Aust. J. Chem.

, 1982, 35, 1481-7

Colouring Matters of the Aphidoidea. XLV*

Synthesis of (f)-Deoxyquinone A Dimethyl Ether
and its Epimer (f)-cis-7,9-Dimethoxy-1,3-dimethyl-
3,4,5,10-tetrahydro-lH-naphtho[2,3-c]pyran-5,lO-dione
[(f)-7-Methoxyeleutherin]
Donald W. Cameron, GeofSrey I. Feutrill and GeofSrey A. Pietersz
Department of Organic Chemistry, University of Melbourne,
Parkville, Vic. 3052.

Abstract
(&)-Deoxyquinone A dimethyl ether (1) has been synthesized from 5,7-dimethoxy-1-naphthol.This
is the first synthesis of an aphin-derived pyranonaphthoquinone, the (+)-enantiomer having been
obtained from natural sources. The (+)-cis epimer (3), 7-methoxyeleutherin, a plant product, was
also obtained for the first time.

The aphin colouring matters are based on coupled pyranonaphthoquinone and/or

pyranonaphthalene moieties,' none of which has hitherto been synthesized. This
paper reports a synthesis of the (+)-trans-dimethyl ether (1). This system as its
(+)-enantiomer, having the absolute configuration shown in structure (I), has been
derived by reductive cleavage of natural protoaphins or dactynaphins, giving deoxy-
quinone A (2).233 Methylation of the latter then gave (+)-(I) as described herein.
The paper also reports synthesis of the (+)-cis epimer (3). The same system,
7-methoxyeleutherin, of undetermined absolute configuration, has been isolated
from seeds of the plant Karwinskia humboldtiana Z U C C . ~
Compounds (1) and (3) are related to one another in the same way as the plant pig-
ments isoeleutherin (4) and eleutherin (5), respectively, and they have been synthesized
by adaptation of Eisenhuth and Schmid's synthesis of the latter pairs5This first required
the unknown 5,7-dimethoxy-I-naphthol (6).
Synthesis of (6) proceeded by initial Friedel-Crafts reaction of succinic acid
monomethyl ester with pyrogallol trimethyl ether. Hydrolysis of the resulting ester
gave the keto acid (7),6 reduction of which with sodium borohydride7 gave the lactone

" Part XLIV, Aust. J. Chem., 1978, 31, 2085.

Cameron, D. W., and Lord Todd, in 'Aphid Pigments' (Eds W. I. Taylor and A. R. Battersby)
Ch. 5 (Marcel Dekker: New York 1967).
Banks, H. J., and Cameron, D. W., Aust. J. Chem., 1972,25, 2199.
Bowie, J. H., and Cameron, D. W., J. Chem. Soc. C, 1967, 712.
Dreyer, D. L., Arai, I., Bachman, C. D., Anderson, W. R., Smith, R. G., and Daves, G. D., J. Am.
Chem. Soc., 1975, 97,4985.
Eisenhuth, W., and Schmid, H., Heh. Chim. Acta, 1958, 41, 2021.
Gardner, P. D., J. Am. Chem. Soc., 1954,76, 4550.
'Cameron, D. W., and Hildyard, E. M., J. Chem. Soc. C, 1968, 166.
 D. W. Cameron, G . I. Feutrill and G. A. Pietersz

(8) (v,,, 1780 cm-I). Clemmensen reduction of (7), or catalytic hydrogenolysis of

(7) or (8), all proceeded efficiently to give the acid (9).' This was cyclized with poly-
phosphoric acid to the tetralone (lo), a known compound previously prepared by
a different route.g This was subjected to reductive removal of the methoxy group
para to carbonyl by means of sodium in liquid ammonia,1° giving the dimethoxy
tetralone (1 1) (57 %). Dehydrogenation with 10 % palladium on charcoal in boiling

