eo eiNH RANG (Chu bien) - e~NG eiNH BJ?tCH - LE TH! ANH eAo NGUY~N MJ?tNH HA - NGUY~N TH!

THANH PHONG

HOR· HOC HUU CO

•

3

(Tcii bdn ldn thit nhlft)

NHA XUAT BAN GIAO DVC

04 - 2006/CXBJ34 - 1860/GD

Ma 56: 7K549T6 - DAI

'Chuang XIII

~ ,

HOP CHAT CHUA NITd

. Hop chat chua nita bao gorn nhieu loai khac nhau, *) Loai hop chat clura m¢t nguyen tii nita, nhu :

- Hop chat nitro (RNOz hoac ArN02) ; Ia dAn xuat the' nhom -OH cua axil nitric HO-N02,·

- Hop chat nitrozo (RNO) : III diin xuat the' nhom -OH cua axit nitro HO-NO.

- Hop chat ankyl hoac arylhidroxylarnin (RNHOH, ArNHOH) : Hi dan xuat the'

hidro cua hidroxylamin NH2-OH.

- Hop chat amin : 130 dan xuat the hidro cua amoniac, nhu RNH2, R2NH, R3N.

- Hop chat co cac chirc khac nhau nhu oxim, amit, nitrin dli dlIQ'C nghien CUu d

chuong cac hop chat cacbonyl va axit cacboxylic,

*) Loai hop chili chua hai nguyen tii nita tnJ len, nhu : - Hop chat mu6i diazoni : [Ar - N ~ N]X-

- Hop chat hidrazo, thi du : Ar-NH-NH-C6Hs.

- Hon ch:it azoxi: Ar-N=N-Ar

YI:' ,J..

o

- Hop chat azo : Ar-N=N-Ar.

- H9l' cMt diamin, thi du : R-CH-CH2 -NH2 ....

I NH2

Loai hop chat di vong chua mot nita duoc xem xet a chuong Hop chat di vong, loai hop chat amino axit diroc xem xet d chuong Amino axit. a day, ta chi xet m¢t so hop chat tieu bieu nhir amin, mu6i amoni, mu6i diazo, chat mall azo va diamin,

3

§1. AMIN

Amin la dan xuat cua amoniac, trong do cac nguyen tu hidro duoc thay the bang cac gee hidrocacbon (no, khong no, tham). Tuy thea s6 g6c hidrocacbon lien ket voi nguyen tir nita rna co cac loai amin bac I, bac 2, bac 3, mu6i amoni bac 4.

RNH2 Arnin hac 1

R2NH R3N

Arnin bac 2 Amin bac 3

+

R4NX-

Arnoni bac 4

Tuy thuoc vao di_ic diem cua g6c hidrocacbon rna ta co cac loai amin nrong irng nhu amin thorn, amin mach hd beo, v.v ...

I. DANH PHAp

Ten cua amin diroc goi thea danh phap gee chirc, danh phap thay the va danh phap thuong.

1. Danh phap g6c - chitc

a) Ten cua amin hop bdi ten goc hidrocacbon va duoi amin hoac azan, neu cac gee gi6ng nhau thl them tien to di-, tri- ... , neu cac goc khac nhau rna eo 3 goc thl goi (viet) . ten cac gee theo vdn a, b, c ... va g6c b giiIa de trong ngoac. Thi du :

CH3NH-CH3

/CH3 C6H5-N <,

C2H5

ElY l(metyl )phen ylamin Etyltmety l)phen ylazan

Etylamin Etylazan

Dirnetylamin Dimetylazan

b) Cac diamin eo ten gee da hoa tri kieu "ylen" + diamin, Thi du :

H2NCH2CH2CH2CH2-NH2 H2N --<Q>-NH2

Tetrametylendiamin

p- Phenylendiamin

2. Danh phap thay the'

a) Ten cua cac arnin hop boi ten hidrocacbon va duoi amin hoac di-, triamin (vci cac di-, triamin) kern thea "Iocant". Thi du :

CH3CH2-NH2 CH3<i=HCH3 NH2-CH2CH2CH2-NH2 H2N--©-NH2

NH2

Metanamin Propan- 2-amin Propan-l,3-diamin Benzen-l,4-diamin

4

b) Ten cua cac amin bac hai, bac ba la ten cua amin bac mot co cac nhorn the _ N-ankyl. Thi du :

CH3-NH-CH3

CH3CH2-NH"':CH3

CH3CH2CH2N(CH3h

N - Metylrnetanamin

N-Metyletanamin

N,N-Dimetylpropan-l-amin

3. Danb phap thttong (ten rieng)

<

Mot s6 amin co ten rieng ducc IUPAC luu dung. Thi du :

Anitin

p-Toluidin

4,4' -Benzidin

4. 'Trong nhi~u hQp chilt _t\lP chuc co chua amin thi nhorn -NH2 diroc coi Ia nhorn the va co ten la amino. Thi du :

Axit 2-aminobutiric

, 4-Aminobutan-2-on

+

5. Khi nhom -NH2 b] proton hoa thanh nhom -NH3 goi la nhom amoni va

ten cua hop chat "amoni" nay duoc goi thea danh phap g6c - chirc hoac danh phap thay the. T hi du :

Phenylarnoni Benzenamoni (Anilini)

Phenylamoni clorua Benzenamoniclorua (Aniliniclorua)

Etyltrimetylamoni hidroxit

N ,N ,N - Trimetyletanamoni hidroxit

6. Cae amin la eac hC1P chilt di vang dUQc 99j ten theo hQp chat di vang (xem chuong 13).

,. , A It!

II. CAe PHUONG PHAP OIEU CHE

1. Ankyl hoa amoniac va ankylamin clla no

a) Ankyl hod bdng ankyl halogenua RX (phuong phap Hoffman, 1850)

Khi ankyl hoa amoniac va amin cac bac bang ankyl halogenua, nguoi ta se thu duoc mot hon hop amin cac hac khac nhau va ca muoi amoni bac 4 tuy thuoc van ti l~

5

mol cua cac chat tham gia philo lIng. De dieu che amin e6 b~e nao d6 can phai eho mu6i amoni tao ra tac dung vm klem :

+NaOH ) RNH2 -NaX-H20

(1)

Amoniae

Arnin bac I

+

R-NH2 + R-X --->- R2NH2X-

+NaOH

-NaX-H20)' R2NH

Amin b~c2

(2)

Amin b~c 1

+ R2NH + R-X ---+ R3NHX-

NaOH -NaX-H20)' R3N

Amin bac 3

(3)

Amin bac 2

Amin bac 3

M1l6i amoni bac 4

..

+NH,

+

+ (CH3[CH2hhN (vet) + (CH3[CH2h)4NBr- (vet)

C6H5NH2 + ~3I) C6H5NHCH3

Phan trng tren xay fa thea CO' che' ~2 VI amoniae va cac amin III nhirng tac nhan nucleophin dt t6t khi phan irng voi ankyl halogenua. Cac amin bac 3 phan iing rat nhanh voi ankyl halogenua de tao ra mu6i amoni bac 4. Cac aokyl halogenua bac 3 khi phan irng voi amoniac hoac amin bac 1 thirong co xu huang tach loai HX d~ tao ra anken (chiem iru the hen phan irng the), Thi du :

+ -

CH3-CH2-CH2-CH2-Br + NH3 SN2 )CH3-CH2-CH2-CH2NH3Br : Su the'

(CH3hC-Br + NH3 ~ CH3-C::::CH2 + NH4Br : Su tach

I

CH3

Khi aryl hoa amoniac bang cac arylhalogenua thirong phai thuc hien phan trng a dieu kien nhiet d(l cao, ap suat cao :

Nhung neu trong phan tit aryl halogenua co cac nhom the hut electron (-I, -C) a vi tri ortho hoac para thi phan ling xay fa dE dang han :

6

2,4-Dinitroanilin

* Phuong phap tot nhat de dieu che' arnin bac mot kh6ng Ian arnin cac bac la ankyl hoa kali phtalimit bang dan xuat ankyl halogenua (phuang phap t6ng hop Gabriel).

0 0 0
II II II
©:CC, .. KOH ©(>-K + RX/DMF ©(" ..
/NH -KX ) N-R
etanol C/
C
II II II
0 0 0
Phtalimit Kali phtalimit Ankyl phtalirnit , COOR-NH2 + ©:C

Amin bac 1 COO-

o II

rcvC-NIH RNH2 + ~ C-NH II

o

Thi du :

©rCH2Br

rAfCO '

1. l8l.~ )NK + DMF CO

[QrCH2-NH2

Benzyl bromua Benzylamin (82%)

o 0

T h I· . 'nh' .. II II h I

rong p ta urut co om lmlll( -C- NH -C-) luang tt! n u trong ety axetoaxetat.

Nh6m -NH- cp hai nhom cacbonyl hut electron manh nen nguyen tir hidro cua ) N-H rat linh dong, de phan ling voi KOH de tao anion >N - phan irng nhanh vOi ankyl halogenua tao ankyl phtalimit. Lien k~t irnit >N-R trong ankyl phtalimit de bi dUt khi thuy phan vci kiem de tao amin bac 1.

7

b) Ankyl hOG bang ancol

Khi co mat xuc tac la thori oxit Th203 hoac nhorn oxit A1203 (hoac d6ng cromat) lJ nhiet dq 300°C thi NH3 hoac amin 1, bac 2 co the duoc ankyl hoa bang ancol :

ROH + NH3

RNH2 + H20

Day la phirong phap trong cong nghiep de dieu ch€ amino

Etylamin

CH3CH2NH2 + C2HSOH ~ (CH3CH2hNH + H20 Dietylamin

Trietylamin Cac amin thorn cling diroc dieu che tuong tu.

Anilin clohidrat

N~Etylani1in clohidrat

C6HSNHC2HS·HCI + C2HSOH ~ C6HSN(C2H5h·HCl + H20 N ,N -Dietylanilin clohidrat

Nguoi ta co the dieu ch€ p~naphtylamin tiI ~~naphtol nhung xuc tac la amoni sunfit, lJ nhiet dq ISO°C.

