mcthylthio-.i-pSrrolealdehydc (m p 105-106O, ‘T(f10 = 0.69, 71 = 3.78, T4 3.12, T S C f I = 7.59 p p rn., .I7$ - 3 8 c / s ?no1 Cnlcd for CEW;?\‘OSC, ;il 0 4 ; TI, 1- X3; N.9 92; S,22.i1 : I’ound C, 41 ; TI, 3 13, h., 10.08; S,22.36), thus giving further ~r;dc!irc~ that 1he original rncthylthiopyrro!c is the 2- imvcr. Additioual evidence agaiiist preferential ,?-thioc.yaiiation in pyrrolcs is obtained from the flirt that 2-mcthylpj-rrole yields 5-thiocyano-2nicthplpyrrolc (m p G3 5-66’, r3 = 4.13, r4 = 3.36 p p.rn , J C H3 ~= 0 80, J c ‘ I 4~ ~= 0.33. = 3.55 c 9 Anal Cnlcd. for CJIJ2S: C, 32.13; $1, 4 38; S ,20.28; S, 23 19: Found: C, 52.22; H, 4 3 0 ; K, 20 21; S, 22 86.) upon thiocyanatiori with cupric thio-ynnatc, the XMR eT,idence for its structure bciiig based on the valucs of the chemical shifts and ring-coupling constants, iii addition t o the sidechain coiipliiigs Since thc qtructure of 111 is proved beyond any doubt by Snyder et al and since it is very improbable that any rearrangement occurred in the transformation of the thiocyanopyrrole to methylthiop>rrole or (prrro1ylthio)acetic acid, the discrepancy betwecii oiir rcsultq and those of Matteson and Snyder rcgarding the structure of the thiocyanopyrrole must hc ascribed to a rearrangement during the cychaat ion of (2-pyrroly1thio)acetic acid with pol>7p1.insphoricacid to 111. Rearrangements during treatment with poljyhosphoric acid, although not analogous to lhat found here, have been observed b,v others A detailed account of the observations reported herc n 4 l bc published in Brlziv Kemi. l o p ’
to have a ketone carbonyl group formed with elimination of one mole of water, and to absorb one mole of hydrogen without reduction of the carbonyl group.5 AIoreover, it has been shown that this dehydration takes place between two tertiary hydroxyl groups of compound I.5 On the other hand, on the basis of the biogenetical viewpoiii t as well as experimental results, Marion and his co-morkers6-8 have pointed out that delcosiiiel (lucaconiiie) (I) probably possesses the same carbon-nitrogen nucleus as lycoctonine, and also that this base is represented by the structure I shown below. In the belief that their conclusions
I
OCHB OCHS 11. R=Hz, R ’ = R ” = A c 111. R = O , R ‘ = R ” = H
are quite reasonable, the present authors nom mould like to propose structures I1 aiid I11 for anhydrodia~etyllucaconine~ and anliydrooxolucaconine (111),4respectively. Compound I11 has previously been obtained from both compound I1 and oxolucneonine through two steps.4The mechanism of the above dehydration is considered to be analogous t o that of the dehydration of oxolycoctonine or
demethyleneoxodelpheline.g
The ultraviolet absorption spectrum of compound 111 in methanol shows a maximum a t 301 ilcknoi~ledgment~Financial support from the mp (log t: 2.01) while compound 11 manifests a Swedish Nal ural Science Research Council and maximum a t 237 mp (log E 3.20). The limiting from the Swedish Technical Rcsearch Council is structure IIa of compound I1 seems to give a good explanation of the marked difference between these acknowlcdgcd. two absorption bands. h similar phenomenon I K S T I l I TTz OF (’(HEMISTRY SALOGROAOV ITZ was observed and interpreted ill the case of some 1IiYIiA-BRITT.4 HORUFCLIIT C V I T E R H r Y O F UPPS4TA Bo G E ~ T B L O Mdelphinine and rieoliiie derivatives. l o ITPPSAI4, SME U L K RAGUARA IIOFFMAX (1) It has been shown that lucaconine is identical with Received April 27, 1961. (9)H.R Sngder, L. A. Carpino, J. F. Zack, Jr.. and J. I‘ LIilL, J . h n .Chem. Soc., 79, 25156 (1957). (10) J. E. htnfield, ST’. Davies, N. IT., Gamble, and S. Rliddleton, J . Cham. Soc 4791 (1956). (11) ST. I):~vi(’sa t i d ( 1957 ).
S
Middleton, Chenz. & I n d , 599
delcosine,2 and therefore anhydrodiacetyllt,caconine is identical n i t h diacetyldelcosine (m.p. 159-161”) obtained by Marion et nL.8 The name “lucaconine” should br revised to “delcosine.” (2) T. -4miya and T. Shima, in preparation. (3) W.I. Taylor, W.E. Walles, and L. Marion, Can. J . Chem., 32,780 (1954). (4) S. Furusawa, Bull. Chem. SOC.Japan, 32, 399 (1059) f5) T. Amiva and T. Shima. Bulr Chern. Soc Javan. 31. 1083(1958). “ (6) V. Skaric and L. Marion, J . Am. Chem. Soc., 80, 4434 (1958): V. Skaric and L. Marion, Can. J . Chem., 38, 2433 (1960). (7) R. A n e t , D. W. Clayton, and 1,. Marion, Can J . Chem., 35,397 (1957). (8) R. Anet and 1,. Marion, Can. J . Chenz., 36, 766 (1958). (9) E. S.Stern, The Alkalozds, Chemistry and Physioloqv, Vol. VXI, R. H. F. Manske, ed., Academic Press In?., New York, 1960, p. 473. (10) K. Wiesner, H. W. Brexver, D. L. Simons, 11. R. Babin, F. Bickelhaupt, J. Kallos, and T. Rogri, Tetrahedron Letten, S o . 3, 17 (1960). .
