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July, 1936 PERMANGANATE OXIDATION OF 2-HYDROXY-1,4-NAPHTHOQUINONE DERIVATIVES 1179

formed. All of the substances listed in Table I gave the the quinone ring without otherwise disturbing the
test, and this was true also of hydrolapachol and of 2480- structure of the chain. In the course of the oxi-
butyl-3-hydroxy-1&naphthoquinone. a
dation the quinone ring is split and then reformed.
Summary One carbon atom of the original ring is eliminated,
It is shown how alkaline potassium perman- another from the side chain taking its place, with
ganate oxidation of hydroxynaphthoquinone de- the result that the chain is shortened by one car-
rivatives can result in a general reaction involving bon atom and the positions of the hydroxyl and

@;c,+fjoH
the following change: the side chain are reversed in the new ring. The
steps involved are fully discussed and many ex-
amples of the reaction are given. It is also shown
R how the oxidation can be of assistance in deter-
mining the structure of the side chain and, if un-
saturated, the position of the double bond.
0 0
82 REMSENSTREET RECEIYED MARCH 25, 1936
Thus it is possible to eliminate CH2 adjoining BROOKLYN, NEW YQRK

On the Oxidation of Z-Hydroxy-l,4-naphthoquinoneDerivatives with Alkaline Potas-
sium Permanganate. Part 11. Compounds with Unsaturated Side ChaiaslJ
BY SAMUEL
C. HOOKERAND AL ~ T E Y E R M A R ~
It has been shown that the novel oxidation re- The three compounds of the type I are yellow,
action described recently by one3 of us is appli- like lapachol, and on oxidation with permanga-
cable to a large number of hydro-xynaphthoqui- nate they behave in an entirely similar manner
nones with saturated side chains in the quinone yielding orange or red quinones of the type 11.
ring, but only one example of a substance contain- The product resultipg from the oxidation of 2-7-
ing a double bond in the side chain was included methylallyl-3-hydroxy - 1,4 - naphthoquinone (I,
in the previous studies, namely, lapachol.aa R = CH3, R’ = H) proved to be identical with
Lapachol (I, R and R’ = CHI) is converted by the substance prepareds by the condensation of
alkaline permanganate in the mld into the next propionaldehyde with hydroxynaphthoquinone,
lower homolog of the type 11, in which CH2 has namely, 2 - a-propenyl-3-hydroxy-1,4-naphtho-
been eliminated and the double bond shifted from quinone. The oxidation product of the cinnamyl
the @,y-to the a,@-position, In order to extend compound similarly was identified by direct com-
this observation the following additional com- parison with the compound 11 (R = C6H6,R’ =
0 0 H) prepared6 by the aldehyde synthesis.
The oxidstiop of the allyl compound presented
some difficulties but conditions eventu9lly were
defined permitting the isolation of the sensitiv’e
reaction product, 2-vinyl-3-hydroxy-l,$-naphtho-
0 quinone (111). This compound, which is de-
I (Yellow) I1 (Orange or red) scribed for the first time, wsls fully identified by
pounds have been examined : the 2-aliyl, 2-y- its conversion on catalytic hydrogenation into 2-
methylallyl, and 2-cinnaniyi derivatives of 3- ethyl-3-hydroxy- 1,4-naphthoquinone { IV), a sub-
hydroxy - 1,4 - naphthoquinone. The materials stance previously preparedgbin this Laboratory by
were in part kindly supplied by Dr. L. F. Fieser, the oxidatioQ of the propyl cofnpound (V).
who has described the prepration of all three of These results fully confirm and eytend the ob-
these quinones.4 servations made in the case of lapachol. Is all
( 1 ) See Editor’s note (11, THZSJOURNAL, SEI 1183 ( 1 9 3 6 ) . four of the examples investigated it has been
(2) Dr. Hooker left no manuscript for the first part of this paper
hut wrote the description of the three oxidations recorded in the found that the oxidation of a yellow alkyl hy-
experimental part --I,. F FIESER. droxynaphthoquinone having a double bond in
(3) NOOPCH, ’ 1 ~ 1 6JOURNAL, (a) 68, 1188 (ICjdO), (111 68, 1174
i1’136) the &y-position in the side chain leads to the re-
( 4 ) I’ieser, ( a ) rhid 48, 3201 ( l W O ) , (I?) 49, 867 (1927) ( 5 ) Hooker, r h d , 68, 1163 (1WfiI.

