Chng I: DN XUT HALOGEN CA HIROCACBON. HP CHT C NGUYN T Mc tiu: a. Kin thc: - SV nm c kin thc c bn v hin i + V cu to, tnh cht l, ha hc + ng dng v iu ch ca dn xut halogen, hp cht c nguyn t -Thy r s lin quan cht ch gia cc cht, cc dn xut, mi quan h gia cc hc phn. + C s ha hc hu c 1. + Cc hc phn ha hc khc nh ha hc i cng,..Trng CSP Nha Trang 1

b. K nng: - Vn dng kin thc o su kin thc m rng ni dung ca cc bi hc lin quan, - Gii cc bi tp ha hc v cc hp cht n chc, a chc, - T hc, t nghin cu. - Lm cc th nghim ha hc c. Thi : - C thc hc tp t gic nng cao trnh chuyn mn. - Tnh trung thc trong hc tp

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2

NI DUNGI.1. DN XUT HALOGEN I.2. HP CHT C NGUYN T

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3

I.1. DN XUT HALOGEN I.1.1. Khi nim v phn loi I.1.2. Danh php. ng phn I.1.3. Tnh cht vt l I.1.4. Tnh cht ha hc I.1.5. iu ch I.1.6. c tnh ha hc ca cc dn xut fluo I.1.7. Gii thiu ring I.1.8. Vi nt v ng dng thc tin ca dn xut halogen i vi mi trng

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4

BI TP XEMINA: - Gi tn cc hp cht theo danh php IUPAC: Cc dn xut halogen ca hi rocacbon (tr. 40,41) I.2. HP CHT C NGUYN T I.2.1. Vi nt v lch s hp cht c magie I.2.2. nh ngha phn loi v danh php I.2.3. Hp cht c magie I.2.4. Mt s loi hp cht c kim khc I.2.5. Hp cht photpho I.2.6. Mt s loi hp cht c phi kim khc BI TP: Tm tt kin thc chng ITrng CSP Nha Trang 5

I.1. DN XUT HALOGEN I.1.1. KHI NIM V PHN LOI a. Khi nim: - Khi thay th mt hay nhiu nguyn t H bng nguyn t halogen dn xut halogen. K hiu: R-X (R gc hidro cacbon no, cha no, thm, X c th l F, Cl, Br, I).

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6

b. Phn loi - Phn loi theo s lng nguyn t X: mono-, di-, tri-, polyhalogen (CH3Cl, BrCH2CH2Br; CHCl3, Br3C6H3,) - Phn loi theo gc R: Dn xut halogen no, khng no, thm.

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7

C th phn loi theo bc ca C lin kt vi X: Dn xut halogen bc 1, bc 2, bc 3. I.1.2. DANH PHP NG PHN a. Danh php: - Danh php thay th ca IUPAC: Tn ca dn xut halogen + tin t halogeno(vit gn halogen-) vo tn ca hidrua nn (mch chnh, vng chnh) V d: CH3CH2CHClCH3 (2-Clorobutan hay 2Clobutan)

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8

BI TP LUYN TP: Gi tn hp cht hu c sau: CHC-CH2-CHBr-CH3 theo danh php thay th A. 4-Bromopent-1-in (hay 4-Brompent-1-in) B. Bromua pentin-1 C. 2-Bromo pent-4-in

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9

D. Bromua pentinBr Br Cl Cl Cl

Cl Bromobenzen 1-Bromo-3-clorobenzen 1,2-Dicloroxyclohexan 1,2-Dicloxyclohex-1-en hay brombenzen hay 1,3-Brom-clobenzen hay 1,2-dicloxyclohexan hay 1,2-dicloxyclohex-1-en

- Tt c cc H thay ht bng cc X cng loi th tn gi thm tin t perhalogeno- (percloro-, perfluoro,...) ca hidrua nn m khng cn dng locant. V d: CCl3-CCl2-CCl3 (percloropropan hay percloprpan), CF3-CF2-CF2-CF3 (perfluorobutan hay perfluobutan ..\TULIEU-CTHUC\CCl4.c3xmlTrng CSP Nha Trang 10

Danh php loi chc: Tn gc hidrocacbon (hay gc ankyl) + halogenua. CH3-Br Metyl bromua, (CH3)3C-Cl tert-Butyl clorua ..\TULIEU-CTHUC\(CH3)3CCl.c3xml BI TP LUYN TP: c tn cc hp cht sau theo danh php loi chc: C6H5-CH2I A. Benzyl Iodua B. Phenyl, metyl iodua C. Phenyl, iodometan D. Iodo benzyl C6H5CHCl2 A. icloro benzan B. Benzyliden diclorua C. icloro benzyliden D. Ddiclorrua benzyl - Danh php thng thng (tn thng thng) Mt s dn xut halogen c IUPAC lu dngTrng CSP Nha Trang 11

(trong du ngoc l tn thay th). V d: CHCl3 Clorofom (Triclorometan) CHI3 Iodofom (Triiodometan) Bi tp luyn tp: Gi tn cc hp cht sau y theo danh php thng thng:CHBr3 A. Bromofom(Tribromometan). B. Bromua metan C. Tribromua metan D. Metyl tribromua CHF3 ..\TULIEU-CTHUC\CHF3.c3xml A. Trifluorometyl B. Fluorometan(Trifluorometan). C. Triflorua metan D. TrifloruametylTrng CSP Nha Trang 12

