792 J.C.S. Perkin I1 ,I -Diphenylalkenes. Part 1V.l Carbonation and Aldol Addition t Reac-tions of I ,I -Diphenylpropenyl AnionsBy Richard Boyce, William S. Murphy,' and Edward A. O'Riordan, Department of Chemistry, UniversityCollege, Cork, IrelandA series of carbonyl compounds, were allowed to react wth carbanions of the type Ph,C=CHxCHR- inliquid ammonia. Exclusive attack a t C-3 was observed. p-Nitrobenzaldehyde reacted by an alternative pathway ;carbanion dimerisation occurred. Carbonation reactions had the same orientation as had the aldol addition re-actions. Preliminary results suggest an initial attack a t C-1 followed by rearrangement to the C-3 carboxylateproduct.IN Part I1 of this series we noted that the orientationof the reactions of 1 ,l-diphenylpropenyl anions withalkyl halides can be predicted by the principle of leastmotion (PLM) .The least stable product predominated.The behaviour of 1,1,3-triphenylpropenylsodium, theexception to PLM, was rationalised by a combination ofelectronic and steric effects. We have now undertakena survey of the addition reactions of 1,l-diphenylpro-penyl anions to aldehydes and ketones in liquid ammonia.Reactions of alkyl substituted ally1 Grignard reagentswith ketones have been extensively studied4 and thesensitivity of the reaction to steric factors noted.4 Thereactions of phenylallylmagnesium bromide and phenyl-allylsodium have also been investigated.5 For ex-ample, it was noted that whereas acetone reacted withbeen disproved.' Such a transition state for the analo-gous reactions of phenylallylsodium in liquid ammoniaseems improbable.*We therefore anticipated that aldol addition reactionsof 1, l-diphenylpropenyl anions (1 a-c), Scheme wouldoccur exclusively at C-3 and override the effects of thehigher negative charge on C-1 in contravention ofPLM.1,2 We find that one isomer only is formed (Tablel), the product of C-3 attack (2), Scheme.From ourinvestigations l s 2 of the reactions of these anions (la+)with alkyl halides, it appears that C-l is more nucleo-philic than C-3. The possibility therefore arises that theinitial kinetically controlled attack by the carbonylcompound at C-1 is followed by a rearrangement to themore stable C-3 isomer (Scheme). We tested thisPhCH===CH=CHd-Na+ 7 PhCH=CH-CH2-CPh,0H1 2 3 bsol;phenylallylsodium to give a mixture of isomers, benzo-phenone reacted exclusively at C-3.5 A sixmemberedtransition state proposed6 for the reactions of allylicGrignard reagents with carbonyl compounds, has nowt We propose ' aldol addition ' to mean the reaction of a car-banion (or equivalent) or an enolate anion with an aldehyde orketone without loss of water.This reaction title is preferable toaldol condensation, which implies loss of water, and shouldremove ambiguity noted by a referee.l Part 111, W. S . Murphy, R. Boyce, and E. A. O'Riordan,Tetrahedron Letters, 1971, 4157.R. Boyce, W. S. Murphy, and K. P. Klein, J . C . S . Perkin I ,1972, 1292.J. Hine, J . Org. Chew., 1966, 31, 1236.M.Cherest, H. Felkin, and C. Frajerman, Tetrahedron Letters,1971, 379, 