Any delay in conducting these operations resulted unsatisfac- torily. ether. employed (2.beyond question by direct comparison with the product taining the p-quinone ether was discarded.substance does not much exceed 9% of the weight of the lized from glacial acetic acid.94 g.085 g. was dissolved in 100 cc. of ether a t the laboratory tempcra- the formation of an orange or red quinone with ture and gradually adding a t intervals of some hours a the double bond in the a. The residue consisted of small.1% alkali.with a few dropsof ether melted a t 121. I t appears total of 145 cc.solution after filtration acitlifictl with t l i l i i l r hydrochloric . material oxidized. none into 2-~-Phenylvinyl-3-hydroxy-l. 58 by the addition to the acid. Crystallization from methyl or ethyl alcohol. were dissolved i n 40 cc. . and ments it was found that it could be best prepared as fol. H. duriiig which niicro.-The re. The by conversion of the substance into ethylhydroxynaphtho- yields of the o-quinone ether and allylhydroxynaphtho..4naphthoquinone. 4. quinone by hydrogenation.4 g. As the result of many experi. The manganese dioxide dium salt of the oxidation product crystallized in the form separated in one to two minutes and was filtered off im. lots). as the substance was found to change rapidly in the alkaline solution. 0 0 chloroform. Calcd. The cinnamyl coni- obtain in a pure condition.5-123. 1IS0 C. used with assurance in the determination of the red-brown crystalline masses scattered here and there over position of a double bond in the side chain.25% alkali for two days none. The violet needles once poured into 100 cc. 71. not heated but was allowed to stand in the dark in a stop. was then added tions previously having been cooled in ice water.4-naphthoquinone into 2-Vinyl-3-hydroxy-l. The manganese dioxide was filtered off promptly aqueous solution of potassium permanganate containing after separation.6 times that specified) and the mixture was Found? C. The yield was about 40% of the weight of the allyl compound oxidized. was added quickly. (10% in excess of the theoretical amount for two to prevent unnecessary dilution. this operation taking about ten minutes.96.-The permanganate oxidation of cinnamylhydroxy- and the solution was filtered from an undissolved resin. of 0. in 50 cc. Both lows. Although somewhat impure the substance as thus obtained is proh- ably suitable for most purposes. 0. washing of the precipitate being avoided 1. The alkaline mother liquor filtrate was quickly diluted with 800 cc.4-naphthoqui- bath at 125-127' for one and one-half hours (5-g. The and washed with 10% alkali.5 g. of water and a t now brown in color was discarded.P-position.respectively. The brown-red crystalline masses were mechanically removed and after being washed Conversion of 2-Allyl-J-hydroxy-1. p.v ~ I ) r I ) l B r i c v# I f C ~ a i l i i i n l i :l ~l t i i \ v r > i t y .4-naphthoquinone solutions were cooled to about l o and quickly mixed as dissolved in 100 cc. of petroleum etber (b. H. of 2-allyl-3-hydroxy-l. naphthoquinone occurs most satisfactorily in a very dilute The precipitated material was extracted with petroleum alkaline solution and even then the yield of the desired ether in the Soxhlet apparatus (yield 61-68%)." In carrying out the allylation of the silcer salt of hydroxynaphthoquinone considerably more benzene was Anal. the identity being established quinone were 54 and 1870. in 50 cc. both solu. Fieser. As the result of a number of trials 2-Vinyl-3-hydroxy-l. The conclusion drawn from the analysis was confirmed pered flask with occasional shaking for two days. Conversion of 2-Cinamyl-3-hydroxy-1. specified by Fieser. These were collected on glass wool mediately. the oxidation product was col- lected as quickly as possible by suction filtration. of water. 