- Dn xut polihalogen: + Ch cha 3 nguyn t: clo, fluo, cacbon gi chung l clorofluorocacbon hay CFC. Ch : Thng mi vn dng tn thng freon V d: CCl2F2 Freon-12 (iclorodifluorometan) CClF2-CClF2 Freon-114 (1,2-iclorotetrafluoroetan) CCl2F-CClF2 Freon-113 (1,1,2-Triclorotrifluoroetan) BI TP LUYN TP: CCl2F-CCl2F c tn hp cht A. Freon-114 (1,2-tetraclorodifluoroetan) B. ifluoro, tetracloroetan C. iflorua, tetracloruaetan D. ifluoro, tetracloroetylen Trang Trng CSP Nha 13

b. ng phn * ng phn cu to + ng phn v v tr nguyn t halogen CH3CH2CH2CH2CH2Cl 1-Cloropentan BI TP LUYN TP:- Gi tn cc dn xut halogen sau: CH3CH2CH2CHClCH3 A. 2-Cloropentan B. Cloropentan C. 4-Cloropentan D. 2-Cloropentyl CH3CH2CHClCH2CH3 A. 2-Cloropentyln B. 3-Cloropentan C. Cloropentan D. 3-Cloropentyl CH3CH2CHCl2 A. 1,1-Cloropropan (Propyliden 1,1-iclorua)Trng CSP Nha Trang 14

B. 3,3-Cloropropan (Propyliden 3,3-iclorua) C. iclorroprpan D. icloropropyliden CH3CCl2CH3 A. 2,2-icloropropan (Izopropyliden iclorua) B. icloroprpan C. 2,2-icloropropyl D. Izopropyiden 2,2-icloro CH3CHClCH2Cl A. 1,2-icloropropan (propylen iclorua) B. 2,3-icloroprpan C. 1,2-icloropropyl D. CloroprpanTrng CSP Nha Trang 15

CH2ClCH2CH2Cl A. 1,3-icloropropan (Trimetylen iclorua) B. 1,3-iclorua propan C. 1,3-iclorua propyl D. Trimetylen icloruaH3 C Br 1-Bromo-2metylxclopropan Br Bromoxiclobutan

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16

- ng phn v v tr lin kt bi CH2=CHCH2Br 3-Bromoprop-1-en (Anlyl bromua) CH3CH=CH-Br -CTCT:

Bi tp luyn tp: Tn gi ca hp cht sau CH3CH=CH-Br l: A. 1-Bromoprop-1-en (Prop-1-enyl bromua) B. 1-Bromo propylen C. Bromua propylen D. Metyl etenylbromuaTrng CSP Nha Trang 17

*ng phn mch cacbon CH3CH2CH2CH2Cl 1-Clorobutan (Butyl clorua) (CH3)2CHCH2Cl 1-Cloro-2-metylpropan (Izobutyl clorua)

Bi tp luyn tp: Gi tn cc ng phn mch cacbon sau: CH2=CHCH2CH2-Cl A. Butylen clorua. B. 4-Clorobut-1-en. C. 1-Cloro butylen-4. D. 1-Clorobut-4-en. CH3CH=CHCH2-Cl A. 1-Clorobut-2-en. B. 2-Butylen clorua. C. 2-Cloro butylen-2. D. But-2-enylcloruaTrng CSP Nha Trang 18

*ng phn cu hnh + ng phn hnh hc

H3C C H(Z)-hay cis-1Clopropen

Cl C H

H3C C H C

H Cl

(E)-hay trans-1Clopropen

H

Br

Br H H

H

Br(Z)-hoac cis-1,2Dibromoxiclopropan

Br(E)-hoac trans-1,2Dibromoxiclopropan

..\TULIEU-CTHUC\DANXUAT-HALOGEN.c3xmlTrng CSP Nha Trang 19

Bi tp luyn tp: Gi tn cc hp cht sau theo danh php IUPACCH 3 H3C CH2Cl Cl Br Br

(a)

Cl (b)

(c)

1). cis-1,3-ibromxiclobutan 3). trans-1,2-icloxiclopentan 5). (E)-1,2-icloxiclopentan

2). 2-Clometyl-1,1-imetylxiclohexan 4). 1-Clometyl-6,6-imetylxiclohexan1 5). (Z)-1,3-ibromxiclobutan

A. a-4, b-3, c-1. C. a-4, b-3, c-6.

B. a-2, b-5, c-6. D. a-2, b-3, c-1.Trng CSP Nha Trang 20

+ ng phn quang hc ..\TULIEU-CTHUC\DOPHANQHOC.c3xmlCl C H H3C CH2CH3 H3CH2C Cl C H CH3

(R)-2-Clorobutan

(S)-2-Clorobutan

Danh php R, S -Theo cng thc phi cnh: + Bn nguyn t hoc nhm nguyn t C* c sp xp theo th t gim dn hn cp: a > b > c > d.Trng CSP Nha Trang 21

Khi nhn phn t theo hng C*d. Nu th t a > b > c i theo chiu kim ng h + Ta ni phn t c cu hnh R (rectus) Ting Latin c ngha l: phi Tri li nu th t ngc chiu kim ng h + Th phn t c cu hnh S (siniter) Ting Latin c ngha l: tri) V d: CH2OH-C*HOH-CHO -OH > -CHO CH2OH > -H.

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22

b

CH=O

C a

dHO

C

d

c Cu hnh (R) c

CH2OH Cu hnh (R)-Glixerandehit CH=O

C a

dHO

C

d

b Cu hnh (S)

CH2OH Cu hnh (S)-Glixerandehit

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23

- Theo cng thc Fes: Nu nhn vo cng thc m d cnh ngang th ng phn R trnh t a > b > c li tri chiu kim ng h cn ng phn S th theo chiu ngc li.(b) CH=O (d) H OH (a) (a)HO (b) CH=O H(d)

CH2OH (c) (R)-GlixerandehitTrng CSP Nha Trang

CH2OH (c) (S)-Glixerandehit24

Bi tp luyn tp: 1. Cu to no di y c gi tn ng theo danh php IUPACCl CH3 H CH 2CH2 CH3

(a)

CH 3

(R)-2-ClopetanOH 3C Br H

(b) (R)-4-Flo-4-metylxiclohexenCH3

F

H Br

Cl

F C

(c)

OCH3

(d)CH2 CH3

Meso-1,2-ddbrom-1,2-metoxyetan

(S)-2-Flo-2-clobutan

A. a, b.

B. c, d.

C. a, c.

D. b, d.25

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2. Hy gi tn cc hp cht sau:OCH 2 COOH OCH 2 COOH

Cl

Cl

(a)Cl

Cl Cl

(b)

