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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,..
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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
NI DUNG
I.1. DN XUT HALOGEN I.2. HP CHT C NGUYN T
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
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 I
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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).
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.
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)
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
D. Bromua pentin
Br 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.c3xml
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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 dng
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(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. Trifloruametyl
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- 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)
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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. Cloroprpan
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CH2ClCH2CH2Cl A. 1,3-icloropropan (Trimetylen iclorua) B. 1,3-iclorua propan C. 1,3-iclorua propyl D. Trimetylen iclorua
H3 C Br 1-Bromo-2metylxclopropan Br Bromoxiclobutan
16
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 etenylbromua
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*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-enylclorua
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H3C C H
(Z)-hay cis-1Clopropen
Cl C H
H3C C H C
H Cl
(E)-hay trans-1Clopropen
Br
Br H H
Br
(Z)-hoac cis-1,2Dibromoxiclopropan
Br
(E)-hoac trans-1,2Dibromoxiclopropan
..\TULIEU-CTHUC\DANXUAT-HALOGEN.c3xml
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(a)
Cl (b)
(c)
(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.
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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.
22
CH=O
C a
d
HO
c Cu hnh (R) c
C a
d
HO
b Cu hnh (S)
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)
(a)
CH 3
(R)-2-Clopetan
OH 3C Br H
(b) (R)-4-Flo-4-metylxiclohexen
CH3
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
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
Cl CH3
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)
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ses-C4H9-X
tert-C4H9-X
-0,5
0
68
51
91
73
119
100
29
R-OH, R-O-R
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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.
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- 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.
- 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.
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H2C
C H
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-F
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+ 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.exe
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- HX
R-Y
X(-)
-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(-)
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
38
R 2 NH.HX R 3 N.HX
R-X -HX
Y +
Cht u
CH
+ X
Cht sn phm
v=k
C X Y
Y C X
..\CCHE-HUUCO\47.MOV
Y +
H
Y C + X
40
CH3
CH3 Br
(-)
Br
HO H
CH
HO
+ Br(-)
CH2CH3
CH2CH3
Chm
- Br
Y Y
C C
CCHE-HUUCO\2SN1.exe
v = k[ > C X]
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(+)
T1
(CH3 )3C-OH
H2 O -H(+)
T2
> C(+)
..\CCHE-HUUCO\13.MOV
Y(-) + > 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.
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+ 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-X
SN1: 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 <.
Trng CSP Nha Trang 43
+ Ngc li CH2=CH-X, C6H5-X u rt kh tham gia phn ng SN2 cng nh SN1 (v hiu ng +C ca X). Th d: SN2 v SN1: CH2=CH-X << n-C3H7-X < CH2=CHCH2-X
+ C ch SN2 ..\CCHE-HUUCO\1-SN2.exe
+ C ch SN1 ..\CCHE-HUUCO\2-SN1.exe
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b. Phn ng tch HX: + Khi un nng R-X no vi base trong dung mi R-OH xy ra phn ng tch X cng vi H v tr ) to thnh anken
-HX H C
b
C
a
Th d:
C2 H5 -Br + NaOH CH 2 =CH 2 +NaBr+H 2O
etanol,t 0 etanol (CH3 )3C-Br+C2 H5OH (CH3 ) 2C=CH 2 +NaBr+C2 H5OH 250 C
Trng CSP Nha Trang 45
C ch ca phn ng tch
..\CCHE-HUUCO\6-E2.exe
..\CCHE-HUUCO\7-E1.exe
C6 H5 -H + X 2 C6 H5 -X + HX
Fe,t 0 C
C6 H 6 + X 2 C6 H 6 X 6
h(askt)
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47
F F + NH2CH2CH3 F
F NCH2CH3 + HF
48
I.1.4.1. i t hirocacbon dng phn ng th a. Th hiro ca ankan v xicloankan vng trung bnh + Xy ra vi X2 l clo hoc brom iu kin chiu sng theo c ch gc SR b. Th H ca anken: + Ch xy ra cc aken thp : C2H4, C3H6 iu kin dng clo t0 ~ 5000C, nu brom ha v tr anlyl ca anken dng N-bromosucxinimit
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c. Th H nhn thm ca aren + Phn ng phi c xc tc xy ra theo c ch SE + Th H mch nhnh no cn phi thc hin phn ng theo c ch gc SR
h R-CH(CH 3 ) 2 +X 2 R-CX(CH 3 ) 2 HX h
To ra: + Dn xut monohalogen dng tc nhn phn ng HHal(HBr, HCl, HI) + Dn xut ihalogen dng tc nhn phn ng HaI2 (Br2, Cl2) hoc Hal-Hal (ICl, IBr, BrCl) a. Cng vo xiclopropan + Dng Hhal cng m vng to ra dn xut monohalogen mch h.
