JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (Registered in U. S. P a t e n t Office)
VOLUME74
(Copyright, 105’2, by t h e American Chemical Society)
NUMBER 22
NOVEMBER 22, 1952
[CONTRIBUTION
Quinone Imides.
FROM THE NOYES CHEMICAL
LABORATORY,
UNIVERSITY O F
ILLINOIS]
XIX. Addition of Active Methylene Compounds to 1,4-Naphthoquinonedibenzenesulf onimide BY ROGERADAMSAND WILLIAMMOJE RECEIVED JUNE 27, 1952
1.4-Naphthoquinonedibenzenesulfonimide adds one molecule of malonic ester, ethyl benzoylacetate, acetylacetone and nitroethane to give the corresponding 2-substituted 1,4-naphthalenedibenzenesulfonamides. The product from nitromethane and 1,4-naphthoquinonedibenzenesulfonimideis a bis-adduct. Various degradation reactions of these products are described. Oxidation of the 2-substituted 1,4-naphthalenedibenzenesulfonamidederivatives from ethyl benzoylacetate, acetylacetone and nitroethane with lead tetraacetate give the corresponding 1,4-naphthoquinonedibenzenesulfonimides, whereas that from malonic ester gives an o-quinone monoimide derivative.
p-Quinones participate in the Michael reaction with active methylene compounds to give various products depending on the substituents in the quinone molecule, the active methylene compound and the catalyst used in the reaction. The reaction between substituted 1,4-benzoquinones having one or two open positions and metallic enolates has been extensively investigated by Smith and coworkers. 1,4-Benzoquinone itself reacted with ethyl cyanoacetate, malononitrile and cyanoacetamide to give 2,5-substituted hydroquinones2; however, when the active methylene compound was acetylacetone, the products were not adequately ~haracterized.~1,4-Naphthoquinone and diethyl malonate react in pyridine solution to give the bis compound I.4
enesulfonimide and diethyl malonate was treated with a drop of triethylamine and allowed to stand a t room temperature for one week, a product separated in 83% yield which had structure 11. The reaction of 1,4-naphthoquinonedibenzenesulfonimide with ethyl benzoylacetate in chloroform under similar conditions gave a 90% yield of I11 and with NHSOzCeHS I
I
il
I
.R
II,.R = Rt = COOCzHj 111. R = COCRH~: RI = COOC~HS IV; R = R1 =- COCH, V, R = H ; RI = COOH VI, R = H ; R1 = COCHB VII, R = CH,; R1 = NO2 VIII, R = CHI; Ri = NHz
acetylacetone, IV in yield. The products 11, I11 and IV crystallized from the reaction mixtures in colors ranging from tan to white whereas I the reactions of p-quinones were reported usually The Michael reaction has now been extended to to give low yields of highly colored products. 1,4-naphthoquinonedibenzenesulfonimide. When Both I1 and I11 were hydrolyzed with aqueous a benzene solution of 1,4-naphthoquinonedibenz- alkali to the acetic acid derivative V. Treatment of IV with aqueous alkali gave the ketone (VI); (1) L. I. S m i t h , el al., T H IJOURNAL, ~ 6 8 , 629 (1936); J . Org. C h e m . , the latter gave no color with ferric chloride whereas 4, 342 (1939); THISJOURNAL, 6 1 , 133 (1940); 6 5 , 441, 1739 (1943); the former gave a deep purple color. 6 8 , 894 (1946); J . Org. Chem., lli, 832 (1950). (2) J . H. Wood, C. S. Colburn, I,. Cox and H. C. G a r l a n d , THIS Nitroethane and 1,4-naphthoquinonedibenzeneJOURNAL, 66, 1540 (1944). sulfonimide in a mixture of chloroform and ethanol (3) M. V. Ionescu, Bull. soc chim., 4 1 , 1094 (1927); E. Bernatek, containing a drop of triethylamine gave VI1 and a Acta Chem. S c a n d . , 6 , 160 (1952). very small amount of a yellow compound which 14) E . F. P r a t t and W E. Boehme. THISJOURNAL, 73,444 (1951). 5557