(1) OMe Me (3) OMe Me

(2) OH H (5) H Me
(4) H Me
(18) OMe H

OMe
I

(9) 0

(10) R = OMs
(11) R = H

OMe 0 OMe OH
I I/ I I

Snider, T. E., Hashem, M. M., Berlin, K. D., Chesnut, R. W., and Durham, N. N., Oug. Puep.
Proced. Int., 1973, 5, 291.
Haworth, R. D., Moore, B. P., and Pauson, P. L., J. Chem. Soc., 1949, 3271.
l o Narasimha Rao, P., Chem. Commun., 1968, 222.
Colouring Matters of the Aphidoidea. XLV

p-cymene then afforded the naphthol (6) (88 %). Its electronic absorption showed
typically naphthalenic fine structure while its 'H n.m.r, spectrum contained only
benzenoid C H resonances apart from appropriate hydroxy and methoxy signals.
Alternative formation from (1 1) by bromination with N-bromosuccinimide or molec-
ular bromine, followed by dehydrobromination, was less satisfactory.
The naphthol (6) was converted into its ally1 ether (12) which underwent Claisen
rearrangement in a boiling mixture of N,N-dimethylaniline and acetic anhydride to
yield the acetate (13) (56 %). Omission of the anhydride resulted in much less efficient
rearrangement. The benzenoid protons H 3 and H 4 resonated as an ortho-coupled
AB system ( J 8 . 5 Hz) consistent with the structure. Hydrolysis of (13) with methanolic
sodium hydroxide then gave the allylnaphthol (14).
On treatment with Fremy's salt (14) was converted into the 1,4-quinone (15). Its
quinonoid proton, 6 6.64, resonated as a triplet ( J 1 . 5 Hz) owing to allylic coupling
with the adjacent methylene group. Reduction with stannous chloride and ring
closure of the quinol with polyphosphoric acid resulted in formation of the dihydro-
furan (16), the newly formed methyl group resonating as a doublet 6 1.53 ( J 6 Hz).
This product underwent oxidative ring opening with ferric chloride to give the hydroxy-
propyl quinone (17) in good yield.
Compound (17) was then treated with an excess of zinc and hydrochloric acid in
tetrahydrofuran and in the resulting reduced form was allowed to react with acet-
aldehyde."," After atmospheric reoxidation this gave a mixture of the (&)-cis-
and (*)-trans-pyranoquinones (3) (51 0/,) and (1) (17%) respectively. They were
separated by preparative thin-layer chromatography and were readily distinguished
by their 'H n.m.r. spectra, in line with the sharp differences previously observed for
the spectra of eleutherin (5) and isoeleutherin (4).13 In particular the two methylene
protons of the cis epimer (3) showed strong homoallylic coupling ( J 4, 3 H z ) ~com-
pared with corresponding values for the trans epimer (1) ( J 2, < 1 Hz).
Preferential formation of the cis epimer as described in the foregoing paragraph
is usefully complemented by thermodynamic preference for the trans system. Thus
treatment of pure cis-compound (3) with phosphoric acid at room temperature gave
an equilibrium mixture of trans and cis epimers (1) (70 %) and (3) (17 %) respectively.
This epimerization at the allylic ether has direct parallel in the thermodynamic
preference of isoeleutherin (4) over eleutherin (5) under similar conditions.14
The synthetic (f)-trans compound (1) was chromatographically and spectro-
scopically indistinguishable from (+)-deoxyquinone A dimethyl ether (1) described
earlier in this paper. For comparison in the cis series we were unable to obtain an
authentic sample of 7-methoxyeleutherin (3), which was originally isolated in only
limited quantity from the plant ~ o u r c e . However,
~ spectra of the natural material,
kindly provided by D r G. D. Daves, and of the synthetic (f)-cis epimer (3), were
indistinguishable.
Attempts to demethylate the trans epimer (1) to deoxyquinone A (2) by using
Lewis acids such as boron tribromide or aluminium chloride resulted in extensive
decomposition. However, treatment with boron trichloride at -78" gave a good

