Aust. J. Chem.

, 1978, 31, 341-6

Some Friedel-Crafts Reactions of y-Butyrolactone

Cheryl A. Kerr and Ian D. Rae

Department of Chemistry, Monash University. Clayton, Vic. 3168.

Abstract Benzene reacts with y-butyrolactone and aluminium chloride to give tetralone, but no detectable amount of 3-methylindan-1-one. p-Dichlorobenzene, p-difluorobenzene and m-dichlorobenzene give exclusively the indanones in good yield. Chlorobenzene gives a mixture of tetralones and indanones in ratio 78 : 22 and the major product of each type arises from alkylation ortho to chlorine. y-Butyrolactone is isomerized to crotonic acid by treatment with excess aluminium chloride at 150" and the indanones probably arise by this route.

Introduction The preparation of tetralone (3,4-dihydronaphthalen-l(2H)-one)from benzene and y-butyrolactone in the presence of aluminium chloride (Scheme 1) was reported1 by Truce and Olsen in 1952. We have explored the scope of this annellation reaction because the tetralones which might be prepared would be useful precursors for a range of substituted naphthalenes. Despite the publicity given to this high-yielding reaction,' it does not seem to have found very much application nor to have attracted further investigation.

Results
The reaction of p-dichlorobenzene with y-butyrolactone and aluminium chloride gave the indanone (1) in 84% yield, and the l H n.m.r. spectrum of the crude product showed that no tetralone had been produced. Similarly the difluoroindanone (2) was produced in high yield from p-difluorobenzene, and no tetralone was formed. Indanone (2) had previously been prepared from p-difluorobenzene and crotonic acid.3 At this stage, we repeated the preparation of tetralone from benzene as
Olsen, C. E., and Truce, W. E., J. Am. Chem. Soc., 1952,74, 4721. Olsen, C. E., and Bader, A. R., Org. Synth., 1963, Coll. Vol. IV, 898. Burgess, D. A,, Rae, I. D., Smith, L. K., and Snell, J. D., Aust. J. Chem., 1976, 29, 1435.

C. A. Kerr and I. D. Rae

described by Truce and O l ~ e n , ' ,and examined the l H n.m.r. spectrum of the crude ~ product for evidence (methyl doublet) that some indanone might have formed. None was detected and we place the lower limit of detection at about 2%. With chlorobenzene, a mixture of cyclic ketones was obtained and the 'H n.m.r. spectrum indicated that it contained 78 % tetralones and 22 % indanones. Separation by gas chromatography gave five fractions in the ratio 17 : 5 : 49 : 14 : 15 (order of elution) which were identified as follows. The first was 4-chloro-3-methylindan-I-one (3) which was identified by melting p ~ i n tand analysis of the 270-MHz 'H n.m.r. ~,~ spectrum. Fraction two was an approximately 1 : 1 mixture of 5- and 6-chloro3-methylindan-1-one (compounds (4) and (5) respectively). The resonances of the aromatic hydrogens were mostly separated in the 270-MHz spectrum and analysed nicely for the two 1,2,4-trisubstitution patterns. Fractions three, four and five were identified as tetralones ((6)-(8) respectively) by means of melting points and 90-MHz n.m.r. spectra. In the tetralones, the H 8 signal appeared at much lower field than the others and the analyses of the spectra were quite straightforward. The 6-chloro-3-methylindan-1-one (5) has been reported6 as a liquid but the comparison sample prepared in this work was a low-melting solid. The n.m.r, spectrum of our authentic sample matched the peaks which had been assigned to the 6-chloro compound in the mixture. 3-Methylindan-1-one was nitrated and the 9 : 1 mixture of 6- and Cnitroindanones was separated by fractional crystallization. Reduction to the amine followed by diazotization and reaction with cuprous chloride gave the 6-chloro-3-methylindan-1-one (5). The 5-chloroindanone (4) appears to be new, but proper characterization was not possible because of the small amount and the difficulty of separation or separate synthesis.

m-Dichlorobenzene gave a single product, the indanone (9) which is a known c ~ m p o u n d p-Xylene reacted with y-butyrolactone at 80' or 110' to give a mixture .~ of ketones for which the gas chromatogram showed at least seven peaks. The 'H n.m.r. spectrum showed no sign of the methyl doublet which would characterize an indanone, and the carbonyl absorption in the infrared was at 1675 cm-I with no sign of a
'Friedlanders Fortschritte der Teerfarbenfabrikation' Vol. 16, p. 688; Ger. Pat. 485,309. Mayer, F., Phillips, H., Ruppert, F. W., and Schmidt, A. T., Bey. Dtsch. Chem. Ges., 1928,61, 1966. Braun, J. V., and Heider, K., Ber. Dtsch. Chem. Ges., 1916, 49, 1268.