383; A. J . Kresge and V. Nowlan, ibid., p. 4297.hypothesis by maintaining the reaction of benzophenonewith 1 ,l-diphenylbutenylsodium at -78". The re-action was quenched at -78" after 6 min. No C-1addition product was observed. Further evidenceagainst the transient involvement of a C-1 adduct isR. H. DeWolfe, D. E. Johnson, R. I. Wagner, and W. G.Young, J . Amer. Chem. SOG., 1957, 79, 4798.W. G. Young and J. D. Roberts, J . Amer. Chem. SOG.,1946, 68, 649.7 H. Felkin and C. Frajernian, Tetrahedron. Letters, 1970, 1045;H. Felkin, Y . Gault, and G. Roussi, Tetrahedron., 1970, 26, 3761.8 D. J. Cram, ' Fundamentals of Carbanion Chemistry,' NewYork, Academic Press, 1965, p.32.R. B. Bates, S. Brenner, C. M. Cole, E. W. Davidson, G. D.Forsythe, D. A. McCombs, and A. S. Roth, J . Amer. Chem. SOG.,1973, 95, 9261974suggested by the results of Kaiser and Hauserlo whonoted that the reverse aldol reaction of sodium l,l,Z,Z-tetraphenylethoxide in liquid ammonia is complete onlyafter 4 h.TABLE 1Aldol addition reactions in liquid ammoniaCarbonyl compoundBenzophenoneFluorenoneAcetophenoneBenzaldeh ydeBenzophenoneFluorenoneAcetophenoneBenzaldeh ydeBenzophenoneBenzophenoneBenzophenoneFluorenoneAcetophenoneBenzaldehydeBenzophenone,I Isolated yields.mined by n.m.r.Carbanion Metal cation Yield () a#aNa+ 97Na+ 71Na+ 36Na+ 40Na+ 50Na+ 36Na+ 44Na+ 33K+ 0Na+ 0Li+ 48Li+ 25Li+ 16Li+ 16Li+ 0(14(14(14(la)(1b)(W(lb)(Ib)(1c)(W(14(1c)(W(W(4)b C-3 Product formed exclusively as deter-No product could be isolated from the reaction of (lc)when the counter-ion was either sodium or potassium.Ph2C=I--CH==CHR1-M+ + R*RsC=O amp;e Ph,C-CH=CHRl1 2 3a, R1 = Hb, R1 = MeC, R1 = PhPh$=CH-CHR' I R*R2COH(2)SCHEMEThe success achieved with lithium (Table 1) is probablydue to its greater ability to co-ordinate to oxygen.llExpt.no.12346678910suggest that both equilibria (Scheme) are unfavourablein this case.In the reactions of benzaldehyde with the anions(la+) the product was invariably an oil even in thecase of (la) where formation of diastereoisomers is notpossible.9-Nitrobenzaldehyde was used in the hopethat crystalline products would be formed. We ob-served dimerisation of (la) ; no aldol addition occurred.The red colour of (la) was replaced by green 12c as 9-nitrobenzaldehyde was added. The green colour per-sisted until the reaction was quenched. By analogywith other results 19b we suggest an electron transfermechanism.Since the aldol addition reactions of (la-c) occurredexclusively at C-3, we hoped that this reaction followedby dehydration would provide a simple synthetic routeto 1 ,l-diphenylalka-l,3-dienes. Efficient dehydrationTABLE 2Dehydration of carbinolsYieldCarbinol Product (Yo) aPh,C:CH*CH,C(OH)Ph, Ph,C:CH*CH:CPh, 96Ph,C:CH*CH,*C(OH)PhMe Ph,C:CHCH:CPhMe b 70Ph,C:CH*CH (Me) *C (OH) Ph, Ph,C:CH*C(Me) :CPh2 90Ph,C:CHCH,C(OH)=BP 0 Ph,C :CH CH :C=PB 0 93a Isolated yields. b Isomerically pure.0 BP = Biphenyl-2,2'-diyl.could be effected in four cases only (Table 2). The re-maining carbinols gave complex product mixturesunder a wide variety of dehydrating