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On the crystal and molecular structure of 1,4-diphenylbuta-1,2,3-triene in connection with its stereospecific synthesis from (Z)-2-phenyl-1-(methylthio)vinyl cuprate and its conversion into (1Z,3E)-2-ethyl-1,4-diphenylbuta-1,3-diene |
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Journal of the Chemical Society, Perkin Transactions 2,
Volume 1,
Issue 4,
1979,
Page 423-426
Wilbert G. M. van den Hoek,
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摘要:
1979 423 On the Crystal and Molecular Structure of I,4-Diphenylbuta-l,2,3-triene in Connection with its Stereospecific Synthesis from (Z)-Z-Phenyl-1-(methylthio)vinyl Cuprate and its Conversion into (12,3€)-2-Ethyl-1 r4-diphenylbuta-l ,3-diene By Wilbert G. M. van den Hoek and Jan Kroon," Laboratorium voor Structuurchemie, Rijksuniversiteit, Padualaan 8, Utrecht, The Netherlands Henk Kleijn, Hans Westmijze, Peter Vermeer, and Hendrick J. T. Bos, Organisch Chemisch Laboratorium, Rijksuniversiteit, Croesestraat 79, Utrecht, The Netherlands The crystal and molecular structure of the title compound (1 ) has been determined by single-crystalX-ray diffraction. Crystals are orthorhombic, space group Pcab, with cell dimensions a = 8.029(7),15 = 13.032(6), c = 22.09(2) 8.and Z = 8. The structure was solved by direct methods and refined by block-diagonal least-squares to R 0.038 for 690 observed reflections. The molecular configuration is cis, which is of significance for establishing the stereochemistry of additions to the inner double bond. Parallel butatriene chains with a mean distance of 3.7 8 are stacked in planes parallel to (010). A NUMBER of methtds have been developed for the syn- thesis of huta-l,2,3-trienes C=C=C=C, but most of them have led to a mixture of (E)-and (Z)-isomers.l Hitherto, two methods have appeared in the literature dealing with a stereospecific -preparation of these compounds. One involves hydroboration of 1-iodoalk- 1-ynes : H i,ii / R1'-.R1-CmC-I -c=c=c=c,H' R' Eragclzts: i, RLHH,; ii, KaORle.Ii112 = allryl Hydroboration studies point to a tram-configuration of these cumulenes (cf. ref. 2). Re~ently,~we found another stereospecific route to buta-lJ2,3-trienes was found by starting from speci fk subst it uted cc-(me t hylthio) vinyl cuprates :bd<MjCuMgBr + 2 Me1 R1R2CX=C=cRIR* (I) (one isomer) 2 t 2 Me2S 3-CUI + MgBrI The configuration of the butatrienes thus obtained was suggested tr~ lie cis, based on hydrogenation studies on (2) (RI = Ph, K2 = H) [ cf. ref. 31. Two 1,3-dienes were obtained upon hydrogenation of (1) with Pd/ CaC0,-H, in chloroform, viz. cisJ&- and trans,trans-lJ4- diphenylbuta-1,3-diene (2). As hydrogenation reactions generally proced in a cis-manner, the formation of cis,cis-and trans,trans-(Z) is indicative of a cis-configur-ation of the starting cumulene (1): There were some reasons, however, which made the assignment of a cis-configuration to (1) somewhat un- certain.For instancr., the reaction of 'cis'-(l) with the diethyl cuprate (3) in tetrahydrofuran (THF) furnished H\ APh YPh Pd/H2 Ph\H.''C=C=C=C 'ti * H/C=C\H /c=c\ph cis41) trans,tr~ns-(21 exclusively (12,3E)-2-ethyl-l,4-diphenylbuta-l,3-diene (5)uporl protonolysis ph,,c=c=c=cH \H THF 'cis'-(l) (41 Ph\c=c#C=C,H H' 'Et (5 1 If one assunies a direct formation of (4)from (1) and (3), adduct (5) can only arise by trans-addition of the cuprate on (1). The trans-addition of organocuprates on s$ hybridized carbon-carbon multiple bonds is very Ituncommon, howe~er.