Some Friedel-Crafts Reactions of 7-Butyrolactone

peak in the indanone position near 1730 cm-l. Butyrolactone itself did not react with aluminium chloride at temperatures below 10O0, but when excess aluminium chloride was used with nitrobenzene as solvent at 150" the lactone was converted into crotonic acid.

Discussion It is plain that the original Truce and Olsen reaction is of rather limited scope. When deactivating substituents, such as halogens, are present on the aromatic ring, there is extensive rearrangement of the C 4 fragment so that 3-methylindan-1-ones are produced. The rearrangement of the alkylating moiety during a Friedel-Crafts reaction is known to occur to a greater extent when the aromatic ring is less reactive,' but the conversion of y-butyrolactone into crotonic acid by aluminium chloride at 1.50" suggests that prior rearrangement of the alkylating agent may also be important in this case. Such rearrangement can explain the formation of 4,7-dihydroxy-3methylindan-1-one from hydroquinone when it was heated with butyrolactone and a mixture of sodium chloride and aluminium ~ h l o r i d e . ~ The temperature of the melt, 180-20O0, is well above that required for the y-butyrolactone-crotonic acid rearrangement. At more modest temperatures, anisole reacts to give y-(4-hydroxypheny1)- or y-(4-methoxypheny1)-butyric acidg which can be cyclized to the tetralone.'' 2-Methoxy-4-methylphenol reacts with y-valerolactone and boron trifluoride etherate to give two tetralones in 23 % overall yield.'' Thus it is only reactive aromatic rings which may be annellated to tetralones, but in many cases redistribution of the ring methyls and dealkylation of methyl ethers are brought about by aluminium chloride.12 Our experience with p-xylene suggests that these reactions will not be preparatively useful when methyl substituents alone are involved. The expected product of this latter reaction, 5,8-dimethyltetralone, has been shown to rearrange to the 5,7-isomer in the presence of A1G1,/HC113 but our mixtures were even more complex. Dealkylation of methyl ethers has been reported in the cases of anisoleg and the methoxy phenol above.ll Truce and Olsenl felt that tetralone formation proceeded by alkylation to give y-phenylbutyric acid as an intermediate. The conversion of m-chlorobenzene into dichloroindanone (9), rather than the alternative 5,7-dichloroindanone, supports this alkylation proposal for the indanone formation also. m-Dichlorobenzene would almost certainly sustain electrophilic attack at the 4-position and hence we identify the initial step as alkylation rather than acylation. This proposal also helps to account for the isomer distribution which we observed for the products, both tetralones and indanones, of the reaction of chlorobenzene with y-butyrolactone. In each case, about 70% of alkylation occurs ortho to the chlorine, i.e, almost indiscriminate ortho-para attack. The same mixture of indanones was obtained when we repeated the reaction of chlorobenzene with crotonic acid and aluminium chloride.14 The
Norman, R. 0. C . , 'Principles of Organic Synthesis' p. 366 (Methuen: London 1968). Bruce, D. B., Sorrie, A. J. S., and Thomson, R. H., J. Chem. Soc., 1953, 2403. Kadyrov, C . S., and Barashkin, V. A,, Zh. Ovg. Khim., 1968, 4, 1302. Birch, A. J., Jaeger, R., and Robinson, R., J. Chem. Soc., 1945, 582. Yuste, F., and Walls, F., Aust. J. Chem., 1976, 29, 2333. 1z Ramadas, S. R., and Sukarman, K. B., Indian J. Chem., 1970, 8,470. l 3 Baddeley, G., J. Chem. Soc., 1944, 232. l4 Ashraf, M. C., Jackson, W. R., and Rash, D., Aust. J. Chem., 1975,28, 197,

C. A. Kerr and I. D. Rae

p values for alkylation of the aromatic ring are known to be small,15e.g. for acetylation, - 9 1; ethylation, - 2.4. A small p value minimizes the substituent contribution

(expressed in its o value) to the reaction rate, and thus high proportions of ortho attack are to be expected in alkylation reactions. Nonetheless, 70 % seems unusually high when compared to the products of ethylation of chlorobenzene in the presence of gallium bromide:I5 ortho, 42 %; meta, 16 %; para, 42 %. By contrast, acetylation of chlorobenzene takes place 99 % in the para position.''