was not further identified. The reaction was unsuccessful if conducted in chloroform ill the absence of ethanol. 2-h-itropropdne aiid 1,.l-naphthociuiiionedibenzenesulfotiil-nide failed to react under the various conditions tried. Catalytic reduction of VI1 with hydrogen resulted in the absorption of three moles with formation of the corresponding amine (VIII). The l,-&naphthalenedibenzenesulfonamides, 111, IV and VII, were easily oxidized with lead tetraacetate in acetic acid a t room ternperature to the corresponding yellow crystalline diimides, IX, X and XI. Oxidation of 11, however, gave the o-quinone nionoimide (XII), which was deep red in color. The infrared s~xctrurnof XI1 showed the presence of ail unsaturated ester carbonyl, an -NH- grouping a t i d il carbon nitrogcii double honcl,
Acknowledgment.-The authors are indebted to hliss Emily Davis, A h . Esther Fett, Irks. Katherine Pih and RIr. J. Nemeth for the microanalyses and to Miss Helen Yliklas for the infrared spectra de terminations. Experimental
-411 melting points are corrected. Diethyl 1,4-naphthalenedibenzenesulfonarnido-2-malonate (II).-Toasolutionof 1 g. of 1,4-naphthoquinonedibenzei~esulfotiimide~ in 25 ml. of benzene was added 0.4 ml. of diethyl malonate and one drop of triethylamine. After standing for one week the small gray crystals that had separated were filtered, washed with benzene and dried. The yield was 1.14 g. (83%). Kccrystallization from aqueous ethanol gave white needles, 11i.p. 187-1238' (dec.). The infrared spectrum showed the presence of the carbon-oxygen double bond aiid thc - S H - linkage. . 4 n d Calcd. for C S H ~ ~ X ~ O ~C, S S :58.37; 11, 4.73; S , 4.69. Found: C , 58.28; €I, 5.00; S , 4.68. Ethyl 1,4-naphthalenedibenzenesulfonamido-2-benzoylSSOiC6H, SSOrCaIis acetate (III).-To a solution of 2 g. of 1,4-naphthoquinonedibciizeriesulfoniinide in 30 nil. of chloroform was added 1 nil. of ethyl benzoylacctate and one drop of triethylamine. After standing for 2 days the feathery white needles that had separated were collected, washed with chloroform and dried. Recrystallization from ethanol gave 2.68 g. (90%) of white iiccdlcs, m.p, 123-124' (dec.) with previous softening a t 118'. The infrared spectrum indicated the presence of thc -NH- grouping and the carbon-oxygen double bond. The compound contained one-half a molecule of ethanol of crystallization as shown by analysis. .InaZ. Calcd. for C ~ ~ H ~ ~ S Z O , S ~ . ~ / ~C,C ~62.65; €~SOH: When a chloroform solution of l,-l.-naphthoquinonedibenzenesulfoiiirriide and nitrornethane I € , 4.79; N, 4.30. Found: C , 63.46; H , 4.92; h-, 4.28. A sample was heated in VUCZLO a t 121O for 12 hours; wt. of was treated with a drop of triethylamine and 0.2787 g . ; loss in weight, 0.0092 g.; calcd. loss iii allowed to stand a t room temperature for two days sample, weight for one-half a mole of ethanol, 0.0099 g.
the bis compound ( X I I I ) was formed in S4'L yield. A small amount of yellow solid, obtained SHSO~CGH,
SHSO2C6Ils
S I I I , I< = so: XI\., I< = I I
as a by-product, was similar, if not identical, to t h a t formed in the nitroethane reaction as shown by infrared spectra. They both showed bright fluorescence when examined under ultraviolet light. Compound XI11 formed solvates with several solvents from which i t was crystallized. These solvated compounds could n o t be desolvated by drying in vacuo over phosphorus pentoxide; under these conditions they decomposed. However, by
