DECEMBER
1957
1745
NOTES
for liquid alcohols, but ether or benzene was used to dissolve solid alcohols. Procedure. The phenol, 0.005 mole ( 1 1 0 mg.) was dissolved in 5 ml. of acetone, and 0.50 ml. of triethyl amine was pipetted into the reaction flask. The 2,4-dinitrofluorobenzene (0.005 mole, f 10 mg.) was dissolved in 5 ml. of acetone. The two solutions were mixed a t room temperature, then refluxed for 0.5 hr. in a water bath. The acetone was removed by evaporation, followed by the addition of 10 ml. of 5% HCI. The derivative crystallized and was filtered and washed several times with water. The precipitate was then ground under 15 ml. of 5% NaOH in a mortar, filtered, and washed oeveral times with water. The crude product was dried for 24 hr. in a vacuum desiccator over “drierite”. The best solvent for recrystallization of derivatives melting below 120” was ethanol or ethanol-water, while acetic acid or acetic acid-water was preferred for those melting above 120’. The reaction procedures failed with 2,4dinitrophenol because of low yield, while pyrogallol and carvacrol gave oils which did not crystallize. The samples of phenols were either technical, practical, or purified grades. The technical and practical grades were not further purified before use. SEVERANCE CHEMISTRY LABORATORY THECOLLEGE OF WOOSTER WOOSTER, OHIO
The first, 0-benzoyl-mi-nitrophenylacetonitrile (111), was synthesized by Thurston and Shrine9 0 C~HE.---C==N--&~ 1 L
0 Cab
N
I11
and its structure was proved by the same authors. The second, 0-benzoyl-9-aci-nitrofluorene (IV) , was first synthesized by Nenitzescu and Isacescu. I n this paper we present evidence for its structure and list several of its reactions. 0-Benzoyl-9-aci-nitrofluorene was prepared by the reaction of benzoyl chloride with sodium 9fluorenenitronate. The infrared spectrum of IV had intense absorption bands a t 5.67 and 6.16 p ; this set of bands in the double bond stretching region of the spectrum is characteristic of nitronic anhydrides. a The isolation of benzamide and ammonium 9-fluorenenitronate from the ammonolysis of IV further confirms the structure assigned. When a solution of IV in carbon tetrachloride was refluxed, nitric oxide was evolved and 9,9’-dibenzoyloxy-9,9’-bifluorenyl (VIII) was formed. The
Reactions of 0-Benzoyl-9-aci-nitrofluorenel EMILH. WHITE*AND WILLIAMJ. CONSIDINE
Received May 31, 1957
Salts of secondary alkyl nitroparaffins react with acid chlorides to yield the products shown in equation I n the alkyl series, the nitronic anhydrides I are relatively unstable and a t temperatures RR’CN02-
IV
J.
+ R”COC1+
Tg
0
RR’C=N-& I
R” +R R ’ C N 4 A-C-R’
(1)
II
0
I1
well below Oo3 they rearrange to the nitroso derivatives 11. The nitronic anhydrides of more highly conjugated nitroparaffins are relatively stable, on the other hand, presumably because a rearrangement to I1 would result in a decrease in resonance energy. Two compounds of this type are known.‘
VI11
first step in this reaction is probably the formation of the nitroso compound V, since this is the se(1) Taken in part from a thesis submitted by William J. quence that has been established for the correConsidine to the faculty of the Graduate School of Yale sponding alkyl nitronic anhydrides. Homolysis University in partial fulfillment of the requirements for the Ph.D. degree. Presented before the Division of Organic of the carbon-nitrogen bond of V would yield nitric Chemistry a t the 130th Meeting of the AMERICANCHEMICAL oxide and the relatively stable radical VII, the dimerization of which would yield VIII. The last SOCIETY, Atlantic City, New Jersey, September 21, 1956.
(2) Author to whom inquiries are to be sent (The Johns Hopkins University, Baltimore 18, Md.). (3) E. H. White and W. J. Considine, J . Am. Chem. Soc., in press. ( 4 ) A compound isolated from the reaction of benzoyl chloride with the potassium salt of 3-nitroindene may be a third example [W. Wislicenus and K. Pfeilsticker, Ann., 463, 40 (1924)l. The authors proposed that the product
was I-benzoyl3-nitroindene, but in view of the oxygen acylation observed with the related nitrofluorene, the product is probably O-benzoyl3-acdnitroindene. (5) J. Thurston and R. Shriner, J. Org. C h a . , 2, 183 (1937). (6) C. D. Nenitzescu and D. A. Isacescu, Bull. SOC. Chim. Romania, 14,53 (1932); Chem. Abstr., 27,964 (1934).
