948
SCOTT S E A R L E S , JR.,
KENNETH -1.POLLARTAND EUGENE F.LUTZ
Vol. '79
A n a l . Calcd. for C121321Si: C, 54.73; H, 8.04. Found: X X I X was characterized by coupling i t in alkaline solution C, 54.38; H, 8.12. with 8-naphthol in 907, yield t o the 4,6-dihydroxy-2-[2'naphthoxymethyl]-s-triazine. After recrystallization from Ulien the reaction was carried out with only two moles of diethylamine in ether at room temperature and worked up acetic acid, glistening leaflets were obtained, m.p. 300' dec. after 24 hr., the substitution was limited to one chlorine A t i d . Calcd. for C14HllN303:C , 62.45; H , 4.11; N, atom, resulting in 6-chloro-2-diazometh_yl-4-diethylamino-s- 15.61. Found: C, 62.45, 62.36; €1, 4.08, 4.16; S,1 5 . 3 , triazine (XX). Yellow prisms (4.5 g., 19%) were obtained 15.62. from ligroin, m.p. 52.5'. Anal. Calcd. for C8HIlClKe: The conversion of XI11 into the carbinol XXX occurred C, 42.39; H, 4.89; C1, 15.64; K, 37.08. Found: C, 42.23; spontaneously with evolution of heat when 4.75 g. of XI11 H , 4.93; C1, 14.91; N, 37.07. 4,6-Bis-ethyleneimino-2-diazomethyl-s-triazine(XXII) was suspended in 50 ml. of xvater and 0.6 g. of coned. sulfuric acid was added. After all had gone into solution, the was obtained in 527, yield by reaction of I1 with etliyleneimine (two moles) and triethylamine (two moles) in boiling carbinol was extracted five times with ether, the combined ether in an analogous manner. Recrystallizat.ion from ethereal extracts evaporated and the solid residue recrysligroin (b.p. 60-70') yielded a ycllow powder, which de- tallized from ligroin. The diazomethyltriaziries in general reacted much more easily with organic acids in the presence composed a t 108" ivithout melting. a small amount of water. Thus the conversion of XI11 Anal. Calcd. for CaH&7: C, 47.28; II, 4.47. Found: of into the acetate X X X I was best effected with 'JOYo acetic C, 47.32; H , 4.52. acid. The spontaneous reaction was completed by refluxing Conversion of the Diazomethyl-s-triazines into the Dihalo- for 10 minutes. After diluting with much water and neugenomethyl-s-triazines.--The finely powdered diazo com- tralizing with sodium bicarbonate, X X X I was extracted pound (I1 resp. XIII) was suspended in carbon tetrachloride with ether. The residue remaining after evaporation of containing one mole of the required halogen and kept at room the ether was recrystallized from ligroin. The reaction of temperature with stirring for 24 hr. If the halogen had not XI11 and X X I with the aromatic acids w-as carried out in yet reacted completely, the reaction mixture was then re- xylene with an excess of the acid and addition of about 1'; fluxed for 2-3 hr., filtered from solid by-products and the of water. After refluxing for 3-4 hr., the reaction mixture solvent removed by distillation. The residue was frac- was diluted with ether and the excess acid extracted with tionated twice under vacuum. In the case of the di-iodo sodium bicarbonate solution. The solvents were then rcderivative XXIV, which decomposes on heating, the crude moved by distillation, the last of the xylene being removrtl product was recrystallized from ligroin. Data of the in- under vacuum. The residue was recrystallizcd from ligroin, dividual compounds are compiled in Table I. in the case of X X X I I I preferably by seeding. Physical Reaction of the 2-Diazomethyl-s-triazines with Acids.and analytical data for the above compounds are compiled The diazomethyltriaziiies I1 and XI11 were dissolved in in Table 11. ether and an excess of hydrogen chloride passed in, followed Z-Chloromethyl-4,6-diamino-s-triazine (XXXIV).--A sat uby refluxing for 3 hr. After filtering off the insoluble hydro- rated solution of ammonia in ethanol (25 ml.) was added chlorides and evaporating the ether, the products XXVII dropwise a t 0" to a solution of 3.2 g. of 2-chloromethyl-4,0and XXVIII were isolated by vacuum distillation or recrys- dichloro-s-triazine (XXVII) in 3 ml. of anhydrous ether. tallization from ligroin. The amount of the insoluble hydro- The yellowish precipitate was collected and recrystallized chlorides could be considerably increased if the treatment twice from 20 ml. of water with addition of charcoal to give with hydrochloric acid was extended for two days. For white needles (1.7 g., 66%). The substan:e XXXIV darkexample, from 12.6 g. of 2-diazomethyl-4,6-dimethoxy-s- ened above 220" but did not melt up to 330 . triazine ( X I I I ) in 1500 ml. of pure anhydrous ether, we ob.lnal. Calcd. for CrI-I&l?i,: C, 30.11; €1, 3.79; C1, tained 10.1 g. of the crude hydrochloride of 2-chloromethyl4,6-dihydroxy-s-triazine(XXIX)(found: -2T, 21.12, 21.25; 22.21; N, 43.89. Found: C, 30.81; H , 3.83; C1, 21.84; C1, 36.02, 36.13). From the mother liquor another crop s,43.37. (0.6 g : ) of X X I X deposited after standing overnight (for COLUXBUS. OHIO analysis rf. Table TI).