conditions.Next, the carbonation reactions of the anions (la-c)were investigated. As we have noted previously,13 theefficiency of carbonation under these conditions is inpart dependent on the metal cation: K+ Na+ Li+.With one exception, the orientation followed the samecourse as the aldol addition reactions. However, initialTABLE 3Carbonation reactionsMetal cationK+Na+Li+K+K+Na+Li+K+Na+Li+Recoveredhydrocarbon679894654893992765Acidyield () a323349767334Acidic products(yo ratio) bc- 1 c-3'10047 53100100100100Isolated yields.a Determined by n.m.r.Aldol additions of the 1 ,l-(biphenyl-2,2'-diyl)propenylcarbanion (4) were unsuccessful. The colour of the anionwas not discharged by the addition of a carbonyl com-pound, and no product was detected. These resultslo E. M. Kaiser and C. R. Hauser, Chem. and Ind., 1965, 1299.l1 E. 34. Kaiser and C . R. Hauser, J. Amev. Chem. SOG., 1967,89, 4567.kinetically controlled attack at C-1 followed by reversaland recombination at C-3 (compare the Scheme) isfeasible. Tentative evidence for this mechanism isla (a) N. Kornblum, R. E. Michel, and R. C. Kerber, J.Amer.Chem. SOG., 1966, 88, 5660, 6662; (b) G. A. Russell and W . C .Danen, ibid., 1966, 88, 6663; (G) E. M. Kaiser, ibid.. 1967, 89,3669.l3 W. S. Murphy and C. R. Hauser, Chem. and Ind., 1969, 832J.C.S. Perkin Iprovided by entries 4 and 5 (Table 3). When carbona-tion was quenched after 15 min, a mixture of C-3 andC-1 isomers was isolated (entry 4). When carbonationwas allowed to go to completion and the resultingethereal suspension of the sodium salt left overnight, theC-3 isomer only was detected.EXPERIMENTALGeneral.-Techniques and apparatus were the same asdescribed previously.lsAldol A ddition Reactions. General Procedure.-Reactionof benzophenone with 1,l-diphenylpropenylsodium (la). A500 ml three-necked flask with a cold-finger condenser con-taining dry ice and acetone and a pressure equalising drop-ping funnel was maintained under a positive pressure of dry,oxygen-free nitrogen.The reaction solution was stirredmagnetically throughout. Anhydrous commercial liquidammonia (300 ml) was further dried by the addition of smallpieces of sodium until the blue colour persisted, and acrystal of iron(n1) nitrate was then added. The blue colourdisappeared, and 1, l-diphenylpropene (4.85 g , 0.025 mol)in dry ether (50 ml) was added. The ensuing red solutionwas stirred 30 min and a solution of benzophenone (5.0 g,0.0275 mol) in dry ether (50 ml) was added. The red colourwas discharged immediately. The white suspension wasstirred 1 min and then poured onto a stirred solution ofammonium chloride (4.7 g, 0.088 mol) in liquid ammonia(200 ml) .The ammonia was gradually replaced by ether,and water (100 ml) was added. The ethereal layer wasevaporated to a white solid (9-20 g, 97.5). One isomeronly (2; R1 = H , R2 = R3 = Ph) was detected in thiscrude product (n.m.r.) . Recrystallisation from hexane-ethanol yielded 1,1,4,4-tetraphenylbut-3-enol (8.2 g, 87)m.p. 136.5-138' (lit.,l* 122.5-123.5') (Found: C, 89.25;H, 6-65. Calc. for C2,H2,0: C, 89-3; H , 6.4); 