1746
VOL. 22
NOTES
mentioned compound was synthesized independently from bifluorenyl (IX) by means of the Prevost reaction. A pyrolysis reaction similar to the one discussed has been reported for 9-iodo-9-nitrofluorene (X) by Nenitaescu and Isacescu.'
x
t
I2
The acid hydrolysis of IV also led to a dimeric product, 9,9'-dichloro-9,9'-bifluorenyl (XII). Fluorenone is another product of this reaction. The formation of these products can be accounted for by the following analogous sequence of reactions.
.C1
Q3
+ NO
A*
IX --+
n The reaction leading to XI is very similar to one repoTted by Steinkopf and Jiirgens,8
i? RHC-N--GIi
T
HCl +RHC-N=O
-f
HzO
Ci
whereas the formation of fluorenone is probably an example of the Yef reaction.Q O-Renzoii-uri-nitrophenylaeetonit~i~e(111) also proved to DIJ triermally labile. The reaction products in this caw were rather complex, however, anci t h e y were nor8wwstigeted :urtheI. EXPERTWENTAL
SalL $1b-nitro$uorene. The potammx salt wa8 prepared from fiuarene and etk>-1nitrate by essentially the method of' wislicenus and vl'aidmuller,l@except that potassium t-bu-
toxide in t-butanol waa used as the base. A 72% yield of the salt was obtained. The sodium and. ammonium salts were prepared from the potassium salt by the methods of Wislicenus and Waldmuller.lo 0-Benzoyl-Q-aci-nitroflmrene (IV). Modi$cation qf the method of Nenitzeseu and Isacescu.B Benzoyl chloride (0.75 g., 5.4 mmoles) was added to a suspension of sodium 9fluorenenitronate (1.40 g., 6.0 mmoles) in 50 ml. of methylene chloride. The mixture was stirred for 24 hr., then filtered. The solvent was removed in Vacuo and the product was recrystallized from acetone to yield 0.745 g. of IV (2.4 mmoles, 45% based on the benzoyl chloride) m.p. 134-135" dec. 5.67 p and 6.16 p. (lit6. 136136").Infrared spectrum, Anal. Calcd. for GoHlsOoN: C, 76.18; H, 4.16; N, 4.44. Found: C, 76.47; H, 4.03; N, 4.28. Ammonolysis of 0-benzoyl-9-aci-nitrofluorene.0-Benzoyl9-a&-nitrofluorene (0.190 g., 0.60 mmole) was dissolved in 10 ml. of absolute ether and the solution was saturated with anhydrous ammonia gas. While protected from the atmosphere with a sodium hydroxide tube, the solution was stirred for 24 hr. The reaction mixture was filtered and the precipitate was washed with 100 ml. of anhydrous ether in small portions. A yellow powder, (0.12 g., 0.54 mmole, 87%) was obtained, m.p. 139-140" dec. (lit.lQ 146-148). The infrared spectrum of this material was identical with that of an authentic specimen of ammonium 9-fluorenenitronate. The yellow filtrate and washes were combined and washed with 5% sodium hydroxide solution and then with water. The ether phase was dried over anhydrous magnesium sulfate. Evaporation of the ether yielded 0.042 g. (0.35 mmole, 58%) of faintly yellow plates. A comparison of the infrared spectrum of this material with that of an authentic sample of benzamide indicated clearly that the product was rather pure benzamide; every absorption band coincided with corresponding bands in the spectrum of the authentic benzamide. Pyrolysis of 0-benzoyl-9-aei-nitrofEuorene.A solution of 0-benzoyl-9-aci-nitrofluorene (1.0 g., 3.2 mmoles) in 50 ml. of carbon tetrachloride was refluxed for 24 hr. in a flask previously fliished with nitrogen and connected to a gas buret filled with mercury. Forty-three ml, of a colorless gas wa5 collected in the buret at 24" and 766 Hg, or 34 ml. a t STP (1.52 mmoles, 48%). The infrared spectrum of the gas was identical with that of a mixture of nitric oxide and carbon tetrachloride. When the gas infrared cell was opened to admit atmospheric oxygen, the gas turned brown and the infrared spectrum now obtained was that of nitrogen dioxide mixed with carbon tetrachloride. When the carbon tetrachloride solution cooled, needles were deposited. This material was redissolved and the volume of the solution adjueted so as just to keep the material in solution a t the boiling point. The solution was then allowed to cool. Tan needles were obtained which after one recrystallization from acetone gave 650 mg. of white prisms, m p . 