" Li, T., and Ellison, R. H., J. Am. Chem. Soc., 1978, 100, 6263.
lZ Pyrek, J. S., Achmatowicz, O., and Zamojski, A., Tetrahedron, 1977, 33, 673.
l 3 Cameron, D. W., Kingston, D. G. I., Sheppard, N., and Lord Todd, J. Chem. Soc., 1964,98.
l4 Schmid, H., and EbnGther, A., Helo. Chim. Acta, 1951, 34, 561, 1041.
 D. W. Cameron, G. I. Feutrill and G. A. Pietersz

yield of the monomethyl ether (18). Its 'H n.m.r. spectrum showed retention of one
methoxy resonance (6 3 -90) and formation of a sharp hydroxy resonance at low field
(12.27) characteristic of intramolecular hydrogen bonding. In view of the instability
of this system towards complete dealkylation the synthesis of non-methylated quinone
A derivatives is being pursued along different lines.

Experimental
Unless otherwise stated infrared spectra were measured as KBr discs, electronic spectra in ethanol
and l H n.m.r. spectra in CDCI,. Chemical shifts are quoted on the 6 scale from SiMe, as internal
reference. Thin-layer chromatography (t.1.c.) was carried out on Merck silica gel GFzs4. Micro-
analyses were by the Australian Microanalytical Service, Melbourne.

Methylation of Deoxyquinone A from Natural Sources

A solution of aphin-derived deoxyquinone A (2)3 (20 mg) in chloroform (5 cm3) was shaken
overnight with silver@ oxide (200 mg) and methyl iodide (0.5 cm3). The mixture was filtered and
the filtrate evaporated to yield an oil. Chromatography on silica and elution of the major yellow
band gave the (+)-dimethyl ether (1) (15 mg, 6873, yellow needles from acetone, m.p. 201-202"
+
(Found: C, 67.4; H, 6.1. Cl,Hl,O, requires C, 67.5; H, 6.0%). [a]i2 10" (c, 0 . 6 in CHCI,).
A,,, (loge) 213, 232infl., 265, 280infl., 411nm (4.51, 4.02, 4.27, 4.09, 3.64). v,, 1653, 1600,
1563cm-'. 6 1 , 3 4 , d , J 6 H z , 3-CH,; 1.54,d, J 7 H z , 1-CH3; 2.16,ddd, J 1 9 , 1 0 , 2 H z , H 4 a x ;
2.67, dd, J 19, 4Hz, H4eq; 3.94, 3.96, s, s, 2 x O C H 3 ; 4.00, m, H 3 ; 4.95, br q, Hl;
6.71, d, J 2 Hz, H 8; 7.25, d, J 2 Hz, H6. mle 302 (M, loo%), 287 (79, 273 (67), 259 (19).

Sodium borohydride (500 mg) was added in one lot to the keto acid (7)'j (2 g) in sodium hydroxide
(10 cm3, 2.5 M) and the mixture was kept on a water bath for 2 h. It was then cooled and acidified
to pH 2 with conc. hydrochloric acid and heating was continued for a further 15 min. The resulting
mixture was extracted with ether. The extract was washed with sodium bicarbonate solution and
water, dried and evaporated to yield the lactone (8) as a colourless oil (1.8 g, 95 %). This was purified
by distillation, b.p. 80°/0.001 mm (block temperature) (Found: C, 62.4; H, 6.3. C13H1605
requires C, 61.9; H, 6.4%). A,,, (loge) 220, 270 nm (3.98, 2.94). v,, 1780, 1604, 1500 cm-l.
1; 1.83-2.80, m, CHZCH2; 3.87, s, 2 x OCH, ; 3.93, s, OCH, ; 5.64, t, J 7 Hz, ArCH; 6.66, d,
J 8.5 Hz, ArH; 6.99, d, J 8 . 5 Hz, ArH. mle 252 (M, loo%), 208 (23).