1,4-Naphthalenedibenzenesulfonamido-2-acetylacetone (IV).-To a solution of 2 g. of 1,4-naphthoquinonedibenzenesulfoniniide in 25 ml. of chloroform was added 1 ml. of acetylacctoiie and one drop of triethylamine. After standing overnight the small pale yellow needles that had separated were filtered, washed with chloroform and dried. The yield was 2.03 g. (84%). Recrystallization from aqueous methanol gave white needles, 11i.p. 206-207' (dec.). The infrared spectrum indicated the presence of the -NH- linkage ant1 the carbon-oxygen double bond. .Innl. Calcd. for Cs7H2aK206S2:C, 60.43; 11, 4.51; S ,5 . 2 2 . Found: C, 60.36; H, 4.60; II',5.24. 1,4-Naphthalenedibenzenesulfonamido-2-acetic Acid (V). -*4 suspension of 0.77 g. of the malonate (11) in 10 ml. of 50yoaqueous potassium hydroxide was boiled for 5 minutes. Addition of 5 ml. of water gave a clear solution which was boilrd for 5 minutes longer. Acidification with dilute aqueous hydrochloric acid gavc a gummy white precipitate which w;ts filtered, washed with water and treated with saturated aqueous sodium bicarbonate. Acidification of the bicarbonate filtrate gave it whitc precipitate which was recrystallized from acetic acid. The yield was 0.56 g. (88%) of sni;ill feathery white needlcs, m . p . 281-232° (tlec.), with previous ddrkenilig at 218". Thc infrared spectrum showed the prcseiice of the - X I - linkage and the carboii--oxygcn double I~ontl. . l ? z d . Calcd. for CaaI-TzoNZOeSa: C , 58.05; €1, 4.06; K, 5,(j.l, I ~ o u n d :C, 57.98; H, 4.08; N,5.38, A solution of 0.50 g. of the benzoylacetatc (111) ill 10 nil. of ZOO/, aqucous potassiuin hydroxide was refluxed fdr 5 minutes. After cooling, the solution was worked up as dcscribed above. The yield was 0.30 g. (82%). A melting point of a mixture of this compound and that described above sliouwl 110 tlepression. Their infrared spectra were also
lization from aqueous methanol gave 0.81 g. (88%) of small feathery white needles, m.p. 216-217' (dec.), with previous The infrared spectrum showed the softening at 183'. presence of the -NH- linkage and the carbon-oxygen double bond. This compound gave no color with aqueous ethanolic ferric chloride whereas IV gave a deep purple color. Anal. Calcd. for CzsHnNzOaSz: C, 60.71; H , 4.48; N,5.66. Found: C, 60.83; H , 4.56; N, 5.36.
The infrared spectrum showed the presence of the carbonnitrogen double bond and the nitro grouping. Anal. Calcd. for C24Hl9N30&: C, 56.57; H , 3.76; N, 8.25. Found: C, 56.63; H,3.74; N. 7.97. Diethyl ( I-benzenesulfonimido-4-benzenesulfonamido1 ,2-dihydronaphthyIidene-Z)-malonate (XII) .-To a mechanically stirred solution of 1 g. of I1 in 20 ml. of acetic acid was added a t room temperature 1.5 g. of lead tetraacetate. e-(1,4-Naphthalenedibenzenesulfonamido-2)-nitroethane After the reaction had proceeded for 10 minutes, 1 ml. of (VII).-To a solution of 1 g. of 1,4-naphthoquinonediben- ethylene glycol was added. The deep red solution was then zenesulfonimide in a mixture of 25 ml. of chloroform and 10 placed in an ice-bath for 1 hour. The deep red solid that had separated was filtered, washed with acetic acid and ml. of ethanol was added 1 ml. of nitroethane and 1 drop of triethylamine. After standing a t room temperature for 24 dried. The yield was 0.87 g. (87%). Recry'stallization hours, 1 ml. of acetic acid was added. After an additional from acetic acid gave ruby red needles, m.p. 173-174' (clec.). 24 hours the small yellow crystals (10 mg.) that had sepa- The infrared spectrum showed the presence of the carbonrated were filtered and washed with chloroform. Evapora- nitrogen double bond, the -XH- linkage and the conjugated tion of the filtrate t o a volume c$ approximately 10 ml. gave ester carbon-oxygen double bond. a pale yellow solid which,.after washing with ether, weighed Anal. Calcd. for C%H2&208Sz: c , 58.57; H , 4.41; s, 0.75 g. (64%). Recrystallization from aqueous ethanol 4.71. Found: C, 58.68; H , 4.50; K, 4.99.' gave small white needles, m.p. 211-212" (dec.). The inBis-( 1,4-naphthalenedibenzenesulfonamido-2)-nitromethfrared spectrum showed the presence of the -NH- linkage ane (XIII).