231and 252 nm (E 11,200 and 11,400); T 2-55-2.9 (m, 4 x Ph),3.94 (t, J 7-5 Hz, =CH), 6.85 (d, J 7.5 Hz, CH,), and 7.67 (s,OH).Dehydration was effected by heating 1,1,4,4-tetraphenyl-but-3-en01 (2-0 g, 0.005 mol) with 25 sulphuric acid (100ml) and acetic acid ( 5 ml) under reflux 24 h.After cooling,the solution was extracted with ether. The ether wasevaporated off to yield 1,1,4,4-tetraphenylbuta-1,3-diene(1.92 g, 96) m.p. 202-203.5O (lit.,15 192-193") (Found:C, 93-85; H , 6.35. Calc. for CZ8Hz2: C, 93-85; H , 6.15);Am=. 227, 248, and 339 nm (E 17,600, 18,000, and 27,200);T 2-53-2-9 (m, 4 x Ph), and 3.2 (s, 2 x H).Reaction of 1,l-diphenylPropenylsodium (la) with aceto-fihenone. The crude product was a yellow oil. It con-sisted of one isomer (2; R1 = H, R2 = Me, R3 = Ph) andstarting materials (n.m.r.). A sample (2 g) was purified bydry column chromatography (95 : 5 hexane-ether) to givethe viscous 2,4,4-triphenylpent-4-en-Z-ol (0.69 g, 35)(Found: C, 84.25; H , 7-3. C23HZ2O requires C, 84.75;H , 7.0); amp;= 253 nm (E 9200); T 2.6-3-2 (m, 3 x Ph),and 8.62 (s, Me).The carbinol (0.4 g, 0.001 mol) was dehydrated as de-scribed above. 1, lJ4-Triphenylpenta-1,3-diene (0.28 g, 70)was isolated, m.p.122-123' (from hexane) (Found: C ,92-15; H , 6-85. C2,H2, requires C, 93.25; H, 6.75) : amp;=244 and 320 nm (c 3000 and 5000) ; T 2.5-2.9 (m, 3 x Ph),l4 W. J. Wasserman and M. J. Kloetzel, J . Amer. Chern. SOC.,1963, 75, 3036.4-09 (t, J 8-0 Hz, q H ) , 7.5 (a, J 8.0 Hz, CH,), 8.07 (s, OH),2-95 (d, J 11.5 Hz, =CH), 3.42 (d, J 11.5 Hz, =CH), and 7.71Reaction of 1, l-dip~enylpropenylsodiu~z (la) with fluoren-one. An excess (120) of fluorenone was used. Oneisomer only was detected by n.m.r. (2; R1 = H, RZ + R3 =biphenyl-2,2'-diyl). A portion (5 g) of the crude oilyproduct was purified by means of Girard's reagent.9-(3,3-Diphenyl~rop-2-enyl)~uoren-9-01 (2.2 g, 7 1 ) was isolatedas a white solid, m.p. 114-116" (Found: C, 90.0; H, 6.0.C28H22O requires C, 89.85; H, 5.9); Lx 238, 259, and301 nm (E 16,700, 18,600, and 9800) ; T 2.2-3-25 (m, 2 x Ph + fluorene), 4-25 (t, J 8.5 Hz, =CH), 7.06 (d, J 8.5 Hz, CH,),and 7.95 (s, OH).The carbinol (0.76 g, 0.002 mol) was dehydrated asdescribed above. The yellow solid 4,4-(biphenyl-2,2'-diyl)-l,l-diphenyZbuta-l,3-diene (0.67 g, 93) m.p. 188-189"(Found: C, 94-65; H , 5.9. C28H2o requires C, 94.4; H,5.6); Am. 243, 262, 272, and 390 nm (E 14,200, 10,600,7600, and 16,000); T 2.0-2.9 (m, 2 x Ph + fluorene +2 x =CH).Reaction of 1,l-diphenylpropenylsodium (la) with benzalde-hyde.The crude product was a yellow oil. One isomer(2; R1 = R2 = H , R3 = Ph) only was detected (n.m.r.).Of this a portion (2 g) was purified by dry column chromato-graphy. The light yellow gum 1,4,4-trifihenylbut-3-enoZ(0.8 g , 40) was isolated (Found: C, 88.1; H, 6.95.C2,H2,,O requires C, 88.0; H, 6.65); hx 252 nm (E11,600); T 2.45-3.15 (m, 3 x Ph), 3.92 (t, J 7.5 Hz, =CH),5-35 (t, J 7.0 Hz, CH), and 7-48 (t, J 7.0 Hz, CH).Reaction of 1,l-diphenylbutenylsodium (lb) with benzo-phenone. The crude product was a gum. One isomer only(2; R1 = Me, R2 = R3 = Ph) was present (n.m.r.). Aportion (2 g) was purified by dry column chromatography(95 : 5 hexane-ether) . 