The tetralone (11)1° (4 g) was dissolved in p-cymene (50 cm3), 10% palladium on charcoal (1 g)
was added and the mixture was boiled overnight under nitrogen. Filtration, evaporation of the
filtrate and recrystallization of the residue from acetone/petrol then gave 5,7-dimethoxy-1-naphthol
(6) as colourless needles (3.5 g, 88%), m.p. 125-127.5" (Found: C, 70.3; H, 6.3. C 1 2 H f 2 0 3
requires C, 70.6; H, 5.9%). i ,. (logs) 228, 277infl., 284, 295, 322, 336 nm (4.66, 3.70, 3.83,
3.86, 3.50, 3.54). v,, 3300, 1635, 1605, 1520cm-l. S 3.94, 3.96, s, s, 2 x O C H 3 ; 5.11, s, O H ;
6.52, d, J 2 H z , H 6 ; 6.81, b r d , J 7 . 5 H z , H 2 ; 7.03, d, J 2 H z , H 8 ; 7.15, dd, J 9 , 7 . 5 H z , H 3 ;
7.74, br d, J 9 Hz, H4. m/e 204 (M, loo%), 189 (34), 161 (26).

The naphthol (6) (3.6 g), acetone (100 cm3), anhydrous potassium carbonate (10 g) and ally1
bromide (9.2 g) were boiled together for 16 h under nitrogen. Then the reaction mixture was cooled
and the solvent evaporated. Water was added to the residue which was then extracted with ether.
The extract was washed with dilute sodium hydroxide and water, and dried. The solvent was removed
and the residue recrystallized from petrol to give the ally1 ether (12) (3 g, 69%), m.p. 64-65" (Found:
C, 74.1; H, 6.6. Cl jH1603requires C, 73.7; H, 6.6%). i,,,, (loge) 230, 276infl., 284, 295, 320,
334nm(4.67,3.71,3.87,3.90,3.44,3.48). v,,,1630,1600,1515 cm-'. 63.93,3.96,s, s , 2 x O C H 3 ;
Colouring Matters of the Aphidoidea. XLV

4.72, td, J 1.5, 5 Hz, H I ' ; 5.38, m, H3'; 6.19, tdd, J 5, 10, 17.5 Hz, H Z ; 6.52, d, J ~ H z ,
H 6 ; 6.84, br d, J 8 Hz, H 2 ; 7.17, d, J 2Hz, H 8 ; 7.21, dd, J 8.5, 8 H z , H 3 ; 7.74; br d, J
8.5 Hz, H 4. m/e 244 (M, 25 %), 203 (100).

Acetate (13)
5,7-Dimethoxy-2-(prop-2'-enyl)naphthalen-~-yl
A solution of the ally1 ether (12) (2.8 g) in dimethylaniline (30 cm3) and acetic anhydride (15 cm3)
was boiled overnight under nitrogen. The reaction mixture was then cooled and solvent evaporated
under vacuum. The residue was extracted with ether and the extract was washed with dilute hydro-
chloric acid and water, and dried. Evaporation of solvent and recrystallization of the residue from
petrol gave the acetate (13) (1.7 g, 52%), m.p. 103-104" (Found: C, 71.0; H, 6.2. C17H1804
requires C, 71 .3 ; H, 6.3 %). 3,,. (logs) 228, 276infl., 283, 289infl., 3 16, 329 nm (4.53, 3.70, 3.96,
3.74, 3.29, 3.28). v,,, 1759, 1630, 1605, 1580, 1 5 1 0 ~ m - ~6 .2.45, s, CH3CO; 3.40, br d, J 6 Hz,
H l ' ; 3.89, 3.94, s, s, 2 x O C H 3 ; 5.08, m, H3'; 5.95, tdd, J 6 , 9 . 5 , 17Hz, H2'; 6.46, d, J 2 H z ,
H6(8); 6.54,d, J 2 H z , H 8 ( 6 ) ; 7.18,d, J 8 . 5 H z , H 3 ; 7.99,d, J 8 . 5 H z , H 4 . m/e286(M,25%),
244 (loo), 243 ( 6 ) .