~OH + NH3 (NH.;hS03

~ 150"C

I3.Naphtol

[3~ N aphtylamin

2. Khli cac h«jp chit chita nitd a) Khit hap chat nitro, nitrozo

Phuong phap khir cac hop chat nitro, nitrozo cho phep dieu ch€ cac amin bac 1 bee va amin thorn, Cho1t khu thuong 13. hidro mci sinh vai platin, platin dioxit Pt0b paladi hoac niken lam xiic mc ; hoac co the la kim loai Fe, Zn, Sn trong moi tnrong axit. Ngoai ra, co the dung (NH4hS, natri hiposunfit. Thong thuong va kinh te nhat Ia dung Fe trong HCI :

8

ArN02 + 6[Hl

uic nha.n kM

Nitrobenzen

Anilin

Toluen

2 ,4-Dini trotoluen

©rCOCH3

2,4-Diaminotol uen

1. Fe/HCl ) r6rCOCH3

2.NaOH/H20 ~

NHZ

1. Zn/HCl ) (CH3h NJ(5\-NHz

2. NaOH/H20 ~

Luong axit HCl thuc te chi can dung 1/40 so "oi luong Hel tinh thea If thuyet, vi sau khi tao Fe2+ thl lai bi oxi hoa thanh Fe3+ va giai phong HCl.

Khi khir hop chat nitro thi su tao thanh san pharn nao chinh phu thuoc VaG gia tri pH vii chat khir cua phan irng. Phan irng klnr trong moi tnrong axit (Fe, Zn trong HCl) san pham cuoi cung se la arnin thorn, Nell khir C6HSN02 thi san pham cuoi cling Iii anilin.

@-N02

2[H] ) !(5\-N =0 2[H]) !(5\-NH-OH 2[H]) !(5\-NH2

-H20 ~ ~ ~

N itrozobenzen

Phenylhidroxy lamin

Anilin

Nell thuc hien khir trong moi tnrong kiem thi sau khi tao ra nitrozobenzen va phenylhidroxylarnin, phan img xay ra nhu sau :

~O+HO-NH-©

NaOH

Azoxibenzen

Azobenzen

IHt'HLlI..lC0J.O.

Dihidrazobenzen

9

b) Khti IWp chat nitrin va amit

Nitrin va amit la cac dan xuat cua axil (xem chuang 11 - HHC2) co th~ bi khir hoan toan tao ra amin bac 1. Cac chat khir thuong dung 13. Zn trong HCI, natri trong ancol etylie tuyet d6i, liti-nhorn hidrua trong ete, hay hidro tren xuc tac la Ni, Pd, hose

ding co the dung diboran ~H6' .

_yO R-C-OH

LSOCl2 ) R-C-NH2

2. NH3 II

o

Axit cacboxylie

Amin bac 1

RX

NaCN

RCN

L LiA1H4! ete RCH2 - NH2

2. H20 )

Amin bac 1

Thi du :

Benzylnitrin

. 2-Phenyletanamin

Propanamin

Khi khir cac hop chat nitrin bang hidro co mat xiic tac la Ni (b nhiet d¢ cao) hoac Pd (b nhiet d¢ thirong) ngoai san pham chinh la amin bac 1, con thu diroc In¢t luong amin bac 2. Boi VI trong qua trinh d6 amin bac 1 se phan u.ng voi andimin tao ra bazo Ship, bazo Ship se bi khir thanh amin bac 2 theo sa do sau :

R-C=N [2H)) R-CH=NH R-CHzNH2) RCH=N-CH2R~R-CH2-NH-CH2-R -NH3

Ankyl andimin c) Khu hap chdt oxim

Cac oxim c6 the bi khir bang H2 co mat Ni xuc tac :

Bazo Ship

Amin bac 2

UN-OH

H2/Ni 90"C

D-NH2

Xiclopenty lamin

d) Khir hap chdt azit

Bang phirong phap nay co the dieu che amin bac 1 khong IAn cac amin cac bac.

10

2HHHOUC03ll

Khi khu azit nguai ta thuong dung liti-nhorn hidrua trong ete khan, hoac hidro hoa co XIJe tac Pd.

NaN~ 1. LiAIH4 fete

CH3[CH2]6CH21 . CH3 [CH2 J6CHzN3 2. NaOH/H20 ) CH3[CHZ]6CHZ -NHZ

1- Azitoctan l-Octanamin (70%)

2-Phenyletanamin (89%)

3. Klui - amin hoa andehit, xeton

Amin co th~ diroc dieu che bang each eho andehit hoac xeton tac dung vci amoniac hoac vai amin khi co mat chert khir, Qua trinh nay goi la qua trinh khii - amin hoa. Thuc te, phirong phap nay dung de tOng hop cac amin bac 1, cac xicloankylamin hoac amin thorn. Nguoi ta thuong tron tAn andehit hoac xeton voi arnoniac va hidro CJ nhiet d¢ 50 - 150°C, duai ap suat cao, co xuc tac Ni :

Phan Ung se tao ra mQt h6n hop cac amin cac bac tuy thea ti l¢ mol ciia cac chat tham gia. Trong phan irng nay d~ tao ra amin bac 1, nhat thiet phai dung du NH3.

Co the thay chat khit hidro bang each them axit fomic :

R' 0

<, '" /

/C=O + R2NH + H-C\ ---»

R'v OH

R' R'"

,,/ t

/CH-N, + H20 + CO2

R'v 'R'"

De dieu che cac metylankylamin, nguoi ta thuong dung HCHO voi amin bac 1 hoac amin bac 2 va mQ1 hrong dir NH3 a 100°C.

RNHz + HCH=O + HCOOH

Thi dl.J. : Trong cong nghiep, nguoi ta dieu che amphetamin - mot loai thuec kich thich than kinh - bang each klur amin hoa I-phenylpropan-2-on vai amoniac, cho du khi hidro voi xuc tic nhir la tac nhan khU.

~-CHZ-C-CH3

~ II

o

NH2 ©-CH2-~H-CH3 + H20

1 -Phenylpropan-z-on

Amphetamin

11

Amoniac, amin b~c I, amin bac 2 co the sir dung trong phan irng khir - amin hoa dt'! dieu che amin bac I, amin bac 2, amin bac 3 va muoi amoni bac 4 rat thuan tien.

Amin bac 1

R"NH2 Hixuc tac

R "CH-NHR" R'/

Amin bac 2

Amin bac 3

Co rtft nhieu chat khi'r hieu dung, nhirng trong phong thi nghiem nguoi ta chon xuc tac la natri xianbohidrua NaBH3CN :

Xiclohexanon

+ H20

N ,N -Dimety lxiclohexylamin

CC1 ch€ cua phan i1ng khir - amin hoa andehit, xeton nhu sau :

..

- Giai doan dau : Phan i1ng cong nucleophin cua NH3 (hoac amin) vao nh6m cacbonyJ tao ra san

pham gern-aminoancol trung gian r6i hop chat trung gian nay mat rurcc tao ra imino

- Giai d0<.U12 : Cac imin bi khLr boi tac nhan khir khac nhau tao fa amino Thi d~1 :

Imin

12

Gem-aminoancol

H2/Ni I C6HsCH2 -CH-CH3

I .

NH2

Arnphetamin

-«)

-'"

,:;

4. Tang hejp amin b~c 1 tit anken

Anken phan img voi boran BH3 hoac 9-B-B--N(9-boranbixiclo)-3,3,l-nonan de: tao ra cac triankyl boran. Cac amin bac 1 co the thu duoc khi cho hop chat nay pharr irng voi cloramin (H2N-O) hoac axit hidroxylamin-O-sunfonic (NH20S03H).

Triankyl bo

Amin bac 1

Trong tnrong hop nay, pharr trng cong cua BH3 vao n6i doi trai voi quy tac Maccopnhicop.

H

O~~CHJ

/,- H

.-;.

~',

NH2

trans- 2- Metylxiclopentanamin

(85%)

1- Metylxiclopenten

Nguoi ta cling co the sir dung enzim dac biet de xiic tac cho phan irng cong NH3 vao n6i d6i clla anken. Thi dlf ;

H COOH ,/

C

II

/C, HOOe H

+NH3

enzim aspartasa

Axit fumaric

Axit L-aspartic

Phan irng nay da diroc su dung trong thuong mai de san xuat axil L-aspartic trong nhieu nam. Trong tI! nhien, dong vat co vti khong the lay nita true tiep thanh hop chat hiiu C(1. Nhirng nguoc lai nhieu thuc vat, vi khuan lai co the su dung ion NH4" nhu mot ngudn nito de tong hop amin trong qua trinh nrong 1\1' nhu khir amino

5. Tang hC1p cac amin tit amit, azit (chuyen vi Hopman va Cuatiut)

Dan xuat cua axit cacboxylic co the chuyen hoa thanh amin bac 1 voi su loai be 1 nguyen C- cacbon trong phan irng chuyen vi Hopman va Cuatiut (Hofmann va Curtius).

13

Su chuyen vi Hopman di tit amit :

°

\I

R-C-NH2

Su chuyen vi Cuatiut di tit azit : o

11 +

R-C-N=N=N

T hi du : Trong thuong mai, ngiroi ta san xuat ducc pham kich thich su ngon mieng tit phan irng chuyen vi Hopman d~ dieu eh€ phenteramin :

CH3 I

C6Hs -CH2 -C-CONH2

\

CH3

2,2-Dimety 1- 3-pheny lpropanamit

Phenteramin

hoac dieu che thuoc giam dau tranylpromin bang phan Ung chuyen vi Cuatiut :

Trany lpromin

trans- 2- Pheny lxic1opropancacbony 1 clorua

Cii hai phan rmg nay deu nrong tt! nhau 6 giai doan chuyen vi g6c R vao nguyen til nitc ella amit hoac azit tao ra san pharn trung gian la isoxianat khong ben, duci tac dung , cua H20 dell tao ra axit R-N-caebamit rat de chuyen thanh amin va loai bO lC duoi dang CO2. So do Co' che cua cluing nhu sau :

1) Tit azit

° R-C';

"Cl

o NaN~ ) R-C/- +

-NaCl G~=N=N

t:. > O=C=N-R +H20

-N2 .

Isoxianat

Axit cacbamic

14

2) Tit amit

o II~

....... C. <, _£.--H + f)H

R i"'N .;--

"-.:1 -HO

H 2

o II~

....... C ....... I ....... H +ElH

R N

\ -HO

Br 2

o II~

R - c, 1 +1r-Br :N:

1 -8r

H

[R-t /

: N: +~ -----+~

? / 'Bf

R-C, .. / N

1 Br

(Dang trans)

H 0

I~ II r» ....... R O-CLN

....... H

Axit cacbamic

* Amin di vong :

? /Br R-C-N

-,

H

O=.C=N-R Ankyl isoxianat

Amin b~c 1

Di dieu ch€ amin di vong, nguoi ta thuang dung phuong phap nhiet phan mu6i diamin bac 1.