2-MethyL1,1,4,4-tetraphenylbut-3-enol (0.98 g, 50), m.p.1O9-11lo (hexane) was isolated(Found: C, 89.0; H, 7.05. C2,H2,0 requires C, 89-25; H,6.65); amp; 254 nm (E 13,600); 7 2-5-3.2 (m, 4 x Ph),3-91 (d, J 11 Hz, =CH), 6.53 (oct., J 11 and 7.5 Hz, CH),7.63 (s, OH), and 8.9 (d, J 7.5 Hz, CH,).Dehydration of this carbinol (0.2 g) was effected as de-scribed above. The white crystalline 2-methyZ- 1,1,4,4-tetraphenyZbuta-1,3-diene, (0.18 g, 90) m.p. 137-138"(ethanol) was isolated (Found: C, 93.45; H, 6.55. C29H24requires C, 93-5; H, 6.5) ; amp;= 243 and 317 nm (E 16,800and 14,000); "i 2-55-3.0 (m, 4 x Ph), 3.36 (s, =CH), and8-36 (s, Me).Reaction of 1, l-difihenylbutenylsodium (lb) with acetophen-one. Only one posi-tional isomer (2 ; R1 = R2 = Me, R3 = Ph) was detected byn.m.r.Of this a sample (2 g) was purified by dry columnchromatography (95 : 5 hexane-ether) . 3-Methyl-2,5,5-tri-phenylpent-4-en-2-01 (0437 g, 44) was isolated as a whitesolid, m.p. 100-101" (hexane) (Found: C, 86.85; H , 7-9.CZ4Hz40 requires C, 87.8; H , 7.3); 252 nm (E13,000); T 2.2-3.1 (m, 3 x Ph), 4.02 (d, J 11.5 Hz, =CH),7-32 (oct., J 11-5 and 6.0 Hz, CH), 8.29 (s, OH), 8.46 (s, Me),and 8.96 (d, J 6-0 Hz, Me). The ratio of diastereoisomerscould not be determined from this spectrum.Reaction of 1,l-diphenylbutenylsodium (lb) with jluorenone.Excess of fluorenone (100) was used. This excess wasremoved from the crude oily product by the Girard reagent.One isomer only (2; R1 = Me, R2 + R3 = biphenyl-2,Z'-diyl) was detected (n.m.r,).A portion (1-52 g) of the15 Y . Zalkind and A. Kruglov, J . Russ. Phys. Chew. SOC., 1929,61, 803.(s, Me,).The crude product was a yellow oil1974 795product so obtained was purified by dry column chroma-tography. 9- ( l-Methy2-3,3-diphenylpro~-2-enyl)fluoren-9-02(0.86 g , 33y0), m.p. 117~5-118~5", was isolated (Found: C,89.4; H, 6.3. C,,H,,O requires C, 89.6; H, 6.2); amp;238, 259, and 307 nm (E 16,100, 15,000, and 2900); T 2.25-3.20 (m, 2 x Ph + fluorene), 4.38 (d, J 11.5 Hz, H), 6.8(oct., J 11-5 and 7 Hz, CH), 7.88 (s, OH), and 8.92 (d, J 7Hz, Me).Reaction of 1, l-diphenylbutenylsodium ( lb) with benzalde-hyde. The crude product (3-61 g, 92) was an oil whichcontained one positional isomer (2; Rf = Me, R2 = H,R3 = Ph) only (n.m.r.) .A portion (2 g) was purified bydry column chromatography and then on p.1.c. Pure2-methyl-1,4,4-triphenylbut-3-enoZ (0.72 g) was thus isolatedas a yellow gum (Found: C, 87.45; H, 7.3. C2,HZzO re-quires C, 87-8; H, 7.0) ; amp;= 252 nm (E 12,000) ; T 2.60-3.25 (m, 3 x Ph), 4.08 (d, J 10 Hz, H), 4.25 (d, J 10 Hz,=CH, overlapping), 5.65 (dd, J 5.5 Hz, CH), 7.12 (s, OH),7.49 (dec., AMNX,, JAX LO, JAM 11-5, J M X 9 Hz, CH), 9.05(d, J 7 Hz, Me), and 9.22 (d, J 7 Hz, Me). This spectrumsuggests that the product is a diastereoisomeric mixturein the ratio of 6 : 10. This ratio is based on the relativeareas of the two methyl doublets. The assignments aretentative and are derived from a