. SOC.,Perkin Trans. I, 1981, 947. 10 P. J. Garratt and K. Grohmann in lsquo;Houben-Weyl, Methoden der Organischen Chemie,rsquo; Georg Thieme Verlag, Stuttgart, 1972, vol. V, part Id, p. 533. Received 28th February 1983; Paper 3/32