The optical activity of the Cecropia juvenile hormones

BlOCHEMlCALANDBlOPHYSlCALRESEARCH

Vol.41,No.4,1970

THE OPTICAL

ACTIVITY

Andre Depa&nent

Received

October

recently,

regulatory

been demonstrated

leading

Cecropia

moth

active (I,

additional, second

it

is

the

a lower

racemic

natural

and

of partic-

male of the

12,14-dihomojuvenate

(although

be difficult

(9). it

to decide with

We therefore

enantiomers

is

wish

their

that

caused data

with

which

this identical

see ref.

substances arose

In our

synthetic

lat-

Gu.4Xti but those

of

are single

considerable effect).

the

bioactivity, from

7).

were

whether

certainty

contribution

by a synergistic

an

accounted

with 6, II

hormones

may possess

alone

hormones

lower

the natural their

that

(8).

toward

potency

even if

enantiomers

from assay

the natural

a trend

to isolate

Structurally,

synthetic

of single

is conceivable

preparation

(II),

(I see ref.

routes

the question

showed

able

(5).

hormones,

Hence,

unnatural

then

The racemic

of these

to distinguish

their

racemic

instead

substances

hormones

stereoisomers,

identical

methyl

12-homojuvenate

of 1.

activities

products

was not possible

activity

formation

(1)

and identification

We were

by various

to the natural

the synthetic

of the

of

species

of the adult

of the extracts

homolog

biological

to be equal

are

tissues

isolation

(4).

JH, methyl activity

have been synthesized

Because

assay

has

on the morphology

JH controls

one JH structure,

species

active

of the endocrine

compound

found

in this

similarly

13-20X

geometry

development

(2).

in abdominal

only

in insects.

Ci6-l0,11-epoxy-7-ethyl-3,11-dimethyl-~,fhans-2,6-tridecadien-

was recognized

for

the

At first

hormones

of two Ckirronomus

that

enzymes

to be a boon for

proved

principle.

methyl

oate),

ter

(3)

by some effects

to the suggestion

JH accumulates

growth

postembryonic

chromosomes

activating

that

during

level

in polytene

tRNAs and their The fact

UniveJ&iXy

bi.tk moth MC not taraceCIA&V&.

&am Xfuz CWLO~& c&pm&

opt&d!

function

at a molecular

pattern

by experiments

HORMONES

Hanzmann

06 &iokZogy, Case Web.teh Restive Clev&nd, Ohio 44106

hoamoned Do&ted a p.eain )?Ob.i/l%f2

its

the puffing ular

S. Meyer and Edith

hormone (JH) is one of the important

Juvenile Most

OF THE CECROPIA JUVENILE

6, 1970

The juven& They &&it

ti.

COMMUNICATIONS

biological

to the

potency

It may thus enantiomers

are

hormones.

to report

that

the

891

natural

Cecropia

hormones

are

not

Vol. 41,No.4,

racemic.

1970

BIOCHEMICALANDBIOPHYSICAL

Furthermore,

figuration

if

it

it

is

Our isolation permitted the

of the

measuring

difference

relatively unnecessary

natural

from

the

rotation

to separate

nearest

the

fourth

batch

1.3720

of silk

in a calibrated

and transferred at four

wavelengths

digital

readout. x

moths

a tube

+o.030°

It is positive

for

sentative

for

(lo),

without

uration.

Similarly, for

which

been reported;

the

absolute

the mode of its However,

in the

(t)-2,3-epoxybutane correct

sign.

we believe concordance tion should

dalton) flask

dm length.

Since

was dissolved

Optical

rotation

*o.o05O *4"

by extrapolation: there

active

is

no reason

the determined

dispersion

values

of both

but there

rotation

qualifications for

configuration

the

semi-empirical

divergence

is,

model

whether

with

for

is

distorted

bond

lOR,llS

config-

(R)-(+)-2,3-epoxy-2,5-

(ethanol)

(ll),

of this

compound

appeared

[M]~6=+11.50,

had

has been deduced

encouraging. (12)

failed

at present,

not

and we have initiated

892

abso-

rotation,

have the

method

information.

and derived and its

the method

a positive

JHs that

results

con-

to be repre-

of a compound

can be computed

an [a]i6=+8.97“

different

structures.

method,

Cecropia

These

a normal

to compounds

to this

the

and exhibited to presume

is sane question

According

[M]8=+20.5'.

dissymmetry"

the optical

with

[a]D=+7“;

are considered

hormone

a "conformational

of the JHs has been established, the desired

was observed

141 polarimeter

as well

as (R,R)-

to predict readily

that it would be premature to conclude-in spite of the above calculated and observed values-that

provide

in chlo-

cm3; c= 0.1214%)

t7.5"

was optically

of

and had been isolated

(v=1.102

case of (R)-(t)-1,2-epoxypropane this

consisted

+o. 009O

synthesis. (13),

The meas-

that

+9O

an [MID =+5"

dimethylhexane from

two components.