[ COSTRIBUTIOS
FROM T H E
DEPARTMENT O F CHEMISTRY, KANSAS STATE COLLEGE]
Oxetanes. V1.l
Reductive Cleavage and Substituent Effects' B Y SCOTT SEARLES, JR., KENNETH A.POLLART AND EUGENE F. LUTZ RECEIVED AUGUST3, 1956
Reductive cleavage of ten oxetanes, having two or fewer alkyl substitucnt,s, has been carried out with lithium a l u ~ n i nun1 hydride and that of 2-phenyloxetane, with lithium borohydride. h single alcohol product was formed in cach case, cleavage of unsymmetrical oxetanes occurring between the oxygen atom and the least substituted a-carbon atom. The ease of cleavage was found to be much affected by substitution, particularly gem-dialkyl substitution at position 3 , which caused marked deactivation. These substituent effects are discussed. The preparations of 2-phenyloxetaxxe and 3-xneLhy~oxetane are described for the first time.
Reductive cleavage of the oxetane (trimethylene oxide) ring would be of obvious value in establishing the structure of new oxetanes, as well as in certain synthetic applications. Reductive cleavage of 1,2-epoxides has been very widely and successfully (1) Earlier papers considered t o be in this series are: (a) S.Searles, 73, 124 (1951); (b) 4515 (1951); (c) S. Searles and C . 1'. Butler. ihid.. 76, 56 (1954); (d) S. Searles, i b i d . . 2313 (1954); S. Searles a n d V . 1'. Gregory, ibid.. 2789 (1954). (2) Portions of t h e dissertations presented by K . A . P. (1956) and t o be presented b y E. F. L. in partial fulfillment of t h e requirement for t h e degree Doctor of Philosophy in Chemistry a t Kansas State College. T H I S JOURNAL,
~ s e d ,and ~ , its ~ extension to oxetanes was suggested by the fairly high degree of reactivity observed for trimethylene oxide in Grignard reactions and in other reactions.' The smooth cleavage of triniethyletle oxide with lithium aluminum hydride, forming n-propyl alcohol, was reported in a preliminary fashion several (3) Lithium aluminnm hydride reductions are reviewed h y W €3 Ihown in hdanis' ''Organic Reactions," Vol. V I , J o h n \Vlley and Sons, Inc., Piew York, pi. Y., 1061, p . 476. ( 4 ) R I . S. Newman, G. Underwood and &I. Renoll, T H I S J U U K N A I . . 71, 3362 (1949).
Feb. 20, 1957
REDUCTIVE CLEAVAGE AND SUBSTITUENT EFFECTSIN OXETANES
years ag0,5 but recently other workers have reported that certain tri- and tetrasubstituted oxetanes were not cleaved by this reagent.6t7 It may be of interest that in this Laboratory reductive cleavage of the oxetane ring with lithium aluminum hydride has been accomplished with all the oxetanes studied in connection with a general program of investigation on these compounds, but none of these possessed more than two alkyl or aryl substituents. The results with eleven representative compounds are presented in Table I. TABLE I LITHIUMALUMINUM HYDRIDE REDUCTION OF OXETANES Substituents None 2-Methyl 2-Ethyl 2-Phenyl 2,2-Dimethyl 2,2-Diethyl 3-Methyl 3,a-Dimethyl 3,a-Diethyl 2,3-Dimethyl 3-Ethyl-2-propyl
Products 1-Propanol 2-Butanol 3-Pentanol 1-Phenyl- 1-propanol 2-Methyl-2-butanol 3-Ethyl-3-pentanol 2-Methyl- 1-propanol 2,2-Dimethyl-l-propanol 2-Ethyl-2-methyl-1-butanol 3-Methyl-2-butanol 3-Methyl-4-heptanol
Conditions5 and yields E, 3 T, 7 Other 45% 32
65%
60
31 36
70
56 (T,14) 73 (E,20) 55 (T,13)
42
66
