NOTES
May 5, 1955
2569
derivative which may be convertible to other inter- furnished 0.204 g. of 1,2-0-isopropylidene-~-glucofuranuand 0.121 g. of 1,2-0-isopropylidene-~-idoesting C 14-labeledcompounds. Furthermore, non- rono-y-lactone furanurono-y-lactone. radioactive 1,2-0-isopropylidene-L-idofuranurono- The above n-glucuronic acid derivative was converted t o y-lactone appears to be an interesting starting ma- D-glucose according to the procedure of Roseman.6 1,2-0-Isopropylidene-L-idofuranose .-Reduction of 0.230 terial for the synthesis of 1.-idose and its derivatives. g. of 1,2-0-isopropylidene-~-idofuranurono-y-lactone with lithium aluminum hydride according t o the method emPreparation of 1,2-O-Isopropylidene-~-xylo-dialdopento- ployed by Roseman6 for the corresponding derivative of nfuranose .-A solution of 22 g. of 1,2-0-iSOprOpylidene-D- glucose, furnished 1,2-0-isopropylidene-~-idofuranose (re. glucofuranose and 5 g. of sodium hydrogen carbonate in 150 crystallized from ethyl acetate); yield 0.178 g., m . ~ 113114", \ c E ] * ~ D-20" ( c 2.7, methanol), recorded' m.p. 112ml. of water was oxidized with 22 g. of sodium metaperiodate according to Sowden.8 The reaction mixture was then 114" and [ C Y ] = -29' (water). filtered and the filtrate was extracted with five 300-ml. porL-Iduronic Acid.-A solution of 1 g. of 1,2-O-isopropylitions of chloroform. The combined extracts were dried dene-L-idofuranurono-y-lactone in 25 ml. of water coritain(sodium sulfate) and evaporated under reduced pressure t o ing 5 ml. of Ainberlite IR-120-H12was heated over the steama sirup which was kept for several days in a desiccator evacubath for 3 hr. The solution was then filtered and the filtrate ated with a n oil-pump to remove the traces of formaldehyde was evaporated under reduced pressure. The residue was and chloroform. The resulting sirupy 1,2-O-isopropylidene- crystallized from methanol by the addition of ethyl acetate and was recrystallized in the same manner. The product, D-sylo-dialdopentofuranose (8.4 6 . ) furnished a semicarbazone derivative, m.p. 202-205" dec. (recordedg202-202.5'). L-iduronic acid, gave a strong naphthoresorcinol test for 1,2-O-Isopropy~idene-~-g~ucofuranono-y-~actone and uronic acids and its freshly prepared aqueous solution was 1,2-O-Isopropylidene-L-idofuranurono--,-lactone .-A solu- acid to litmus; yield 0.3 g., m.p. 131-132", [ C Y ] ~ ~+37" D tion of 0.8 g. of sodium cyanide in 30 ml. of water was (3.5 min.) + +33" (28 min., 4 hr.) ( c 3 , water). cooled t o 0 " and added to an equally cold solution of apAnal. Calcd. for C&11007: C, 37.11; H, 5.15. Found: proximately 4 g. of 1,2-0-isopropylidene-~-xylo-dialdopento- C , 37.10; H, 5.38. furanose and 1.2 g. of sodium hydrogen carbonate in 40 mi. of water containing several lumps of solid carbon dioxide. (12) Product of Kohm and Haas C o , Philadelphia, Pa After evaporation of the carbon dioxide, the mixture was DEPARTMENT O F CHEMISTRY kept at 0" for 2 days, then a t room temperature for 3 days, THEOHIO STATE UNIVERSITY and was finally heated at 60" for 5 hr. with aeration and COLUMBUS 10, OHIO concentration of the solution. The concentrated solution was then evaporated under diminished pressure to dryness and the residue was boiled briefly with 50 rnl. of methanol, cooled, 100 ml. of diethyl ether was added, and the precipi- Purines. IV. The Infrared Spectrum of Purine tate of the sodium salts and sodium hydrogen carbonate and Certain Substituted Purine Derivatives filtered, washed with ether and dried. The dry precipitate B Y C. H. WILLITS,J . C. DECIUS,K. L. DILLE AND BERTE. was dissolved in 20 ml. of water and the solution, after adCHRISTENSEN justment to pH 2 with 4 N hydrogen chloride, was extracted 10 times with 50-ml. portions of ethyl acetate. The comRECEIVED1-OVEMBER 22, 1954 bined extracts, after drying (sodium sulfate) and evaporation of the solvent, furnished a partly crystalline residue The biological importance of pyrimidine comwhich was lactonized, according to the method of Sowden,2 by heating under reflux with 40 ml. of toluene for 3 hr. pounds has led to rather extensive studies of The resulting clear solution was decanted from the small their infrared spectra2 for information which amount of insoluble material, cooled and gradually diluted might lead to their qualitative or quantitative with petroleum ether (b.p. 35-55"). The crude mixture of determination or to their identification. This the lactones which separated (1.47 g.) was dissolved in 6 ml. of ethyl acetate, 1.5 ml. of petroleum ether was added, work has been helpful in elucidating several of the structural features of certain pyrimidine compounds and the solution was added to a 2 (diam.) X 25 cm. column of Florex XXX'O and Celitell (4: 1 ) . The column was then and to