Cch trnh by bi thi c ch phn ng 1: - V c ch phn ng: +) Xc nh r phn ng xy ra theo c ch no, gii thch l do v sao?

+) Nn ni vn tt hng tn cng ca cc tc nhn (nh tc nhn thn hch trong phn ng th, base trong phn ng tch,...), tnh hnh hc ca trng thi chuyn tip, quan trng hn l ha hc lp th ca sn phm. - V nh hng ca dung mi: +) Xc nh tnh cht in tch ca cht nn, tc nhn, trng thi chuyn tip (tp trung in tch, trung ha hay phn tn in tch). +) Xc nh dung mi phn cc phi proton (DMSO, HMPA, DMF,...), dung mi phn cc hu proton (MeOH, RCOOH, H2O,...). So snh mc phn cc (da vo hng s ) ca cc dung mi. +) Xt s solvat ha cht nn, tc cht v trng thi chuyn tip. Dung mi no solvat ha tt hn trng thi chuyn tip (tc dung mi c phn cc cao hn) s lm gim nng lng hot ha v lm tng vn tc phn ng. +) Trong trng hp phn cc ca dung mi khng nh hng nhiu, cn xt n tnh cht cng, mm ca chng.

1/ Trnh by c ch v ha hc lp th ca phn ng thy gii (R)-3-cloro-3,7dimetyloctan.

Phn ng xy ra theo c ch SN1 v cht nn tam cp, tc nhn thn hch yu l nc. - Phn ng xy ra qua 2 giai on: G1: chm, tch nhm xut, hnh thnh carbocation, l giai on quyt nh vn tc phn ng.

G2: carbocation to thnh phng, v mt l thuyt tc nhn thn hch c th tn cng ng u t hai pha mt phng a n hn hp tiu trin. Thc t, sn phm l hn hp tiu trin c mt t nghch chuyn do tc nhn thn hch tn cng t pha trc s km u i hn do nhm xut va i ra, cn tr mt phn s tn cng t pha ny.

(nhiu hn)

(t hn)

2/ ngh c ch thch hp khi cho phenyletylcarbinol trin quang tc dng

vi SOCl2, kt qu cho thy clorur to thnh c s lu tr cu hnh. Nu hn hp phn ng c cho thm pyridin th kt qu thu c thay i nh th no?

Gi s xt ng phn (S): phn ng xy ra vi s hnh thnh cloro sulfitalkyl.

Phn ng hnh thnh cloro sulfitalkyl khng c s ct t lin kt C-O, do cu hnh (S) vn c gi nguyn. Tip theo, Cl rt gn tm phn ng pha trc, tn cng vo tm carbon bng i in t c lp, ng thi vi s ct t li n kt C-O. Sn phm c s lu tr cu hnh. Phn ng trn c s gii phng HCl. Trong mi trng khng dung mi cng nh khng c s hin din ca base, HCl khng phn ly. Khi thm pyridin, l mt base yu, n s gip HCl phn ly ra tc nhn thn hch Cl -, phn ng xy ra theo c ch SN2.

C ch phn ng SN2: Cl- tn cng t pha i din vi nhm xut (-OSOCl) ca phn t cloro sulfitalkyl. Phn ng xy ra ch 1 giai on, s tn cng ca tc nhn thn hch Cl- vo carbon tm phn ng xy ra ng thi vi s ra i ca nhm xut -OSOCl. Trng thi chuyn tip, tm carbon c 5 ni. Sn phm c s nghch chuyn cu hnh.

3/ Gii thch tc phn ng: Me-I + Cl- MeCl + IMeOH HCONH2 k 1,0 12,5

HCONMe2 120,000

MeCONMe2 7,400,000

- Nhn xt: y l phn ng SN2 xy ra trn cht nn trung ha, tc nhn thn hch c s tp trung in tch v trng thi chuyn tip c s phn tn in tch.

- Theo th t dung mi trn, tnh cng ca dung mi gim dn (tc tnh mm tng dn). Dung mi c xu hng chuyn t phn cc hu proton (dung mi cng) sang dung mi phn cc phi proton (dung mi mm). - MeOH l dung mi c kh nng to ni hydrogen vi tc nhn thn hch bng i in t c lp trn oxygen. Do , dung mi ny solvat ha tc nhn thn hch mnh hn TS. Tc nhn thn hch gim hot tnh, vn tc phn ng gim mnh. - T DMF (HCONH2) sang MeCONMe2, phn cc ca dung mi tng dn, cc dung mi ny solvat ha khng hiu qu ion m (l tc nhn thn hch), do hot tnh ca tc nhn thn hch c tng ln. Tuy nhin, cc dung mi ny li solvat ha TS mnh hn cht nn, nng lng hot ha gim, vn tc phn ng gia tng. phn cc ca dung mi cng tng, s solvat ha TS cng mnh hn, vn tc phn ng tng ln nhiu hn.