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V O l . 81
COMMUNICATIONS TO THE EDITOR
nitrogen trifluoride and ammonium fluoride (Equation l), although the presence of other nitrogen fluorides was postulated.
TABLE I EQUILIBRATION OF cis- AXD trans-4METHYLCYCLOHEXYLMERCURIC BROMIDES Expt.
Solvent
Temp., OC.
Starting isomer
1
Pyridine
95
tsans-
2 3
Pyridine Pyridine
95 95
transcis-
Method of analyiis
5: 61s..
Isolation 54 of products Infrared 62 Infrared 54
%
t;,anP-
4G 48 46
4SH3
+ 3Fz +NF3 + 3XHaF
(1)
Yields of NF3 were about 670, based on the fluorine consumed. Evidently the ammonia was largely converted to nitrogen and hydrogen fluoride 2NH3
+ 3F2 +Nz + 6HF
(2)
\Ye have reinvestigated this reaction in a packed brating conditions, was cleaved stereospecifically T-shaped copper reactor, using both an excess of with retention of configuration by mercuric bro- fluorine and of ammonia. Nitrogen was employed mide. The resulting mixture of cis- and trans-4- to dilute the reactants, and reaction proceeded xnethylcyclohexylinercuric bromides contained an smoothly with moderate evolution of heat. LVith excess of the cis-isomer. Also the equilibration excess fluorine, results paralleled Ruff's, although of the cis- and trans-4-methylcyclohexylmercuric KF3 yields were higher but, with excess ammonia, bromides was carried out in dioxane a t 98' using NzF4 also was obtained. The conditions employetl benzoyl peroxide as the catalyst. In these cases, are summarized in Table I. greater decomposition occurred than in the equiliTABLE I bration in pyridine, product recovery being 65REACTIOSCONDITIONS 70%. Again, the cis-isomer was present in greater Excess S I 1 3 Excess Iit concentration. 1.1 : 1 (Stoichiometric 1 . 5 : 1 to 2 . 0 : 1 Ammonia-fluorine Although the present data do not permit an exact ratio = 1.33:l) determination of the ,4 value for the bromomercuri 5 : 1 to 20 : 1 5.0:l group, they indicate that the A value is approxi- Ntrogen-fluorine ratio mately 0. This lack of a preference for an equaCopper shot or gauze Copper gauze torial over an axial conformation probably is due, Reactor packing 1 . 5 to 2 . 3 a t least in part, to the long carbon-mercury bond Fluorine flow rate 1 . 3 to 2 . 5 liters/hr. liters/lir. and the high polarizability of the mercury atom, which minimize the a,a-1,3, bromomercuri group, The yields of NF3 in the excess fluorine reaction hydrogen atom interactions. Eliel and Haber were from 39 to 66% based on Equation 1. T h e proposed that the relatively small equatorial combined product from a series of runs analyzed preference of the bromo group ( A = 0.73 kcal./ by mass spectral analysis had the composition: mole) is due to a,a-1,3 London force^.^ This type NF3>88.257,; CF4, 9.40%; NzO, 2.35%. The of attractive force, and more specific interactions, infrared spectrum agreed with a reference specmay be important with the bromomercuri group. trum of NF3.3 (Carbon tetrafluoride probably was The absence of a conformational preference for the an impurity in the original fluorine.) Ammonium bromomercuri group indicates that steric inter- fluoride also was isolated and identified by actions are not necessarily directly related to the chemical and infrared analysis. radii of the groups involved. The results presented In the excess ammonia reaction, unreacted anihere suggest that certain groups with large radii, monia was removed by water scrubbing or adsorbed such as the bromothallo group, may prefer the on CaC12 or Linde molecular sieves. The gaseous axial conformation. products then were passed through a -78' trap Dinitrogen tetrafluoride and collected a t - 1DG'. (4) E. L. Eliel and R. G . Haber, THISJ O I I R Z I A I . , 81, 1249 (1959). DEPARTMENT OF CHEMISTRY FREDERICK R. JESSES was purified by removing more volatile impurities from a trap held a t - 142' (methylcyclopentane). OF CALIFORNIA VXIVERSITY 4, CALIFORNIA BERKELEY LAIRDH. GALE The infrared spectrum of this purified fraction RECEIVED OCTOBER 19, 1959 exhibited the same bands as reported by Colburn and Kennedy1 and was virtually identical with that of a pure sample of NzF4prepared in our laboratory T H E FORMATION OF DINITROGEN by NF3 pyrolysis. The band a t 8.0 p and the TETRAFLUORIDE IN THE REACTION O F doublet a t S.92-8.97 1.1 are ascribed to C?Fe present FLUORINE AND AMMONIA in the original fluorine. Based on the fluorine conSir: The preparation of dinitrogen tetrafluoride verted to NF3 and N2F4,the yields of NzF4 were as (NzF4) by the pyrolysis of nitrogen trifluoride over high as 11%, while NF3 yields ranged from G to copper was reported recently.' XVe now wish to 24%. The isolation of N2F4and the higher yields of report the formation of this compound by the vapor phase reaction of fluorine and ammonia in a packed NF3 obtained in our work are believed due, a t least partly, to the use of a packed reactor. The copper reactor. Ruff and Hanke2 investigated the vapor phase copper packing reduces the intensity of the reaction reaction of fluorine and ammonia in an unpacked and prevents the conversion of ammonia to copper reactor using both an excess of fluorine and nitrogen and hydrogen fluoride. We wish to acknowledge the assistance of Mr. C. of ammonia. The products in both cases were W. Schoenfelder in some phases of this work, and (1) C. R. Colburn and A. Kennedy, THIS JOTRNAL, 80, 5004 (1958). to thank Mr. L. Adlum for the infrared analyses, (2) 0. Ruff and E. Hanke, 2. anorg. ZL. d i g e m . C h e m . , 197, 394 (1931).
( 3 ) IC. L. Pace and I,. Pierr?, J . Cliein. Phys.,
23, 1248 (1%;).
Dec 5 , 1959
COMXUNICATIONS TO THE EDITOR
6339
and Mr. D. Y. Yee formerly of New York University 240°, C22H250jN (C, 68.1; H , 7.06; N, 3.20), for determining the mass spectrum of the nitrogen which gave an intense orange color with ferrous trifluoride sample. This work was supported by the sulfate.I0 Accordingly, a propenyl group is atAir Force under Contract No. AF33(616)-5222, tached to C-3, The C-8 position should be vacant Mr. Forrest Forbes, Project Engineer. because of the positive diazo coupling reactions of REACTION MOTORSDIVISION SCOTTI. MORROW I and derivatives. Taking into account the presTHIOKOL CHEMICAL CORPORATION DONALD D. PERRY ence of three C-CHI groups in monascaminone, DENVILLE, NEW JERSEY MURRAY S. COHEN these results can be expressed by the partial strucRECEIVEDSEPTEMBER 21, 1959 ture I, and evidence to extend this to VI was provided by structure considerations of monascorubrin (following communication). MONASCORUBRIN. I. "MONASCAMINONE," A DEGRADATION PRODUCT
Sir: Monascorubrin, first isolated by Nishikawal from Monascus purpureus Wentii, belongs to the group of azaphilones2 such as sclerotiorin3 and c23r o t i o r k 4 hfonascorubrin, m.p. 134-136', Hz60S5 (C, 72.2; H, 6.66), [ ~ ] ' ~ 7 0 0 -1500' (C 0.1% in EtOH), C-CH3 2.5, reacts with ammonia6 192', C23H2704N to give m ~ n a s c a m i n e , m.p. ~ (C, 72.2; H , 6.93; h', 4.10), [ c Y ] * ~ ~ ( ; o-2600' (C 0.125% in CHClJ, which when treated with zinc in various media is converted into monascaminone (I),8 m.p. 186O, Cz2H29O2N(C, 77.8; H, 8.50; N, 4.08), [ a ] D O o , XEt,"," in mp 253 (4.73), 302 (3.95) and 352 (3.78),:,"v in cm.-' 1710 (C=O). Hydrogenation of I furnished dihydromonascaminone (II), m.p. 97-98', X",t,o," in mX 239 (4.69), 1717 an.