288.5-289.5", undepressed when mixed with authentic 9,9'dibenzoyloxy-9,9'-biu.orsnyi. An additional 101 mg. waE obtained from the mother iiqunr. A total of 0.75 g. of product was obtained (1.3 mmolea, 83?&).The infrared Rpectrum of this materiai was identical aich that of authentic 9,9'-dIbenzoyioxy-9,9 '-bifluorenyl. Bi$uw$idene (IXj. lidodz.fication of the method oj' Graebe and rStindt.11 A. mixture of fluorene (25 g., 0.15 moie) and plumbous oxide ( 1 0 g., 8.45 mole) in a flask was immersed in an QQ bath at a t,emperacure of 250". Over the coiirae of I h.7" the temperature wae raised to 310' amd it was held a t 311i*-820nfor l.5 hr.The reaction mafia was ~ o o 1 . dan? extracted wit.h boiling kJeuzeno. The hot benzene sohtioz wa? fi.;tor.i.d, m 3 the volume of the boiling solvent, w a sc? BE jbat :,o keep the mat,eria! in 5olution. Picric
.-I-I"
-I.
DECEMBER
1957
onto a column of alumina. The column was washed with additional ether until no further colored material was eluted. The red ether solution was evaporated and the residue was recrystallized from benzene to give 1.74 g. (0.0053 mole, 7%) of red needles, m.p. 187-189' (lit." 1880). 9.9'-Dibenzoylosy-Q,9'-bifluorenyE'2 (VIII). A mixture of bifluorylidene (0.332 g., 10 mmole), silver benzoate (0.458 g., 2 mmoles), and iodine (0.254 g., 1 mmole) was refluxed in 50 ml. of dry benzene until the initial red color of the mixture was discharged. The yellow solution was filtered hot and evaporated. The residue was extracted with boiling acetone and the resulting material was crystallized from the same solvent to yield 0.400 g. (0.7 mmole, 70%) of yellow rods, m.p. 281-284'. Clarification of a solution in acetone with Norite and further recrystallizations from acetone gave white Drisms melting- a t 288-289.5'. Infrared spectrum, Aft: 5.8b p. Anal. Calcd. for C40H2~04:C, 84.19; H,4.59. Found: C, 84.19; H, 4.80. Acid hydrolysis of 0-benzoyl-9-aci-nitrofEuorene. A solution of 0-benzoyl-9-aci-nitrofluorene (0.125 g., 0.4 mmole) in 25 ml. of 90% aqueous dioxane 0.1N in HCl was kept at room temperature overnight. The solution was poured into 375 ml. of ether and the ether phase was washed with five 125-ml. portions of water. The ether was washed with two 125-ml. portions of a 5% sodium bicarbonate solution and then it was dried over magnesium suffate. The sodium bicarbonate extract was acidified with 6N HC1 and extracted successively with 250 ml. and 125 ml. of ether. The ether extracts were dried over magnesium sulfate and evaporated to give 0.042 g. (0.34 mmole, 87%) of white needles of benzoic acid, m.p. 116-118' (lit. 121.4'). The infrared spectrum of this material was essentially identical with that of authentic benzoic acid. The first ether solution was evaporated to give 79 mg. of a yellow oil which was chromatographed on alumina. Two fractions were eluted with a 5% benzene-95% hexane mixture. The first fraction consisted of yellowish white crystals. Recrystallization from benzene-hexane and then benzene gave 0.040 g. (0.10 mmole, 0.20 meq., 50%) of white prisms, m.p. 238-241' dec. (lit.la 236'), undepressed when mixed with authentic 9,9'-dichloro-9,9'-bifluorenyl of m.p. 238241'. The infrared spectrum in KBr was identical with that of an authentic specimen of 9,9'-dichloro-9,9'-bifluorenyl. The second fraction consisted of 0.018 g. (0.10 mole, 2570) of yellow crystals of fluorenone. Sublimation of this material yellow plates, m.p. 67-69' (lit.14 83-84). The infrared speetrum was identical with that of an authentic specimen of fluorenone. 