Date of Graduation

1971

Document Type

Dissertation/Thesis

Abstract

The o b je c tiv e s of th is in v e s tig a tio n were th re e fo ld : 1 ) to s y n th e s iz e a r e p r e s e n t a t i v e s e r i e s o f n in e t r a n s - 2 - a ry lc y c lo h e p ty l m ethanesulfonate e s te r s , 2 ) to stu d y th e chem ical r e a c t i v i t y o f the members of t h i s s e r i e s and 3) to attem pt to c o r re la te chemical r e a c tiv i ty w ith a n t i ­ tumor a c tiv ity . Anti-tumor te s tin g d a ta was to be supp lie d by the Cancer Chemotherapy N ational Service Center a t th e N ational Cancer I n s tit u te . S ynthesis of these compounds involved, f i r s t , the s y n th e sis of the ap p ro p riate benzene d e riv a tiv e s . Then, e ith e r an ary l lith iu m d e riv a tiv e , or an a ry l Grignard r e a g e n t , was added to c y c lo h e p ta n o n e . The r e s u l t i n g t e r ­ t i a r y a lc o h o l was dehydrated to a ffo rd th e o l e f i n . The a ry l s u b s titu tio n p a tte rn s in the o le fin s were confirmed by nmr sp e c tro sc o p y . H ydroboration o f th e o l e f i n s a f f o r d ­ ed the tr a n s - 2 -ary lcy clo h ep tan o ls. M ethanesulfonate e s te rs were prepared from these a lc o h o ls . A stu d y of th e r e a c t i v i t y o f t h e s e m e th a n e s u lfo n a te e s te r s towards c y s te in e in a b u ffe re d aqueous medium was attem pted. However, the ra te of h y d ro ly sis of the e s te rs was of such magnitude that no re a c tio n w ith cy stein e could be observed. The ra te s of s o lv o ly s is of these e s te rs were then stu d ie d . The d ire c tio n of the observed ra te d iffe re n c e s w ith in the s e rie s was explained on th e b a sis of resonance fa c to r s , s te r i c in te r a c tio n and anchim eric a s s is ta n c e . At the time of th i s w ritin g the d ata supplied by the Cancer Chemotherapy N ational S ervice Center were incomp l e t e . No c o r r e l a t i o n o f ch em ical r e a c t i v i t y w ith a n t i ­tumor a c tiv ity could be attem p ted .

Share

COinS