The foregoing acetate (13) (1.6 g) in methanol (10 cm3) was hydrolysed under nitrogen with
10% sodium hydroxide solution (5 cm3) at 60' for 1 h. Then the solution was acidified with dilute
hydrochloric acid and extracted with ether. The ether extract was washed with water, dried and
evaporated, and the solid residue was recrystallized from petrol to give 5,7-dimethoxy-2-(prop-
2'-eny1)-I-naphthol(14) as colourless crystals (1.3 g, 95 %), m.p. 100-101" (Found: C, 73.4; H, 6.7.
C15H1603 requires C, 73.7; H, 6.6%). I,,, (logs) 234, 280infl., 286, 296, 319, 333 nm (4.73, 3.73,
3.82, 3.83, 3.48, 3.49). v,,, 3400, 1635, 1610, 1515 cm-I. 6 3.55, br d, J 6 Hz, H 1'; 3.93,3.95,
s, s, 2 x O C H 3 ; 5.24, m, H3'; 5.43, s, OH; 6.09, tdd, J 6 , 9.5, 17.5Hz, H2'; 6.48, d, J 2 H z ,
H 6 ; 7 . 0 3 , d , J 2 H z , H 8 ; 7 . 0 5 , d , J 8 H z , H 3 ; 7 . 6 9 , d , J 8 H z , H 4 . m/e244(M,100%),229 (46).

A solution of the naphthol (14) (1.3 g) in ether (10 cm3) was added to Fremy's salt (2.8 g) in
borate buffer of pH 10.6 (200 cm3) and the mixture shaken for 15 min. The resulting yellow precipi-
tate was filtered off and recrystallized from acetoneipetrol to yield the quinone (15) as yellow needles
(1.02g,73%),m.p. 116-117.5"(Found: C,69.6; H, 5.6. C15H1404require~C,69'7;H,5.5%).
1-,, (logs) 216, 250infl., 267, 412nm (4.54, 4.06, 4.20, 3.58). v,,, 1650, 1622, 1598, 1560cm-'.
6 3.26, m, H I ' ; 3.95, 3.96, s, s, 2 x O C H 3 ; 5.16, m, H3'; 5.92, tdd, J 7 , 9.5, 17.5Hz, H2';
6.64, t, J l . 5 Hz, H 3 ; 6.73, d, J 2 . 5 Hz, H 6 ; 7.27, d, J 2 . 5 Hz, H8. mie258 (M, loo%), 243 (18).

A solution of the foregoing quinone (15) (500 mg) in ethanol (5 cm3) and tetrahydrofuran (10
cm3) was shaken with stannous chloride (1.5 g) and conc. hydrochloric acid (2.5 cm3). To the result-
ing colourless solution deoxygenated polyphosphoric acid (60 cm3) was added and the mixture was
stirred on a water bath under nitrogen for 1.5 h. The red complex was decomposed with ice and
extracted with ether. The ether extract was washed and dried, the solvent was evaporated and the
residue subjected to preparative t.1.c. on silica in toluene. The band of high RFgave a solid (263 mg,
52%) which was recrystallized from acetone/petrol to give the dihydvofuran (16), m.p. 156-157'
(Found: C, 69.4; H, 6.2. Cl5Hl6O4requires C, 69.2; H, 6.2 %). A,,, (loga) 220, 255, 325, 339,
354nm (4.65, 4.38, 3.87, 3.92, 3.92). v,,, 3390, 1642, 1620, 1528cm-I. 6 1.53, d, J 6 H z , CH3;
2.90, dd, J 15.5, 7 . 5 HZ, CHAHB; 2.40, dd, J 15.5, 9 HZ, CHAHB; 3.90, 4.00, S, S, 2 x 0 C H 3 ;
5.00, m, H 2 ; 6.40, d, J 2 . 5 H z , H 7 ; 6.59, s, H 4 ; 6.75, d, J 2 . 5 Hz, H 9 ; 8.72, s, OH. mle
260 (M, loo%), 245 (28), 217 (25).