(1). 2,4-D. (2). 2,4,5-T (3). Axit 2,4-diclophenoxiaxetic (4). Axit 2,4,5-triclophenoxiaxetic

A. a-1,4. b-2,3. C. a-2,3. b-1,4.

B. a-1,3. b-2,4. D. a-3,4. b-1,2.Trng CSP Nha Trang 26

3. Hy gi tn theo danh php IUPAC hp cht sau:Br

Cl CH3

A. 1-Brom-3-clo-4-metylnaphtalen B. 4-Brom-2-clo-1-metylnaphtalen C. 2-Clo-4-brom-1-metylnaphtalen D. 3-Clo-1-brom-4-metylnaphtalenTrng CSP Nha Trang 27

I.1.2. TNH CHT VT L a. Nhit si -Nhit ca dn xut halogen > t0s ca hidrocacbon tng ng. V d: t0pentan = 360C < t01-clopentan = 1070C Nu gc R nh nhau t0s tng ch yu theo A v phn cc ha ca nguyn t halogen (F < Cl < Br < I).Nu X nh nhau t0s tng theo chiu di ca mch cacbon (CH3X < C2H5X < C3H7X < C4H9)Trng CSP Nha Trang 28

Bng VI.1. Nhit si (0C) ca mt s dn xut halogen v ca hidrocacbon tng ng.Hp.cht CH3-X C2H5-X n-C3H7-X i-C3H7-X n-C4H9-X i-C4H9-X Hidrocacbo Fluorua n X=F X=H -62 -89 -42 -42 -0,5 -10 -78,5 -38 -2,5 -10 32,5 16 Clorua X = Cl -24 13 47 37 78 69 Bromua X = Br 3,5 38 71 60 102 91 Iodua X=I 42,5 72 102,5 89 130,5 120

ses-C4H9-Xtert-C4H9-X

-0,50

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6851

9173

11910029

b. Tnh tan R-X u khng tan hoc tan rt t v khng c

kh nng to lin kt hidro.

0,574g 0,08 SC2H5Cl = >SCCl4 = >SCl2CHCHCl2 0,0 100gH 2O 100V d: R-X d tan trong cc dung mi hu c R-H,

R-OH, R-O-RTrng CSP Nha Trang 30

c. Ph hp th R-X hp th vng t ngoi tng t cc R-H V d: CH4 = 125 nm, CH3Cl 1 = 151 153 nm, 2 = 173 nm. Nguyn t X c th gy hiu ng batocrom khi tham gia lin hp.-Trn ph hng ngoi R-X c cc cc i c trng cho lin kt C-Hal sng nm nhng vng kh pht hin c th: + C-F 1000 1400cm-1, C-Cl 600 800cm-1 C-Br 500 600cm-1, C-I 500cm-1.Trng CSP Nha Trang 31

- Ph hng ngoi v ph cng hng t proton (ht nhn) ca mt s R-X trnh by cc hnh VI.2 v VI.3.

I.1.3. TNH CHT HA HCC(+) (-)

X

- Lin kt C-X lun lun phn cc lm xut hin trng tm tch in (+) v (-). + X gy hiu ng cm ng m (ht e v pha mnh) c phn cc ha kh cao + Hiu ng cm ng ng.Trng CSP Nha Trang 32

- Nguyn t X lin kt vi > C = hay nhn thm gy ra hiu lin hp p-

H2C

C H

X

X

- Kt qu s phn cc CCl gim, lin kt C-Cl ngn li kh b t d li trong phn ng ha hc.Trng CSP Nha Trang 33

C2H5Cl (D) 2,02 dC-Cl (A0) 1,78

C6H5Cl 1,58 1,69

CH2=CHCl 1,44 1,69

Nng lng lin kt C-Hal (kJ/mol)

EC-F = 486 >> EC-Cl = 327 > EC-Br = 285 > EC-I = 214- Kh nng phn ng ca lin C-X vi tc nhn nucleophin bin thin theo nhng trnh t sau: + Nu gc R trong R-X nh nhau R-I > R-Br > R-Cl > R-FTrng CSP Nha Trang 34

+ Nu X trong R-X nh nhau: C6H5CH2X, CH2=CHCH2X > C2H5X > CH2=CHX; C6H5X - Cc phn ng c trng cho lin kt C-Hal: + Phn ng th nucleophin - C ch phn:..\CCHE-HUUCO\1-SN2.exeTrng CSP Nha Trang 35

+ Phn ng tch phn t HX

H

C

C

X

- HX

C

C

+ Phn ng vi kim loi

a. Phn ng th R-X + Y(-)

R-Y

+

X(-)

Tc nhn Y(-) c th l nhng anion HO(-),C2H5O(-), CN- hoc nhng phn t trung ha c cp e t do: H2O, NH3, C2H5OH, CH3NH2,36 Trng CSP Nha Trang

-Thy phn bng kim (iu ch ancol) (-) axeton R-OH + X(-) R-X + HO CH3CH2Br + HO(-) CH3CH2OH + Br(-)

- Tng hp Uyliemx (Williamson iu ch ete) R-X + R-O(-) R-O-R + X(-) C2H5-Br + C6H5O(-) C2H5-O-C6H5 + Br(-)

- Tng hp este R-X + R-COO(+) R-COO-R + X(-)

Trng CSP Nha Trang

37

- Tng hp Conb (Konbe, iu ch nitrin) R-X + CN(-) R-CN + X(-) C6H5CH2Cl + CN(-) C6H5CH2CN + Cl(-) - Tng hp Finkenstein (Finkelstein, trao i halogen) R-X + I(-) R-I + X(-) CH3CH2Br + KI CH3CH2I + KBr

- Phn ng Hopman (Ankyl ha) tng hpnamin

Trng CSP Nha Trang

38

R-X + NH3 R-NH 2 .HX R-X -HX

R 2 NH.HX R 3 N.HX R-X -HX

CH3CH2Br + NH3 CH3CH2-NH2. HBrC ch phn ng th: - Cc phn ng trn c th xy ra theo c ch SN2 hoc c ch SN1. + C ch SN2: ..\CCHE-HUUCO\1-SN2.exe - Giai on chm quyt nh tc phn ng hnh thnh hp cht trung gian. - Giai on nhanh X(-) tch ra khi hp cht trung gian to thnh sn phm. Xem c ch phn ng...\CCHE-HUUCO\2-SN1.exeTrng CSP Nha Trang 39