35-55'). and crystal. of dilute liytlrochloric acid (1:3).potassium permanganate. 116-117'. of a 25% atoms of oxygen) in 100 cc. for CllHSOl: C. 71.4-naphthoquinone is difficult to the following method was adopted. 0. p. a volume equal to that of the filtrate. HOOKERAND AL STEYERMARK SAMUEL VOl. .rl-naphthoqui- The mass was soaked with cold 0.of dark violet needles.54. Complete purification for analysis presented considerahlc difficulty as the substance underwent partial change in all the sol- vents used. of warm water and the deep violet After standing for al)out eight iiiinutcs. Analysis gave figures agreeing sufficiently well with those required quired starting material was prepared by the method of by 2-viny1-3-hydroxy-l. of 1% sodium hydroxide solution an above. the surface of the &ask surrounded by a finely divided yel- low substance undoubtedly resulting from one or other of Experimental Part the changes above referred to. The o-quinone previously obtained3b as described above and substanti- ether was rearranged a t a temperature lower than that ated further by a mixed melting point determination..alkali. Purification was finally accomplished by dis- moval of CH:! adjacent to the quinone ring with solving 0. and as an additional compound 0 commenced to separate from the acid solution soon after 111 the precipitation of the oxidation product.79. the material being heated in an oil. About 140 cc. To 1 g. When that the reaction is a very general one and that the cloud had cleared sufficiently the deposit was filtered the relationship between lapachol and its product off and discarded. The and the whole set aside for five days during which the so- oxidation occurred rapidly. m. 4. ethyl acetate or IV 1' acetone decreased rather than increased the purity of the substance..5'.4-naphthoquinone. The solution was then allowed to go to dryness in an Erlenmeyer flask tilted so as to promote of oxidation extends to other cases and can be more rapid evaporation.pound.05. benzene.(Ifroill I Iic w i i i i l \ i o i i p i t ~ l i i ~ t l i(i>h l i v r ~ u i i : i l y \ iI. sropic t m n g v nrctllt:\ 1oriii<. The fraction con. acetic acid.

and to Dr. Botanical Gardens. 10 cc. For purification it was dissolved in 6 cc. longifolia. Prof. Also a Synthesis of Lapachol. melting point determination.. of potassium permanganate in tion of lapachol with potassium permanganate.6 Oxidation in more strongly alka- points of similarity being further confirmed by a mixed line solution gave less satisfactory results. Rodway. still alkaline. instead of that of hydroxylapachol proposed by ilicifolia and L. lapachol had been isolated. polymorpha were collected ing. K. to Lt. G. Hobart. Rodway. numbering the formulas and notes and making minor editorial then the Government Botanist. J.5 polymorpha from Tasmania. Kew.-In addition t o the matter the constitution of an hydroxyisolapachol. washed with water and dried it melted a t 134-135' and gave a dark crystalline air dried. 784 (1895). dr'oxy-1. The orange. and of L . The experimental part has been constructed by consolidat. 69.4-naphthoquinone. H. descriptions of the experiments written near Macquarie Harbour. Its Occurrence. Chcm. L. . and as a t least one other hydroxyiso. Hobart. HOOKER BY SAMUEL In a paper published in 1895 the late Dr. ibid.silaifolia from the Sydney district. New York Botanical Gardens. Washed and air microscopic needles was collected. R . Sir D. and he succeeded raw material had been secured in hope of eliminat- in converting the lomatia coloring matter into the ing all doubts regarding the structure of lomatiol. on the west coast of Tasmania: and those by Dr.67. For one sample of L. Director of the Royal (4) Hooker. forwarded by Mr.1 g. 1381 (1896).