Thi dy trong dieu ch€ pirolidin hoac piperazin :

CHzCHzNHz .HCl 1

CHz -CHzNHz

Pirolidin

............ NHz·HCI HzN H
I
CHz -.......cHz () + 2NH4Ci
1 + , ---).
CH NlfCHz
-......~z HC!. z N
I
H
Piperazin , J _ ;

III. TINH CHAT V~T LI

1. Tinh chat v{lt Ii thong thuong

Cac amin -thap nhu metylamin, dimetylarnin, trimetylamin va etylamin Ia cac chat khi kh6ng mau b dieu kien thuong va co mui gjn gi6ng amoniac, chay diroc va de tan

15

trong mroc. Cac amin cao han la cac chat long, co mot s6 U. chat rAn (xem bang XIII.l), co mui tanh ciia ca.

Bang XIII. 1. Hang so v,t If eua mQt so amin

Cong thia: Ten g(Ji t, (0C) tnc (oC) Di) tan pKa
(g/100g H2O)
NH3 Amoniac tan 9,25
CHrNH2• Metylamin - 6,5 - 92,5 tan 10,63
(CH3hNH Dimetylamin 7,5 - 96 tan 10,73
(CH3hN Trimetylamin 3,5 -:-124 tan 9,79
CHrCH2NH2 Etylamin 16,6 - 81 tan 10,75
CHr[CH2h-NH2 n-Propylarnin 48 - 83 00 10,53
CtI3[CH2]6NH2 n-Heptylamin 180 - 1 00 10,63
H2N[CH2h-NH2 Etylendiamin 116 8,8 00 7,00; 10
H2N-[CH214-NH2 Tetramety lendiamin 158-160 28 de tan 9,35; 10
C1;Hs-NH2 Anilin 184 -6 3,6 4,6
C1;HsNHCH3 N -Metylanilin 196,3 - 57 0 4,85
CJfsN(CH3h N,N-Dimetylanilin 192,5 2,5 kh6 tan
m-CH3C1;~NH2 m-Toludin
(3-Aminotoluen) 203,2 -43,6 0,74 4,69
P-CH3C1;~NH2 p-Tol11din
( 4-Aminotoluen) 200,4 43,7 kh6 tan 5,12
p-C1;H4(NH2h p-Diaminobenzen
(1,4-Diaminobenzen) 267 140 3,8 3,29; 6,0
m-C1;H4(NH2)2 1,3-Diaminobenzen 287 62,8 35,1 2,65 ;
4,88
-{)-NH2 Xiclohexylarnin - - - 10,64
OH Piperidin - - - 11,20
Q Pirolidin - - - 11.27 Cac arylamin Hl cac chat long hoac chat ran khong mall, de bi oxi hoa trong khong khi tao ra cac chat co mall t6i.

16

Nhiet d¢ soi cua amin, nhat 13. cua amin bac mot va amin bac hai, eao hon nhiet d¢ soi cua hidrocacbon urong irng, Do la do su phan cue cua phan til va nhat la do co lien ket hidro kieu N - H ... N. Amin bac ba soi a nhiet d¢ thap hon cac amin bac mot va bac hai co cung phan til khoi vi khong co lien ket hidro.

Khi so sanh voi ancol co phan til kh6i wong duong thi amin co nhiet d¢ soi thap hon vi lien ket hidro N - H ... N yeu hon ° - H ... 0 va cao hon hidrocacbon. Thi du :

72 36

73 78

73 56,3

74 118

Cac amin thap tan t6t trong ruroc chu yeu nho su tao thanh lien ket hidro giira phan tir ruroc va amin cac bac khac nhau. Cac amin co g6c hidrocacbon cang cao thi d¢ tan cang giam,

2 Ph"?' •

. 0 cua amln

a) PhD' khoi (MS)

Theo quy luat, trong phO khoi hrong s6 khoi M+ cua cac hop chat chua mot nguyen tU nita la mot s616. VI vay, ta co the xac dinh duoc 51! co mat cua nguyen tir nito trong phan tir. Neu ion phan tu co s6 kh6i le, co the coi hop chat hitu co chua biet co 1 nguyen tu nita. Neu s6 khoi chan 5Uy ra hop chat co the kh6ng chua hoac chua 2 nguyen tit nito. Thi du : Metylamin co M+ ::: 31 dvC va mophin cong.thirc C17HI9N03 co M+ = 285dvC.

Cac amin beo trong ph6 MS thuong co S\,J phan manh 0 vi trf o. so voi nhorn amino luang ur nhu 51! phan manh cua ancol, lien ket C-C canh nguyen lU nita bi gay t<;10 ra cac goc ankyl va cation chua nita:

clit a

Thi du : Ph6 MS cua N-etylpropylamin co manh : = 58 va : = 29 phu hop vdi kha nang cat kieu c.

17

100

60 40 20

~,
58
-------- 29
mJz = 72 m1z= 87 =M+
III II II .I 20

40

60

80 90 100

mlz 140

[CH3 tCH2 _N'fiCH?H2]:\ CHj + [CH2 ~NH-CH2CH2CH3r

tal z= 87 CH3. \ m/z -15 m/z ~ 72

, [CH3CH2 -NH=CH2t + CH3CHi

m/z = 58 29

b) Phd hong ngoai

Trong phc hong ngoai co the nhan dang duoc amin bac 1, bac 2 a vach hap thu dac trung eho dao dong hoa tri ella lien ket N-H a 3300 - 3500 em-I. Aneol cling hap thu a vung nay nhirng pic hap thu ella amin nhon sac han va cuong d¢ thi yeu han pie cua nhom hidroxyl. Amin bac 1 co dao dong hoa tr] ella lien ket N-H a 3350 em -1 den 3450 em -1, amin bac 2 co pic dan a 3350 em -1 ; Amin bac 3 khong co tin hieu vung nay vi khong con lien ket N-H.

Dao dong bien dang ella lien ket N-H 0650 - 900 em-I va 1560 - 1650 em -I.

Dao dong hoa tri ella lien ket N-C a 1030 - 1230 em -I (vach yeu) d6i voi amin

mach he, doi voi amin thorn co 2 vach manh a 1180 em -1 - 1360 em -I.

c) Pho' cong huang lit hat nhdn

+ Pho cong hirong tir hat nhan proton (IH-NMR) :

D¢ chuyen dich hoa hoc ella nguyen ti't hidro lien ket voi nita trong amin bac 1 va bac 2 khong duoc d~e trung lam, no co the bi thay d6i va phu thuoc van nhieu yeu to nhu d¢ tinh khiet ella mau, dung moi rna n6 hoa tan, nong d¢ ella mau va nhiet de? khi do.

18

JH HHL: cJCCl38

Cac pic thuong bien d6i trong khoang rong khi thay d6i dung moi, vi vay nguyen tir hidro lien ket voi nguyen tu nita ella amin luang tir nhu nguyen IU hidro trong nhom hidroxyl cua aneol.

D¢ chuyen dich hoa hoc ella nguyen tir hidro lien ket voi eaebon gan nguyen tir nita (nrong nr ankan) bi dich chuyen do tfnh hut electron ella no. Do do co d¢ chuyen dich hoa hoc chuyen ve tnrong manh han so voi ancol,

-Ta co the so sanh d¢ chuyen dich hoa hoc ella hidro trong nhom -CH3, -CH2, -CH trong ankan, amin va aneol qua bang XIII.2.

Sang XIII.2. £)Q djch ehuy~n hoa h9C cua mQt s6 hQp chat (ph61H-NMR)

Chd: OCH1 Clui: OCH2 Cluj! °CH
CHrCH3 0,56 CH3CHrCH3 1.33 (CH3hCH 1,50
CH3-NH2 2,47 CH3CHrNH2 2,74 (CH3hCH-NH2 3,07
CHrOH 3,39 CH3CH2-OH 3,59 (CH3hCH-OH 3,94 + Ph6 cong huang tir 13C-NMR.

D¢ dich chuyen hoa hoc cua 13C_NMR cua nguyen tiI egan ke nguyen tu nita a tnrong yeu, S,! chuyen dich nay khong 100 nhu trong aneol.

Bang XIII. 3. So sanh dQ djch chuy~n hoa h9C eua 13C_NMR eua C trong nh6m -CH3, -CH2-, >CH- cua ankan. amin va aneol

Chdt OCH3 Chat OCH2 Chat °CH
CHrCH3 7,3 CH3CH2-CH3 15,9 (CH3hCH 25,0
CHr-::NH2 28,3 CH]CH2-NH2 36,9 (CH3)2CH-NH2 43,0
CHrOH 50,2 CH3CHrOH 57,9 (CH3hCH-OH 54,9 ~ J ~

IV. TlNH CHAT HOA HQC

Trung tam phan ung cua arnin Ia nguyen tu nita. Tinh chat cua no diroc quyet dinh hoi su co mat clla cap electron n va S,! phan cue cua lien ket N-H. Amin bac mot va bac hai co day du hai tinh chat nay. Tinh chat hoa hoc cua nguyen tu nita chiu anh huang ella cac g6c hidrocacbon lien ket voi no, m~t khac no lai anh huang den tinh chat ella g6c hidrocacbon, nhat Ia d6i voi g6c hidrocacbon thorn.

19

1. Tinh bazo

Trang phan tu amin, nguyen tu nita co Call true hmh thap, voi mot cap electron tu do. Tirong tu nhir amoniac, cac amin deu co tfnh bazo do cap electron n b nguyen til nita. Cap electron nay ket hop voi proton H+ d~ tao ra lien ket cong hoa tri thIT nr :

Etylrnetylamin

Mu6i amoni bac 4

Trong dung dich mroc, cac amin t<.10 thanh cac hidrat, cac hidrat nay phan li tao ra ankylamoni va ion hidroxyl.

RNH2 + H-OH

+ +

[RNH3]OH ~ RNH3 + OH

Ion ankylamoni (axit lien hop)

Lire bazo cua arnin bieu hien b hang so Kb hoac pKb. ,

Nguoi ta cling co the do hrc bazo cua amin RNHz boi hang sO' K, hoac pKa cua +

axit lien hop RNH 3.

RN"H3 + H20 ~ K - [RNH2][H30+]

a -

Nhu vay, tinh bazo cua amin cang tan khi K, va pKa cang Ian va pKb cang nho. Tinh bazo cua amin phu thuoc vao cau t<.10 phan liI va mar d¢ electron cua nguyen tir nito.

..

MQi yeu to lam tang mat d¢ electron a nguyen tiI nito -N- trong phan tir amin

I +

trung hoa va giai toa dien tfch duong a nguyen tir nita trong ion anky lamoni R NH 3 dell

lam tang tinh baw. Nlnr vay, nell thay the nguyen tu hidro trong NH3 hay trong RNHz

20

bang cac g6c ankyl R- co hieu irng day electron +1 va +C deu lam tang tinh bazc, Ngiroc lai, neu thay H bang cac g6c co hieu irng hut electron (-I, -C) thl larn giam tinh bazc. Nhu vay, tinh bazo cua amin trong dung moi khong phan cue tang tit amin bac 1 den bac 2, bac 3. Cac ankylamin (nhu metylamin, ... ) deu co tfnh bazo manh han amoniae.