Y +Cht u

C

X

Y

CH

X

Y

C

+ X

Trng thi chuyn tip (phc hot ng)

Cht sn phm

v=k

C X YY C X

E

..\CCHE-HUUCO\47.MOV

Y +

C

X

HY C + X

Trng CSP Nha Trang

40

Phn ng thy phn 2-bromobutan bng kim theo c ch SN2H3C HO(-) H H3C-H2C(-)

CH3

CH3 Br(-)

C

Br

HO H

CH

HO

C

H

+ Br(-)

CH2CH3

CH2CH3

v = k[sec-C4H9Br][HO(-)] *C ch SN1: S chung:C Br

Chm- Br

C

Y Y

C C

Y

CCHE-HUUCO\2SN1.exe

v = k[ > C X]Trng CSP Nha Trang 41

(CH3 )3C-Br (CH3 )3C -Br

(+)

E

T1

(CH3 )3C-OH H2 O -H(+)

T2

> C(+)

..\CCHE-HUUCO\13.MOVY(-) + > C X

Y C < + X(-)

nh hng v cu to gc R n kh nng phn ng th nucleophin + Nu R trong R-X l nhng gc no, bc ca R cng cao: - Th kh nng phn ng SN2 ca R-X cng gim.Trng CSP Nha Trang 42

+ Kh nng phn ng SN1 ca R-X li cng tng - Do R(+) sinh ra cng bn. Th d: SN2: CH3-X > C2H5-X > (CH3)2CH-X > (CH3)3C-XSN1: CH3-X < C2H5-X < (CH3)2CH-X < (CH3)3C-X + Nu R trong R-X l nhng gc khng no, gc thm, kh nng phn ng SN2, cng nh SN1 u rt cao: - V trng thi chuyn tip trong SN2 n nh - Cacbocation trong phn ng SN1 c bn vng ha nh hiu ng +C ca >C=C HCl). + Cng c th thay th HHal bng PHaI3, PHaI5 (PI3, PBr3, PCl3, PI5, PBr5, PCl5, SOI3, POBr3, POCl3)+ HX + PX3 (Ar - CH2)R-OH + SOX2 + SOX2 (Ar - CH2)R-X + H2O 3(Ar - CH2)R-X + H3PO3 (Ar - CH2)R-X + POX3 + HX (Ar - CH2)R-X + SO2 + HX 2(Ar - CH2)R-X + SO2 + H255

Trng CSP Nha Trang

CH 3CH 2 CH 2 Cl + H 2 O CH 3CH 2CH 2OH + HCl OH-

CH 3CH 2 Cl2 +HOH CH 3CHO+2HCl OH -

CH 2 ClCH 2Cl+2HOH CH 2OHCH 2OH+2HCl OH -

CH 3CCl2CH 3 +HOH CH 3COCH 3 +2HCl OH -

CHCl3 +3NaOH HCOOH+3NaCl+H 2O OH -

Dn xut halogen (Ar-CH2) R-X tc dng vi: Y(-): -OH (-), -OR, -CN, -SR, -NH2, -R, RCOO(-),

-Ac: CH3COO(-)Trng CSP Nha Trang 56

+ S cc phn ng th nguyn t Hal bng tc nhn Y(-): (H2O, -OH(-), -Ac(-), R(-), NH3, CN-, OR,) + H2O (Ar - CH )R-OH + HX2

+ NaOH + NaAc (Ar - CH2)R-X + NaR' + NH3

(Ar - CH2)R-OH + NaX (Ar - CH2)R-OCOCH3 + NaX (Ar - CH2)R-R' + NaX

(Ar - CH2)R-NH2 + HX + NaCN (Ar - CH )R-CN + NaX 2 + NaOR' (Ar - CH )R-OR' + NaX2Trng CSP Nha Trang 57

I.1.5. C TNH HA HC CA HP CHT FLUO (Sinh vin t nghin cu)Ch : + Cc dn xut fluo m nguyn t C ch

lin kt vi 1 nguyn t F l nhng hp chtkhng bn d b tch HF + Cc dn xut m nguyn t cacbon cha hai

hoc ba nguyn t fluo rt bn.Trng CSP Nha Trang 58

I.1.6. GII THIU RING I.1.6.1. Metyl clorua CH3Cl a. Cu to..\TULIEU-CTHUC\CH3Cl.c3xml b. Tnh cht - L cht kh dng lm cht sinh hn trong CN ng lnh, lm tc nhn metyl ha. - Tinh khit bo ha CH3OH bng HCl di p sut cao c. iu ch

CH4 + Cl2(d) Trng CSP Nha Trang

CH3Cl + HClAlodan59

I.1.6.2. Clorofom CHCl3 a. Cu to ..\TULIEU-CTHUC\CCLOROFOM.c3xml b. Tnh cht - Cht lng l dung mi ph bin - Tc dng vi kim long mui HCOONa

CHCl3 + 4NaOH

HCOONa + 3NaCl + 2H2O

- Kim c CO TULIEU-CTHUC\PHOSGEN.c3xml

CHCl3 + 3NaOH

CO + 3NaCl + 2H2O

- Vi khng kh ngoi nh sng b oxi ha thnh phosgen rt c. 2CHCl3 + O2 2COCl2 + 2HClTrng CSP Nha Trang 60

c. iu ch t C2H5OH hoc CH3CHO, CH3COCH3 vi CaOCl2, Cl2, NaOH

CH3-CHO + 3Cl2 CCl3-CHO + 3HCl CCl3-CHO + NaOH CHCl3 + HCOONa -----------------------------------------------------------CH3CHO + NaOH + 3Cl2 CHCl3 + HCOONa + 3HCl CH3COCH3 + 6Cl2 CCl3COCCl3 + 6HCl CCl3COCCl3 + 2NaOH + H2O 2CHCl3 + 2HCOONa --------------------------------------------------------------------------CH3COCH3 + 2NaOH + 6Cl2 + H2O 2CHCl3 + 2HCOONa + 6HCl

