TRNG I HC KHOA HC T NHIN SEMINAR C CH PHN NG HU C ti: PHN NG CNG NC, ALCOHOL VO AlDEHYDE VA KETONE Nhm 2 HVTH: BI TH THU HNG TRN TH HUYN TRANG PHAM NGOC N GVHD: TS. L VIT TIN LOGO NI DUNG Phn ng cng nc (H 2 O)
2 Phn ng cng alcohol (ROH)
3 Phn ng cng vo C=O 1 LOGO Trong hp cht carbonyl, lin kt C=O lun lun phn cc v pha O, to nn hai tm phn ng: tm chiu tac kich thn hch trn C, va tm chiu tac kich thn in t trn O.
+ Nguyn t Oxygen cho phn ng theo kiu cho nhn in t nn phn ng xy ra nhanh v lin kt khng bn nn khng dn n sn phm.
+ Phn ng trn Carbon thng xy ra trong giai on chm ca phn ng (giai on quyt inh tc phn ng) va lin kt to thnh bn dn to ra sn phm phn ng. Do phn ng c trng ca nhm C=O la phn ng cng thn hch.
www.themegallery.com 1.PHN NG CNG VO C=O. C O C O LOGO C ch chung cho phn ng cng Nucleophile vao hp cht carbonyl + - 1.PHN NG CNG VO C=O. LOGO Nc l cht thn hch yu nn phn ng cng H 2 O vo aldehyde hay ketone xy ra chm v thun nghich cho ra hydrat hay gem-diol. Do c hai nhm OH gn trn cung mt carbon nn cac hp cht gem-diol khng bn, nm trong trng thai thun nghich vi cht u. 2. PHN NG CNG H 2 O: phn ng hydrat ha LOGO Trng thai cn bng phu thuc vao cu truc ca aldehyde, ketone va phn ln la phu thuc vao cu truc hydrat. 2. PHN NG CNG H 2 O: phn ng hydrat ha Formaldehyde, aldehyde va ketone mang nhm th rut in t, trong dung dich chng hu nh dng hydrat. Th d : C H H O + H 2 O C OH OH H H Formandehyde 0,1% Formandehyde hydrate 99,9% LOGO 2. PHN NG CNG H 2 O: phn ng hydrat ha Th d : Cl 3 CCHO + HOH Cl Cl Cl H O O Ph Ph O O O + HOH Ph Ph O O O O H . . . H . . . H H . . . ... LOGO Acetone gn nh khng cho hydrat. Khi cho acetone trn vi H 2 O 18 nhn thy nng acetone cha O 18 tng dn theo thi gian. 2. PHN NG CNG H 2 O: phn ng hydrat ha O + H 2 O 18 OH H 3 C CH 3 O 18 H O 18 H 2 O + H 3 C H 3 C H 3 C H 3 C C O CH 3 + H 2 O H C OH CH 3 H OH 58 % LOGO 2. PHN NG CNG H 2 O: phn ng hydrat ha LOGO Vai tr ca cht xc tc acid l hot ha nhm carbonyl lm cho in tch dng nguyn t carbon carbonyl tng ln v do tc nhn Nucleophile H 2 O d tn cng vo. 2. PHN NG CNG H 2 O: phn ng hydrat ha Xc tc acid V H 2 O l cht thn hch yu nn phn ng cng H 2 O vo aldehyde hay ketone xy ra chm v thun nghch. Phn ng xy ra nhanh hn khi c xc tc acid hoc base. LOGO 2. PHN NG CNG H 2 O: phn ng hydrat ha C ch xuc tac acid c bit HA O HA O H HOH OH OH 2 + A OH O OH OH O - H + A + slow H H Gem hay diol C ch xuc tac acid chung LOGO Ion hydroxide c tnh thn hch mnh hn nc, phn ng vi nhm carbonyl nhanh hn nc. 2. PHN NG CNG H 2 O: phn ng hydrat ha Xc tc base OH HOH OH OH O + slow O OH OH + C ch xc tc baz c bit C ch xc tc baz chung HOH OH OH O slow OH + B - + HOH O OH BH + + BH OH + B - + H 2 O LOGO 3. PHN NG CNG ALCOHOL (ROH) 3.1. Cng alcohol vao Aldehyde Alcohol cng vao aldehyde cho sn phm la hemiacetal va acetal.
Cung nh nc, alcohol la cht thn hch yu nn phn ng cng thn hch alcohol vo hp cht carbonyl xy ra kho khn va thun nghich. H 3 C H OH O H H 3 C CH 3 OH + H + hay HO - OCH 3 Hemiacetal Acetal H 2 O + H 3 C H OH CH 3 OH + H + OCH 3 H 3 C H OCH 3 OCH 3 LOGO www.themegallery.com - Hemiacetal: to ra khi cho 1 phn t aldehyde cng vi 1 phn t alcohol.