-To a solution of 5 g. of 1,4-naphthoquinonediand the nitro grouping. benzenesulfonimide in 60 ml. of chloroform was added 5 ml. Anal. Calcd. for C?&1N30&: C, 56.34; H , 4.14; of freshly distilled nitromethane and two drops of triethylS , 8.21. Found: C , 56.60; H , 4.25; N, 8.17. amine. After standing for two days a t room temperature Recrystallization of the yellow solid by-product from cy- the cream colored solid was collected, washed with chloroform and dried. The solid weighed 5.05 g. Recrystallizaclohexanone-ethanol gave yellow needles, m.p. 328-329' (dec.). The infrared spectrum showed the presence of the tion from aqueous tetrahydrofuran gave 4.80 g. (84%) of small white needles, m.p. 157-162" (dec.), with previous -SH- linkage and the nitro grouping. No reaction took place between 2-nitropropane and 1,4- darkening a t 142". The crystals gradually turned pink on naphthoquinonedibenzenesulfonimide in chloroform alone standing in the air. Recrystallization from various solvents gave solvated or in a mixture of chloroform and ethanol with a drop of triproducts as described below. None showed perfect analyethylamine as a catalyst. a-(1,4-Naphthalenedibenzenesulfonamido-Z)-ethylamine ses, but they were indicative of solvation. Ethanol: small white plates, m.p. 165-168' (dec.); with (VIII).-A suspension of 0.60 g. of VI1 in 30 ml. of ethanol was reduced catalytically with 1 g. of Raney nickel and hy- darkening a t 150'. Anal. Calcd. for C4sHs5~5010S4.C2HjOH:C, 57.59; H , drogen a t atmospheric pressure. Dilution of the solution with water gave 0.49 g. (88%) of the crude amine. Re- 4.22; N,7.15. Found: C, 57.03, 56.90; H , 4.01, 4.01. h-,7.44. crystallization from acetonitrile gave small white prisms, Ethyl acetate: smallowhite needles, m.p. 165-167' (dec.) m.p. 209-210" (dec.). The infrared spectrum showed the with darkening a t 152 . presence of the -SH- linkage and the NHz grouping. Anal. Calcd. for C~SHJ~N~OIOS~.CSHI"OZ: C, 57.95; H, Anal. Calcd. for C Z ~ H Z ~ N ~ O C,~ 59.85; S Z : H , 4.81; N, 4.38; N, 6.76. Found: C, 57.44, 57.54; H , 4.67, 4.95; N, 8.73. Found: C, 80.05; H , 4.63; N, 8.89. Ethyl 1,4-naphthoquinonedibenzenesulfonimido-2-ben-6.03. Aqueous acetone: small white needles, m.p. 157-162' zoylacetate (IX).-To a mechanically stirred solution of 2g. of I11 in 20 ml. of acetic acid was added a t room tempera- (dec.), with darkening a t 122". Anal. Calcd. for C45H35?i5010S4.C3HaO: C, 58.11; H , ture 2.5 g. of lead tetraacetate. The product began t o separate after 10 minutes. After the reaction had pro- 4.17; N,7.06. Found: C,57.18; H,4.01; N,7.23. ceeded for 20 minutes, 1 ml. of ethylene glycol was added. Tetrahydrofuran: small white needles, m.p. 157-162" The reaction mixture was then placed in an ice-bath for 30 (dec.), with darkening a t 140'. minutes. The product was removed by filtration, washed Anal. Calcd. for C ~ & ~ ~ ; ~ O I O S ~ . C ~ C,H 58.49; SO: H, with acetic acid and dried. The yield was 1.87 g. (97%). 4.31; N, 6.96. Found: C, 57.04, 57.71, 57.72; H , 4.45, Recrystallization from chloroform-cyclohexane gave long 4.53, 4.67; N. 7.24. . . yellow needles, m.p. 196-197' (dec.). The infrared specA solution of the compound from tetrahydrofuran in warm trum showed the presence of the carbon-nitrogen and carglacial acetic acid was cooled. The unsolvated compound bon-oxygen double bonds. wasobtained as small colorless needles, m.p. 215-216' (dec.). Anal. Calcd. for C33H?6N20&: C, 63.24; H , 4.18; N, This could be converted to the tetrahydrofuran solvated 4.47. Found: C, 63.51; H , 4.46; N,4.43. compound by recrystallization from tetrahydrofuran. 1,4-Naphthoquinonedibenzenesulfonimido-2-acetylace- Anal. Calcd. for C45H3sN50~~S4: C, 57.87; H , 3.78; K, tone (X).