Tng hp Civetone t du c Sn phm

Yuen -May Choo * , Kay.Eng Ooi v Ing- Hng Ooi

Du c Vin nghin cu ca Malaysia , 50.720 Kuala Lumpur, Malaysia 911
Hon i etyl oleate , xc tc bi WCI6 v SnMe4 , cung cp diethyl 9 octadecenedioate ( mong mun
bt u nguyn liu cho qu trnh tng hp civetone ) nng sut 99 % . Dieckmann ngng t ca diethyl
9 octadecenedioate 2 -etoxycarbonyl- 9 - cycloheptadecenone ( 63 % sn lng ) , cc thy phn decarboxylation phn ng trong mang li civetone (93%) . Xc nh tt c cc sn phm l bi 1H
cng hng t ht nhn , hng ngoi v quang ph khi lng d liu. y l bo co u tin ca qu
trnh tng hp civetone t cc sn phm du c c ngun gc t .
T kho: Cy , civetone , diethyl 9 oetadecenedioate , 2 ~ etoxycarbonyl- 9 - cyeloheptadecenone ,
ethyl oleate , Hon i , du c .
Civetone ( 9 - cis- cycloheptadecenone ) , thng c gi l
Cy , l mt xeton macrocyclic chnh c tm thy trong cc tuyn tit cy hng . Civetone l mt
macrocyclic 17 nhm xeton mang mi x hng, m t c d chu mi trong cc dilutiorL Do tnh
linh hot ca ln vng , civetone d kin s c mt nh cis v trans ng phn . Tuy nhin , hp cht
ny xy ra trong t nhin nh cc cis- hnh thc ( 1} .
Civetone c tm quan trng thng mi nh mt loi nc hoa vt liu do mi c trng ca n v
c s dng rng ri trong ngnh cng nghip nc hoa l thnh phn c bn cho li kp
nc hoa. Civetone c tng hp thnh cng ( 2-8 ) , tuy nhin, do cc bc nhiu ngi tham gia ,
ngi ngho sn lng v tnh trng khan him nguyn liu ban u , n khng c
sn xut trn quy m thng mi i vi instanc ~ bt u t axit phloionic , cis- civetone c tng
hp trong mi mt bc vi sn lng tng th ch c 2,8%
Trong bi bo ny, chng ti bo co tng hp thnh cng ca cive ~ giai iu t oleate ethyl ch bin
t du c Chng ti cng bo co vic xc nh cc sn phm trung gian , 2 - ethoxyca ~ bonyl -9 cycloheptadecenone , m vn cha c bo co. TH TC THC NGHIM
Vt liu . WC16 v SnMe4 c mua t Aldrich
Cng ty Ha cht ( Milwaukee, WI ) . Thuc th KH ( 20 % phn tn trong du khong) c mua t
Fluka ( Buchs ,
Thy S ) . WC16 c tinh ch bng chn khng thng hoa di kh nit 200 ~ Benzen v toluen l
mua t Merck ( Darmstadt , c ) v l sy CaC12 v chng ct ln sng phn t 3A .
Tetrahydrofuran ( THF ) ( BDH , Poole , Vng quc Anh ) c chng ct t natri kim loi trong mi
trng kh tr .
Cc dung mi khc l loi thuc th v s dng trc tip . Sc k lp mng phn tch (TLC ) l thc
hin trn Merck Analtech tm knh hu thun ,
Precoated vi silica gel ( UV254 , dy 0,25 mm ,
Merck 9385 , 230-400 li } .
Phng php . Ph 1H cng hng t ht nhn ( NMR)
thu c trn JEOL JNM - PMX60 SI v JNMFXl00
quang ph k { JEOL , Tokyo , Nht Bn } vi tetra * ngi th nn c gii quyt ti Ha hc v
B phn cng ngh , du c Vin nghin cu ca Malaysia , PO
Hp 10.620 , 50.720 Kuala Lumpur, Malaysia . methylsilane nh l tiu chun ni b. Hng ngoi
quang ph (IR) c ghi li trong cloroform trn mt Hitachi ( Hitachi , Ltd ,
Tokyo , Nht Bn ) 270-30 quang ph . in t tc ng khi lng
quang ph ( EI - MS ) c ly t mt JEOL JMS - DX303 my quang ph .
Chun b ethyl oleate . Axit oleic l 99 % tinh khit , phn lp t tch thy phn du c, c
esterifled vi ethanol kh trong s hin din ca mt lng xc tc axit sunfuric m c 110 ~ trong
2 gi . tinh khit etyl oleat thu c c chng ct gim p sut
Hon i etyl oleate . Cc chn khng thng hoa tinh khit

WC16 ( sng bng, tinh xanh m , 0,39 g , 6,6 cng c % ) l

chuyn giao, theo nit , thnh 100 ml , hai c
y trn v nng ; 20 ml benzen kh
sau c thm vo. SnMe4 ( 0,19 g , 7,2 cng c % ) c thm vo
chm t mt ng ht vo bnh phn ng ti phng
nhit ( 28 ~ Hn hp ny c cho php khuy cho
10 ma . Mt gii php ca etyl oleat ( 4,66 g , 0.015 cng c ) trong
8 ml benzen kh c thm vo cng mt lc, v cc kt qu
hn hp c khuy cho mt ma 10 . Hn hp ny l
nhit 70 ~ ( tm du ) thm 20 h . Vo cui
phn ng , 10 ml dung dch NaOH 10 % c thm vo dp tt
phn ng . Hn hp ny c chit xut vi 2 60 mL
diethyl ether / xng du ete ( 60-80 ~ C ) ( 1:4 , vol / vol) . cc
Lp hu c lin tc ra sch bng 5N gii php HC1 ,
NaHCO3 bo ha , dung dch nc mui v
kh trn Na2SO4 . Chit xut kh c lc , v
dung mi d tha c loi b bng cch bay hi quay 40 o C.
Cc sn phm th v tp trung lc u
kim tra bi TLC cho tinh khit ca h . Sc k ct silica gel
vi diethyl ether / xng du ete ( 60-80 ~ C ) nh
ra gii dnh s c lp ca hai sn phm mong mun ,
9 - octadecene v diethyl 9 octadecenedioate ( 1 ) ( n
1).
9 - Oceadecene . Hon i etyl oleate vi cht xc tc
WC16/SnMe 4 cung cp 9 octadecene nng sut 97%. 1H
EtO2 C ~ - ~ CO2E t
[1]
55 ~
3 gi / KHf [ HF
/ Argon kh
5 % NaOH / THF / EtOH
Tro ngc 5 h
[2] [ 31
63 % 93%
n 1
Bn quyn? 9 nm 1994 AOCS bo JAOCS , Vol. 71 , khng . 8 ( thng 8 nm 1994 )