Trong dung moi phan eire (nhu H20 chang han) thi amin bac 2 co tinh baza 100 han bac 1 ; amin bac 2 co tinh baza 100 han amin bac 3.

Anilin va cac amin thorn co tinh bazo yeu han amoniac do C6Hs- co hieu irng -to Thi du :

(CH3hNH >

pKb: 3,23

NH3 > 4,75

(CH3hNH > (CH3hN

pKb: 3,23 4,20

(<:ZH5)2~H > (C2I1S)3N

pKb: 3,07 3,13

Trang day anky lamin cac bac, amin bac hai co tinh bazo rnanh nhat, Hien nrong nay diroc giiii thich bang su solvat hoa cua ankylamin trong dung dich mroc. SI! solvat hoa phu thuoc vao s6 nguyen ttt hidro trong ankylamoni va hieu ung khong gian loai mot. Amin bac 3 co nhieu nhom d<1y han nhirng lai giam ve kha nang solvat hoa vi it hidro han va vi hieu Ung khong gian ;

Amin bac hai :

R

I H

R-N+H 0/ ... "'-

I H

H ... 0 <,

/ H H

Amin bac ba:

R 1

R-N+ .,...I1 ... H-OH I

R

SI! han kern nhau ve tinh bazo cua amin bac mot va bac ba phu thuoc vaogoc hidrocacbon. T hi du :

(CH3hNH

pka: 10,77

>

21

10,93

10,63

10,87

Cac amin thorn co tfnh bazo yeu hem amin beo, neu bac cang cao tfnh bazo cang giam (do cap electron n cua N dii tham gia lien hop voi vong benzen) hay cac g6c aryl co hieu ling -C tang len. Thi du :

C6HSNH2 > (C6HshNH

pKa 4,6 0,9

> (C6HShN

(Khong con tinh bazo)

Neu trong nhan benzen co nhom day electron thi tfnh baw tang. Cac nhom hut electron Him giam mat d¢ electron (; nguyen tir nita lam giam tinh bazo. Thi du : Hang s6 pKa cua mot s6 chAt dang p-XC6H4NH2 va m-XC6~NH2 25°C (bang XIII-4 va XIII-5).

Nh6m the' OCH3 CH3 H Cl Br CN N02
pKa 5,34 5,10 4,60 3,98 3,86 1,74 1,00 Nhom tht pKa
0- p- m-
CH3 4,39 5,10 4,69
CH30 4,49 5,34 4,20
Cl 2,61 3,98 3,52
N02 -0,29 1,00 2,50 Chit Y : Doi voi amin thoro co nhom the du hut hay d!ly electron 6 vi tri ortho deu lam giam tfnh bazo so voi cac amin thoro co nhom the 6 para va meta. D6 co the do nhieu Ii do nhu c6 hieu img tnrong cua nhorn the i:J vi tri ortho.

Cac amit R-CONH2 tuy co nhom -NH2 nhung khong co tinh baw, khong tao thanh cac ion khi phan u.ng voi dung dich axit do hieu irng lien hop cua c'~p electron voi oxi tao fa cau tnic ben:

22

va do nang hrong proton hoa amit cao boi oxi co d¢ am dien cao han, hie do amit khong con hieu irng cong hirong cau tnic nita :

5-

o

II 5+ + -C~NH3

Dieu do cling duoc bieu hien 6' nang hrong proton hoa a amit cao han i:J amino Sau day la sCI do so sanh nang luong proton hoa cua amin va amit (hinh XIII-I) :

i

z ..