~-~ must be noted that the protonolysis of (4)into (5) will most likely take place with retention of configuration (cf.refs. 6-8). On the other hand, compound (4)[and thus (5)] could also be formed by a direct cis-addition of (3) on trans-(lj, but this would necessarily imply that hydrogenation of the inner double bond in (1)occurs by a trans- rather than a cis-mechanism. A trans-hydrogenation cannot a priori be ruled out, as in a few cases partial trans-hydrogenation has been ob~erved.~-ll An unequivocal determination of the configuration of the title compound, 1,4-diphenylbuta-1,2,3-triene,was therefore imperative, and we now report results of an X-ray study. EXPERIMENTAL 1,4-Diphenylbuta-1,2,3-triene(l),synthesized from (4-2-phenyl-1-(methy1thio)vinyl cuprate and methyl i~dide,~ was crystallized from toluene as yellow, plate-like crystals which are thermally unstable and light-sensitive.Addition of Diethylcuprate (3) to (1).-To a well-stirred suspension of Et,CuMgBr (0.0100 mol), prepared from EtMgBr (0.0200 mol) and a 1 : 1 complex of CuBr-LiBr (0.0100rnol) in tetrahydrofuran (30m1),8 was added (1) (0.0100 rnol) at -50 "C. Stirring was continued, the temperature of the reaction mixture being raised slowly (30 min) to 20 "C. The reaction mixture was then poured into a saturated solution of NH4C1 in water (100 ml) containing some NaCN (0.5g). The product was isolated by extracting with pentane (3 x 50 ml).After washing the combined extracts (water) and drying (MgSO,), solvent was removed in VUCUQ. The crude (12,3E)-2-ethyl-l,4-diphenylbuta-1,3-J.C.S. Perkin I1 microfiche).* Scattering factors for carbon were taken from ref. 15, and for hydrogen from ref. 16. Final positional FIGURE Key to the atomic numbering in the 1 cis-diphenylbutatriene molecule (1) parameters for the C atoms are listed in Table 1,H atoms in Table 2. TABLE1 diene (5) was analyzed by n.m.r. spectroscopy and further purified by column chromatography (A120, $-5% aqueous hexane) giving pure (5) as a colourless oil (yield 80%). N.m.r. data for PhCH1=C(CH,4-CH35)-CH2=CH3-Ph(5) (6 values from SiMe,, solvent CDCl,) : 7.47 (ZPh, m), 7.36 (2-H,d, J2,3 15.0 Hz),6.80 (3-H,d, J2.3 15.0Hz), 6.65 (1-H, s), 2.58 (4-H, q, J4,57.5 Hz), and 1.27 (5-H, t, J4,57.5 Hz).The orientation of H-1 and the ethyl group was deduced from the CH coupling constant J(H1,CH,) which is 6.2 Hz, characteristic for a cis-orientation.12 Crystal Datu.