-' (C=O), 288 (3.53) and 343 (3.69),;::v and octahydromonascaminone (111), m.p. 181', XE2" in mp 226 (3.90) and 282 (3.11). Thorough spectroscopic comparisons of I1 and derivatives with synthetic hydroxyisoquinolines established the nucleus to be 7-hydro~yisoquinoline.~ Beckmann rearrangement of inonascaminone oxime, m.p. 211°, gave n-heptylamine. Treatment of I with sodium borohydride afforded monascaminol (IV), m.p. 196-197', C22H3102N (C, 77.1; H, 9.10; N, 4.31), ":A: in mp 256 (4.80)) 307 (3.88) and 352 (3.77), which when heated in polyphosphoric acid a t 150' gave dehydromonascaminol (V), m. 192-3', C Z ~ H Z ~ (C, O N81.3; H, 9.34), XZ"; in mK 225 (4.33), 262 (4.59), 318 (3.75) and 352 (3.69). The infrared peak a t 1710 cm.-' in I, and comparisons of the ultraviolet peaks of I V and V with I demonstrate that the nheptoyl chain must be attached to the aromatic nucleus through one saturated carbon atom. Permanganate oxidation of I afforded pyridine-l,34-tricarboxylic acid. Ozonolysis of O-acetylmonascaminone, m.p. 76-79', gave acetaldehyde, and subsequent hydrogen peroxide oxidation of the nonvolatile ozonolysis product furnished an acid, m.p. (1) H. Nishikawa, J. Agr. Chcm. SOL J a p a n , 6, 1007 (1932). (2) A. D. G. Powell, A. Robertson and W. B. Whalley, Ckem. Soc., Special Publ., No. 5, 27 (1956). (3) G. B. Jackman, A. Robertson, R . B. Travers and W. B. Whalley, J. Chcm. SOL.,1814 (1958); J. H.Birkinshaw and P. Chaplen, Biochcm. J . , 69, 505 (1958); H. Watanabe, J . Pharm. SOL.Japan, 7 3 , 807 (1952): Y.Yamamoto and N. Nishikawa, ibid., 79, 297 (1959). (4) G. B. Jackman, A Robertson, R. B. Travers and W. B. Whalley, J. Chem. Soc., 1825 (1958). ( 5 ) Analyses of monascorubrin and derivatives also agree with the CzzHz601 formula adopted by Nishikawa' and Powell, ct al.2 (6) Hence the name azaphilones. (7) Also a fungal metabolite; described as monascorubramine in reference 2. ( 8 ) Described as dideoxymonascorubramine in reference 2. (9) These results will be reported elsewhere in detail.
CHjH U-C-H
c c)C-C * ,H
H
H H
H
(10) H.Ley, Chr. Schwarte and 0. Miinnich, Bcr., 67, 349 (1924).
CHEMICAL INSTITUTE MAMORU OHASHI SAGOYA UNIVERSITY SHO-ICHIRO KCMASAKI CHIKUSA,NAGOYA SHOSCKIYAMAMURA OF CHEMISTRY DEPARTMEST TOKYO KYOIKU UNIVERSITY (INQUIRIES TO) OTSUKA, BUNKYO, TOKYO KOJI XAKANISHI PHARMACY DEPARTMENT SACOYA CITYUNIVERSITY MIZUHO,SACOYA HISASHIKOIKE RECEIVED SEPTEMBER 9, 1959 MONASCORUBRIN. 11.' STRUCTURES OF MONASCORUBRIN AND MONASCAMINE
Sir: Probable structures I and I1 are assigned to monascorubrin arid monascarnine, respectively, and the partial structure of inonascaminone (111)' is completed. Comparisons oi the ultraviolet arid infrared (16qO-1530 cm.-' skeletal stretching rcgion) of I and I1 and their dihydro derivati\-es suggested that the conversion involved was meiely an exchange of -0- for -SH-. Furthermore. production oi I11 under various conditions indicated the absence oi skeletal rearrangements, and thus the framework of 111 is retained in I and 11. The five-membered lactone? and keTABLE I INFRARED CARBONYL BANDS,CM Monascorubrin ( I ) (CCI,) Monascamine (11) (CC14) Monascamine-HC1 (KBr) N-Methylmonascamine ( CCl,) Tetrabromomonascamine2 ( KBr) Secomonascamine ( I V ) (KBr) Tetrabromosecomonascamine* (KBr) Secomonascamine-HC1, Form A (Nujol) Form B (KBr)
1759 1734 1745 1733 1796 1703 1795 1715 174.5
1729 1705 1718 1712 1742 1742 1725
(1) Paper I, preceding communication. (2) Though definite structures cannot yet be assigned t o t e t r a bromomonascamine, m.p. 88-91', CtrHlaOlNBr4, and tetrahromosecomonascamine, m.p. 138-140°, C!xiH~v0&TBrr.their infrared spectra serve t o demonstrate the presence of an a-bromo-y-lactone. The lactone is lost as carbon dioxide during the conversion of I1 t o 111.