~ The results of possible to carry out my intentions and it was not Dr.045g.lincto~io. . those of L. had already courteously announced the determi- ward H. Director of the Botanical Gardens. Hooker was assisted by Dr. of 1% alkali. Hooker and modified only to the extent of also for the seeds of L.July. was suggested for the lomatia coloring matter. and it was my intention to and Lomatia longifolia are more or less surrounded pursue the work as soon as a sufficient supply of is closely related to lapachol. THISJOURNAL. Charles Sprague Sargent of the Arnold Arboretum of Harvard (3) Rennie. J .ing point established its identity with the compound pre- 1. tinctoria and L. I t solution. 1936 MARCH solution of sodium hydroxide and then nearly but not com. Rennie's work together with the study of nu. the name lomatiol New South Wales. J.4-naphthoqui.-Col.1 g. 61. NEWYORK BROOKLYN. seeds of the two species above referred to. F. of a 0. F.. J. about 50 miles from In the experiments Dr. Rennie (6) The seeds of L. of L.-A solution of 0. 611 (1892). until after an interval of many years that I was merous compounds which I had obtained from able to resume the investigation. with some abridgment. SOC. Part 11. lapachol led me to assign to the lomatia coloring Occurrence of Lomatio1. prepared by the aldehyde condensa.&with which it is undoubtedly identical. known vinyl derivative of hydroxynaphthoqui- tate was collected.03g. H. The summary was supplied by the undersigned. of water was cooled in an ice-bath and quickly added to a similarly cooled solution of 0. I am indebted to Mr. Ed. After two hours the filtered been converted into the corresponding compounds solution was partially precipitated by cautiously adding of the side chain -CH=CHR. Hooker. The yield was none has in this way been isolated. of the (2) The theoretical part of this paper is from an original manu. Cotmitt.potymorpha. yielding approximately 0.5% STREET 82 REMSEN RECEIVED 25. 1936 LOMATIOL AND ITS RELATION TO LAPACHOL 1181 acid.principally near EagJehawk Neck. The hitherto un- dilute hydrochloric acid until the mother liquor. Of the seeds changes. hydroxy-@-lapachonewhich I had previously pre. and script written by Dr. University. Maiden.. Conversion of Z-r-Methylally1-3-hydroxy-1. FIESBR. Lomatiol. 0. the seeds of L.enaphtho. washed and air dried.pared from propionaldehyde by condensation with hy- tion. ibid.1*2 C. The resulting dark red precipitate consisting of pletely reprecipitated with dilute acid. and for another. siloifolio were kindly sent to me by the late Mr.. I have also examined Dr. Summary quinone into Z-a-Propeny1-3-hydroxy-l. Comparison of its properties and a mixed melt- was compared directly with 2-P-phenylvinyl-3-hydroxy.Small of the New York ( 5 ) Hooker.6 The seeds of all At the time of this later publication Dr. New York City. Tasmania. Relation to and Conversion into Lapachol. Prain. Sydney. Botanical Gardens.68.Small. L. K. Manganese dioxide sepa. Rennie3 showed that the yellow coloring nation of leaving the further study of the col- matter with which the seeds of Lornatia ilicifolia loring matter to me.. Constitution. 1163 (1936). the various droxynaphthoquinone. Conditions arose subsequently which made it im- pared indirectly from lapach01.finctorio I have to thank Dr.4-naphthoquinone having in the 2-posi- rated in a few minutes leaving an almost colorless solution tion side chains of the type -CHzCH=CHR have which rapidly became purple. S. Extending an observation regarding the oxida- none. The substance sodium salt which dissolved in water to an intensely violet when crystallized from alcohol melted a t 166-167". (1) See Editor's note (1).. of the crotyl com- three similarly constituted derivatives of 3-hy- pound in 10 cc. Rennie. had become red. For the several specimens from Chile I am indebted to I. crystalline precipi.