-To a mechanically stirred suspension of 1.35 g. 7.49. Found: C, 57.52, 57.97; H , 3.65, 3.91; N, 7.17. of IV in 10 ml.. of acetic acid was added a t room temperaThe infrared spectrum showed the presence of the -NHture 2.5 g. of lead tetraacetate. After the reaction had proceeded for 1.5 hours, 1 ml. of ethylene glycol was added. linkage and the nitro grouping. Evaporation of the filtrate from the crystallization of the The product was removed by filtration, washed with acetic acid and dried. The yield was 1.16 g. (86%). Recrystal- main product of the reaction in vacuo t o remove the tetrahylization from benzene gave small lemon-yellow plates, m.p. drofuran gave 0.20 g. of a pale yellow fluorescent solid. Re180-181' (dec.). The infrared spectrum showed the pres- crystallization from cyclohexanone-ethanol gave yellow ence of the carbon-nitrogen and carbon-oxygen double needles, m.p. 328-329' (dec.). The infrared spectrum showed the presence of the -NH- linkage and the nitro bonds. grouping. The spectrum of this compound and the yellow Anal. Calcd. for C ~ , H Z ~ N ? O ~ c S, ~ 60.66; : H , 4.15; N, compound formed in the nitroethane reaction were almost 5.24. Found: C, 60.68; H , 4.30; N, 5.26. identical. Bis-( 1,4-naphthalenedibenzenesulfonamido-2 )-methane a-(1,4-Naphthoquinonedibenzenesulfonimido-2)-nitroethane (XI).-To a suspension of 0.5 g. of VI1 in 10 ml. of (XIV).-To a suspension of 3 g. of lithium aluminum hyacetic acid was added 1 g. of lead tetraacetate. The mix- dride in 50 ml. of tetrahydrofuran was added portionwise 1.73 ture was heated a t the boiling point for one minute during g. of X I I I . After the addition was completed, the excess which time the amide went into solution. After the yellow lithium aluminum hydride was destroyed with ethanol. Acidification with aqueous hydrochloric acid gave a creamsolution had cooled, 1 ml. of ethylene glycol was added. After cooling in an ice-bath for one hour the product was colored precipitate which was filtered, washed with water filtered, washed with acetic acid and dried. The yield and dried. The colored impurities were removed by washing with 20 ml. of hot chloroform. Recrystallization from was 0.40 g. (82%). Recrystallization from ethyl acetatecyclohexane gqve yellow needles, m.p. 178-279' (deg.). aqueous ethanol gave 1.0 g. (60%) of small white needles,
the orange prisms that had separated were collected, washed m . p . 247-248" (dec.). The infrared spectrum showed the with acetic acid and dried. The yield was 0.30 g. (91%). presence of the -SH- and methylene linkages. .I 71ui. calcd, for c ~ ~ H ~ ~60.79; ~ ~[ I , ~4.03; ~ s Recrystallization ~ : from nitromethane gave orange prisms, m.p. 199-200' (clec.). The infrared spectrum showed the S , 0.30. Found: C, 80.79; H, 4.08; S , 5.93.
c,
Bis-( ,4-naphthoquinonedibenzenesulfonimido-2 ane (XV).-A solution of 0.33 g. of XIV and 1 g. of lead tetraacetate in 10 ml. of acetic acid was heated to the boiling point then allolvecl to cool, T,, this solution :iddcd 0.8 ml. of ethylene glycol. After stxnding overnight
~CUNTRIBTTIOS FROM
'1 HE
presence of the carbon-nitrogen double bond and the meth-
ylene linkage.
A n d . Calcd. for CPSHS~SIOSS~: C, 61.07; H , 3.64; S , 6.33. Found: c , 60.89: 15, 3.63; 9, 6.40. URBASA, ILLISOIS
SOYES CHEMICAL LABORATORY, UNIVERSITY OF TLLIXOIS]
Quinone Imides. XX. Additions to 1,4-Naphthoquinoned~benzesulfonirnide B Y ROGER ADAMSAND 'CVILLIAKAfOJ'd RECEIVED JL-LY 3, 19.52 Hydrazoic acid, diazomethane, benzenesulfinic acid, acetic acid, phenol and p-naphthol add t o l,~-iiaphthoquinonedibenzenesulfonimide to give the corresponding 2-substituted 1,~-naphthalenediberizenesulfonamides.
