Perfumes related to ambergris. (1970)

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PERFUUES RETATED

TO

ATB]qRGRIS

A Thesis ^presented

the UnivcrsitY of

^Auckland

for the ^{degree of}

Doctor of

^PhllosoPhY

feith

^N.

^JobIin

by

Departnent University

o.f

Chernlstry

of Auc*land January

¹⁹⁷⁰

IABLE

0f

COI,ITEi{TS

-

AESIRACT

INTBODUCTION

Drsfltssroil

Synthcsis of ^{Perfirnes fron} 2-Oxonanoyl 0xide Synthesis of

Per.firnes

fron llartoyl

^Oxlde Approaches

to the Slmthesis of ^iles

^Perf\rmes

Oxide

Cleavages

of ^{ilanoyl Oxide and} its Derivatives

The Hass

Spectra of

^Sone

^Epineric Anbrei'nolides

l{ass Spectra 1 and

² Mass

Spectra 3 and

4

l{ass Spectra 5 and

6 Hass

Spectra 7 ^and

⁸

EXPENIUEI{IAI

REFERENCES DIAGRA}G

REACTIOI ^SCIIEI'IES FRACMEN1AITON SCSEUES

ACTNOWTEDGE!fr}TTS

Pace

i

1

I I

30

37

4

54

,6

59 60 69

71

r31 142 151 155 158

I

I

(i)

ABSTRACT

2-Oxonanoyr

oxide (ez) has

been

converted to ^{the 2-hydmxy} ether (g:) ana the 2-oxo ether (90) uottr of ^vhich

Possess

anbergris-type odourg similar to that of the odiferous

^conpound

^(t ).

The route which affords the highest yield is via ^the intermediates

(e+), (Z:)r (Cg) ana (fe;, and this sives ^23I of the 2-oxo ether

(ee) ana fl% ot the hydroxy ether (el) fron

Z-oxomanovl

oxide'

^A

tuo-step transfornation of

^nanoyl.

oxide (ee) into the _Perfune

⁽¹ )

has been achieved by oxidising nanoyl oxide vith

^chromiwn

trioxide in ^acetic acid, and then reducing the resul-ting ^lactone

(:f) airectLy to its cyelic ether (1).

Attenpts were nade to synthesise neu anbergris-tlPe perfunes, and successful preparation of the internal ketal ^(tOe)

showed

that contrary to expectations this ketal ig ^odourless.

Conparison of the nass spectra of the lactones (54), (f:)t (:e), and (t45), with those of their ^{cB epiners} (52), ($)' ^(5g),

and (146) respectively,

shoved

that the trans-fuseil ^{lactones loge}

carbon dioxide upon electron-inpact while the cis-fused isoners

do not.