April 5, 1956
1-P-BROMOBENZOYL-2-NITRO-3-PHENYLCYCLOPROPAN€C
in the spectra indicated that the derivatives vicre not identical. Anal. Caled. for CrPHl6S506Ur: C, ,5021; H , 3.07. Found: C, 50.50; H, 3.60; C, 50.61; H , 3.37; and C, 49.45; H, 3.29; for the derivatives of Ia, I b and IC, respectively. 4-Phenyl-l-p-brornophenyl-l,d-butandione, XIV, and its Copper Eno1ate.-Ia (1 g., 0.0029 mole) was added to a solution of sodium hydroxide ( 2 g.) in 95% alcohol (40 ml.). T h e red mixture was left at room temperature overnight, then poured into ice-water, acidified with dilute sulfuric acid, and extracted with ether. T h e ether extract was shaken with saturated aqueous cupric acetate, and the green cupric enolate was separated and washed with ether and with water. T h e enolate, melting a t 224-227' dec., was shaken with a mixture of ether and dilute hydrochloric acid. The ether layer was washed with water, dried (AIgSO,), and concentrated. T h e orange residue of XIV crystallized from methanol as light or:rnge plates (0.25 g., 27%) melting at
1175
The ultraviolet absorption spectrum (2.83 X 10-5 ,VI in
u.S.p. 95% ethanol) of the second analytical sample showed a maximum at 286
rnp, t 21,000; there wCisa shoulder on the curve; by extrapolation of the main absorption through this shoulder and subtraction, there remained a second maximum at 259 mp, E 4,100. Hy&olysis of the Enol Ether XV to the Diketone X1V.XV (0.20 g., 0.0006 mole) was dissolved 111 boiling methanol (10 ml.), and concd. hydrochloric acid ( 5 drops) was added. The solution was boiled for one hour, theii poured into water (75 inl.) and extracted with ether (two lo-?]. portions). T h e ether extract was washed with water, drled (MgSO4), and evaporated. The residue crystallized from methanol as The light tan plates (0.07 g., 38%) melting a t 79.5-80'. melting point of a mixture with the analytical sample of S I V was the same.
3-Carbomethoxy4-benzyl-6-p-bromophenyl-Z-pyron~
79-SI '.
(XVII).-To a boiling solution of sotliuiii (o.(;u g . , 0.026 I n a n identical experiment, I b was coiivcrted into S I V mole) atid dimeth)-l nidoniitc ( 3,!I6 g . , 0.030 niole) in ab(0.30 g., 33%) melting at 77-80". The enolate (0.30 g., solute methailol (160 inl.), Ie ( 2 M g., 0.IJll) mole) was added. 3?0/,),melting a t 224-237" dec., was obtained from an iden- The solution \vas rcfluxctl ior 1.5 hours, theti set aside overtical experiment with IC, but a portioii of the material was night a t room tcmperaturc. I t \ u s then acidified with lost so t h a t the yield of SIV (0.11 g., 137,), melting at acetic acid t o pH 6, and coiiceiitratccl. ?'lie product, in79.5-S0°, was lower. T h e melting poiiiis of the samples of itially a s a n oil, later solidified. An ana1ytic:tl s:iniplc of XIV obtained in these experiments v-ere undepressed when XVII (0.12 g., 2.5%) melting ut 1-46-1-18" was prepnretl mixed with the light tan analytical sample, melting at 80by three recrystallizations froiii nicthanol. S0.5". obtained from a mixture of In and Ib. .-lnal. Calcd. for C d I , j 0 4 B r : C, 60.17; IT, 3.79. A ? d . C:ilcd. for CIGHI302Br:C, 00.57; H, 4.13. Found: C, 59.90; H, 3.83. Found: C , 60.58; H , 1.33. The residues froin the cry>talliz:ition of S V I I werc tlis3-Methoxy4-phenyl-1 -p-bromophenyl-2-buten-l-one solvrd in benzene ant1 the solution was pnsserl through a (XV).-In separate experiiiients, niethanolic sodium nicth- srr,all c11rorn:itogr:iphic coliiniii ~ ) : ~ c k cwit11 d inagiicsiuiii trioxide ( 3 0 inl., 1 .V) IV:IS added to each stereoisomer of I ( 1 silicate-Hy-Flo. The most mubile component (0.15 g.), g., 0.002!) inole), :ciid thc mixture was left a t room tcmperamelting a t 83-!)!1°, was iwl:itec!. Aftcr three recrystallizature for one da>-. Tlic red solution was poured into icetions froin nicthanol, the sulj>t:iiicc (0.07 g . j nicltrd a t water (I60 g.) awl cstrt;ctctl n-it11 ether (tliree .lO-ml. por99.5-10-Lo; the nieltini: point of a iiiiitui-c w i t h S'i IWS untionsj. The cornl)i~ictlctlicr cxtracts w x e wished with 5y0 tlcpresscd . aqueous sodium hic;irl)on:itc ( 3 ) nil.), then with \vntcr (two -,liiol. C.ilctl. fcr C,;IIl:,02Br: C, 0 1 . G d ; 11, ,i.?~i'. 70-rnl. portions). The ctlicr solutioii was dried (LIgSO,) Found: C , W.70; 11, .j.;2. and the solvriit IV'I- i-eniovc(l. The rcsi(lue w:is cr>-stnllizetl S V I I \\:is :ilw ni:rtle fi-oiii I:i < t : : d froiii I!) 1)y the above from alwAutc inctlitir!ol. Thick or:iiigc ncetllcs of S V (0.20 procedurc. S V I I (0.19 g., 105;; I ol)t;iiiit.cl froin 1 g. of 1:t g., 20%; 0.99 g., 31Jr;; and 11.95 p., 2t;C from I n , 11, and melted a t i-&:I-14.5.5'; thxt (0.05g., .1Yc7,)f r o m 1 g. of Ih incltiiiz a t 10'7.5-103.