--Cl,Hl,, M = 204.27. Orthorhombic, u =8.029(7), b = 13.032(6), G = 22.09(2) A, U = 2 312 k3, 2 = 8, D, = 1.174 g crnw3, F(000)= 864. Mo-K, radi-ation, h = 0.7107 A, ~(Mo-K,) = 0.72 cm-l. Space group Pcab (No. 61, Dgi *) from systematic absences. Cell dimensions were measured and data collected on a four-circle automatic Nonius diffractometer by means of Zr-filtered Mo-K, radiation. A single crystal of dimensions 0.1 x 0.3 x 0.4 mm was used and data collected by the moving-crystal-moving-counter technique with a variable scan angle (0.8 + 0.35tanO)".In the range of 28 0.2-44", 1416 reflexions were measured, of which 690 having I 22.50 (I)were considered observed. Data were correc- ted for Lorentz and polarisation effects, but not for absorp- tion or extinction. All calculations were carried out with the X-Ray '76 system of crystallographic programs 13 implemented and extended by the local versions. The structure was solved by use of MULTAN.14 The phase set with the highest COMB FOM (3.693) gave an electron-density map from which all carbon atoms could be identified. The structure was refined by block-diagonal least-squares, first isotropically (R 0.113)then anisotropically (R 0.087).The 12 hydrogen atoms, located from a difference-Fourier map, were added ; their co-ordinates were included in the refinement, but their thermal para- meters were restricted to a value of B 8 piz. Refinement was continued until convergence: R 0.038 for 690 observed da.ta. The maximum shift in the last cycle was 1.40; the maximum peak height in the final difference-Fourier map was 0.10 ek-3. Thermal parameters for the carbon atoms and observed and calculated structure factors have been deposited as Supplementary Publication No. SUP 22379 (10 pp., 1 * The space-group setting used is obtained from the standard one by interchanging b and c; equivalent positions, apart from those generated by the centre of symmetry, are: x,y,z; Q + x, --y, 3 -r; Q -x, & + y, -2; -x, p -y, Q + z.Final fractional co-ordinates of the carbon atoms ( x lo4), with estimated standard deviations in parentheses Atom X Y z C(1) -45(5) 2 619(4) 193(2) C(2) -610(5) 2 611(3) 765(2) C(3) -1 203(5) 2 581(4) 1291(2) C(4) -1 903(5) 2 542(4) 1832(2) C(5) 963(5) 3 418(3) -76(2) C(6) 1324(5) 3 374(3) -696(2) C(7) 2 280(6) 4 127(4) -963(2) (78) 2 889(6) 4 933(3) -631(2) C(9) 2 541(6) 4 988(3) -I6(2) C(10) 1593(5) 4 237(3) 256(2)-1 732(5) 3 296(3) 2 319(2) :::;; -755(5) 4 175(3) 2 247(2) C(13) -584(6) 4 867(3) 2 716(2) (214) -1 426(6) 4 709(3) 3 252(2) C(15) -2 405(6) 3 850(3) 3 328(2) -2 562(6) 3 146(3) 2 863(2) RESULTS AND DISCUSSION The atom numbering scheme is shown in Figure 1 and the molecular packing in Figures 2 and 3, viewed in the direction of a and b respectively.It can be seen that the molecule is in a cis-configuration. It is concluded that the coupling of the two vinyl groups of (Z)-2-phenyl-l- (methy1thio)vinylcuprate occurs via an extremely TABLE2 Final fractional co-ordinates for the hydrogen atoms (X 103) Atom X Y Z H(1) -44(5) 198(3) -9(2)H(4) -272(5) 194(3) 195(2) H(6) 71(4) 279(3) -91(2) H(7) 257(5) 405(3) -141(2) H(8) 368(4) 546(3) -83(2) H(9) 314(4) 556(2) 23P)H(10) 125(4) 426(3) 69(2) H(12) -3(4) 424(3) 183(2) W13) 18(4) 554(3) 264(2) W14) -121(4) 518(3) 360(2) W16) -324(4) 372(3) 370(2) H(16) -339(4) 254(3) 291(2) stereospecific mechanism with the formation of cis-1,4-diphenylbutatriene. The cis-geometry of (1)shows that catalytic hydrogenation of the inner double bond of this cumulenic system occurs in a cis-manner.The addition * See Notice to Authors No. 7 in J.C.S. Perkin 11,1978, Index issue. 