the discovery of what may be characteristic developed with a mixture of the same solvents ( 4 : l ) and absorption bands associated with the presence of (using a fraction collector) the eflluent was collected in 5-ml. fractions and evaporated with a n infrared lamp. Fractions the pyrimidine ring system.3 10-13 contained crystalline 1,2-0-isopropvlidene-~-iodo- The infrared spectra of the quinazoline comfuranurono-y-lactone, which was recrystallized from acetonepounds have been studied in this Laboratory4 petroleum ether. Fraction 13 gave a mixture, and fractions and several structural problems of these compounds 14-20 furnished crystalline 1,2-~-isopropylidene-~-glucofuranurono-y-lactone, which was recrystallized from ethyl have been reso1ved.j I t was observed in the course of this work that a group of frequencies (due to acetate and petroleum ether. Further amounts of products were obtained on rechromatography of the combined mother C=N and C-C structures) common to the quinliquors and of fraction 13, followed by recrystallization as azoline ring (1478-1317, 1566-1581 and 1612before; total yield 0.546 g. of 1,2-O-isopropylidene-n-gluco1628 cm.-l) systems did not appear in the quinfuranurono-y-lactone, m.p. 120°, and 0.568 g. of 1,2-0-is;propylidene-L-idofuranurono-y-lactone, m.p. 137-138 , azolone or quinazolinedione structures. [?Iz6D + ? l o ( c 1.82, acetone). Sowden,2 in certain variaRecently Rlout and Fields6 have published the tions of 111s procedure, has found this compound contaminatinfrared spectral data of guanine, adenine, hypoxaning 1,2-~-isoprop~~lidene-~-glucofuranurono-~-~actone and thine and xanthine. A11 four of these purines were reports m.p. 128-130'and ( a ]+87.5" ~ (water). A n d . Calcd. for CgHl>Oe:C , 50.00; H , 5 . 5 5 . Found: (1) This work was supported in part by grants from t h e Division C, 50.09; H, 5.72. of Research Grants and Fellowships, National Institutes of Health, Public Health Service. Published with t h e approval of t h e M o n o In a parallel experiment, condensation of the same amounts of sodium cyanide and 1,2-0-isopropyliderie-~-xylo- graphs Publication Committee, Oregon State College, a s Research Paper No. 265, School of Seience, Department of Chemistry. dialdopentofuranose in the presence of 1.5 g. of sodium car(2) I. A . Brownlie, J , Chem. S o c . , 3062 (1950); C. L. Angyal and bonate (in place of 1.2 g. of sodium hydrogen carbonate) Experimental8
(8) T h e experiments described have been carried o u t with unlabeled materials b u t were later applied t o t h e production of D-glucoseC,-Cl* through employment of codiuni cyanide-C'J. (9) 1;. Iwadare, B d i . C h m . S < i r . J o p n u . 16, 40 ( 1 9 4 1 ) ; J . C . SOWd e n . T H I SJ o u K N . ~ ~ .7, 3 , 5496 (1951). (10) Prodcict of the 1:Ioriilin C o . , Warren, Pa. ( 1 I ) Produrt o f J u h n - l l a n v i l l s CI),, New York, N . T.
R . L. Werner, i b i d . , 2911 (1952); H . W . Thompson, D. L. Nicholson a n d L. N. Short, F a v a d a y SOC.L o n d o n , 9, 222 (1951). (3) L. N. Short and H . U'. Thompson. J . Chcm. SOL.,169 (1952). (4) H. Culbertsan, J . C. necius a n d T(. I < . Christensen, THISJOERN A I . , 1 4 , 4834 (1932). ( 5 ) 11. Culbertsan, C . IVillits and I3 I:. Christensen, i b i L , 76, 3 5 3 3 (1954). (0) 15. R. Rlout a n d A l . Fields. i b i d . . 1 2 , 479 (1930).
25iO
Vol. i 7
NOTES
2-Amino-6-methylpurine
0 4000
3000
2000
moo
1400
1600
FREQUENCY
1200
DO0
800
(cmrl).
Fig. 1.
rcported to have intense absorption bands in the regions 1670-li00 and 1558-1610 cm.-' which these investigators attributed to C=C and C=N stretching modes in the purine ring system; a third band characteristic of this type of compound was located in t h e region of 935-957 cm.-l. Since this Laboratory in the course of other work had acquired a substantial number of other purine derivatives i t appeared worthwhile to obtain their infrared spectra for purposes of comparison with the observations of Blout and Fields as well as with the related pyrimidine and quinazoline structures.
Discussion Due to the absence of tautomeric effects as well as to the influence of substituents, the study of the infrared spectrum of purine free base itself should be most fruitful in the search for absorptions characteristics of this ring system. The infrared spectra are composed of vibrations due to the component parts of the molecule as well as to those of the molecule as a whole; many of the latter are to be found in the region below 1350 cm.-I. Examination of the data in Table I1 indicates several regions of intense absorption which will be designated as group I (2500-3500 cm.-'), group I1 (1550-1700 cm.-l), group I11 (1000-1550 cm.-I), group IV (below 1000 cm.-') for purposes of discussion. Group I (2500-3500 cm.-').-This region contains