I.1.6.3. Cacbon tetraclorua CCl4TULIEU-CTHUC\CCl4.c3xml

a. Cu toTrng CSP Nha Trang 61

b. Tnh cht - Cht lng, bn trong: + Khng kh + nh sng + Hi nc + Khng tc dng vi nhiu tc nhn ha khc nht l clo,. - Dng lm dung mi, dng dp tt m chy c. iu ch CS2 + CCl2SbCl CCl4 + S2Cl2 I.1.6.4. Cloruabenzen C6H5Cl a. Cu to3

..\TULIEU-CTHUC\BENZYL-CLORUA.c3xmlTrng CSP Nha Trang 62

b. Tnh cht - Cht lng c th iu bng cch clo ha benzen - Dng tng hp phenol v DDT C6H5Cl + HOH C6H5OH + HCl C6H5Cl + CCl3CHO (p-ClC6H4)2CHCCl3 + H2O c. iu ch Bt Fe, t C6H6 + Cl2 C6H5Cl + HCl I.1.6.5. Vinyl clorua CH2=CHCl a. Cu toNaOH,3000C, 200atm0

..\TULIEU-CTHUC\CH2=CHCl.c3xml

b. Tnh cht - L cht kh, rt quan trng trong tng hp polimeTrng CSP Nha Trang 63

c. iu ch - T axetilen 500 C CH CH + HCl CH2 = CH Cl - T etilen 500 C CH2 = CH2 + Cl2 ClCH2 CH2Cl ClCH2 CH2Cl CH2 = CH - Cl + HCl - T etan CH3 CH3 + Cl2 ClCH2 CH2Cl + 2HCl0 0

ClCH2 CH2Cl CH2 = CH Cl + HCl hoc ClCH2 CH2Cl CH2 = CH2 + 2HClCH2 = CH2 + HCl + O2 ClCH2 CH2 ClTrng CSP Nha Trang 64

ClCH2 CH2Cl CH2 = CH Cl + HCl 1.6.6. Tetrafluoroetilen CF2=CF2 a. Cu to..\TULIEU-CTHUC\CF2=CF2.c3xml

b. Tnh cht - L cht kh, c nhiu tnh cht rt qu: + Chu nhit + Khng tan trong mi dung mi + Khng tc dng: Axit Baz Cht oxi haTrng CSP Nha Trang

65

I.1.7. VI NT V NG DNG THC TIN V TC HI CA MT S NHM DN XUT HALOGEN I VI MI TRNG..\TULIEU-CTHUC\TTRSAU-DDT.c3xmlCl Cl Cl CH CCl3 DDT Cl Cl Cl Cl Cl CH2Cl CH2Cl

Trng CSP Nha Trang

66

..\TULIEU-CTHUC\CD-DIOXIN.c3xmlCl Cl CH CCl3 DDTCl Cl Cl Cl Andrin Cl Cl Cl Cl 2, 4, 5-T Cl Cl Cl OCH2COOH

Cl CH2Cl Cl Cl Cl

Cl CH2Cl Cl AlodanO Cl

O Dioxin

Cl

Bi tp: VI.1, VII.2, ,VI.8...\TULIEU-CTHUC\TDCO-2,4,5-T.c3xml

Trng CSP Nha Trang

67

I.2. HP CHT C NGUYN T I.2.1. VI NT V LCH S HP CHT C MAGIE (Sinh vin nghin cu gio trnh Ha hc hu c L Huy Bc) I.2.2. NH NGHA- L nhng hp cht cha nguyn t ca cc nguyn t khng phi l organnogen, lin kt trc tip vi nguyn t C.Trng CSP Nha Trang 68

I.2.3. PHN LOI CC HP CHT C NGUYN T - Lin kt trong hp cht c nguyn t k hiu> C E. Da vo nhm kim loi

+ Hp cht c kim ca kim loi nhm 1+ Hp cht c kim ca kim loi nhm 2 + Hp cht c kim ca kim loi nhm 3

+ Hp cht c kim ca kim loi nhm 8Trng CSP Nha Trang 69

+ Hp cht c phi kim in hnh l P (phospho) I.2.4. DANH PHP a. Hp cht c nguyn t trong E ch lin kt

vi gc hu c (R) v hidro (H):Tn ca hp cht ny l: Tn ca cc gc hu c v hidro (nu c) + Tn ca nguyn t E Th d: (CH3CH2)2Mg, (CH3)3CLi, ietylmagie tert-Butyllithi Al(C2H5)3 TrietylnhmTrng CSP Nha Trang 70

b. Hp cht m hidrua nn c tn l elementan (CH3CH2)3Bi; CH3CH2AsH2; Trietylbismutan Etylaran Pb(C2H5)4 Tetraetylpumban (CH3)2PH; CH3SiH2Cl; imetylphotphan Clometylsilan (CH3)3SiOH Trimetylsilanol. c. Hp cht c nguyn t c phi t l anion RnEXm Tn gc hu c + Tn ca nguyn t E (it lin) + Tn ca anion X (vit ri)Trng CSP Nha Trang 71

CH3MgI

Metylmagie iodua

(C3H7)2TiCl2 ipropyltitan iclorua CH3SnH2Cl ihidrometylthiec clorua

d. Cc hp cht c photpho cha lin kt P-O-CTn gi nh este ca cc axit v c tng ng (CH3O)2POCH3 imetyl metylphotphonat (CH3CH2O)3P Trietylphotphit

Trng CSP Nha Trang

72

I.2.5. HP CHT C MAGI.- Cu trc kh phc tp, n gin c th vit: RMgX.