+0.011"

Since

[hiID = +l o" , can be expected

to be

+0.021"

appropriate

such as epoxides.

it

S.E.

between

configuration

applicable angles,

we felt

is

578 nm

has elaborated relation

Since

atom that

546 nm

two JHs,

the optical

Brewster an empirical lute

curve. the

con-

that

436 run

the solution

dispersion

figurations

C-10,

The material

+17"

that

on a scale

preparation

292.85

(9).

at 589 nm was estimated

evident

absolute

JH preparation.

and 28OC by means of a Perkin-Elmer

t25O

The rotation

its

weighing

of 1.000

365 nm

$

into

out a carbon

center

mg of a pure

II (wt.

pure

involves

chiral

pear-shaped

into

was carried of the

the preparation with

of their

dextrorotatory.

hormones

90.2 mol% of I and 9.8 mol% of from

the determination are

the two JH hormones

was performed

roform

in

they

the optical

between distant

urement

may aid

known that

RESEARCH COMMUNICATIONS

the

explained,

of the uncanny the configuraexperiments

that

Vol.41,No.4,

BIOCHEMICAL ANDBIOPHYSICALRESEARCH

1970

Acknow&dgmenb-This Health thank

Service

with

Hans Hirschmann

investigation Grant for

HD 00984

COMMUNICATIONS

has been supported

from

most valuable

the

Hational

by the U.S.

Institutes

Public

of Health.

We

advice.

References 1.

M. Lezzi and L. I. Gilbert, H. Laufer and T. K. H. Holt,

2.

J.

Ilan,

J.

Ilan

P&oc. Nat. Acad. Sci., U.S.A. 64, 498 J. Exp. Zooe. 173, 341 (1970).

and M. Patel, N&u&e

178,

J.

RioA

Chem. 245,

1275

(1969);

(1970).

3.

C. M. Williams,

4.

H. Rbller, K. H. Dahm, C. C. Weeley Ed. Engk?. 6, 179 (1967).

212 (1956).

5.

A. S. Meyer, H. A. Schneiderman, E. Hanzmann Acad. Sci., U.S.A. 60, 853 (1968).

6.

K. H. Dahm, B. M. Trost and H. Rol ler, J. Amu~. Chem. Sac. 89, 5292 (1967); G. W. K. Cavill, D. G. Laing and P. J. Williams, AU&L. J. Chem. 22, 2145 (1969); E. E. van Tamelen and J. P. McCormick, J. Ameh. Chem. Sot. 92, 737 (1970), where further references are listed.

7.

W. S. Johnson, S. F. Campbell, A. Krishnakumaran Nat. Acad. Sci., U.S.A. 62, 1005 (1969). and K. H. Dahm, Recent

and B. M. Trost,

8.

H. Roller

9.

A. S. Meyer, E. Hanzmann, H. A. Schneiderman, Ahch. 8iochem. Giophqd. 137, 190 (1970).

P&ogh.

Horn.

and A. S. Meyer, Res. L. I.

J. H. Brewster, 1. Ama. Chem, Sot. bi, 5475 (1959): listed in Topics Sttieochem. 2, 1 (1967).

11.

P. Karrer

12.

P. A. Levene

13.

H. J. Lucas and H. K. Garner, P. J. Leroux and H. J. Lucas,

and A. Walti,

/f&v.

Ckim.

Acta

Chem. Znt.

and J. H. Ko, Phoc.

10.

and W. Kaase,

An9ew.

893

Pfioc.

24, 651 (1968). Gilbert

and M. Boyette,

subsequent

3, 244 (1920).

1. giokZ. Chem. 68, 415 (1926). J. Amen. Chem. Sm. ibti. 73, 41 (1951).

NaX.

70, 990 (1948);

references