1979 425 FIGURE Projection of the structure of (1)along a. Molecules with centres of gravity on the same x level are drawn similarly2 TABLE3 Interatomic distances (A) (a)Involving C C(l)-C(2) 1.3 43 (6) 1.256(6) C(3)-C(4) 1.322 (6) 1.446(6) 1.402( 6) 1.379(7)c(5)-c(6) 1.372(7) 1.388(7)C(7)-C(8) C(9)-C(lO) 1.377(6) 1.390(6)C(4) -C( 11) 1.462(6) 1.39 7 (6) C(12)-C( 13) 1.381(6) 1.3 79 (7) C(14)-C(15) 1.378(6) 1.383(6) C( 16)-C ( 1 1) 1.389 (6) (b) Involving H C(1)-H(l) 1.09(3) C(4)-H(4) 1.06(4) C(6)-H( 6) 1.02(3) C(7)-H( 7) 1.03(4) C(8)-H( 8) 1.04(3) C(9)-H(9) 1.04( 3) C(10)-H( 10) l.OO(3) C(12)-H(12) 1.08(3) C( 13)-H( 13) 1.08(3) C(14)-H(i4) o.99(4) C(15)-H(15) 1.08(4) C( 16)-H( 16) 1.04(4) (a) of ethyl cuprate (3) must be either trans or must follow another route leading to the adduct (4).Bond distances are listed in Table 3 and bond angles in Table 4. In the butatriene chain the central C=C (sfl-sfl) bond is 1.256(6) A, the terminal C=C (S+S$~) bonds are 1.343(6) and 1.322(6) A. These values com- pare reasonably well with 1.26072) and a mean value of 1.348(3) A respectively, found in a low-temperature X-ray diffraction study on tetraphenylbutatriene (6)l7 and with data for other butatrienes quoted in ref. 17. The chain, as can be inferred from the bond angles, deviates significantly from linearity and is bent.Also a slight departure from planarity of the butatriene skeleton is found (a planar D2hconfiguration is adopted in an electron-diffraction and spectroscopic study on tetra-fluorobutatriene 18919). These distortions are also present > ' :3.m ;(&,I 1 I ° I 1 / (b) / I - r - I I I 13.876 I 0 I ' I (-)I2 2'2 If FIGURE (a) Projection of the butatriene skeletons in (1)on the plane through the butatriene chains [(OlO) plane], which are 4. stacked in the [loo] direction. (b) Projection of the butatriene skeletons in (6) on the plane through the butatriene chains [nearly parallel to (OlO)] which are stacked in the [OOl] direction 426 in (6).17 The phenyl groups are rotated out of the C(5) ,C(l)-(4),C(ll) plane ; pertinent torsion angles are 6.2" for the C(5)-(10) phenyl ring and 0.4"for the C(l1)-(16) ring.Corresponding torsion angles in (6) are 4I Q FIGURE Projection of the structure of (1)along b. Jfolecules3 with centres of gravity on the same y level are drawn similarly appreciably larger owing to intramolecular overcrowding. In spite of this difference in the molecular shape in the structures of (1) and (6), the butatriene chains are arranged similarly, vix. mutually parallel. In (1) the TABLE4 Bond angles (") (a)Involving C C(5)-c ('y-C( 2) C(2)-C( J) -c (4) C(1)-C (5)-C (6) C( 6)-C (7) -C( 8j C(8)-C( 9) -C ( 10) C(4)-C( 11)-C( 12) C(l2)-C( 13)-C(14) C(14)-C( 15)-C( 16) C(16)-C ( 11)-C (4) C( 10)-C(5)-C( 1) 125.5(4) 17 7.0 (5) 119.2(4) 120.9 (4) 120.1(4)122.7 (4) 121.3 (4) 119.9(4) 120.1 (4) 119.8(4) C(1)-C( 2)-c(3) C(7)-C(8)--C(9)C(9)-C( 10j-c(5) C(11)-C( 12)-C( 13) C( 13)-C( 14)-C( 15) C(3)-C(4)-C( 11) C(5)-C (6)--C(7) C(10)-C( 5)-C( 6) C(15)-C(16)-C(11) C(16)-C(l1)-C( 12) 177.I(5) 126.8 (4) 120.3( 4) 119.4(4)121.2(4) 118.1(4)120.4( 4) 120.3(4)120.4(4) 118.9(4) jb) Involving H C(5)-C( 1)-H( 1 j