The structure of mucidone, a metabolite of a streptomyces species

Letter0

Tetrahedron

No. 41. PP 4159 - 4160, 1972.

THE STRUCTURE OF MJCIDDNE,

Por~n

Pmrr.

Prlntod

In Qeat

Britan.

A METABOLITE OF A STREPTOMYCES SPECIES by

G.Sipma, Central

B.van

Research

Introduction Iowa

isolated

carried

by Morris responsible

reportedly

in high

value

(lower

isolated

smell

On the

basis

I

proposed

as

the

purity,

limit

of

the

odour

having

of

the

the

river

water,

structure

Cedar

largely

River

odour.

for

Dougherty, the

Cedar

was found was

Since

the

to

isolated, threshold

1:300.000.000,

the for

Rapids,

actinomycetes ces

be approximately

was proposed

representing

of

a substance

musty

responsible

evidence,

near

Streptomy

cultures

to

7 September 1972)

two genera

predominating

laboratory

name mucidone

best

the

was found one

and spectroscopic

partial

publioation

and characteristic

be the The

Works,

From the

the

From

detection)

water.

chemical

of

and odour.

a strong

to

river

taste

problem.

organoleptic

was believed

of

Frutal

(Holland)

1961, the water

musty

2 from

for

substance

persistent

al

Polak’s

3, Amersfoort

During

a severe

et --*

be mainly

and D.K.Kettenesl

UK 30 Aumat 1972; aooepted for

in

and conclusion

(U.S.A.)

Wal,

Laboratory,

P.O.Box (Beoeived

der

the

objectionable

this

and

substance.

Campbell

and Morris3

compound.

0

(CgHg)CH(CH3)2

I

Because

of

our

a more definite original

NMR spectra It fruity, from

of

was not

is of

river

able

synthetic

interest

water

to

are

note

must

have

of

II

been

with

the of with

be that

caused

From the and

structure

synthetic

must

and chemical

Dougherty,

identical

that

The conclusion

(possibly

by Dr.

odour

mucidone.

to deterioration

II

to

of

show that

sample due

of

structure

supplied

been

possible,

of

correlation

the

a synthetic

estery.

constituent

in

for

kindly

we have

comparison water

interest

proof

sample,

compounds

I I

II

in combination should

original latter

those

of

very

strong

presence

4159

with

the weak musty of

tried of

of

mucidone. from

However,

the

the

to

river

UV,

IR and

sample.

in odour

and can be described

of

an extremely

the

material

strong

model

Direct

original

odour

give

the

synthesis to

isolated

material.

L

geosmine4).

we have

be assigned

compound

the

is

the

by the

II

structure

IR and NHR spectra

as

isolated

smelling

trace

No. 41

4160

Structure

determination

3,6-disubstituted carrying

an

The should the

end

From the

IR and NMR spectra

the

was also of

identity

mucidone

154

the

in

fact,

(II)

lead

groups),

(C12Hl202)

isomers

IV reasonably

was still

being,

butyl-2-pyrone

gave

positional

of

of

data

alkyl

us to with

assume

one of

that

the

mucidone

alkyl

is

a

groups

group.

in good agreement

interpretation

spectral

(R1 and R2 being

mass spectrum

be C7H15.

degree

of

isopropyl

reported

spectrum

The available

2-pyrone

instead

of

the

the

the

those

than

3-isoamyl

molecular that

obtained one.

from

in

the

could

be

We found

homologue

Dr.

RI + Rp compounds,

Dougherty.

the

usually

NMR spectrum in error,

that,

IV showed

so that

made as model

However,

sample

assumed.

ion,

were

differences

original

less

the IV,

published

Notably,

of

one CH,

and

matched

with

lacking. MS data

for

III

indicated

the

indeed,

The UV required that

molecular

mass

6-ethyl-3-iso-

a convincing

match

of

the

IR,

NMR. and UV spectra. The 2-pyrones They

have

been

illustrated prepared

in

the

following

Table

the

have

method

not

previously

described

been

by N.K.

reported

Kochetkov

in

et --

the

literature.

al.5.

cc RI

RZ RI

R2

’

0

0

b.p.‘C/mm

Hg

ni”

‘max

C2Hs

“-C5H11

138-l

Ill

C2H5

-iso-CSH11

135-13773

1.5013

IV

-iso-CSH11

C2H5

135-13713

1.5015

223 my; 301 mp;

log log

c 3.69 E 3.86

(4925) (7250)

II

-i so-C4Hg

C2hs

9O-92/0.7

1.4952

224 mu; log 303 mu; log

e 3.52 E 3.51

(3300) (8170)

225 mu; log 301 m; log

e 3.52 E 3.91

(3300) (8200)

Reported

Acknowledgement running

and

UV spectrum

The authors

Interpretation

of

for

thank IR,

40/3

“’ -

natural

Mrs.

1.5023

mucidone:

J.J.Kettenes-van

den Bosch and Mr.

NIlR and UV spectra,

for

valuable

ti.Zeckendorf

for

J.D.Dougherty

and

spectra. References 1.

To whom all

correspondence

2.

R.L.Morris,

Water

G.W.Ronald,

J.Amer.Water

3.

Sewer

should

be addressed.

Works 109, Works

76

(1962);

s,

1380

Ass.

J.D.Dougherty,

R.D.Campbell,

and R.L.Morrls,

J.D.Douqherty

and R.L.Morris.

J.Amar.Water

4.

N.N.Gerber,

5.

N.N.Kochetkov,

6.

W.J.le

Noble

Tetrahedron

Letters

L.J.Kudryashov and J.E.Puerta,

1968,

R.L.Morris, (1963). Science Works

152,

1372

(1966);

59,

1320

(1967).

2971.

and B.P.Gottlch, Tetrahedron

Ass.

Letters

Tetrahedron 1966,

1087.

2,

63

(1961).

assistance running

mass

in