The addition of hydrazoic acid to quinones was infrared absorption spectra characteristic of the first studied by Oliveri-Mandala, who reported that azido g r o ~ p i n g . ~ =Iromatic compounds add to p-quinonedibenzenep-benzoquinone with hydrazoic acid gives azidohydroquinone.' From a-naphthoquinone or @- sulfonimide to give monoaryl p-phenylenedibenznapht oquinone, however, the products are, respec- enesulfonamide derivatives4 This reaction has tively, 2-arnino-l,4naphthoquinoneand +amino- now been extended to 1,4-naphthoquinonedibenz1,2-naphthoquinone2 which arise presumably by enesulfonimide. I n the presence of a small amount intramolecular oxidation-reduction of the initially of boron trifluoride etherate as a catalyst, phenol and @-naphthol added t o 1,3-naphthoquinonediformed azidonaphthohydroquinones. When 1,I-naphthoquinonedibenzenesulfonimide benzenesulfonimide. The products, 2-(p-hydroxy(17 in acetic acid was treated with an aqueous solution phenyl~~-l,4-naphthalenedibenzenesulfonamide of sodium azide, 2-azido-l,4-naphthalenedibenzene-and _"-(P-hydroxy-oc-naphthyl)-l,4-naphthalenedisulfonamide (I) was formed in 94Fo yield. This henzenesulfonamide [VI) were obtained in very was reduced with aqueous sodium hydrosulfite t o good yields. Attempts to arylate 1,4-naphthoh m i n o - 1,I-naphthalenedibenzenesulfonamide(11). quinonedibenzenesulfonimide with aryldiazonium salts; and N-nitrosoarylamides,6 which have been NHSO>CEH, SS02CI H used for the arylations of p-quinones, were unsuccessful. Diazomethane and its derivatives' have been added to various p-quinones to give substituted pyrazoles.' The addition of ethereal diazomethane to a chloroform solution of 1,4naphthoquinonedibeiizenesulfonimide gave the corresponding p y a zole (1X3. .Attempts to add phenylazide to 1,4s € i SO2 c 6 1 I -, XHSO~C6Ha
ri+ s '4'.+'\ s '
1-11
, \ ~
I
H
SHSOzCaHj 1
naphthoquinonedibenzenesulfonimide, which gave substituted triazoles with p-quinonesj8 were unsuccessful. Benzenesulfinic acid and some of its derivatives have been added to p-quinone to give the correThe 2-azido-1,4-naphthalenedibenzenesulfonamide (9) J . I€. Boger, THISJ O U R N A L , 73, ,5248 (1951). was readily oxidized in acetic acid to the orange ( 4 ) R . Adams and K. R.Eilar, ibid.,73, 1149 (1951). 2 -azido - 1 , 4 -naphthoquinonedibenzenesulfonamide (.5) D. E. Kvalnes, ibid.,56, 2478 (1934); G. B. Marini-Bettolo a n d (111). This added a molecule of hydrazoic acid to C. Rossi, Cass. chim. i t a i . , ?a, 208 (19.12). (6) >I. Akagi and K. Hirose, J . Phnvm. S o r J a p a n , 62, 191 (1942); give 2,3-diazido-1,4naphthalenedibenzenesulfonA , , 46, 6169 (1951). amide (I17). -411 of the azides prepared showed C. 17) H . yon Pechmann, B w . , 28, 85.5 11896): 32, 2292 (1899); NHS02CeH6 IV IX, R = OCOCH: S ,R = OH
( I1 E O l i v e r i - h n n d a i i and li. Calderao. Gazz. rhim. i t a l , 45, I , 307 '1915); IC. Olirt.ri-kIandalB, i h i d , 45, 11, 120 (I!jl.j). ' 2 ) L. P Fieser anrl J. 1.. Hartrvell. T i m J O U R N A ~ , , 67, 1482 I1035i: +e? also A Kurezvnski. IIiiif i o i 0 ' : m . L ] 35, 1186 (1'3?1)
1,. I: Fieser anrl M. A. Peters, Tars J O U R N A L , 53, 4080 (1Y31), IS Bergmann and F. Bergmann, J . Org. Chem., 3 , 125 (1938). ( 8 ) I.. Wolff, A1711., 394, 68 (1812): 399, 274, 287 (1913); I;. D Clicittawxv a n d G. D. Parks, J Chem Sor , 127, 1309 (1i125)