+ Cng thc thng l: RMgX (R gc ankyl,ankenyl hay aryl; X l Cl, Br hay I). R-MgX R(-) + (+)MgX iu ch: R-X + MgEte, khan

R-Mg-X

- Dung mi l: Ete etylic hay anizoleTrng CSP Nha Trang 73

tetrahidrofuran, N,N-imetylanilin, benzen, xiclohexan,... - Dn xut R-X l ankyl halogenua bc 1, c th dng vinyl bromua, bromobenzen (do kh nng phn ng km) ng dng tng hp cc cht hu c I.2.5.1. Tnh cht ha hc ca hp cht c magi. R(-) Mg2(+) X(-) - Lin kt > C Mg phn cc mnh nn cc hp

cht c magie c kh nng phn ng cao.Trng CSP Nha Trang 74

I.2.5.2. Phn ng vi cc hp c H linh ng nh H2O, R-OH, NH3, axit amic R-CONH2 a. Phn ng mnh lit vi H2O R-MgX + HOH R-H + Mg X(OH) b. Phn ng vi ancol R-MgX + R-OH R-H + MgX(OR) C2H5-MgBr + HO-C2H5 C2H6 + MgBr(OC2H5) c. Phn ng vi amin R-MgX + HNH-R R-H + MgX(HNR)Trng CSP Nha Trang 75

d. Phn ng vi axit cacboxylic R-MgX + HOOC-R R-H + R-COOMgX - Bng phng php ny Zeremtinff thc hin phn ng cho CH3-MgX tc dng vi hp cht hidro linh ng iu ch v o th tch metan to ra. I.2.5.3. Phn ng th halogenua bng dn xut halogenua v dn xut ankoxi a. Vi halogen R-MgX + I2 R-I + MgXITrng CSP Nha Trang 76

C2H5-MgBr + I2 C2H5-I + MgBrI b. Vi dn xut ankoxi R-MgX+ CH(OC2H5)3 R-CH(OC2H5)2+MgX(OC2H5) R-CH(OC2H5)2 + HOH R-CHO + 2C2H5OH

I.2.5.4. Phn ng cng vi oxi, lu hunh, CO2, oxitetylen

a. Phn ng vi oxi R-MgX + O2 R-O-O-MgX R-O-O-MgX + XMg-R 2R-O-MgXTrng CSP Nha Trang 77

R-O-MgX + HOH R-OH + MgX(OH) b. Vi lu hunh to thnh sn phm cui cng mecaptan HCl R-MgX + S R-S-MgX

R-S-MgX + HOH R-S-H + MgX(OH) - Mun hn ch sn phm ph tin hnh phn ng nhit thp.c. Tc dng vi CO2 sn phm cui cng to thnh axit cacboxylic R(-)-Mg(+)-X + O = (+)C = O(-) R-CO-OMgXTrng CSP Nha Trang 78

R-CO-OMgX + HOH R-COOH + MgX(OH) d. Phn ng oxit etilen thy phn sp to thnh ancol

R - MgX +

H2C

CH2

R - CH2 - CH2 - OMgX R - CH2 - CH2 -OH + MgX(OH)

O R - CH2 - CH2 - OMgX + HOH

I.2.5.5. Phn ng vi hp cht cacbonyl v hp cht nitrin - S phn ng chung R(-)-Mg(+)X + O(-)= C(+)< R-C-OMgXTrng CSP Nha Trang 79

R-C-OMgX + HOH R-C-OH + MgX(OH) a. Phn ng vi anehit formic ancol bc 1H R - MgX + H H R C H OMgX + HOH R H CH2 OH + MgX(OH) C O R H C OMgX

b. Vi ng ng ca HCHO ancol bc 2

Trng CSP Nha Trang

80

R' R - MgX + R' R' R C H OMgX + HOH R C H O R C H R' C H OH + MgX(OH) OMgX

c. Phn ng vi axeton to thnh ancol bc 3R' R - MgX + R' R' R C R"Trng CSP Nha Trang

C R"

O

R R'

C R"

OMgX

OMgX + HOH

R

C R"

OH + MgX(OH)

81

d. Phn ng vi este thy phn to thnh ancol R' bc 3R - MgX +R' R C OR" R' R C R OMgX + HOH R OMgX R' C OR" R' O R C OR" OMgX

+ R - MgX

R

C R R' C R

OMgX

+ R"- OMgX

OH

+

MgX(OH)

e. Phn ng vi hp cht clorua axit v anhirit axit. R-MgX + R-CCl=O RRC(Cl)-OMgXRRC(Cl)-OMgX + R-MgX R2RC-OMgX + MgXCTrng CSP Nha Trang 82

I.2.6. HP CHT C LITI

I.2.6.1. Phng php iu ch- T dn xut halogen trong dung mi ete hoc hexan nhit thpR X + 2Li R Li + Li X

CH3CH2CH2CH2 Br + 2Li CH3CH2CH2CH2 - Li + Li Br (CH3)3C Cl + 2Li (CH3)3C Li + Li Cl

C6H5 Br + 2Li C6H5 Li + Li BrTrng CSP Nha Trang 83

I.2.6.2. Tnh cht ha hc- Tham gia nhiu phn ng tng t R-Mg-X nhng kh nng phn ng cao hn

a. Phn ng vi hp cht c H linh ng,CH3Li + H2O CH4 + LiOH (CH3)3CLi + HOCH3 (CH3)3CH + CH3OLi

C4H9Li + H-CH2-C6H5 C4H10 + C6H5CH2LiTrng CSP Nha Trang 84

b. Phn ng cng vo nhm C = O axit hoc ancolC6H5Li + CO2 C6H5COOLiH3O+

C6H5COOLi + H2O

H3O+

C6H5COOH + LiOHCH2=CH-CH(OLi)-C6H5

CH2=CHLi + C6H5CHO

CH2=CH-CH(OLi)-C6H5 + H2O CH2=CH-CH(OH)-C6H5 + LiOH

-Phn ng vi xeton tng hp vi ancol bc 3c phn nhnh cao gc RTrng CSP Nha Trang 85

C(CH3)3 (CH3)3C Li + (CH3)3C C(CH3)3 (H3C)3C C C(CH3)3

O H3O(+) [(CH3)3C] 3C - OLi + H2O

OLi [(CH3)3C]3C - OH + LiOH

I.2.7. HP CHT C KM I.2.7.1. Phng php iu ch: - C th dng R-Zn-R hoc R-ZnX V d: (CH3CH2)2Zn ietyl km, CH3CH2-ZnI etyl km ioduaTrng CSP Nha Trang 86