R~NHi-

o

II + R~C-NH3

- - j - -j- D.<> khO." On ~nh ~ua SI,I proton hoa cua amit so voi amm

-------- +--------- ---

RNH3

80° (amin) 80° (amit)

~~~:~ c~u :oc ella I

- -afiUt-do s\r-iien -hqp - - - - - - - --

o II R-C~NH2

Tien trmh phan ling

Hinh Xlll-J. Nang hrong proton hoa cua amin va amit

2. Philo itng vdi andehit va xetoo

a) Amoniac va amin bac 1 : (xem chuang andehit, xeton)

Phan img cong cua amin vao cacbon cua nhom cacbonyl tao san pham trung gian cacbinolamin roi sau do tach mroc d~ .tao ra cac imin :

R

)c=O

R'

OH R I

+ NH ~R" ~ """C~NHR ~

2 R'/

Andehit hoac xeton

Axit yeu

Amoniac

hoac amin bile I

. ..

23

b) Amin bac 2 : Phan ling cong nuc1eophin cua amin bac 2 vao nhom cacbonyl tao ra san pharn trung gian la cacbinolamin, sau do tach mroc d~ tao ra enamin.

"

R-C-CHzR" + NHRZ

1\

o

axil yeu

R"

N(R"

R-C/ -H20

I ""CH-R'

OH I

H

R"

N(R"

R r( -~CH-R'

Andehit hoac xeton

Arnin bac Z

Cacbinolamin

Enamin

3. Phan ling cua amin b~e 1 va b~e 2 viii dan xua't eua axit

Do la cac phan ling cong nucleophin cua amin bac 1, bac 2 va NH3 vci nhom cacbonyl ella dAn xuat axit de tao ra cac amit hoac amit the (xem chuang axit).

"

R-C=O + NHRz -----t

I

Y

o

1\ "

R-C-NR2

Dan xuat axil

Amin bac 1, hoac bac 2

Amit

(Y: Cl, OOCR, SR', OR')

4. Phcin ling the" nucleophin viii dan xu~t halogen

R -CH2X + NR~ --7 (Xem chuang dan xuat halogen).

5. Tac d1}ng vdi axit nitrd HN02

Khi tac dung voi axil nitro, cac amin bac khac nhau se eho cac san pham khac nhau. a) V iii amin bac mot

Amin thorn bac mot p~an Ung vci axit nitro trong moi tnrong axit b nhiet d¢ thap se tao ra mu6i diazoni [ArN=N]X-b~n :

Amin thorn

- +

(NaN02 + H )

Phenyldiazoni clorua

Amin beo bacmot tac dung vci axit nitro se sinh ra ancol tuong irng va giai ph6ng nita:

24

C2HSNH2 + HONO

HCI

Co chi! phan irng 4.0 mu6i diazoni trong axit rnanh qua 5 giai doan :

+ HN +

NaN02 + H --"-? 02 + Na

+

HO-NO + H+ ~ H-O-NO t

H

+

NO + H20

cation nitrozo

+.. .. +

[N=O ~ N=O:]

Ion nitrozo phan Ung voi amin tao ra N-nitrozoamin

•. +

RNH2 + NO

H t+

RN-NO ---4 RN-N =0 + H+

t I

H H

Bazo

Axit

N ~ Nitrozamin

Sau do:

+

RNH-NO + H+ ~RNH=N-OH

RN=N-OH'

+

RN=NOH2

-H20) R - N:N : cation ankyldiazoni.

Trong moi tnrong axit noi chung, tac nhan nitrozo hoa tao N-nitrozamin thirc t€ Ia N203 :

2HN02 ~ N203 + H20

.~ + t -N02,

RNH2 + CUN-O-N=O ~ RNH2-~ O-N=O

0-

+ -H+

~ RNH2 -N=O RNH-NO

N ~ Nitrozamin

Cation ankyldiazoni phan Ung v(ji anion trong dung dich d~ tao ra muoi diazoni. Cation ankyldiazoni rat khong ben sf: lac dung vci mroc (hoac voi tac nhan nucleophin nao do trong dung dich) di tao ra ancol hoac co the tach bot proton de tao ra anken.

25

b) Viii amin bac hai

Amin beo bac 2 cung nhu arnin thorn bac 2 phan trng voi axit nitro tao ra nitrozamin (chat long nhu dau khong tan trong mroc).

(CH3)z NH + HONO

HCl

Dimety lni trozamin

Cac nitrozamin rat de thuy phan trong moi tnrong axit d~ tao ra amin ban dau, (Do do co thl! dung phan ling nay d~ tach amin bac 2 ra khoi h6n hop). Cac chat nitrozamin la nhirng chat rat dQc va Ia mot trong nhimg chat gay benh ung thu b nguoi,

Cac arylnitrozamin .khong ben, khi dun nong de chuyen vi nhom nitrozo vao vi tri

ortho hoac para, hoac de bi khir tao hidrazin. .

N - Mety Ianilin

Metylphenylnitrozamin NO ON-<Q)-NHCH3 + @-NH-CH3

@-~-N=O 250"C CH3

!+2H @-~-NH2

CH3

Mety lphenylhidrazin

c) V6i amin bac ba

Cac amin bee bac 3 vi kh6ng con hidro lien ket voi nito ntra nen knong phan irng , voi axit nitro; Cac amin thorn bac ba se cho cac san pharn the b vi tri para lil chu yeu :

=«. /CH3

~N""" + HO-NO

CH3

p- Nitrozo-N -dimetylanilin .

Cac p-nitrozo-N-diankylanilin rat de bi thuy phan trong dung dich natri hidroxit do nhom nitrozo eo hieu Ung lien hop Am voi nhom N-diankyl :

(CH3nQ@-NiJ NaOH,H20 (CH3nNH + Ho-@-NO

p-N itrozophenol

26

6. Phan itng the' ella nguyen ill' hidro trong nhom amino a) Phdn ling ankyl hoa : (xem phan dieu che)

Cac dan xuat halogen R-X nhu CH3Br, ... phan irng VOl amin cac backhac nhau k~ ca amin beo, amin thorn, tao thanh hon hop amin va mu6i amoni bac bon :

+ RNH2 + RX ;;::::::::::: R2 NH2X-

+ +

R2NH2X- + RNH2 ~ R2NH + RNH3X-

+ +

R3NHX- + RNH2 ~ R3N + RNH3X:

+

R3N + RX ~ R4NX-

Mu6i ankylamoni bac b6n *

Cac mu6i ankylamoni bac bon [abcdN] co cau true til dien nrong nr hop chat

Cabcd. Neu cac nhom the trong muoi amoni khac nhau thi co the xuat hien d6ng phan Quang hoc :

'1'

I \

j \

, \ , ,

r \

/ + \

r N '

{ 1111 .............._ '.

L:.!.'~ll- ----~

, ~

'... ".,.;;'

, "' .... -

M~t phAng guong

Cac hop chat amoni bac bon tlnrong de dang raxemic hoa do co can bang

Cac amin bac ba kieu R1R2R3N va amin bac hai R1R2NH co th~ co tinh Quang hoat, nhirng thuc t€ khOng th~ tach rieng cac chat d6i Quang duoc vi co su chuyen dich can bang rat nhanh gifta hai dang hinh thap d6i xung nhau ella amin ;

27

Neu co cau tnic cirng nhac a nguyen tir nita (nghia la cac nhorn the khong quay diroc) thi co dong phan Quang hoc, Thi du :

b) Phun ung axyl hod

Amin phan ling de dang voi axit, cloruaxit hoac anhidrit axil. Khi do nguyen tir hidro trong nhom amino (-NHb >NH) diroc thay the boi cac nhom axyl R-C=O tao I

ra cac amit the:

Anilin

Axetanilit (amit the)

(hoac CH3COCI, (CH]COhO)

Nguyen nr hidro thii hai cua nhom -NH2 khong bi the VI khi tao ra amit the thi c~p electron n cua arnit the dii tham gia lien hop vai nhorn >C = O. Cac amit the nay khong ben, trong moi truong kiem de hi thuy phan tao ra amin ban dAu.

C6HSNHCOCH3 + NaOH ~ C6HsNHz + CH3COONa

Vi vay, ngiroi ta co the bao v~ nhom amino trong t6ng hop httu co bang phan img axyl hoa va d~ tach cac amin bac ba ra khoi hon hop cac amin b~c mot, bac hai.

Co ch€ chung cua phan imgaxyl hoa nhu sau :

0-

I +

CH3 -T =0 + H2 N-C6HS ~ CH3 -T- NH2 -C6HS

Z Z

(Z=OH, Cl. OCOCH~)

28

-z-

c) Phdn ung sunfonyl hod

Tuong nr nhu phan irng tren, ngtroi ta c6 the thay cac chat axyl hoa tren bang benzensunfonyl clorua (mot clorua axit) khong phan img voi amin bac ba nhung pharr img voi amin bac mot, amin bac hai tao ra cac sunfamit the. Cac sunfamit the' cua amin bac mot con c6 nguyen tu hidro linh dong tan diroc trong kiern, con sunfamit the cua amin bac hai kh6ng tan trong kiem :

R2N-SOz-C6Hs + HCI (Khong tan trong kiern)

Benzensunfonyl clorua

RNH2 + CI-S02-C6Hs 4 RNH-S02-C6Hs + HCI NaOH t tan trong kiern

RN(Na)-SOrC6HS + H20

Nho pharr irng sunfonyl hoa, nguai ta c6 the phan biet va tach bac cua amin va tach biet hon hop cac amin c6 bac khac nhau.

d) Phdn ling viti hap chdt ca - kim

Chi c6 .amin bac mot va bac hai phan ling voi hop chat co - kim CHrMg-Br (metyl magie bromua) tao ra hidrocacbon.

R2NH + CH3MgBr 4 CH4 t + R2NMgBr

Ngiroi ta dua van th~ tfch khi metan do diroc d~ dinh hrong so nguyen tir hidro linh dong (phirong phap dinh hrong Xerevitinop).

e) Phdn.ung vai caebon disunfua (CS2)

Cac amin bac mot phan img vci CSz tao fa isothioxianat 13. nhtrng chat c6 khil nang pharr ling cao (tlnrong duoc 'dung d~ nhan fa nguyen tir hidro linh dong trong ancol hoac amin).

Ankyl isothioxianat

Phenyl isothioxianat

N - Ankyl-N' -phenylthioure

29

g) Phdn ling halogen hOG

Cac amin bac mot, bac hai ben khi co m~t halogen (CI2, Br2) trong moi tnrong kiern thuong 4\0 ra hop chat co lien k~t N-halogen (>N-X)

RNH2 N~~H) RNH-Cl ---+ RNCl2

Trong dieu kien nay, cac amin bac mot, bac hai thorn co th~ bi halogen hoa a nhan thorn hoac bi oxi hoi.

h) Phdn ung tao cacbilamin (R-N~C)

Cac amin bac mot co khi nang phan img v6i CHCl3 trong kiern, nrou 4\0 ra isonitrin (co mui tanh ca me rat dl}c tnrng, rat doc),

Phenylisoni trio Phan irng nay duoc dung dt hh~n fa amin bac mot.

6. Phan oog oxi hoa

Tuy thuoc van amin ban dau, cac chat oxi hoa, dieu kien ti~n hanh oxi hoa rna cac amin se cho cac san phAm khac nhau. D6i v6i amin bac mot, phan U'ng oxi hoa xay fa ratphtrc tap, Thi du, vOl axil pecacboxylic (RC03H) amin bac mot tao ra cac san pham nhu N-ahkylhidroxylamin, oxim, nitrozoankan hoac nitroankan;

RCH2-NH2 R-CH2-NH2 R-CH2-NH2

R -CH = N -OH (Oxim)

R -CH2 - N02 (Nitroankan)

Amin bac hai bi oxi hoa bbi H202 tao ra da.n xuat N.N-diankylhidroxylarnin R2NH H20z) R2N -OH

Amin bac ba trong dieu kien nay tao fa amin oxit :

HZ02 ho~c ) CH3CO]H

Amin oxit

30

Khi co mat KMn04 hay HzOz thi anilin bi oxi hoa thanh nitrobenzen:

Oxi hoa anilin bang KZCrZ07 trong H2SO4 se diroc hon hop nlt nhieu chat trong do co p-benzoquinon.

'l , Phim ltog the' hidro d nhan thom cu.a amin thorn