On Anhy drodiacetyllucaconine (Diacetyldelcosine,’ M.P. 159-161’) and Its Derivatives
Sir : I’reriously, it was shown that ai1 aconite nlkagave anhydrodiloid, lucaconine (I) (Cn4H3,07S), acetyllucaconine (11) (C28H4,0sS)on treatment with acetyl chloride.4Compound 11has been found
,
I
JULY
IIa
Furthermore, the formation of anhydrodihydrodiacetyllucacoiiine (IV) (C2J14308iV) from compound I1 by hydrogenation, may be expressed in the following way (I1+ IIh +-IV) (Scheme A). The ultraviolet absorption spectrum of compound IV shows only end absorption. Compound I11 was recovered unchanged after being subjected to the conditions leading to the hydrogenation of compound 11.
OCHB OCH‘;
2617
COMMUNICATIONS
1961
ic IIb
“mercuric a ~ e t a m i d e , ” ~and mercuric trifluoroacetate5 have also been used. An excellent variant of this method has been developed by Cava, Litle and Napier,6 who prepared a-diazo ketones by the action of sodium hydroxide on the monotosylhydrazones of a-diketones. We now report on two new methods for the oxidation of the monohydrazones of a-diones which appear to have considerable general utility. (i) “,4ctivated” manganese dioxide7 rapidly oxidizes the hydrazones in chloform solution to the corresponding a-diazo ketones in high yield. In a typical experiment 1.OO g. of 1-mesitylglyoxal 2-hydrazone8 was dissolved in 15 nil. of chloroform (reagent grade) and to the solution was added 1.5 g. of “activated” manganese dioxide; the mixture was stirred for 1 hr. a t room temperature, with initial cooliiig t o abate the exothermic reaction. It mas then filtered and the solvent was evaporated to give a quantitative yield of 2-diazo-2’,4’,6’trimethylacetophenone, m.p. 59-61 O dec. The infrared spectrum of this product was indistinguishable from that of a recrystallized sample, m.p. 59-61’ dec., of the authentic diazo ketone prepared by oxidation of the hydrazone with mercuric oxide.* The latter method gives a less pure crude product in 75% yield. Manganese dioxide has also been used for the preparation of 2-diazopropiophenone, 2-dias0-2~,4~,6‘-trimethylpropiophenone, 2-diazo-2-phenylacetophenone (azibenzil) , 3-diazo-Z-butanone, 3-diazo-D-camphor, and 2diazo - 1,5,5- triniethylbicyclo [2.2.lJheptan 3 -one from the corresponding hydrazones ; the scale varied from 0.060 g. to 10 g. of hydrazone and the weight of manganese dioxide used was cor, 1.5 times that of the hydrazone. In every case the diazo ketone was obtained directly from the reaction mixture in 90-100% yield and mas free from significant amounts of impurities as vouchsafed by its infrared s p e ~ t r u m . ~ (ii) a-Diazo ketones may also he prepared by oxidation of the corresponding hydrazones in methanolic solution containing sodium hydroxide with calcium hypochlorite. I n a typical experiment, 0.100 g. of D-camphorquiiioiie monohydrazone4 was dissolved iii 5 ml. of methanol and 1 ml. of 0.05~11aqueous sodium hydroxide was added, the solution was stirred with 0.250 g. of calcium hypo-
-
Scheme A
Acknowledgment. The authors are grateful to Professor Harusada Sugiiiome, President of Hokkaido University, for his unfailing kindness in encouraging this work. DEPARTMENT OF CHEMISTRY FACULTY OF SCIFJCE
TAKASHI AMIYA T A K E 0 8HIhlA”
HOKKAIDO USIVERSITY SAPPORO, JAPAN Received May 1, 1961 (11) Present address: Teikoku Rayon Research Laboratory, Iwtlbuni City, Japan.
Preparation of a-Diazo Ketones
Sir: The preparation of a-diazo ketones by the oxidation of the monohydrazones ofa-keto aldehydes or a-diketones has long been kn0wn.l The oxidizing agent most irequcntly used has hcen mercuric oxide,’ ofteii in the p r e m ~ c eof bases2;silver _.
( 1 ) T. Curtius and K. Thun, J . prakt. Chenz., [2] 44, 171
(1891).
(2) Cj. C. D. Scnitzescu and E. Solomonica, Org. SynIheses, Coll. Vol 11,496 (1943). ( 3 ) 0. Dick and K. Pflaumer, Ber. 48, 223 (1915). (4) M. 0. Forster and A. Zimmerli, J . Chem. Soc., 97, 2156 (1910). (5) M. S.Newman and A. Arkell, J . Org. CFem., 24, 385 (1959). (6) AI. P. Cava, It. L. Litle, and D. It. Kapier, J . dmer. Chem. SOC.,80, 2257 (1958). ( 7 ) J. Attcnbiirrovi-, 4. F. B. Camrron, J. H. Chapman, K. MI. Evans, B. A. Hems, A. l3. A. Jansen, and T. IValker, J . Chenz. Soc., 1094 (1932). (8) R. C. Fuson, L. J. Armstrong, and W.J. Shenk, Jr., J . dmer. Chern. Soc., 66,964 (1944).
.