Conclusion
The reaction of y-butyrolactone with aromatic compounds in the presence of aluminium chloride seems likely to give tetralones when the aromatic ring is activated towards electrophilic substitution, albeit with production of mixtures when methyl and methoxy groups are present. From dihalobenzenes, the 3-methylindan-1-ones are produced in good yield. Chlorobenzene is an intermediate case where both tetralones and indanones are produced, and the major products arise from initial alkylation ortho to chlorine. Experimental
Infrared spectra were recorded for paraffin mulls or liquid films on a Perkin-Elmer 257 grating infrared spectrometer. 'H n.m.r. spectra were recorded for dilute solutions in CDC13 on Perkin-Elmer R32 (90 MHz) and Bruker HX270 (270 MHz) spectrometers, the latter at the National N.M.R. Centre, Canberra.

4,7-Dichlovo-3-methylindan-I-one) (I
p-Dichlorobenzene (8 .O g, 0.05 mol), y-butyrolactone (1 .O g, 0.01 mol) and anhydrous aluminium chloride (6.0 g, 0.05 mol) were heated together and worked up as described below for the difluoro (1.8 compound to give 4,7-dichloro-3-methylindan-1-one g, 84% yield) as pale brown crystals, m.p. 95-97" (lit.16 100-101"). N.m.r. spectrum: 1.43, 3H, d, J 7.0; 2.38, IH, dd, J 19.0 and 1.5; 3.06, lH, dd, J 19.0 and 7.5; 3.58, IH, m; 7.27, lH, d, J 8.5; 7.50, lH, d, J 8.5.

Anhydrous aluminium chloride (6.0 g, 0 05 mol) was added, over 5 min, to a solution of y-butyrolactone (1 .O g, 0.01 mol) inp-difluorobenzene (6.2 g, 0.05 mol) and the mixture was heated under reflux for 16 h. The mixture was cooled and mixed with ice and hydrochloric acid, and the product was extracted into methylene chloride (3 x 20 ml). The methylene chloride solution was washed successively with 5% sodium carbonate solution and with water, and dried over MgS04. The solvent was removed under reduced pressure to leave a dark brown solid which was recrystallized (2) from hexane to yield 4,7-difluoro-3-methylindan-1-one (1.3 g, 59% yield) as pale brown crystals, m.p. 41-43" (]its3 46-48"). The infrared and IH n.m.r. spectra were identical with those of an authentic sample.
8

This compound was prepared by the method described above in 61 % yield from y-butyrolactone (1.0 g, 0.01 mol). The m.p. 75.5-76" agreed well with that reported4 (77-80"). N.m.r. spectrum: 1.46, 3H, d, J 7 . 0 ; 2.38, lH, dd, J 1 9 . 0 and 2.0; 3.04, lH, dd, J 19.0 and 7.5; 3.63, lH, m; 7.63,2H, S.
l5 l6

Stock, L. M., and Brown, H. C., Ada Phys. Ovg.Chem., 1963, 1, 35. Braun, W., and Ruske, M., Fr. Pat. 1,377,962, Nov. 6, 1964 (Chern. Abstr., 1965, 62, 7709h)

Some Friedel-Crafts Reactions of y-Butyrolactone

Chlovotetvalones and Zndanones

Chlorobenzene, treated as described for the compounds above, gave a mixture of chloro ketones which was subjected to gas chromatography at 280" on a 20 ft by 318 in. column packed with 20% SE 30 on a support.

This compound was isolated from fraction one as colourless crystals, m.p. 47-47.5" Oit.' 55" and liL4 47'). N.m.r. spectrum: 1.46, 3H, d, J 7 . 0 ; 2.35, lH, dd, J 19.0 and 3.0; 2.95, l H , dd, J 19.0 and 8.0; 3.47, lH, m; 7.35, lH, t, J 7 . 5 ; 7.53, lH, dd, J 7 . 5 and 1.0; 7.65, lH, dd, J 7.5 and 1.0.
5-Chloro-3-methylindun-I-one (4) and 6-Chloro-3-methylindan-I-one (5)

Fraction two was a brown oil which contained almost equal amounts of these two compounds. N.m.r. spectrum: 1 e46, 3H, d, J 7.0; 2.35, lH, dd, J19.0and 4.0; 2.95, lH, dd, J l 9 . O and 8.0; 3 .48, lH, m. The following signals in the aromatic region were assigned to compound (4) : 7.356, dd, J 8.0 and 1 .5, H 6; 7.495, br, H 4; 7.662, d, J 8.0, H 7. The following signals were assigned to compound (5): 7.448, d, J 8 . 0 , H 4 ; 7.566, dd, J 8 . 2 and 2.0, H 5 ; 7.68, d, J 2 . 5 , H7.