- iu ch t dn xut R X v ZnR I + Zn R ZnI 2R ZnI R Zn R + ZnI2

I.2.7.2. Tnh cht ha hca. C tnh cht ha hc tng t R-MgX - Kh nng phn ng km R-MgX,

- Tc dng vi R-CHO v R-CO-R R-OTrng CSP Nha Trang 87

H3O(+)

R-Zn-R + > C = O > C(R)-Ozn-R > (R)C-OH - Khng phn ng vi CO2 b. Sinh ra cc sn phm trung gian trong mt s phn ng thng dng. - Kh dn xut R-X thnh ankan trong mi

trng H3O(+)R-X R-H

- C ch phn ng:Trng CSP Nha Trang 88

- C ch phn ngR-X R-ZnX Zn Zn,H(+)

R-H + ZnX2

- ehalogen ha vic-ihalogen to thnh anken

trong mi trng ete.R2CX-CXR2 + Zn R2C = CR2 + ZnX2X R2C CR2 X + Zn X R2C CR2 ZnXTrng CSP Nha Trang 89HX

R2C = CR2 + ZnX2

-Tch dn xut 1,3-ihalogen xiclopropanC R2C X C chphn ng C R2C X CR2 + Zn X R2C XZn CR2 + Zn X etanol R2C C CR2 + ZnX2

RC C X R2C

C CR2 + ZnX2

R

Trng CSP Nha Trang

90

I.2.8. HP CHT C PHOSPHO I.2.8.1. Gii thiu hp cht c phospho - Hp cht ca P vi oxi, halogen rt phong ph v tng i bn, vi H km bn - Chia lm 2 loi: + Loi c lin kt trc tip gia P v C (lk P-C)...\TULIEU-CTHUC\DXUAT-PHOTPHO-03.c3xml

- Loi lin kt gin tip gia P v C qua mtTrng CSP Nha Trang 91

nguyn t khc (P-O-C) I.2.8.2. Hp cht c phospho loi P-C a. Phosphin hay phosphan

- Phn bit phosphin bc 1, 2, 3 (R-PH2, RRPH,RRRP) -D b oxi ha nhng hp cht ca P ha tr 5

Trng CSP Nha Trang

92

OH CH 3CH 2 PH2 CH 3CH2 P O CH 3CH 2 PH CH 3CH 2 (CH 3CH 2)3P CH 3CH2 P CH 3CH2 (CH3CH 2)3P O O OH OH

b. Ankylidenphosphoran hay phosphoni ylua (ylit phospho)

(C6H5)3P tc dng vi R-X bc 1, 2 cc muiphosphoni (tng t mui amoni).(C6H5)3P + CH3CH2Br (C6H5)3P(+)CH2CH3Br(-)Trng CSP Nha Trang 93

-Nguyn t H rt linh ng c th tch ra di dng proton bi mt baz mnh (C4H9Li, C6H5Li,..)[(C6H5)3P(+)CH2CH3]Br(-) + C4H9Li (C6H5)3P(+)- (-)CHCH3 +C4H10 + LiBr hay (C6H5)3P=CHCH3

- Hp cht phospho sinh ra trong phn ng trn

gi l: ankylidenphosphoran hay phosphoni ylua(ylit phospho).Trng CSP Nha Trang 94

- Ankylidenphosphoran + RCHO hay RCOR to ra anken RRC = O + (C6H5)3P = CRR RRC=CRR +

(C6H5)3P = O- Phn ng ny gi l phn ng Vittic tng hp ankenO + (C6H5)3P = C(CH3)2Trng CSP Nha Trang

C(CH3)2 + (C6H5)3P = O95

c. Axit ankylphotphonic v este. - L nhng hp cht cha nhm PO3H2 lin kt vi C.CH3P(OH)2 = O, Axit metylphosphonic CH3CH2 P(OCH3)2= O imetyl etyl phosphonat

- iu ch cac iankyl phosphonat bng cch un nngtriankylphosphit (RO)3P vi xc tc R-I y l phn ng chuyn v Acbuzop (CH3O)3PCH3I,2000C

Trng CSP Nha Trang

CH3 PO(OCH3)2

96

- C th iu ch bng phng php khc cngiankyl phosphit vo > C = OCCl3CH=O + (CH3O)2POH CCl3CHOH-PO(OCH3)2

imetoxi(2,2,2-triclorohidroxietyl)phosphat

- Sn phm trn lm thuc tr su mnh tn thng mi l triclorophon hay clorophos hay ipterex.Trng CSP Nha Trang 97

- Mt s dn xut phc tp ca CH3PO(OH)2 (axit metylphosphonic) l:CH3POF[OCH](CH3)2 (sarin) CH3POF[OCH(CH3)]C(CH3)3 (soman).

I.2.8.3. Hp cht c phospho loi P-O-C - Gm nhng ete khc nhau ca cc axit

phosphor, thiophosphor, phosphoricTrng CSP Nha Trang 98

thiophosphoric, c hot tnh sinh hc cao, dnglm dc phm, cht phng tr dch hi. a. Este ca cc axit phosphor v thiophosphor - Phalon haytris[2-(2,4-iclorophenoxi)etyl] phosphit iu ch t PCl3 v ancol dng tr c diTrng CSP Nha Trang 99

CTPT v CTCT:Cl Cl OCH2CH2O Cl P OH2CH2CO Cl

OCH2CH2O Cl

Cl

Merphos l tributyl trithiophosphit iu ch t PCl3 v C6H5SH..\TULIEU-CTHUC\DXPHOT-04.c3xml

Trng CSP Nha Trang

100

Cl

Cl O CH2 CH2 O Cl Cl O CH 2 CH2 O P O CH2 CH2 O Cl Cl

..\TULIEU-CTHUC\DXUAT-PHOTPHO-03.c3xml

Trng CSP Nha Trang

101

PCl3 v C4H9SH tc dng lm rng l[CH3(CH2)2CH2S]3P. b. Este ca axit phosphoric.

