The structure of lucidone and methyl-lucidone

Tetrahedron LettersN0.40,Pp. 4243-4246, 1968. PergamonPress. Printedin GreatBritain.

8. H. Ia D8paM

of chwlst~,

(Received in Japan 18 June

tlniT8r8ltg

of

M8l*y8,

1968;received in UK for publication 5 July 1968)

fnmtheroetofLinden Underoaaud methyl-linderom,[email protected] bwn

8howl

po88ihb

to

h8T8

bLogm8tie

8tluctllr88 prwumor

(I)and (II)mapectively, ud theirtotal (III)b8 recently beenrsported.2

(I,R-ocBj)

(0, R - Oq

m,a-

(V,R - H)

a)

In&niagthO

CbhWOfO~OXt~Ct@

Ofthe

(III)

frrritOf8tited

&xci~,&~thrwyall~crgrrtalliwcmpotmdanemobtalmd.Omofthw~e~ma aa methylvlbdemm (II),*ilo the othertwo, deiaignated lucidonemd mawl-lucidone8x.0

888ignadrtructur0a (IV)ud (V)m3pmtlvely ba~edoaevl&nce de8cribadbalcw. Iacidme,Cl&O; Lu

@+256),n.p. 16b-165°,)/2

bcidic &tOH)244 and 355 my/ (log6 4.40awl 4.51),&

4243

1720,1650,lbl0and 1595 ca-l, (tasicEtOH)238, 290 sh. and

4244

344 mp

No.40

is molic, fornr l rombeImoats &&'1,05, + m.p. 245-2470

(log& 4.32, 4.17 d4.271,

and a brow-gram

copper

* m.p. 305309" (dac.).It ia converted by -1 cl&ate C30?1220e~,

miLphte In acetone 8olUtionintha occUrring

pmrmce

ofan&droU8

pota8si~carbmate

tothemtUmJly

n.p. 126-127°),~~ IDBt~l-lucidocw,~~o;(~27O), r.p. I.U-EL6'(re8cUdifled,

1720,1670 and1620 au-',h,

@to@ 240 Md359m/(4 bgt

4.34ud4&66),wirichintm

w axaliclcldinmstbsnol.Horevigorous ~drolysiaofluddene

can be ~edtolucldona

rdthsthanollc &drochloricacidgaW lnsteadanethylathar, ~6~04~m.p.126-12g", VB (addie

1715,1645,I.625 and 1590 an-',A, A_

EtOH) Y

ad

359 I/L (logE 4.35and 4.531,

of the IR and bait EtOIi) 244,292 and349 m/* (log6 4.35,4d9 and 4.30).Carpariron

UV dataof luddone,mat&l-lucIdone and lucidone ethyletherulth thatof (I)and ita derivative.8 and of otherlamm

(IV),(V)and (VI)for the threepigmentsrespacti*.

8t~cture8

fmita

4r5 allowed,&priori., arwuptionof lcylcwlopentemdlone8

alkallne~l\~~~~ch~~~CI~caCid,a~fr~l~g~tlon

overpllhdiuk8tro~tmcarboMtOwtdch

m.p.1O6-lO6o,pLl3 4.36),x_

1'720, I.673 and1635 a-? A_

dibdm-d~=ti-

(VII), GQo;

bcddic MM)

254-275m/A(logE

(basicPltOH) 251 and 279 IB/L(loge 4.32and 4.38).b8iC -18

WTO lpdrocintmmh of

m8Ultedina

of (IV)

acid.Uogous

r8WtiOMNOrOilrrO

0bstiintiO

of (VII)

atNCtUrrl8tUdiO8

llnderonu(I). Ths =

8tNOtlU-l

a88iUt8

8pW2tl-a Of (n), (800 TatiO)r

(V), (VI) a&

(VII) M

ahO

COMi8tWltdt.h

the

4245

NO.40

TAX&

tHt

Spsctnl Data (CDC$, 100 Xc.) In p.p.mn. h

m+

(8

=.

(VI)

@II)

5.81

5.75

5-H

5.82

5.92,5.9l++

4-?3

3.93

3.91,3.90++

titio-Ii

7.35(m)

7.356)

7.356)

z or He

7.69,7.72(d) (Jfi16 c/s)

8.00,7.69(d) 7.937 7.62*+

7.66,7.74(d) (JIB16 c/s)

3.89 7.356)

4.18,4zo++

l'- NH3

4.15(q),1.49(t)

4-oQI2c83

3.0 (m)

-??-?2+ An endic proton m indicated tq a broadsign&lmar 12 p.p.m.; d - doukht, m = mlltiplet, t - tIQilet, q - quut@t. ++ Signml8 trap &nor ircrsr. In

w

adition,

the twR spaetn

of (IV), (v), (VI)

and

(VII)ahha a

emu. aput-

e&the ring 5-protonandtheadjacentb-methogl(or4-0Ui2CIi3) indimtivaof the presence

of %xternaltautcmer#muchBE (VIIIa)or (VIIIb)and(IX)or (X).Althoughthe proportion of theainorlaaarla quitelouin (IV),(VI)and (VII)itin appreciable In (V)dthappmxi.mte ntio of3r2, albeitthe assigmentof protonsigmla to wchtautawr is uncertain.The

(b)

I-

VIII,

R-~orOC&Xj 7

m

No.40

4246

~le&~&.

The authorthmb

DN. K. Siemum md B.S. Iwin for ths Due spctm

and Dr. H.C.Woodsfor the MEI spmtm and for helpfQldimussions.

1. A.K.Ictmg,HA

Im and K.Y.Sb, J. Chen.SW., 4338 (1962).

2. H.H.Ia and C.H.Tan,J. Clwm.Sot. (C),1563 (1967). 3. For a study of pignsntsin tha mot of Lind01'8 lug&&,

soo

B.H.Ise ud C-H.h,

J. C&Q. Sot.,27&3 (1965). 4. S. For&n, F. He&i

and 1. Nilsson, Acta Chew Seaad.,a, I.206(1964).

5. J.A. Elvidgeaad B. Stevens, J. Chm. Sot.,2251 (1965).