C(3)-C(4)-H(4)C (5)-C( 6)-H (6)C( 6)-C( 7)-H (7) C( 7)-C (8)-H (8)C( 8)-C(9)-H (9) C( 9)-C(10)-H( 10) C(11)-C( 12)-H (12)C(12)-c( 13)-H (13) C( 13) -C( 14)-H( 14) C(14)-C(15)-H(15)C(15)-C (16)-H (3.6) 119(2)122(2) 113(2) 120(2) 117(2)123(2) 118(2) 117(2) 118(2)119(2)125(2) 119(2) H(1)-C( 1)-C( 2)H(4)-C (4) -C ( 1 1) H(6)-C( 6)-C (7) H(7)-C(7)-C(8)H(8j-C( 8)-C( 9) H(9)-C( 9)-C ( 10)H(1O)--C(lO)-C(5)H(12)-C(12)-C( 13)H( 13)-C( 13)-C( 14) H(14)-C(14)--C( 15) €€(15)-C( 15)-C( 16)H( 16)-C( 16)-C ( 11) 1l6(2) 126(2) 112(2) l21(2)120(2j122(2) 115(2)122(2)122(2) 121(2j 121(2) 115(2) J.C.S.Perkin II central C=C bond makes contacts with the terminal C=C bonds, while in (6) only contacts between the terminal C=C bonds are present. These arrangements can best be inferred from Figure 4. The crystal structure of the photodimer product of (6) is known 2o and the formation of this compound can be understood from the packing of the butatriene chains. There is only one independent plane-to-plane contact between phenyl rings C(5)--C(10) at x,y,z and C(5') --C(l0') at -x, 1 -y,-2 with an interplanar distance of 3.38 A and a centre-to-centre distance of 4.08 A.Other phenyl-group interactions consist of C --.C, C ---H, and H * -H contacts with normal values. [8/%46 Received, 13th February, 19781 REFERENCES M. Murray in Houben-Weyl, ' Methoden der Organischen Cheniie,' Thieme, Stuttgart, 1977, vol. 5/2a, p. 963. 2 T. Yoshida, R. M. Williams, and 15. N. Negishi, J. Arne),. Chem. Soc., 1974, 96, 3688. H. Westmijze, J. hfeijer, and P. Vermeer, Tetvahedmn Letters, 1975, 2923. G. H. Posner, Org. Reactions, 1972, 19, 1. J. F. Normant, Synthpsis, 1972, 63,80. 6 J. F. Normant, G. Cahiez, M. Bourgain, C. Chuit, and J. Villieras, Bull. Soc. chzm. France, 1974, 1656. H.Westmijze, J. Meijer, H. J. T. Ros, and P. Vermeer, XPC.TYav. chim., 1976, 95, 299. 8 H. Westmijze, J. Meijer, H. J. T. Bos, and P. Verrneer, Rec. Tvav. chim.,1976, 95, 304. @ A. P. G. Kieboom and F. van Rantwijk, ' Hydrogenation and Hydrogenolysis in Synthetic Organic Chemistry,' Delft Xrniversity Press, 1977. lo H. Gutman and H. Lindlar, ' Chemistry of .\cetylencs,' ed. H. G. Viehe, Marcel Dekker, New York, 1969, ch. 6. l1 M. F. Shostakovskii and A. V. Rogdanova, ' The Chemistry of Diacetylenes,' Wiley, New York, 1974, p. 144 l2 U. Vogeli and W. von Yhilipsborn, Ovg. iWagnr.tzcResonance, 1975, 7, 617. l3 J. M. Stewart, The X-Ray program system, version of 2976, Technical Report TK 446, Computer Science Center, University of Maryland, College Park, hlaryland, U.S.A. l4 G. Germain, P. Main, and M. $1. Woolfson, Actn Cvyst 1971 A27,368. l5 D. Cromer and J. Mann, Ada Cryst., A24, 321. l6 R. F. Stewart, E. R. Dayidson, and W. T. Simpson, J. Chem. Phys., 1965, 3175. l7 2. Berkovitch-Yclhn and L. Leiserowitz, Acta Cvyst., 1977, B33, 3657. l8 A. Rlmenningen, G. Gundersen, A. Borg, M. Granberg, and F. Karlsson, Acta Chem. Scand., 1975, A29,395. F. A. Miller, A$@. Sfiectvoscopy, 1975, 29, 461. 2o 2. Berkovitch-Yellin, M. Lahsv, and L. Leiserowitz, J. Anzer. Chenz. Soc., 1974, 96, 918.
ISSN:1472-779X
DOI:10.1039/P29790000423
出版商:RSC
年代:1979
数据来源: RSC
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