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 )