LC Behaviour of Fluorinated Allylic Monomers
24 1=[ 11 95 ]
1
H NM R (C DC l =TM S, d p p m , J Hz ), 4 , 62 (2 H , O CH CH CH , d ,
3
2
2
J ¼ 5, 3 ), 5, 3 5 (1H , O CH C HCH , d d , J ¼ 1 0 ,5 J ¼ 1 , 5) , 5 , 48 (1 H ,
2
2
O C H CH CH , d d , J ¼ 1 7, 3 J ¼ 1 ,5 ) , 6 ,0 8 (1 H , O CH CHCH , m ,
2
2
2
2
J ¼ 10 , 5 J ¼ 17 , 3 J ¼ 5 ,3 ) , 7 ,0 0 t o 7 ,5 ( 8H ) .
a r
4-[4-(Allyloxyphenyl)]phenyl-3-(perfluoro-n-alkyl)propanoate
(EC4, EC6 and EC8)
Es t e ri fic at io n of 2 w i t h 2 - F- al k y lp r op a no i c a ci d s p rev i ous l y p re-
p a r e d (2 - F-b u t yl p rop a no ic a ci d a nd 2 - F- hexy l p ro p a n oi c a ci d ) or com -
m e rc ia lly av ai lab l e ( 2- F- oct y lp r op a no i c a c i d ) w a s p erf orme d usi n g
d ic y c lo he xy l c ar bo d i i mi d e ( D CC ) ca t a ly z ed by 4 -( N,N-d i m et hy l a mi no) -
p y r id ine . In a t y p ica l ex p e rim en t , a sus p ensi o n of 1 1 mmo l of 2 - F-
a l ky lp r o p an o ic a ci d s a nd 1 0 mm ol of 4 -( 4 -a l l yl ox y p heny l )p he no l ( 2 )
in 30 m L d ry d ic hl or om et ha ne w a s p re p ar ed . T hen 1 1 mmo l of d i cy cl o-
he xy lc ar b o d iim id e ( D C C) a nd 1 ,1 mm ol of 4 -( N , N-d i m et hy l a mi n o) p yr -
id in e w e re ad d e d a nd t he so lut i on w a s st i rre d a t roo m t emp e ra t ur e fo r
3
ho u rs . T he s o lut i on w a s f il t ra t ed t o el i mi na t e t he d i cy cl o hex y l ur ea
a n d t he s o lve nt w a s re mo ve d und er v ac uum. T he 4 -[ 4- (a l l yl o x y p he-
ny l) ]p he n yl - 3- (p er fl uo ro- n- a lk y l )p ro p a no a t e ( EC 4 ꢂ EC 8 ) w er e p uri -
f ied by c o lum n c hro m a t og ra p hy ov e r si li ca ge l usi ng d i chl or ome t ha ne
a s t he e lua nt .
1
F o r E C 8 : H N MR ( CD C l =TM S, d p p m , J H z) , 2 , 60 (2 H , CF CH , t t ,
3
2
2
J ¼ 8, 1 J ¼ 18 , 4) , 2 ,9 5 ( 2H , C F C H CH2 , t , J ¼ 8 , 1) , 4 , 63 (2 H ,
2
2
OCH CH CH , d , J ¼ 5 ,3 ) , 5 ,3 2 ( 1H , O C H CH CH , d d , J ¼ 1 0 ,5
2
2
2
2
J ¼ 1, 5 ), 5, 4 7 (1H , O C H C H CH , d d , J ¼ 1 7 ,3 J ¼ 1 , 5) , 6 , 08 (1 H ,
2
2
O C H CHCH , m , J ¼ 1 0, 5 J ¼ 1 7, 3 , J ¼ 5 ,3) , 7 , 00 (2 H , d , J ¼ 8 , 8) ,
2
2
ar
7
,1 5 (2 H , d , J ¼ 8 ,7 ) , 7 ,5 1 ( 2H , d , J ¼ 8 ,8 ), 7 , 58 (2 H , d , J ¼ 8 , 7)
a r
a r
ar
19
F N. M. R. (C D Cl =C FC l , d p p m ) , ꢁ8 2 ( CF , m) , ꢁ1 1 5 .5 [( CF ) , m] ,
3
3
3
2 a
ꢁ
1 23 [( CF ) , , , m] , ꢁ1 24 [ (C F ) , m] , ꢁ1 2 4 .5 [( CF ) , m] , ꢁ1 2 7
2
b c d
2 e
2 f
[
(C F ) , m ] MS ( 70 eV ) m =z ( %) , 4 1 ( 10 0 %), 6 9 (4 1 , 3 %), 7 7 (3 5 , 1 %),
2
g
1
8 5 (2 2, 1 %), 66 0 ( 11 , 6 %) , 7 00 ( 29 , 5 %) .
3. RESULTS AND DISCUSSION
The c ho ice o f t he mo le c ul ar p a ra me t er s of t h is ser ie s of mon om ers w a s
d et e r m ine d fr o m p re vi ou s w or k s d es c ri b ed i n t he l i t era t u re [1 5 , 1 6 ].
The s e c o mp o un ds a re l ist e d i n Fi g ur e 3 . T he cor resp o nd i ng mes o-
m or p hic p ro p e r t ie s a re re p or t ed i n Fi g ure 4. Ea ch mon om ers na med
Ax , Bx , Cx an d D x d i ff er t o ea c h ot h er b y one mol ec ul a r p a ra me t er.
The c o rr e la ti on b et w e en t he ir me so mor p hic p rop ert i es a l lo w s us t o
co n s id e r t he s e ri e s d es cri b ed i n t he p re se n t w ork a nd cod e d EC x.
The va lue ‘‘x ’’, d es c ri b ed i n t he Fi g ure 4 , eq u a l t o 4 , 6 or 8 , cor re sp ond s
t o t he fl uo ri n at e d me t hy l ene uni t s i n t he F- a l ky l t a i l.