3224
BOOK REVIEWS
Vol. 84
NMe2 I
R
..
,
0
Me0
IX X XI
OH
R:OH
R = OCOOCHMe2 R = CH(COOEt)CONHBu7
CONHR‘ I
RO
I
0
I
I
OH
I
OH
XI1 : R = M e , R ’ = B d XlII : R = R ’ = H
degradation of 6-demethyl- 6-deoxytetracycline .8 The acid IX was converted to the corresponding JVhen the synthetic (XIII), in the presence of isopropylcarbonic mixed anhydride X6 [m.p. 132’ cerous chloride (1 mole/inole) was subjected to the (dec.). Found: C, 6432; 13, Ii.77; N, 3.411in action of molecular oxygen in dimethylformamide/ the usual manner, and condensed with the magne- methanol solution, brought to apparent pH -5 sium derivative of ethyl S-tert-b~tylmalonamate~with glycine/sodium hydroxide, i t was transformed (IC), in acetonitrile to yield the crude acylmalonamate into racemic 6-demethyl-6-deoxytetracycline XI.6 The latter, by direct treatment with excess [B.HCl. 0.5Hs0, m.p. 223-226’ (dec.). Found: sodium hydride in dimethylformamide a t 3 2O0, C, 54.94; H , 5.46; X, 5.661. The characteristic ultraviolet spectrum [AXm,, 111p ( E ) , 267 (19,300), gave 2-N-tert-butylcarbamoyl-4-dimethylaniiiio--l,1a,5,5a,6,11- hexahydro - 1,3,12- trihydroxy - 10- 347 (15,300) in 1leOH~O.Ol:hr HC1; 248 (16,600), inethoxy - 11 - oxonaphthacene (XII)6 [ n i p . ,-261 (15,600),--L‘X4 (10,100), 383 (18,300)in 215-216’ (dec.); AX,, nip (E), (initial) 254 IIeOH/O.Ol iV NaOH] and the paper chromato(12,900), 325 (9,3001, -42C) (2l,(iUO), 436 (26,700), graphic behavior [toluene/’pyridine/water, nitro-496 (22,400) i n AIeOH, 0.01 HCl. Found: methane/ 1-butanol/toluene/pyridine, ethyl aceC , 66.95; H , 6.80; S,Ci.041 Hydrolysis and de- tate/nitromethane/’chloroform, ethyl acetate/ alkylation of XI1 in hot Ab56 hydrobroinic acid chloroform/pyridine, ethyl acetate/water] of this gave 4-dimethylarnino-4,4a,5,5a,6,1 l-hexahydro-1,- racemic substance were identical in all respects with 3,10,12-tetrahydroxy-ll-oxonaphthacene-2 - carbox- the corresponding properties of an authentic sample amide (XIIIJG [m.p. 223-224’ (dec.). Found: of 6-demethy1-6-deoxytetra~ycline.~It is of much C, 63.27;H , 5.51; Tu’, 6.T.31. The highly character- interest that the synthetic racemic material was found t o be exactly half as active as the levorotaistic and time-variable ultraviolet spectrum [AX,,, tory antibiotic of natural provenance when assayed iiip ( E ) , (initial) 260 (12,000), 326 (10,300),-40s turbimetrically against K . plzeunzoniae. jl(;,(iOO), 429 (23j(X10), 451 (20,100) in hIeOH/ Acknowledgment.---The authors are indebted to 0.01 AV HC1; 247 (13,G00), -262 (13,000), 37s (9>5[10),-447 (17,9(HI),470 (24,tXOj, 495 (22,900) 1Zr. E. J. Rianco for the preparation of intermediates. 111 AIeOH, 0.01 S XaOH] and the piper-chromatographic behavior [ethyl acetate ’nitroniethane 1 ( 8 ) I
