BRUCEGRAHAM, A . M. GRIFFITH, C. S. PEASEAND B. E. CHRISTENSEN 1 CONTRTRVTION FROM TKE
VOl. ti7
DEPARTMENT OF CHEMISTRY, OREGON STATECOLLEGE^ ]
PtrJrirmO M w b l s Derived from Pyrimidines
c. s. PEASE AND B. E. CHRISTENSEN
BY BRUCE GRAHAM, A. hf. GRIFFITH,
the amino alco-
the Mannieh reaction. A t the suggeshn of Dr. Lyndm ,?mall, this Labratmy m-des&mk the prepration of amino
I
CHa
Experimerttal 5-eF.-Forty-three grams of a c e t s m h e ErydhcWoride (0.45 mde) was dissdved in and Bardhn.6 absofute alcohof. and added to an dcohdic sdution of Since guanidine an$ acetamidine were also so&m ethoxide (10.4g. of sodium (0.45mole) in 300 ml. found to condense with e t b c ~ ~ y k n e a c e t y l of - a h d a t e akohol). Sjeventy-twograms of ethoxymethyieneacetylacetone (0.46 mole) was added slowly with shakacetom, it was possible to prepare two additional ing. The mixture was refluxed for one hour and the akoacetyf for inttzrme&tes. hoi removed under reduced pressure. The residue was Amim hh€s prepared from these sitbstituted extracted with petroimtn ether. The latter proved to be selective tben ethyl ether, making possible the sepapyrimidines are destxikd in this paper. These more of a colored impurity. Fifty grams of crude prodwere ob*d by the reduction of the amino ke- ration uct was obtsined in this way. This was distilled at retones which were prodraced by the Mannich re- duced pressure; yieM 43 t. (63%); b. p. 62-64' at 3 mm. action. The reactions are indicated in ( I ) , (2), The melting point was 23 . I t was soluble in water. Anal. Calcd. C8HloNaO: N, 18.66. Found: N, 18.56. The picrate of this compound was prepared from an lUHl ethereal solution of the acetyfpyrimkline and an ethereal solution of picric wid. The resulting mixture was a b e d HN=C-R ----f to stand twenty-four hours, and the precipitate was then recrystallized from dry ether. The melting point was 120". 5-A*I-2-&04-Xll ' '&e.-Eighteen and four-tenths grams (0.19 -wanidme hydrochloride was disolved in 200 ml. of absolute ethanol, and 4.4g. of sodium in 200 ml. of absolute akohol (0.19 mole sodium ethoxide) was added to the guanidine solution. A white CHa precipitate formed. Thirty grams (0.192 mole) of ethoxymathyleneacetykcetone in 100 ml. of absohte alcohol was added with shaking, causing the formation of yellow crystals. The mixture was refiuxed gently for one hour, cooled, and filtered. The precipitate was washed with 300 ml. of cold water and then recrystallized from 500 ml. of 75% ethanol. The yield was 23 g. (80%) of very light CHI yellow crystals. The melting point in a sealed tube was 22;" uncor. I t sublimes above 150'. Anal. Calcd. for CrH,N80: C, 55.61; H, 6.OO; N, 27.80. Found: C, 35.74;H, 6.16;N, 27.92. An alcoholic soIution of the acetylpyrimidine, wheii \