Nhorn -NH2, -NHR, -NR2 trong amin thorn la cac nhom the hoat hoa nhan thorn trong phan irng the electrophin va dinh huang nhom the sau vao cac vi trf ortho hoac para.

a) Phdn Wig halogen hod

o nhiet dQ thuong, cac halogen nhu clo hay brom trong mroc de dang phan irng v6i anilin (tirong 11,1' nhu phenol) tao ra 2,4,6-trihalogenanilin :

HO

C6HsNHz + 3Brz 2) 2,4,6-Br3C6HZNHz + 3HBr

Mu6n thu dircc san pham the halogen mot Ian, nguoi ta phai giam bot su heat dong cua nhom -NH2 bang each axyl hoa nhom -NH2 thea sCI do sau :

C6HjNH2 + CH3COCl 4 C6HSNH-COCH3 + HCl Axetanilit

[ CH3CO-N~Cl + HCI

CH3CONH -C6HS + ClZ H20) p-Cloaxetanilit

CH3CO-NHy + HCI Cl

o-Cloaxetanilit

Sau do thuj' phan cac axetanilit trong moi tnrong kiem se thu dircc san pham the clo mot Hill:

CH3CONH-@-Cl + NaOH ~ HzN-@-CI + CH3COONa p-Ooanilin

b) Phdn ling sunfo hod'

Khi dun anilin voi axit H2SO4 d~c a 180°C, ngiroi ta thu duqc. axil p-aminobenzensunfonic (goi tat la axil sunfanilic). Phan img xay ra nhir sau :

31

Axit sunfamic

-<

! > 180"C

>l80°C )H2N-@-S03H : Axit sunfanilic

Neu sunfo hoa bang H2SO4 dac hoac oleum du se lhu duoc san pham th€ true tiep vao vi tri meta (vi nhom -NH2 dli chuyen thrum nhorn - N-

I +

~H3

<Q>-NH2 + h2X4f --> <Q>-NH3HX4 H,SO, , 0 + H20

S03H

Cac amit cua axit sunfanilic (sunfanilamit) la cac chat khang sinh co tac dung chua benh. tt« du cac khang sinh chua benh viem hong, benh kiet li, v.v ...

H2N-@-S02NH2

.s=: ~NH

H2N~S02 -NH-C\ NH2

Steptoxit

Sunfaguanidin

N H2N -@-S02 - NH--@

Sunfadiazin

Sunfatiazol

Sunfametazon

c) Phdn ung nitro hod

Khi nitro hoa cac amin thorn bang RN03 d~c hoac hOn hop HN03 d~c va H2S04 d~c thuong thu duoc san pham the nhorn -N02 a vi trf meta :

32

-w

os:

+

NHN03 HN01

- )

NaOH

)

8. SI}' chuy~n vi tit nguyen tit nitd vao vong thom

Cac amin the' cua amin thorn co diu tao dang AR-N-X, trong d6 X co th~la nhom ankyl, halogen, hidroxi, nitrozo, nitro -N02, sunfo -S03H hay arylazo, trong nhtrng dieu kien thfch hop (nhu e6 axit) co th~ chuyen vj vao vj trf ortho hay para trong vong thorn. Co che' chuyen vi Iii. 51! the electrophin vao nhan thorn, SEAr. So d6 chuyen vi:

ehuyen vi

<Q( NH ~ hoac ~ NH -©-- x x

co xuc tac H+

tu a«.

a) Chllytn vi nhom ankyf

Khi dun n6ng mu6i halogenhidrat cua arylankylamin thl nhom ankyl R- chuyen den vi trf ortho hoac para eiia nhan thorn :

Co eM phan trng dUQc nhieu nguoi chap nhan 11\ :

+

C6H5NHR + HX -)0 [C6HsNH2R]X-

b) Chllyin vi nguyen tlf halogen hay chllyln vi Onson (Olson) D6 la chuyen vi nguyen tll halogen tll' nita vao vong thorn :

J?=\\_N-C-CH3 ~III •

00

HCl, CH~COOH to

~NH-COCH3 Cl

o- hoac p--Ooxetanilit

SHHtlOUCOJA

33

Cl

~ +HCI

l8-l-NH - COCH J

Axetanilit

0- hoac p-c!oaxetanilit

c) chuYlfli vi nh6m arylazo

D6 III SI,!' chuyen nh6m diaminobenzen cua diazoaminobenzen (hay diphenyltriazen) thanh p-aminoazobenzen :

... ------- ..

Diphenyltriazen

Diphenyltriazen -111 tinh the rnau vang c6 tnc :: 90°C, dUQ'c dieu che' ttt muoi phenyldiazoni clorua vOi anilin :

Neu vi trf para cua hop chat triazen co nhom the thl nhom phenyldiazo se chuyen vi den vi trf ortho :

CHr@-N"N-NH-@-cH3 P-CH3-C6~rNH2.Ha. CH3-@-N "~CH3

SI,I' chuyen vi nhom arylazo 111 loai chuyen vi xay ra qua giai doan tao thanh ion aryldiazoni va amin tlJ' do. Sau ion aryldiazoni tic dung vim nhan thorn cua amin thorn theo co che me eleetrophin :

H+ +

C6HSN=N-NH-C6HS ~ C6HsN=N + C6HSNH2 --+ o-ho~cP-NH2C6Hs-N=N-C6Hs t

d) Chllye'n vi nhom nitrozo

Khi e6 m*[ HO, nh6m nitrozo cua nitrozamin thorn Sf! chuyen vi VaG vi trf ortho hoac para (chuyen vi Fiso-Hep)

p-Nitrozo-N-metylanilin Co che phan ung xay ra nrong tl,!' nhu co che' Onson :

H+ + -H+ -@-

C6HsN-NO ~ C6HSNH-CH] + NO -------) ON NH-CH3

I

CH3

0- Nitrozo-N - metylanilin

e) Chllye'n vi benzidinic

Khi cho axit manh tic dung v(1i hidrazobenzen se co sJI chuyen vi lam dm lien ket N-N tao ra lien ket C-C:

<Q>-NH - NH--\Q) ~ H2N-\Q>--<Q)-NH2

Hi.drazobenzen

Benzidin

34

SHHHilUC03B

, v. GIOI THI~U RIENG

1. Cac mono-, di· va trlmetylamin : CH3NHZ' (CH3)zNH va (CH3hN Cac chat nay co mui tuong t'! arnoniac, tan 16t trong mroc. CO th~ dieu chI! chung bang each metyl hoa NH3 hoac cho NH4Cl Hie dung voi fomon :

+

2NH4Cl + 3HCHO ---+ 2CH3NH3Cl + CO2 + H20

Trong cong nghiep, ngiroi ta dieu che tir NH3 va CH30H b nhiet d¢ 450°C, ap suat cao co chat xuc tac Alz03. .

Chung iii cac chat khi co th~ chay diroc va tan t6t trong mroc, Metylamin iii chat dau d~ t60g hQP mot s6 thu6c trir nam, hoac duoc pham nhu adrenalin (thu6e ngu), ephedrin (thu6e nho mui),

Adrenalin

C6HS CH -CH - NH -CH3 I I

OH CH3

Ephedrin

2. AnDin, C6HSNH2

Anilin la amin thorn quan trong nhst, ducc phal hien Mn dau tien vao nam 1826, khi chung khan phammau indigo. Sau do duoc thay trong nhua than da (1834) va diroc Zinin t6ng hqp tir nitrobenzen (1842).

Anilin la chat long, khong mau, de Iau trong khong khi se bi nhu6m vang r6i nau den do bi oxi hoa. Anilin la chat rat doc, it tan trong mroc, tan vo han trong nrou, ete va benzen, Anilin diroc dung trong cong nghiep de san xuat duoc pham, pham nhuom va chat hru hoa cao suo

3. Phenylendiamin, H2N-C6H4-NH2

Phenylendiamin (cac d6ng phan ortho, para, meta) la cac chat ran ; diroc dieu che lir cac d6ng phan dinitrobenzen urong tmg,

Cac dong phan m-phenylendiamin va p-phenyldiamin duqc dung d~ t6ng hop pham nhuom,

Dong phan o-phenylendiamin de tham gia phan ung tao fa cac di vong ngirng tu chua nita, duoc dung de t6ng hop quinoxalin, benzimidazin.

35

4. Amin dUQc phan b6 rqng rai trong tht!c v~t va dqng v~t

B6i VI amin c6 tfnh bazo nen co th€ tach cluing ra khoi thuc vat khi chier bang dung dich axil, sau d6 t<i.i tao lai amin khi cho tac dung voi bazo (amin HI. nhlmg ch,at hGu CO' dau nen dtroc tach ra). Cac amin thu duoc tif thirc v~t thea con duong nay phai ke de'n la cac ankaloit, do Ia nhirng di vong chua nita, co tinh bazo (xem chuong 14).

§2. MUDI TETRAANKYLAMONI vA TETRAANKYLAMONI ~IDROXIT

+ + -

([R4 N]X- va [R4 N]OH

'"

I. MUOI TETRAANKYLAMONI

1. Di~u che'

Mu6i tetraankylamoni thuong diroc dieu che bang each ankyl hoa cac amin bac mot, bac hai hoac bac ba voi hrong du cac dan xuat cua halogen nrong d6i hoat dong :

+ -

RNH2 + 3RI + 2NaOH ~ [R4 N] I + 2NaI + 2H20

+ -

R3N + RI ~ [R4N]I

+ -

(CH3hN' + CH31 ~ [(CH3)4N]I

Trong mu6i tetraankylamoni iodua thl bon lien ket C-N deu hoan toan nrong dirong nhau.

Muoi tetraankylamoni III nhiing chat ket tinh, trung tfnh, phan Ii manh trong dung dich ruroc, Neu goc ankyl km kieu (CH3[CH2]nN\CH3hCH2-C6H5)Cl- thl se duoc dung lam chat trao d6i ion.

2. Tinh cha't hoa hQC

Neu cho mu6i tetraankylamoni iodua tac dung voi kiem se co phan ling thuan nghich nen nguoi ta khong tach diroc tetrametylamoni hidroxit :

+ - + -

[(CH3)4N]I + KOH ~ [(CH3)4N]OH + KI

36

Co th~ dieu che cac tetraankylamoni hidroxit t6t hen neu ta cho mu6i

+ -

tetraankylamoni iodua [R4 NJ I phan trng voi bac hidroxit, tach b6 AgI ket tua roi lam

bay hoi nhe hoi rnroc se thu diroc tetraankylamoni hidroxit hay con goi la bazo amoni bac bon:

+ + -

[R4 N]I + AgOH ~ [R4 NJOH + AgI J..

_ J

II. BAZO AMONI B~C BON

+

Cac bazo amoni bac bon thuong la cac chat ket tinh. Thi du [(CH3)4 N]OH.5H20

co nhiet dQ nong chay la 63°C.

Cac muoi tetraankylamoni va cac bazc amoni bac bon co th6 ton tai dong phan quang hoc neu cac gec ankyl khac nhau.

Cac bazo amoni bac bon la nhiing bazo manh urong duong voi cac bazc kiem (Ba(OHh hoac KOH), no co the hap thu CO2 hoac tac dung voi axit manh de t<,1O rnuoi va mroc :

+ - + -

[R4 N]OH + HCI ---» [R4 N]CI + H20

Nhirng bazo amoni khong ben diroi tac dung cua nhiet, dt bi phan huy de tao ra amin bac ba va anken (neu gee R> CH3).

R R

J J

R-C-C-R OHrl~I-'

! H NR3-1

!"-","-"",-"",-",,-,,,_,_j

Phan iing tach co the xay ra theo co che E I hoac E2, phd bien thirong la thee co che E2. Huang cua phan ling thee quy tftc Hopman nghia la nhorn bi tach NR3 bi tach cimg vci nguyen til hidro P b cacbon bac thap,

[CH3 - CH -CH - CH2]-

J + I I OH

H N(CH3hH

CH3 -CH2 - CH = CH2 (74%)

CH3-CH=CH.:...CH3 (26%)

Dac biet voi bazo amoni bac bon co R=CH3 thi se thu diroc metanol va amin bac ba.

37

Quy tac Hopman co huong tach cis, ngucc voi quy tlic Zaixep, co the duoc dien dat ngan gon nhu sau :

Khi phan huy mu6i oni (amoni, sunfoni, photphoni) thi olefin bac thap se duoc tao thanh vcri hieu suat cao nhat,