(17)
5,7-Dimethoxy-2-(2'-hydroxypropyl)-l,4-naphthoquinone
A solution of the foregoing product (16) (200 mg) in acetone (5 cm3) was shaken with saturated
ferric chloride solution (7 cm3) and water (5 cm3) for 10 min. It was then extracted with chloroform.
 D. W. Cameron, G. I. Feutrill and G. A. Pietersz

The chloroform extracts were evaporated and the residue purified by flash chromatography on
silica eluting with toluene. The major yellow band gave a solid which was recrystallized from carbon
tetrachloride to give the quinone (17) (171 mg, 77%), m.p. 147-149" (Found: C, 65.3; H, 6.1.
CI5Hl6o5requires C, 65.2; H, 5.9 %). I.,,, (loge) 216, 250infl., 267, 280infl., 41 1 nm (4.40, 4.06,
4.16, 3.97, 3.58). v ,,,, 3400, 1650, 1623, 1597, 1560cm-l. 6 1.29, d, J 6 H z , CH3; 2.11, d, J 5 Hz,
O H ; 2.65, m, CH,; 3.94, s, 2 x O C H 3 ; 4.04, m, H2'; 6.71, d, J 2 . 5 Hz, H 6 ; 6.72, br s, H 3 ;
7.23, d, J 2.5 Hz, H8. mle 276 (M, 19%), 232 (81), 204 (100).

(+)-cis- and ( f )-trans-7,9-Dimethoxy-I,3-dimethyl-3,4,5,lO-tetrahyd~onaphtho[2,3-c]pyran-5,lO-dione

(3) and ( 4
The quinone (17) (100 mg) in tetrahydrofuran (6 cm3) was treated with an excess of zinc in
concentrated hydrochloric acid (1 cm3). The resulting colourless solution was added to a mixture
of acetaldehyde (3 cm3) and tetrahydrofuran (3 cm3) and allowed to stand at room temperature in
a stoppered flask for 6 h. It was then exposed to air for a further 14 h, diluted with water and extracted
with ether. The extract was washed, dried and evaporated. The residue was subjected to t.1.c. on
silica in toluene/ethyl acetate 3 : 1, the plate being developed several times to effect separation. This
resulted in the separation of two major yellow bands. The band at higher RF gave the (*)-cis isomer
(3), as yellow needles m.p. 179-180' from acetone/petrol (55.8 mg, 51 %) (Found: C, 67.6; H, 6.2.
C17H18O5 requires C, 6 7 5 ; H, 6.0%). I.,,, (loge) 215, 232infl., 265, 280infl., 411 nm (4.55, 3.97,
4.24,4.03, 3.58). v,, 1650, 1594, 1560 cm-'. 6 1.35, d, J 6 Hz, 3-CH3; 1.54, d, J 6.5 Hz, 1-CH3;
2.17,ddd, J 1 8 , 1 0 , 4 H z , H 4 a x ; 2.71,dt, J 1 8 , 3 H z , H 4 e q ; 3.57,ddq, J 1 0 , 3 , 6 H z , H 3 ; 3.94,
3.95, s, s, 2xOCH3; 4.84, ddq, J 4 , 3, 6.5Hz, H l ; 6.71, d, J 2 . 5 H z , H 8 ; 7.23, d, J 2 . 5 H z ,
H 6. mle 302 (M, loo%), 287 (79), 273 (79), 259 (21). Lit. values4 for 7-methoxyeleutherin (3) from
Karwinskia humboldtiana: I.,,, 217, 264, 406 nm; mle 302, 287. The quoted coupling constants
were respectively within 1 Hz of those given above for (i.)-(3). The quoted chemical shifts were
within 6 0.02 with the exception of the value for H 1, incorrectly recorded as 4.483 The correct
value, 4.84, was confirmed by reference to the spectrum of natural material. For eleutherin (5)
H 1 has 6 4.85.13 The electronic, 'H n.m.r. and mass spectra of natural material were qualitatively
indistinguishable from those of the synthetic.
The band at lower R, gave the (+)-trans isomer (1) which was recrystallized from acetone (18.6
mg, 17%), m.p. 228-230" (Found: C, 67.2; H, 6.1. C17H1805 requires C, 6 7 5 ; H, 6.0%). A,,,
(loge) 215, 232infl., 266, 280infl., 411 nm (4.55, 3.93, 4.21, 4.04, 3.60). v,, 1650, 1597, 1560 cm-l.
6 1.34, d, J 6 . 5 H z , 3-CH,; 1.53, d, J 7 H z , 1-CH3; 2.16, ddd, J l 9 , 10, 2Hz, H4ax; 2.66, dd,
J 1 9 , 4 H z , H 4 e q ; 3 . 9 4 , 3 . 9 6 , s , s , 2 x O C H 3 ; 4 . 0 0 , m , H 3 ; 4 . 9 6 , b r q , J 7 H z , H 1 ; 6.71,d,
J 2.5 Hz, H 8; 7.25, d, J 2.5 Hz, H 6. mle 302 (M, loo%), 287 (86), 273 (76), 259 (23). It was
chromatographically indistinguishable from a sample of (+)-deoxyquinone A dimethyl ether (1)
and had indistinguishable electronic, infrared and 'H n.m.r. spectra.

