Isolation and structure of insecticidal components from Mammea americana L.

Tetrahedron Letters No.3, Pp. 251-254, 1970.

ISOLATION

AND STRUCTURE

Pergamon Press.

OF INSECTICIDAL

L. Crombiex,

D.E. Games,

COMPONENTS

N.J. Haskins

Printed in Great Britain.

FROM MAMMEA

AMERICANA

L.

and G.F. Read,

Department of Chemistry, University College, (University of Wales), Cathays Park, Cardiff (Received in UC 3 December 1969; accepted for publication 19 December 1969) The light active

1

phenyl

.

In recent

claimed

given

mustard

beetles

Search

which

has,

liquors

isolated

Mammein

this.

shown

from their

more

toxic

it was isolated?

component

in isolation

to mustard

beetles

By combination

but no test results

2 have

(I-IX) against approaching

that

column

of a colourless

and preparative

crystalline

than the most active

substance,

separation

and chemical

layer

residues

information

from

this

F+ =

n-Pr

;R,=M%C:CHCH*.

;R,=MqCHC&CO.

(II)(B/BB)

b=

n-Pr

;R+=Me,C:CHCH,.

;R3=EtMeCHC0.

(III)(B/BC)~

%=

n-Pr

;l$ =Me,C:CHCH,.

R3 =PrCO.

4 =

n-Am

;F$ =MeZC:CHCH2 .

R,=EtMeCHCO.

rr,=

Ph

;% =Me, CH.CH, CO.

Rr =Me, C:CHCH, .

R, =

Ph

;% =M+C:CHCH,

R3=Me,CHCH2C0.

h=

Ph

;&=EtMeCHCO.

F =

Ph

;% =Me, C:CHCH,, . ;R>=EtMeCH.CO.

(VII)(A/AB) (VIII)(A/BB)

mammeisin.

4

and five 4-

III as impurity)

compounds

using

of spectroscopic

(VI)(A/BA)

c

(I-IVJ2

(I containing

of the seeds

has continued

(V)(A/AA)~

constituents

L. is insecticidally

separation.

(IV)(C/BB)

major

coumarins

of the crystalline

(I)(B/BA)~

a

4

americana

that none of these have activity

components

and has resulted

four 4-alkyl

of the literature

Screening

in fact,

for the active

chromatography, 50-53O,

we have

of the seeds of Mammea

to be the insecticidal

to support

of the mother

m-p.

work

extract

(V-IX) 3 .

coumarins

has been been

petroleum

of mammein,

1,4

b

minor

constituent

.

;Rj=Me2C:CHCH2 .

of mammein, 194

6

t Present address: Department of Chemistry, Nottingham University, A similar insecticidal product was isolated from M. Aiticana seeds 251

Nottingham,

NG7 2RD.

252

NO.3

substance efforts

has been

shown

it has not proved

The substance /-+_3,,+753°,

(4.57)nm.,

indicating

mass-spectral

active

(Xb), though

the two closely

/-R.D.

both accurate

formulae

293.7(4.39),

of (Xa) and

to separate

(X) was optically

as the molecular

E 4.501,

Major

possible

/-+_~40-1075~7and

q4HJo4 (log

to be a mixture

320(4.19)nm;

mass-measurement

Amax(o.O~-~OH)

fragmentations

are summarised

w

111’267.5

1

It had hmax (C4OlE-HC1)222.2

P

I.

= metastable Indicates Loss

&[7y&+ C, 2 Hz6 0,

,

C-56)

t-55)

(-28)

(~-42)

and acetic

acid

(M-60)

from

group,

(mull).

Fragmentation

of the ion m/e 370 by loss of a butenyl

(Xa)

R:

(Xb)

R=

radical

of compounds

substituents. d

with a maximum

to give m/e 313 followed possessing

confirmation

peroxide,

In*211

A

-1

mx204.1

of the presence

by oxidative

ion suggest

the

at 1745 cm -' in the infrared radical

to

by Loss of butene

3-methylbut-2-enyl,

give

m/e

315,

to give m/e

and 2-methylbutyryl

293

a,r b, CI d, e, f. 9, h, i j

in (X) was provided hydrogen

in agreement

3.72(1)s. 3.50(l)dd. JJHz,8Hz 8.2-8.6(2)1x1, 9.OO(3) t. J7Hz 7.81(3) 5. 2.73(l) s. d. -J7Hz m. s. 8.18(3 s.

r

Chemical

3 3 c

the molecular

of an acetate

257, are characteristic

2

m/e229(17)

presence

and by loss of a butyl

substituent.

m/e257,C14Hs05'(100)

mass measured of ketene

332.4

m e 1 f 18h7q6(54)

( 5

peak

or 3-methylbutyryl

257.8(4.06),

‘(1)

m/e315,C,sHq905r(39) m

gave

below:

b”) de370,

(5)

1:2).