This compound was isolated from fraction three as colourless crystals, m.p. 63-63.5" (lit.I7 65.5-67'). N.m.r. spectrum: 2.22, 2H, m; 2.70, 2H, t, J 6 . 0 ; 3.08, 2H, t, J 6 . 0 ; 7.28, lH, t, J 8 . 0 ; 7.57, lH, d, J 8 . 0 ; 7.99, lH, d, J8.O.

This compound was isolated from fraction four as a colourless semicrystalline solid (lit." m.p. 30-31"). N.m.r. spectrum: 2.24, 2H, m; 2.35, 2H, t, J 6.0; 3.03, 2H, t, J 6.0; 7.29, lH, s; 7.31, lH, d, J 8 . 0 ; 8.00, lH, d, J 8 . 0 .

PChloro-I-tetralone (8) This compound was obtained from fraction five as colourless crystals, m.p. 93-94" (lit." 94"). N.m.r. spectrum: 2.20, 2H, m; 2.70, 2H, t, J 6 . 0 ; 2.96, 2H, t, J 6 . 0 ; 7.20, lH, d, J 8 . 0 ; 7.45, lH, dd, J 8.0 and 3.0; 8.03, lH, d, J 3.0. Isomerization of y-Butyvolactone
Powdered anhydrous aluminium chloride (6.04 g, 0.05 mol) was added to y-butyrolactone (1.06 g, 0.01 mol) in nitrobenzene (15 ml). No crotonic acid could be detected in the solution after it was heated at 100" for 1 h, but conversion was about 25% complete (as judged by lH n.m.r.) after 30 min at 150". Another solution was heated at 150"for 5 h and then worked up to give crotonic acid (0.32 g, 30%) which was identified by comparison of its n.m.r, spectrum with that of an authentic sample.

3-Methylindan-1-onez0 (12.0 g) was nitrated with KN03/H2S04 as described for the parent i n d a n ~ n e . ~The crude product (15.0 g) showed two methyl doublets in the 'H n.m.r, spectrum, ' with area ratio 9 : 1 (1 .45 and 1 .35 ppm respectively). Recrystallization from hexane gave a number
l7 ls

Badder, F. G., El-Assal, L. S., and Doss, N. A,, J. Chem. Soc., 1959, 1027. Schroeter, G., Gluschke, A., Gotzky, S., Huang, J., Irmisch, G., Laves, E., Schrader, O . , and Stier, G., Bev. Dtsch. Chem. Ges., 1930, 63, 1308. l9 Jungmann, A., Justus Liebigs Ann. Chem., 1927, 451,40. 20 Hochmann, H., and Le Claire, C. D., J. Am. Chem. Soc., 1943, 65, 59. 21 Ingold, C. K., and Pigott, H. A,, J. Chem. Soc., 1923, 123, 1469.

C. A. Kerr and I. D. Rae

of early fractions with m.p. 78-79' which were essentially pure 3-methyl-6-nitro-1-indanone. The nitro compound (2.3 g) was hydrogenated in ethanol (50 ml) over 10% Pd/C (0.2 g) to give the amine, m.p. 101-102", in quantitative yield. This was diazotized and treated with cuprous chloridez2 to give a mixture of compounds from which 6-chloro-3-methylindun-I-one, m.p. 30-31, was isolated by gas chromatography (Found: C, 66.1 ; H, 5.0. C,,H,ClO requires C, 66.5; H, 5.0%). The n.m.r. spectrum showed: 1.40, 3H, d, J 7.3; 2.31, lH, dd, J 19.2 and 3.5; 2.97, lH, dd, J 19.2 and 7.5; 3.43, lH, m; 7.452, lH, d, J 8 . 2 ; 7.567, l H , dd, J 8 . 2 and 2.2; 7.680, 1H, d, J 2.2.

Acknowledgments

This work was supported by the Australian Research Grants Committee. We thank Mr David Burgess for helpful discussion and for some assistance with the experimental section, and acknowledge some discussion with Professor Franz Effenberger.

Manuscript received 18 August 1977

22

Vogel, A. I., 'A Textbook of Practical Organic Chemistry' 3rd Edn, p. 600 (Longmans: London 1964).