comparison with relatedsystems .I6Reaction of 1 , 1,3-triphenylpropenyl-lithium ( lc) with benzo-phenone.The crude product (5.85 g) was an oil whichcontained one isomer (2; R1 = R2 = R3 = Ph) only(n.m,r.). A portion (2 g) was purified by dry columnchromatography and recrystallised from hexane-ethanol togive pure 1,1,2,4,4-pentaphenylbut-3-enol (0.95 g , 47-5y0),m.p. 140-142" (Found: C, 89.9; H, 6.6. C,amp;amp; re-quires C, 90.2; H, 6.2) ; amp;, 245 and 265 nm (E 9800 and6900) ; T 2.45-3.30 (m, 5 x Ph), 3-46 (d, J 11 Hz, =CH),5-5 (d, J 11 Hz, CH), and 7.46 (s, OH).Reaction of 1,1,3-triphenylpropenyLlithium (lc) withacetophenone. The crude product (5.19 g ) was an oil whichcontained one positional isomer (2; R1 = R2 = Ph, R3 =Me) only (n.m.r.). A sample (2 g ) was purified by drycolumn chromatography followed by recrystallisation fromhexane-ethanol to give pure 2,3,5,5-tetrapheny@ent-4-en-2-01 (0.3 g, 15), m.p.1376-140deg; (Found: C, 88.75; H,7.0. C,,Hz6o requires c , 89.25; H, 6.65) ; k= 247 and265 nm (E 12,300 and 8900); T 24-3.2 (m, 4 x Ph), 3.32(d, J 11 Hz, =CH), 6.25 (d, J 11 Hz, CH), 8.05 (s, OH), and8.41 (s, Me). The ratio of diastereoisomers could not bededuced from this spectrum.Reaction of 1,1,3-triphenylpropenyl-lithiu~ (lc) withfluorenone. The crude product (5.79 g) contained oneisomer (2; R1 = Ph, R2 + R3 = biphenyl-2,2'-diyl) onlyaccording to the n.m.r. spectrum. A sample (2 g) waspurified by dry column chromatography and recrystallisa-tion from hexane-ethanol. Pure 9-( 1,3,3-triphenylprop-2-enyl)$uoren-9-o1 (0.5 g, 25) was obtained, m.p.101-103"(Found: C, 90-3; H, 5.9. c,amp;amp; requires C, 90.65; H,6.75); 1- 220, 232, 264, and 312 nm (E 17,100, 16,200,11,000, and 1600); t 2.3-3-4 (m, 3 x Ph + fluorenyl),3.95 (d, J 11.0 Hz, H), 5.95 (d, J 11.0 Hz, CH), and 7.82Reaction of 1,1,3-tri~henylPropenyl-lithium (lc) with benz-aldehyde. The crude product (8.96 g) contained one posi-tional isomer only (2; R1 = R2 = Ph, R3 = H) according tothe n.m.r. spectrum. A sample (2 g) was purified by drycolumn chromatography and recrystallisation from hexane-ethanol. Pure 1,2,4,4-tetraphenylbut-3-enoZ (0.3 g) was(s, OH).isolated as an oil (Found: C, 89-0; H, 6.2. C,,H,,O re-quires C, 89-35; H, 6.4) ; amp;= 220 and 259 nm (amp; 15,800and 12,200); t 2.3-3.5 (m, 3 x Ph), 3.8 (d, J 11 Hz, =CH),5.14 (d, deformed, J 11 Hz, CH), 6.2 (s, -OH, overlapping),and 6-36 (9, deformed, CH).The ratio of diastereoisomerscould not be deduced from this spectrum.Reaction of 1,l-diphenylpropenylsodium (la) with p-nitrobenzaldehyde. 1,l-Diphenylpropene (4.85 g) in drytetrahydrofuran (10 ml) was added to a solution of sodiumamide (0.025 mol) in liquid ammonia (250 ml). A redcolour appeared. This solution was stirred 30 min. p-Nitrobenzaldehyde (4.56 g , 0.03 mol) in dry tetrahydrofuran(50 ml) was then added. The red colour was replaced by agreen colour which persisted. After 30 s the reactionmixture was added to a solution of ammonium chloride(4.7 g) in liquid ammonia (150 ml).The product was thenisolated as described above. The crude product (8.67 