Nho phan (mg nhiet phan tetraankylamoni hidroxit, ta co the xac dinh duoc cau tao cua amin nao do chua ro cau tao. Mu6n the nguoi ta cho amin do tac dung voi metyl _ iodua du de tao ra mu6i tetraankylamoni. Tuy thee lucng CR3I phan ling co the suy ra bac cua amino Sau do cho mu6i tetraankylamoni iodua tac dung voi AgOR de chuyen ra dang bazo amoni b~c b6n roi nhiet phan dang hidroxit se thu diroc mgt trong cac san phdm la anken. Xac dinh cau tao cua anken sinh ra trong phan irng nhiet phan se suy ra cau tao cua g6c ankyl trong amin va biet duoc cau tao cua amin b~A dau.

A' + -

§3. MUOI DIAZONI ([ArN:=N]X)

, ~ J

I. PHUONG PHAP OIEU CHE

1. Diazo hoa amin thom (Phuong phap Grixf1- Griess, 1858)

Phuong phap co ban va thuan tien d~ dieu ch€ mu6i diazoni Iii diazo hoa amin thom bbi axit nitro trong moi truong axit manh va a nhiet d¢ thap 0 - soc.

Ingon (1958) dii nghien cuu phan U'ng diazo hoa cho bi€t co che' phan irng xay fa (xem trang 25) va cho bier tee dQ phan ling phu thuoc vao nong d¢ axit v6 co (ReI) axit nitro va arnin thorn :

Khi diazo boa cac amin thorn co nhom hut dien tu (nhorn c6 hieu tffig -I ; -C) lam tinh bazo giam se khien cho phdn irng diazo hoa kh6 khan vi giai doan cham quyet dinh t6c d¢ phan Ung la nitrozo hoa amino Ngiroc lai nhtmg amin co nh6m the dAy electron (nhu OCR3, -OR ... ) lam tinh bazo tang. do do phan ling diazo hoa de dang.

38

Khi diazo hoa phai lily du axit vo co, cli mot mol amin thorn can phai lay tit 2,5 den 3 mol axit vo co va mot rnol NaN02• nhiet d¢ phai thap 0 - 5°C vi muoi diazoni chi ben trong rnoi tnrong axit v:t a nhiet d¢ thap, Neu diazoni hoa trong moi tnrong thieu axit thi hieu suat 4-0 rnuoi diazoni thap do rnuoi diazoni bi chuyen thanh triazen ben han :

C6HSN=N-NH-C6Hs + HX Diphenyltriazen

Neu du axit thi phan ling theo chieu phan huy triazen thanh muoi diazoni. Muoi

diazoni co cau tnic ion.

Axit HX tlurong dung Ia HO. dOi khi dung H2SO4 va HBF 4' Tuy thuoc vao tinh bazo elIa amin thorn rna khi dieu ch€ muoi diazoni co the thuc hien cac thao tac khac nhau.

Thi du : d6i vm amin thorn co tinh bazo kern (co nhieu nhom hut electron), ngum ta phai hoa tan amin thorn trong H2SO4 darn d~c hoac CH3COOH bang r6i cho tit tit dung dich do vao axit nitrozylsunfuric. Con d6i voi amin thorn co tinh bazo manh thl nguoi ta hoa tan cluing hoac 4-0 nhu nrong trong mroc hay trong dung moi vira lam lanh vita eho tac dung v6i. HN02. Vi mu6i diazoni chi ben trong moi Wang axit a nhiet d¢ thap nen ngiroi ta thuong chuyen hoa ngay rna khong tach chiing ra khoi dung dich. Muon co tinh the mu6i, nguoi ta phai dung each dirci day,

2. Tit mu6i arylamoni halogenua vdi ankyl nitrit

Muoi clorua cua amin thorn tac dung vci ankyl nitrit nhu etyl nitrit hay amyl nitrit trong moi tnrong HCI du :

+ -

[ArNH3]Cl + RO-NO

HOdu

+

[ArN=N]Cl + ROH + H20

+

C6H5NH30 + C2H50-NO

HOdu

+

Sau phan ling cho them C:!HsOH vao, muoi [C6HSN =N]CI se 1<,1.0 k€t tinh,

3. Tit hejp eMt nitrozo vdi hidroxylamin hay vdi NO

39

~ J ~ ~

II. TINHCHAT V/!.T LI

Mu6i diazoni 13. cac chat dien giai, thirong d~ tan trong mroc, khotan trong dung moi httu co nhu ancol etylic hay hidrocacbon.

Cac mu6i phenyldiazoni clorua, sunfat hay nitrat la cac chat khong ben, d~ n6 khi va cham.

; J ;

III. TINH CHAT HOA HQC

1. ·cau true clla rnu6i diazoni

Bang phirong phap chieu tia Ronghen cho thay hai nguyen tu nita trong ion diazonibenzen va hai nguyen tu cacbon (CI va C4) nam tren mot dirong th!ng. Mot c~p electron 1t cua nhom - N ~ N - co true song song voi true cac electron 1t cua vong +

benzen va tao nen mot he lien hop, Cap electron 1t thii hai cua nhom nay (-N=N-) co

true th~ng g6c vci true cua cap thu nhat :

ON=N-H~~N ¥

M~t d¢ dien tfch dirong cua ion diroc phan b6 d hai nguyen tit nita nhirng nguyen tit nita gan vong benzen mang dien tich 100 han. Mu6i diazoni co cau true ion.

Hop char diazoni thorn duoc dung rong riii trong phong thf nghiem cung nhu trong cong nghiep dua vao kha nang phan U"ng cao cua no.

2. Cae phan itng cua rnu6i diazoni kern theo sJ!.lo;:ti be> nitd

Cac phan U"ng -loai be. nhom nita N=N thueng r;it da dang. Thong thuong nhom (N=N) diroc the bOi. mot nhom Y nao do (nhu OH, OR, SH, SR, halogen, CN, N02 ... ) thea sa do:

+ y-

[ArN=N]X -----+ ArY + N2 + X-

Phan ring nay thuong xay ra thea co che the nucleophin SN 1 hoae the goc ~ va can pha] dun nong. Sau day la mot so phan ring the cua hop chat mu6i diazoni :

40

+ [ArN=N]Cl

I

CuBr

CuC!

OH

©

KI

a) Cac phdn ling tao thanh ddn xudt halogen tham, xianua tham, sunfoxianua

Cac phan irng tao thanh dan xuat halogen thorn, chu yeu Hi. dAn xuat do va brom tlurong duoc xiic lac bang muoi dong (I) va duoc goi III phan ling Sanmayo (Sanlmayer)

NaN02 +HCl 0-5°C

P-CH3 -C6H4 -Cl + N2 p-Clotoluen (75%)

NaN°2+HBr O°C

m-CH3C6H4NH2 NaN02+ HCl o-SOC

(92%)

CuCN C

(NaCN+Cu2Cl2) m-CH3-C6H4 - N

(67%)

Phan irng San maya xay ra thea co che g6c. SI,l phan cat lien ket C-N cua ion +

C6HsN =N hi do su chuyen ffi¢t electron tit Cu + sang nguyen tir nita tich dien dirong :

'" l e

C6HSN~N + Cu+ ch;lm) C H· + N2 + Cu2+

(1) 6 S

nhanh (2)

41

Toe d¢ phan img v == k[C6HsN2Cl][CuCl]. Nhu vay, giai dean (1) la giai doan quyet dinh toe dQ phan ling. Vi v~y, ngoai dan xuat halogen thom ngiroi ta con thu duoc mot it biphenyl do :

Trong phan img, nguoi ta thirong dung CU2C12 duoi dang huyen phil. De dieu che dan xuat flo, nguoi ta dun mu6i diazoni cua axil tetrafloborie (pharr Ung Schiemann). Mu6i diazoni nay de ket tinh khi eho du HBF4 vao dung dich rnu6i diazoni, Ngiro! ta dieu che HBF 4 bang each eho axit boric hoac anhidrit boric phan Ung v6i HF.

m-CH3 -C6H4 - NH2 1. NaN02 + HCl ~ [m-CH -C H _ N21BF- -----:~t°-=~)o

2.HF+BF3 - 3 6 4 4 -N2,-BF~

De dieu che dan xuai iot thorn. nguai ta thuc hien phan (mg the SN 1 rat de dang vi tfnh nuc1eophin cua C C_tlO han cC va Br-. Sau khi duoc muoi diazoni, ngiroi ta khong can phai chuyen C6Hs N2 CI thanh C6HSN2I+ rna cho phan Ung luon voi KI se duoc dan xuat iot thorn ;

NaN02 +HO 0" -Soc

KI,2S"C

75%

b) Phdn ling 1(;10 thanh. phenol

Khi dun nong dung dich mu6i diazoni thi thu duqc phenol va giai phong nita :

Ion diazoni bi thuy phan giai phong N2 b lanh, neu dun nong phan irng xay ra nhanh han.

Phan ling dien ra thea co che the nuc1eophin SN 1 : [Ar-N~N]X- ch~m Ar+ + N2 t + X-

Ar+ + HOH ~ ArOH + H+

Trang phan irng xuat hien Ar", Ia cacbocation thorn, ben do c6 cac electron n cua yang thorn lien hop, N6 c6 phan ling cao voi cac tac nhan nucleophin trong dung dich va tao thanh san pharn. De tang hieu suat phan trng 1<.lO phenol, ngiroi ta khong dung mu6i

42

6HHl-1iJUCOJS

'~

,.

diazoni clorua rna thuong dung mu6i diazoni sunfat vl trong qua trlnh phan irng do tinh nucleophin ella Cl 100 han H20, se tao fa san pham la dan xuat halogen thorn ArCL Thong thuong tinh nucleophin cua ion HS04 yeu han ruroc va kich thuoc khong gian 100 nen khong canh tranh diroc voi mroc. Thi du :

H 0 to 2' )

-N2

(80%)

Neu thay dung moi H20 bang aneol etylie trong mroc thi thu diroc san pham chinh la ete :

+ •• to

[C6HsN::=N]CI + C2HsOH/H20 --------)0 C6HS -O-C2HS + N2 + HCI

Etyl phenyl ete (72%)

c) Phdn ling tao ra ArH

Mu6i diazoni co the bi khir thanh hidrocacbon thorn, dong thai giai phong nita.

H

Trong phan trng co the dung chat khir la hipophotphoro H3P02 (H-~-O-H) hoac

°

CzHsOH khan. Phan img xay fa thea co che g6c.

+ [0

[C6HSN==N]Cl + C2HsOH ----)0 C6H6 + N2 + CH3CH=O + HCI

(khan tuyet d6i)

Benzen

Axetandehit

d) Phdn taig ((10 ra Ar-Ar (Phan irng Gomberg)

Cac mu6i diazoni khi co mat xuc tac kiem (nhu CH3COONa hoac NaOH) co tht phan irng v6i cac aren (nhu benzen, toluen, xilen ... ) tao ra diaryl,

Thi du :

(21%)

43

Q-<Q>;CH~; CHr<Q!

CH3 1Am, @

(66%) (19%) (14%)

Phan irng Gornbe xiiy ra thea co che g6c.

+ C6H5CH3/NaOH, 5° C -N2,-HCI

NhC1 cac phan rmg tren rna ngiroi ta co th~ t6ng hop mot s6 dan xuat the cua benzen khi khong the dung phirong phap the true tiep diroc, Thi du : vi khong th~ dieu c he true tiep 1,3,5 - tri brornbenzen tu benzen va brorn nen ngtroi ta d8: tien hanh thea phan U'ng sau :

Benzen

Nitrobenzen

Anilin

2,4,6- Tri braman i lin

NaN°2+HCI O-SoC

+

N=N

BrABr -

9 Cl

Br

Br Br~ + N2 Br

e) Phon ung /(10 h9P chat ca - kim

Dung b¢t kim loai khir mu6i kep diazoni voi mu6i kim loai hay mu6i diazoni ella axit HBF4. Thi du :

3. Cac phan iiog khong gild ph6ng nitd

a) T ae dung vai kie'm tao ra aryl diazotat

Khi cho mu6i diazoni tac dung voi dung dich kiem (pH> 1 0) tao fa aryldiazoni hidroxit.

+ +

[ArN=N]Cl + KOH ----4 [ArN=N]OH + KCl

Aryldiazoni hidroxit

44

Aryldiazoni hidroxit Hl mot chat khong ben trong moi tnrong kiern, d~ bi d6ng phan hoa tao ra diazohidrat c6 tfnh axit yeu :

+

[ArN=N]OH ~ Ar-N=N-OH

Aryldiazoni hidroxit Diazohidrat