Epimevization of the (f )-cis Compound (3) in Phosphoric Acid

The ( f )-cis compound (3) (30 mg) was mixed with 90% phosphoric acid (4 cm3) and allowed
to stand at room temperature for 4 h. The mixture was then poured into ice water and extracted
with ether. The extracts were washed with water, dried and evaporated to yield an oil. This was
subjected to t.1.c. on silica in toluene/ethyl acetate 3 : 1, the plate being developed several times
to facilitate separation. The yellow band at higher RF gave recovered cis epimer (3) (5 mg) while
the band at lower RF gave the trans epimer (1) (21 mg). The two epimers were chromatographically
indistinguishable from their respective authentic materials and each pair had identical infrared
absorption and 'H n.m.r. spectra.

The trans isomer (1) (15 mg) in dry dichloromethane was cooled to -78" and treated with an
excess of boron trichloride. The mixture was stirred at -78' for 15 min, then quenched with water
and extracted with dichloromethane. The extract was washed with water, dried and evaporated to
yield a solid. Recrystallization from acetone gave the quinone (18), orange needles (15 mg, 7973,
m.p. 176-177.5" (Found: C, 66.7; H, 6.0. C16Ht605requires C,66.7; H, 5.6%). I.,,, (loge)
217, 235infl., 267, 283, 430 nm (4.56, 3.92, 4.17, 3.97, 3.66). v,, 1667, 1647, 1600 em-'. 6 1.35,
Colouring Matters of the Aphidoidea. XLV

d, J 6 Hz, 3-CH3 ; 1 .56, d, J 6.5 Hz, 1-CH3; 2.19, ddd, J 19, 10, 2 Hz, H4ax; 2.62, dd, J 19,
3 , 5 H z , H4eq; 3.90, s, OMe; 3.98, m, H 3 ; 4.98, b r q , J 6 . 5 H z , H l ; 6.62, d, J 2 . 5 H z , H 8 ;
7.17, d, J 2.5 Hz, H 6 ; 12.27, s, OH. mle 288 (M, loo%), 273 (68), 259 (26), 244 (29).

Acknowledgments
We thank Dr G . D. Daves for spectra of 7-methoxyeleutherin. We are indebted
to the Australian Research Grants Committee for financial support and acknowledge
an Australian Postgraduate Research Award (to G.A.P.).

Manuscript received 25 February 1982