g)was an oil. A portion (2 g) was purified by dry columnchromatography to give 1,1,6, g-tetraphenylhexa- 1,5 diene(0-33 g), m.p. 106-107" (lit.,17 108O) Found: C, 93.65;H, 6.95; M , 390 (ebullioscopic). Calc. for Camp;26: C ,93.25; H, 6.75; M , 3861; z 2-60-3.0 (m, 4 x Ph), 3.95(t, J 7.0 Hz, X H ) , 7.72 (s, CH,), and 7-79 (s, CH,).The reaction was repeated using a one-fold excess of p-nitrobenzaldehyde. The reactants were stirred 2 h beforethe reaction was quenched by addition to ammoniumchloride.To astirred suspension of potassium amide (0.025 mol) inanhydrous liquid ammonia was added 1,l-diphenylpropene(4.85 g, 0.025 mol) in dry ether (30 ml). The red solutionwas stirred 30 min and then poured in a nitrogen atmosphereonto a large excess of powdered carbon dioxide.After 2 h,water (50 ml) was added. The aqueous layer was acidifiedand a white precipitate (2.0 g, 32) was obtained. Then.m.r. indicated that one isomer only was present. Onerecrystallisation from acetic acid afforded 4,4-diphenylbut-3-enoic acid (Found: C, 80.65; H, 5.75. Calc. for Cl6HI4O2:C, 80.55; H, 5.85); m.p. 116-117" (lit.,18 112-113');amp; 252 nm (E 12,500); T -0.8 (s, OH), 26-2-98 (m,2 x Ph), 3.69 (t, J 7.5 Hz, =CH), and 6.72 (d, J 7.5 Hz,Carbonation of 1, l-diphenylbutenylpotassium (lb) . Thereaction was carried out as described above. 2-Methyl-4,4-diphenylbut-3-enoic acid (3-1 g, 49) was isolated(Found: C, 80.85; H, 6.4. C17H1,OZ requires: C, 80.95;H, 6*3y0), m.p. 182-184"; Lx 215 nm (E 13,600); T-0.85 (s, OH), 2.5-2.9 (m, 2 x Ph), 3-55 (dd), 4.82 (dd),and 5.10 (dd, ABX,, JAB 16.0, JAX 6.0, and J B X 2.0 Hz),and 8-22 (dd, J 6.0 Hz, Me).When the carbonation reaction was allowed to standovernight before work-up a solid (3.12 g, 50) was isolated(Found: c , 81-2; H, 6-15. Calc. for Cl7Hl6O2: c, 80.95;H, 6-3), m.p. 100-103deg;; A,, 252 (E 9000); z -0.85 (s,OH), 2-4-24 (m, 2 x Ph), 3.4 (dd), 4.72 (dd), and 5.0 (dd,ABX,, JAB 16.0, JAX 6-0, andJBx 2-0 Hz), 3-74 (d, J 10.0 Hz,=CH of 3-addition product), 6.5 (dd, J 6.5 Hz, Me of l-addi-tion product), and 8.55 (d, J 7-0 Hz, Me). Integration ofthe n.m.r. indicated that 2-methyl-4,4-diphenylbut-3-enoic acid and 2,2-diphenylpent-3-enoic acid were presentin the ratio 53 : 47.The yield of dimer was unchanged.Carbonation of 1,l-di~henyl~ropenylpotassium (la).CH,).l6 L. M. Jackman and S. Sternhell, ' Applications of NuclearMagnetic Resonance Spectroscopy in Organic Chemistry,'Pergamon, London, 1969, p. 163.A. W. Schmidt and C. Hartmann, Ber., 1941, 74B, 1326796 J.C.S. Perkin ICarbonation of 1,1,3-t~i~henyl~rop~n~~~o~assizcnz (lc). (Found: C, 83.8; H, 5-9. Calc. for C,,H,,O,: C, 83.9;The reaction was carried out as described for (la). H, 5.7), m.p. 161-163' (1it.,l8 166-167'); amp; 255 nmTriphenylbut-3-enoic acid (3.76 g, 48) was isolated (E 17,881); T -1.05 (s, OH), 2.4-3-05 (m, 3 x Ph), 3.37(d, J 11.0 Hz, H), and 5.52 (d, J 11.0 Hz, CH).Annalen, 1929, 473, 1. 3/2248 Received, 1st November, 197312,4,4-l8 K. Zeigler, F. Crossman, H. Kleiner, and 0. Schafer
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