+ HBr CH 3 - CH2 - CH2Br 1- Bromopropan + Br2 Br - CH 2 - CH2 - CH2 - Br 1,3-dibromopropan
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b. Cng vo anken + Cng HHal (HBr, HCl, HI) trong dung dch khng c peoxit theo c ch AE (theo qui tc Maccopnhicop) CH3 - CHBr - CH3 (95%)
CH3 - CH = CH2 + HBr CH3 - CH2 - CH2Br (5%)
Peoxit
c. Cng vo ankaien lin hp v ankin -Dng mt hoc hai phn t Hhal hoc HaI2 i vi ankaien xy ra theo hng cng hp 1,4 hoc 1,2 (1, 2)
CH2 = CH - CH = CH2 + Br2 (1, 4) (1, 2) CH2 = CH - CH = CH2 + HBr (1, 4)
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CH3 - CH = CH - CH2Br
53
I.1.4.3. i t ancol dng phn ng th + Nhm OH ca ancol (ancol bc 3) c th thay th bng Hal nh tc dng ca HHal (HI > HBr > 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 + H2
55
Dn xut halogen (Ar-CH2) R-X tc dng vi: Y(-): -OH (-), -OR, -CN, -SR, -NH2, -R, RCOO(-),
-Ac: CH3COO(-)
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+ S cc phn ng th nguyn t Hal bng tc nhn Y(-): (H2O, -OH(-), -Ac(-), R(-), NH3, CN-, OR,) + H2O (Ar - CH )R-OH + HX
2
(Ar - CH2)R-NH2 + HX + NaCN (Ar - CH )R-CN + NaX 2 + NaOR' (Ar - CH )R-OR' + NaX
2
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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 + HCl
Alodan
59
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
- Kim c CO TULIEU-CTHUC\PHOSGEN.c3xml
CHCl3 + 3NaOH
CO + 3NaCl + 2H2O
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
a. Cu to
Trng 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 to
3
..\TULIEU-CTHUC\BENZYL-CLORUA.c3xml
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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 to
NaOH,3000C, 200atm
0
..\TULIEU-CTHUC\CH2=CHCl.c3xml
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 + 2HCl
0 0
ClCH2 CH2Cl CH2 = CH Cl + HCl hoc ClCH2 CH2Cl CH2 = CH2 + 2HCl
CH2 = CH2 + HCl + O2 ClCH2 CH2 Cl
Trng CSP Nha Trang 64
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 ha
Trng CSP Nha Trang
65
66
..\TULIEU-CTHUC\CD-DIOXIN.c3xml
Cl Cl CH CCl3 DDT
Cl Cl Cl Cl Andrin Cl Cl Cl Cl 2, 4, 5-T Cl Cl Cl OCH2COOH
Cl CH2Cl Cl Cl Cl
Cl CH2Cl Cl Alodan
O Cl
O Dioxin
Cl
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.
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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 phi kim in hnh l P (phospho) I.2.4. DANH PHP a. Hp cht c nguyn t trong E ch lin kt
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)
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CH3MgI
Metylmagie iodua
72
R-Mg-X
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
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)
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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 + MgXI
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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
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-OMgX
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R-CO-OMgX + HOH R-COOH + MgX(OH) d. Phn ng oxit etilen thy phn sp to thnh ancol
R - MgX +
H2C
CH2
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-OMgX
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b. Vi ng ng ca HCHO ancol bc 2
80
C R"
R R'
C R"
OMgX
OMgX + HOH
C R"
OH + MgX(OH)
81
+ R - MgX
C R R' C R
OMgX
+ R"- OMgX
OH
MgX(OH)
C6H5COOLi + H2O
H3O+
C6H5COOH + LiOH
CH2=CH-CH(OLi)-C6H5
CH2=CHLi + C6H5CHO
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 iodua
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- iu ch t dn xut R X v Zn
R I + Zn R ZnI 2R ZnI R Zn R + ZnI2
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:
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- C ch phn ng
R-X R-ZnX
Zn Zn,H(+)
R-H + ZnX2
R
C C X R2C
C CR2 + ZnX2
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
nguyn t khc (P-O-C) I.2.8.2. Hp cht c phospho loi P-C a. Phosphin hay phosphan
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
(C6H5)3P = O
- Phn ng ny gi l phn ng Vittic tng hp anken
O + (C6H5)3P = C(CH3)2
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C(CH3)2 + (C6H5)3P = O
95
CH3 PO(OCH3)2
96
imetoxi(2,2,2-triclorohidroxietyl)phosphat
- Sn phm trn lm thuc tr su mnh tn thng mi l triclorophon hay clorophos hay ipterex.
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I.2.8.3. Hp cht c phospho loi P-O-C - Gm nhng ete khc nhau ca cc axit
CTPT v CTCT:
Cl Cl OCH2CH2O Cl P OH2CH2CO Cl
OCH2CH2O Cl
Cl
100
Cl
..\TULIEU-CTHUC\DXUAT-PHOTPHO-03.c3xml
101
103
..\TULIEU-CTHUC\DXUAT-PHOTPHO-03.c3xml
So vi hp cht cha clo hp cht c phospho c mt s u im sau: - Hot tnh tr su bnh rt cao
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.
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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:
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C 6H5
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 H3C
As H3C O O Na H2N As O ONa
poliorganosilan, poliorganosiloxan,
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I.2.10.1. Ankylsilan
CH3SiH3, (CH3)2SiH2, (C2H5)4Si, - C th iu ch bng cch cho SiCl4 tc dng
I.2.10.3. Ankylhidroxisilan (hay silanol) (CH3)3SiOH, (CH3)3Si(OH)2, sinh ra khi thy phn ankylclorosilan.
I.2.10.5. Poliorganosilan
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X lin kt vi gc R- (R-: no, khng no, thm). I.1. Danh php thay th: - Thay th, loi chc,
R -H, Ar - H
R - CH = CH2 Cng HX
hO T
R - OH
gX bn H
Th H b ng X
Y ng b
R-X
l 2, PX 3 SOC X, H
T ch HX
X h (- ) T Y h N
R-Y
>C=C<
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