Kinetics and Isotope Effects in Solvolyses of Ethyl Trifluoromethanesulfonate

Rearrangement Studies with 14C. XL. The Acetolysis of 2-Phenylethyl-1-14C Triflate

“…For the unreacted 1-OTf-d, present in the same reaction mixture, the analogous extents of D-scrambling were 24 and 3 3 z , respectively, at 3.25 and 5.0 h. These results thus demonstrate that similar to 1-OTs, extensive return processes also occur during the acetolysis of 1-OTf. Such behavior together with the nearly identical 14C-scrambling in the reaction products from 1-OTf-1-14C and ~-O T S -I -~~C suggests that acetolyses of 1-OTf and 1-OTs are mechanistically similar, thus lending further support to the conclusion of Streitwieser and co-workers (5,6), arrived at for the ethyl and propyl systems, that solvolysis of triflates is no more limiting than that of tosylates. As shown in Scheme 1, the overall extent of 14C scrambling in the 1-OAc-14C from the acetolysis of either 1-OTf-1-14C or 1-OTs-1-14C would be the composite result of product formation from the ethylenebenzenium ion (the k , process) and from direct displacement (the k, process) which may involve rearranged starting material that resulted from ion-pair returns (3,4).…”

Synthesis and structure of two crystalline forms of (cyclooctatetraene)thorium(IV) dichloride-bis(tetrahydrofuran)

“…® 156(2) C (5) ®689 (2) ..,2004(4) ® 001)(2) CUd .,547 (2) .. 2202(4) -.. 073(2) C (7) ®400 (2) .. 2291(4) -.. 817 ( z) cun .. 336(2) ®2 7(4) ® (2) C (9) .. 230 ctn ®1477(6) -e344(2) CU,O) ®0 (2) ®1 ( 5) -®429(2) C(11) -®032(3) .. 1411(1) -e2 ( 3) C (12) .. 063 (2) .. 1387 (7) -.. 138 ( 2) C (13) .. 603 (2) .. 0 5(4) .. 347(1) C (14) .. 758 (2) .. 0174 (5) 114 on CU.5) .. 838 (2! ) • .iU01 ( U .. 265{2) CU.6) .. 8(2) ~12- .. 807 (2) iH (2) ® 2(1+)…”

“…{3) .,o ., (2) '4) o4755U) .. 2098 (4) ® 5290 ( 1, 0(1) @00 U) .. 1 5(7) .. 2337(4) 0 (2) o14 (8) .,Q un (4) 0(3)…”

“…0(4) .,3 U) .. 4 ( 8) .. 5 (4) CU) -@017CU .. 372(1) .. 3352 ( 7) CC2) (2) .. 393(1) ., 3044( 7) CC3)…”

“….. 3 (8) .. 4(10) 2®8 (9) 141>4 (7) ""m4(9) ( 2) 1 .. 05 (2) 1mJ (2) 1<~>6 (1) 1®3{2) 2@7 (2) e9 (4) 1.5 (4) 2®7 (5) 1 .. 4(4) -.. 7(6) .. 6(6) .. 7USJ 3 .. 9(9) 2 .. 3 (12) 6.0(16) 2 .. 0(8) .. 01 (.1) -.. 31 (2) .. 9(2) <!>2(1) ®5(1) -®5 (1) e5 (3) .. 9(4) -<!>1(4) .. 9(4) -.. 2(5) . .. 1 -.,.…”