- iclorophos hay imetyl (2,2-diclorovinyl)phosphat iu ch t (CH3O)3P v cloral tc dng tr su (CH3O)2POOCH=Cl2 - Mevinphos hay imetyl(1-metyl-2-)Trng CSP Nha Trang 102

metoxicacbonylvinyl)phosphat iu ch t (CH3O)3P vCH3COCHClCOOCH3, tr su c i vi ng vt mu nng. (CH3O)2POOC(CH3)=CHCOOCH3OCH 3 H3CO P O O CH3 C C H C O OCH 3

Trng CSP Nha Trang

103

-Thiometon hay o,o-imetyl-S-(2-etylmecaptoetyl)ithiophosphat c tc dng tr su: (CH3O)2PSSCH2CH2SCH2CH3OCH 3 H3CO P S S CH2 CH2 S CH2 CH3

..\TULIEU-CTHUC\DXUAT-PHOTPHO-03.c3xml

d. c tnh chung ca cc cht phng tr su bnh c phosphoTrng CSP Nha Trang 104

So vi hp cht cha clo hp cht c phospho c mt s u im sau: - Hot tnh tr su bnh rt cao

- Rt nhiu loi su bnh chu tc dng ca hpcht c phospho - bn km d b phn hy trong t nhin

tr thnh nhng sn phm khng c i viTrng CSP Nha Trang 105

ngi v ng vt. - Ch cn dng mt lng nh ch phm cho mt n v din tch cn x l - Tc dng nhanh chng - C c cao i vi ngi v ng vt. - S dng phi tun th nghim ngt cc qui nh

v phng c.Trng CSP Nha Trang 106

I.2.9. HP CHT C ARSEN- C 3 nhm ng ch . I.2.9.1. Cc arsin (hay arsan)RRRAs

V d: CH3CH2AsH2, (CH3CH2)2AsH, (C6H5)3As Etylarsin ieylarsin Triphenylarsin (Etylarsan) (Ddietylarrsan) (Triphenylarsan) - C th b oxi ha thnh hp cht cha oxi ca As+5:Trng CSP Nha Trang 107

CH3AsH2 + [O] CH3AsO(OH)2 (CH3)2AsH + [O] (CH3)2AsO(OH)

(CH3)3As + [O] CH3As=O- Cc hp cht clo ca arsen c tnh c cao nhiu cht c dng trong chin tranhH Cl As Cl CH CHCl Cl As C 6H5 As ClTrng CSP Nha Trang 108

C 6H5

N

I.2.9.2. Axit arsinic v axit arsonic - Axit arsinic RRAsO(OH) v axit arsonic RAsO(OH)2 - Mui natri ca mt s axit loi ny dng lm thuc cha bnh. OH H3CAs H3C O O Na H2N As O ONa

I.2.9.3. Cc dn xut ca arsenazobenzen C6H5As=AsC6H5, mt s dn xut dng lm thuc tr bnh da liuTrng CSP Nha Trang 109

- Hp cht xanvaxan v novarsenolHO H2N As As OH HO NH2 H2N As As N H OH CH2SO2Na

I.2.10. HP CHT C SILICGm nhiu loi: Ankylsilan, ankylhalogenosilan, ankylhidroxisilan, ankylsilylamin,

poliorganosilan, poliorganosiloxan,Trng CSP Nha Trang 110

I.2.10.1. AnkylsilanCH3SiH3, (CH3)2SiH2, (C2H5)4Si, - C th iu ch bng cch cho SiCl4 tc dng

vi hp cht c magie hoc c km.I.2.10.2. Ankylhalogenosilan CH3SiCl3, ClCH2SiCl3 tricloro[clorometyl]silan

- Sinh ra khi cho SnCl4 tc dng vi CH3MgCl.Trng CSP Nha Trang 111

I.2.10.3. Ankylhidroxisilan (hay silanol) (CH3)3SiOH, (CH3)3Si(OH)2, sinh ra khi thy phn ankylclorosilan.

I.2.10.4. Ankylsilylamin (hay silazan)(CH3)3SiNH2, sinh ra khi cho triankylclorosilan tc dng vi amin

I.2.10.5. PoliorganosilanTrng CSP Nha Trang 112

- L polime c mch lin kt (- Si Si Si -)I.1.10.6. Poliorganosiloxan (hay silicon) - L polime c mch lin kt

- Si(CH3)2 O Si(CH3)2- Si O- Si(CH3)2,TM TT KIN THC CHNG I V BI TP I. Dn xut halogen

- L nhng hp cht hu c cha nguyn tTrng CSP Nha Trang 113

X lin kt vi gc R- (R-: no, khng no, thm). I.1. Danh php thay th: - Thay th, loi chc,

I.2. ng phn: - C y cc loi ng phn(ng phn mch C, v tr nguyn t X, lin kt bi, hnh hc, quang hc).

I.3. Tnh cht: - C nhit si cao hn R-H caoTrng CSP Nha Trang 114

nht l cc hp cht R-I- Lin kt CHal lun lun phn cc, nguyn t X c phn cc ha cao kh nng phn

ng cao vi tc nhn nucleophin.- Kh nng phn ng: R-I > R-Br > R-Cl > R-F. C6H5CH2-X > CH2=CHCH2X > CH3CH2X

> CH2=CHX > C6H5X,Trng CSP Nha Trang 115

- Ba loi phn ng quan trng: + Phn ng th nucleophin + Phn ng tch nucleophin

+ Phn ng vi kim loi hot ng+ C ch phn ng th SN2, SN1. + Phn ng tch E2, E1.

I.4. Cc phng php iu ch v ha tnh:Trng CSP Nha Trang 116

R -H, Ar - H

R - CH = CH2 Cng HXhO T

R - OHgX bn H

Th H b ng XY ng b

R-X

l 2, PX 3 SOC X, H

T ch HX

X h (- ) T Y h N

R-Y

>C=C