/-~_{&180"

and combustion

with an 8-acyl

M+430,C2hHso07

m/e388,Cz2&806

25O)

ethanol

225(4.25),

a 4-alkyl-5,7_dihydroxycoumarin

intensive

t-elated isomers(

(c., 0.04%,

for the two components.

despite

stripping

(re 1'la b'l't 1 1 y checked

of 2-methylof 2-methyl-

with coumarins

(Xa) k.-Y -4.64s. 6.85d. J7Hz 1, 7.80m. my 8.98d. 57Hz "3 (Xb) k,T 01 P3 91 =Y

-4.59s. 6.15m. 8.76d. J7Hz 8.2-8.6;. 9.02t. 57nz

and 3-methylbutyryl and 3-methylbutyric of established

side chaiIs acids

structure),

using and

253

No.3

the

acids

esters 7 . of

were

separated

The

insecticidal

dimethyl

lated

and

based

on

ethers

ment

the

confirmed

by

0.5

greater there

above

examination

structure,

gin

B was

found

and

to be

more

peelings, fruit,

known

is

the

as

of

well

flesh

that as

has

and

insecticidal are

B

(XII),

oxidative (X)

in the

all

and

isolation

of

test,

isopropyl

and

mixture

was

the

of

two

n.m.r.

types

relationships

deacy-

latter

is in complete

presence

proton

been

of

uncouplers at

0.05

have

Mammea

might

and

pg/ml.

is

data.

agreeof

acyl

been

by

/-e.g.

(V17

M. americana. of being

6

methods

the

toxic of

and

found at

substantially Recently

coumarin

In the

light

structure.

to mosquito

of of

the

suranlarvae,

test.

distributed

Although

toxic1

for

been

(1)-(1X).

roots.

to be

are

shows

acetylated

predicted

both

it has

phosphorylation

compounds

longifolia be

(X)

oridative

than

phosphorylatlon,

suspected

qf

of

of an antibacterial,

from

types

seed,

effectiveness

injection)

to houseflies

coumarin

long

the

acid

structure

Xb)

the

expected

formic

Gibbs

and

a~

the

with The

(Xa

confirms

above

effectiveness

than

boiled

mixture

(X) uncouples

the

uncouple

active

the

(topical

surangin

to

and

presented

(I)-(X)

insecticidal

results,

when

spectrophotometric

above

Substance

a report

on methylation,

~35-238~.

m.p.

insecticide

of

compounds

8

and

chromatography

methods.

to houseflies

appeared

It

the

resonance

pg/ml.

toxity

related

of

are

of

(XI)

gas-liquid

formed,

88-90°,

fragmentation,

Assignments double

by

(X)

chromone

given

group

below

m.p.

information

In further the

substance

the

examination

substituent.

that

to

mass-spectral

with

identified

(n.m.r.),

cyclised

N.m.r.

and

much

in the valued

connerions

as

pulp

and

an

edible

between

this

No.3

254

and the

uncoupling M.

Dr. the

testing

Elliott

were

Research

by

his

and

P.

Mr.

beetles.

of

carried

a preliminary

provided

us with

Kenyon

(Tropical

Service,

out

a comparison Products

Mayaguez,

Donnellan

and

specimen

Rico)

and

the

of

McFarlane

B.

in keeping

us

Woodstock

possess

and

(U.S.D.A.

supplied

data,

respectively. Dr.

B.S.

We appreciate

M.H..Gaskins

provided

insecticidal

examination

surangin

and

Ltd.,

might

other

N.

Mrs.

Station)

Research

compounds

mass-spectral

Institute)

Puerto

(Shell

these

this,

investigation.

Experimental

Boyce

to us that

determinations J.F.

deserve

(Rothamstead C.B.C.

Dr.

suggested

the

coumarins

Needham

Dr.

kindly

Research

contained

colleagues,

McCormick

A.G.

and

the

Centre)

DZ-. A.

of

of

mustard

activity

made

and

against

Agricultural uncoupling

activity

with

the

Joshi

efforts

Agricultural

mammea

kernels.

REFERENCES

1.

2.

3.

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5.

Pagdn,

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1944, 7,

L.

D.E.

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