9,9'-Dichloro-9,9'-brenyl (XII). ModiJication of the method of Graebe and Mantz.16 Dry chlorine gas was passed through a solution of bifluorylidene (0.50 g., 1.5 mmoles) in 25 mi. of chloroform until the deep red color was discharged. The resulting yellow solution was evaporated to dryness. The crystalline residue was recrystallized twice from a benzene-hexane mixture and twice, after clarification with Norite, from hexane to give 0.149 g. (0.37 mmoIe, 24%) of white prisms of XII, m.p. 239-242' dec. (lit. 2340;16 23523613). 0-Benzoyl-aci-nitrophenylacetonitrile (111). Modification of the method of Thurston and Shriner.4 Benzoyl chloride (1.50 g., 10.5 mmoles) was added to a stirred suspension of sodium phenylcyanomethanenitronate (3.00 g., 16.3 mmoles) in 30 ml. of dry methylene chloride a t room temperature. During five days of stirring in darkness, the benzoyl chloride reacted completely. The reaction mixture was then poured (12) Method of C. Prevost, Compt. rend., 196, 1129 (1933). (13) J. Schmidt and H. Wagner, Ann., 387, 147 (1912). (14) E. Huntress, E. Hershberg, and J. CW, J . Am. Chem. Soc., 53,2720 (1931). (15) C. Graebe and B. Mantz, Ann., 290,238 (1896).
1747
NOTES
into water and the organic phase was washed with a sodium bicarbonate solution. The methylene chloride solution was dried and then evaporated in vacuum to yield 2.74 g. (10.3 mmoles, 96%) of 111, m.p. 108-109' dec. Recrystallization from a methylene chloride-pentane mixture yielded 2.30 g. (8.65 mmoles, 82% based on benzoyl chloride) of pure 0-benzoyl-aci-nitrophenylacetonitrile, m.p. 115-116' dec. (lit.4 116" dec.). infrared spectrum,.~ a t 4.50 p, 5.67 p, and6.18~. Pyrolysis of 0-benzoyLaci-nitrophenylacetmitde.A solution of I11 (1.06 e.. 3.98 mmoles) in CCL (18.6 ml.) was refluxed for one day in a system' free of oxygen. Fifty ml. (STP) of nitric oxide were evolved. The solvent was removed and the residue subjected to molecular distillation at 0.1 mm. Hg.A small volatile fraction was obtained with an odor reminiscent of benzoyl chloride. A second fraction was obtained at ca. 100". Treatment with pentane yielded crystalline material, m.p. 129-131', Xz::.5.62 M. Annl. Calcd. for C16H10N202: C, 71.99; H, 4.03; N, 11.20. Found: C, 71.76; H, 3.96; N, 11.06. The nonvolatile residue was a viscous oil with an absorp tion band at 5.74 p. It may possibly be the dimer corresponding to VIII.
THEJOHNS HOPKINSUNIVERSITY 18, MD. BALTIMORE YALEUNIVERSITY NEWHAVEN,CONN.
Preparation of Some Substituted Allyl Hydroperoxides from Bromides' JOSEPH HOFFMAN Received March 12, 1967
The preparation of allyl hydroperoxide from allyl alcohol by way of the methanesulfonate has been described.2I n the case of substituted allyl hydroperoxides, often the required alcohol is not available. It has now been found that such hydroperoxides may be prepared conveniently from substituted allyl bromides. These bromides are readily prepared by reaction of the appropriate olefin with Nbromosuccinimide,s and treatment of them with potassium hydroxide-hydrogen peroxide in an aqueous methanol medium at room temperature gives the hydroperoxides. These hydroperoxides can be extracted with benzene and purified through their sodium salts and subsequent distillation. By this procedure, CY- and p-diisobutylene hydroperoxides were prepared : 2-neopentylallyl hydroperoxide from 2,4,4-trimethyl-l-penteneand 2,4,4trimethyl-2-pentenyl hydroperoxide from 2,4,4trimethyl-2-pentene. The method was extended to (1) This research was supported by the United States Air Force through the Air Force Office of Scientific Research of the Air Research and Development Command under contract No. AF 18(600)787. (2) H. S. Mosher and S. Dykstra, J . Am. Chem. Soc., 79, 3474 (1957). (3) K. Ziegler, A. Spaeth, E. Schaaf, W. Shumann, and E.Winkelmann, Ann. 551,80 (1942).