Hemiacetal khng bn, thng khng tach ra khoi hn hp do nm cn bng vi cht u.
Tng t nh trong phn ng cng nc, C cu aldehyde cung nh hng n kh nng phn ng, hng s cn bng thp hn phn ng cng nc.
Xuc tac base hoc acid lam tng tc phn ng. 3. PHN NG CNG ALCOHOL (ROH) LOGO www.themegallery.com Trong mi trng base: ion alkoxide (RO - ) c to ra la cht thn hch mnh hn so vi alcohol (ROH), nn phn ng cng xy ra nhanh hn. 3. PHN NG CNG ALCOHOL (ROH) R 1 C H O OR 2 R 1 C H O OR 2 OR 2 + R 1 C H OH OR 2 HOR 2 , - . . . . . . . . . . . . . . . . . . . . . . . . . . . . + OH + HOH OR 2 O H R 2 . . . . . . . . . . . . . . C ch : LOGO Trong dung dich acid: proton hot ha nhm carbonyl lam tng tc phn ng.
C ch: 3. PHN NG CNG ALCOHOL (ROH) . . R 1 C H O R 1 C H OH O - R 1 C H OH OR 2 + H R 1 C H OH HOR 2 H H R 2 . . . . . . . . . . . . . . LOGO www.themegallery.com Nu nng xc tc H + cao, alcohol c th bi proton ha to ra ion oxonium lam mt tinh thn hch. Lm gim nng tc nhn nucleophil ROH lm chm tc phn ng.
3. PHN NG CNG ALCOHOL (ROH) LOGO www.themegallery.com -Acetal: Trong mi trng acid mnh, hemiacetal phn ng vi mt phn t alcohol cho ra acetal. Hemiacetal bi proton ha thanh ion hydroxonium, ion nay mt 1 phn t nc thanh ion alkyloxonium. Ion nay bn do cng hng vi O, s cng 1 phn t alcohol vao ion alkyloxonium cho acid lin hp ca acetal. 3. PHN NG CNG ALCOHOL (ROH) R 1 C H OH 2 OR 2 R 1 C H OH OR 2 H + - H 2 O R 1 C H OR 2 R 1 C H OR 2 . . . . . . . . . . . . . . . . . . . . R 1 C H OR 2 R 1 C H OR 2 R 1 C H OR 2 ROH O H R -H + OR . . . . . . . . . . . . . . . . . . . . . . C ch: LOGO www.themegallery.com Acetal la hp cht bn, c th c lp sau khi trung hoa hn hp phn ng, va tinh ch. Acetal d dang bi thy phn bng dung dich acid loang thanh aldehyde ban u. C ch thy phn tng dng nh c ch to acetal nhng theo th t ngc li.
cn bng chuyn dich sang phi: dung lng tha alcohol, hoc ct loi nc ra khoi phn ng.
2. PHN NG CNG ALCOHOL (ROH) LOGO www.themegallery.com 3. PHN NG CNG ALCOHOL (ROH) 3.2. Cng alcohol vao ketone: Ketone cho phn ng cng vi alcohol to hemiketal va ketal. Do ketone c hot tinh vi tac cht thn hch kem hn aldehyde nn s cng alcohol kho khn hn. C ch phn ng xy ra tng t nh vi aldehyde. LOGO 3. PHN NG CNG ALCOHOL (ROH) Ha hc lp th: trong phn ng to hemiacetal -Formaldehyde: to thnh mt sn phm. -Nu R1 khc H: Sn phm to thnh l hn hp hai ng phn quang hoc (i phn hoc xuyn lp th phn).
R 1 C H OH OR 2 LOGO www.themegallery.com 3. PHN NG CNG ALCOHOL (ROH) Ha hc lp th: trong phn ng to hemicetal -Nu R1 ging R2 : to thnh mt sn phm. -Nu R1 khc R2: Sn phm to thnh l hn hp hai ng phn quang hoc (i phn hoc xuyn lp th phn).
Cc aldehyde v ketone mang nhm rt in t d dng cho ra hemiacetal v hemiketal nhng rt kh khn to thnh acetal v ketal. LOGO NG DNG: bo v nhm C=O - Phng php ny dng bo v nhm chc andehyde hay ketone, sau ti to li bng phn ng thy phn trong mi trng acid. O O OCH 2 CH 3 HOCH 2 CH 2 OH Acid catalyst O O OCH 2 CH 3 O + H 2 O HOCH 2 CH 2 OH O CH 2 OH O O CH 2 OH Ethyl 4-oxopentanoate 5-hydroxy-2-pentanone + CH 3 CH 2 OH H 3 O + + 1.LiAlH 4 2. H 3 O + Khng th phn ng trc tip 3. PHN NG CNG ALCOHOL (ROH) LOGO