ArN=N-OH ~ ArN=N-O- + H+ Aryl diazotat

Duci tac dung cua kiem, diazohidrat se' chuyen thanh dang rnu6i ben aryl diazotat ton tai duoi hai dang d6ng phan, Dong phan E (hay isodiazotat) ben va dang Z (hay dang n-diazotat) kern ben. Khi axil hoa diazotat se lai tao ra muoi diazoni :

Ar-N=N-OH

Z -Diazotat (n-Diazotat) E-Diazolat (isodiazotat)

De phan bier n-diazotat hay isodiazotat, co the cho chung lac dung voi phenol hay dimetylanilin, khi d6 chi co dang n-diazotat rnoi tham gia phan ling ghep con dang isodiazotat khong phan irng.

b) Phdn ung ghep

.

Ion aryldiazoni la mot lac nhan electrophin khong hoat dong manh nhirng co the tac dung voi nhimg hop chert thorn co tlnh nucleophin cao (nhtrng hop chat giau mat d¢ electron) nhu amin, phenol hoac cacbanion cua cac chat co hidro linh dong kieu

_ /COOR

CH\COOR'

Phan trng nay thuoc loai phan ling the electrophin rna ion aryldiazoni ia tac nhan electrophin (goi lit cau tu diazo). Cac hop chat giau mat d¢ electron goi la cau tu ghep. San pham cua phan img thuong la cac chat mau azo duoc sir dung trong pham nhuom :

-HX) Ar-N=N-!Q)-y

Diu tu diazo + Cau tu ghep

Hop chat azo

Y : thuong lil cac nhom day electron rnanh (nhu -NR2, -0-, ... ) Phan ling tren goi la phdn ung ghep.

4S

+

Ion diazoni [ArN=N] la tac nhan electrophin yell vi dien tich duong a nita bi giai

toa vao vong benzen va co kich thuoc khong gian nrong d6i Ian. Vi vay, d~ tang kha nang phan irng nguoi ta thtrong dua vao vong aren cac nhorn the hut electron a vi trf ortho hoac para. Con dill tu ghep thuong co cac nhom day electron, thi du nhu cac nhom -OCH3, -OH, ankyl...

Khi ghep ion diazoni vao vong aren thi phan img xay ra thee quy tac the vao vong benzen (chu ~ Uti tien vao vi trf para).

- Pharr Ung ghep voi amin thorn bac mot, bac hai va hac ba : Khi thuc hien phan irng ghep voi amin thorn, moi tnrong t6i I1U a pH khoang 5 - 9. Nell pH < 5 phan irng ghep+ xay !:_a kh.O khan vi amin thorn t6n tai duoi dang muoi do su proton hoa amin thorn (ArNH2 Cl). Dang muoi nay khong tham gia phan irng ghep. Nell pH ~ 10 thi Call tu diazo da chuyen thanh anion aryl diazotat khong con kha nang ghep :

CH3

C6HsN =N N < + net

. CH3

p-Dimety laminoazobenzen

Neu ghep voi amin thorn bac 1 va bac 2, phan irng the electrophin xay ra a nguyen tit nita cua nhom -NH va -NH2 tao thanh cac aryltriazen. Ar-N=N-NH-Ar' :

C6HS -N =N -NH-C6HS (83%) 1,3-Diphenyltriazen (diazoaminobenzen)

C6HS~=N~H2

p- Aminoazobenzen

Khi co du amin thorn trong moi tnrong axit, dun nang thi diazoarninobenzen se tham gia phan img chuyen vi vao nhan benzen tao rap-aminoazobenzen.

..

C6HSN =N-NH-C6Hs

C6HS-N=~2

D6i voi amin bac 2 va bac 3 thi cation diazoni se U(n cong vao cacbon a vi tri para de tao ra san pham :

46

- N girng t1,1 voi phenol : Khi ghep mu6i diazoni vao vong benzen ella cac phenol thi se thu duoc cac hidroxiazobenzen.

Phan ling diroc tien hanh 0 moi tnrong co pH toi Uti Ia 9 - 10 vi ion diazoni co tfnh eletrophin yeu, phai chuyen phenol thanh dang phenol at d~ lang mat d¢ electron a cau tir azo do -0- co tinh day electron manh han.

pH=9-10

@-N=N-@-OH + HCI

Phan Ung ghep diroc dung trong t6ng hop chat mau va pham nhuom azo. - Ghep voi cau tir khong co nhan thorn :

Do la phan ling ghep cua ion diazoni voi eacbanion lien hop duoc sinh ra tit cac hop chat co hidro linh dong kieu -CH-, -CH2 rna a vi trf a co cac nhom hut electron.

Thi du arendiazoni tac dung voi cacbanion lien hop diroc sinh fa tir dietyl malonat:

/COOCzHs

CHz" + NaOH ~

COOCZHs

(~

.L)'-'C-OCzHs

CH" _ + Na+ + H20

COOCZH5

Phan ling ghep nay xay ra rat phuc tap, do 51! chuyen dich ella nguyen nr hidro a nguyen tu C cua lien ket N-C moi tao ra cac arylhidrazon Ar-NH-N=C(COO~H5).

4. PhilO \ing khit

Mu6i diazoni co the diroc khir bang chat khir (nhu Na2S03) tao ra cac hidrazin thorn

+4[Hl

Phenylhidrazin (82%)

Phenylhidrazin la nhirng tinh th~,_!1-6ng chay a 23°C, soi a 240°C, rat d~ bi oxi hoa trong khong khi. No diroc dung rong rai de nhan bi~t cac hop chat andehit, xeton va cac gluxit (W tao thanh hidrazon va ozazon). Ngoai ra con diroc dung d~ tong hop nhieu san pham khac co ling dung rong rai nhu antipirin, piramin va pham nhuom.

47

Nha hai loai phan irng cua mu6i diazoni, nguoi ta co the t{jng hop duoc nhieu loai hop chat hOU co quan trong khac nhau. Dac biet 13. tbng hop chat mau azo lam co so cho cong nghiep nhuom.

§4.DIAMIN

~ .:J

I. PHUONG PHAP TONG HQP

Cac diamin bee va thorn co the duoc tcing hop nhu cac monoamin a tren. Chat dan gian nhtit 13. etan-Lz-diamin hay etylendiamin NHz-CH2-CH2-NH2 dieu ch€ ttl etan -1, 2-diclo.

Hoac co the khii cac hop chat oxim, nitrin., Cac hop chat diarnin thorn co the duoc dieu che bang each khu cac hop chat nitro nrong img.

Thi du :

CH3-C-CH2 -C=N-OH

II I .

N-OH CH3

Pentan-l,4-diamin

Na/C2HsOH) H2N -[CH2]4 - NH2 hoac H2/Pd

Butan-l,4-diamin (tetrametylendiamin)

02N~02

Fe/HCl

H2N-@-NH2 Benzen-l,4-diamin

~ J ~

II. TI~H CHAT HOA HQC

Cac diamin co tinh chat tuong t\l nhu monoamin di'i neu a tren. Ngoai ra, cluing con co nhirng tinh chat rieng dac trung khac :

.48

a) Phdn ung viii cae muoi kim loai cllllye'n tie'p (d6'i viti cae 1,2-diamin)

- Khi phan trng voi muoi cua kim loai chuyen tiep Cu2+, Co2+ ... , cac L2-diamin thuong tao phirc tan eo mall. Thi du :

- Khi phan irng voi axil nitre tao ra hop chat yang imin, cac nhorn amin a vi tri nguoc nhau (anti) :

NH2 N~NCr

/ I

R- CH- CH - R' + HN02 + HCl ___..,. R - CH- CH- R'

I I -N2,-er

NHz NH2

R-CH

___..,. I /CH - R' + H+

H-N

+

___..,. R - CH - CH - R'

~

Cac imin nay co kha nang phan irng cao nrong nr nhu ctylcn exit (phan irng rna CH2

yang, cong, trung hop, v.v ... ). Cac imin Yang 3 canh kieu H-N( I can nguyen tir

CH2

. CH2

hidro dinh vci nguyen tu nita van eo th~ tiep tuc ankyl hoa cho dan xuat R - N( I CH2

- Cac diamin thorn cua benzen gom cac dong phan 0-, p- va m-phenylendiamin 13 nhiing chat rim, tan diroc trong mroc, co nhieu irng dung trong tong hop htru co nlur de dong yang tao ra cac hop chat di Yang khac nhau tuy thuoc vao chat phan irng :

&NH2 r?-\Y~

l.8-l- + HN02 -----+- 0 _,.;N + 2HzO

NH2 NY

Benzo-l ,2,3- triazole

o~

+ C-R

HO/

Axit

~~ +2H20

~ _....C-R

NH

2-Ankylbeoziroi4azol

7HHHCIlJC03A

49

O~C/R I ,pC, o R

o-Dixeton

I

rrY(N~:-R·

~ 9'C-R . N

4 2,3~Diankylquinoxalin

(khong ben)

Piazthiol

Cac diarnin thorn (p- va o-phenylendiamin) e6 kha nang tham gia phan irng ghep d~ tao ra cac chat mau,

- Cac diamin eo th~ bi khir de tao ra nitrin :

III. UNG DVNG V A NGUON TV NHIEN

- M¢t lirong 100 diamin nhu hexametylendiamin, p-phenyldiamin diroc dung trong cong nghiep d~ san xuat to sci loai poliarnit, poliuretan, polieaebamit... (xem chirong XVII).

- Mot s6 diamin la san pham cua qua trinh chuyen hoa sinh h9C cua cac amino axil nhu putrescin (butan-l.4-diamin) hay cadaverin (pentan-l ,5-diamin) :

H2N~CH2~CH2-CH2~CH~NH2 I

COOH

Ornithin

Putrescin

50

lHtlHUUCCl3B

HZN -CHz -CHZ -CHZ -CHz -CH - NHZ -C02) NHZ -[CHZ Js - NHZ I

COOH

Lysin Cadaverin

Putrescin va cadaverin co mui kho chiu cua xac chet.

_.., "'" J .....

§5. CHAT MAO AZD VA PHAM NHUQM AZD

J ..

I. CHAT MAU AZO

1. Dinh nghia

Chit mau azo la cac chit trong phan tit co nhorn azo -N;:;N- lien ket v6i g6c hidrocacbon. Thi du :

Azobenzen

C6HS-N;:;N-@-CH3 4- Metylazobenzen

2. Ten gqi

a) Ten azo

Chat dan gian dau tien goi lil azobenzen, co cau true phan tit b dang trans, Hl tinh the mall do gach, co Amax (trong etanol) la 318 nrn. COn cac hop chit azo khac co the coi nhu Iii dan xuat ella azobenzen. Thi du :

Br--@-N = N--@-Br 4.4-Dibromazobenzen

02~N=~

p- Nitroazobenzen

Nguoi ta co the coi nhom arylazo Ar-N=N- Iii nhom the khi hop chit azo co cau tao phirc tap, Thi du :

C6Hs-N=N-@-S03H 02N-@-N=N--@-N(CH3)z

Axit p-phenylazobenzensunfonic

p-(p- Nitropheny lazo )-N,N -dimetylanilin

Hop chit azo duoc di~u ch€ bang phan irng ghep giira mu6i diazoni vqi amin thorn hoac phenol, dan den su tao ra hai loai hop chat mau azo la aminoazo va hidroxiazo.

Aminoazobenzen

<QjN = N--<Q>--oH

Hidroxiazobenzen

51

Cac hop chit mau aminoazo thuong co tinh bazo do trong phan tir con co nh6m

.. ...

-NH2 hoac -N< co the ket hqp v6i axit tao mu6i tan trong mroc. Con hop chat mau

hidroxiazo thuong co tinh axit do trong nhom -OH co H linh dong.

b) Ten thuang

Nhieu chit mau azo co ten rieng, Thi du :

@-N=-N-@-NH2.HQ

"Yang anilin"

Chi thi mall heliantin (chat chi th] mall "metyl da cam")

NH2 NH2

~N=N-©@-N=N-r¢©

S03H S03H

D6COnggO

c) Ten h¢ thong diazen

Ten h¢ thong diazen la t6 hop ten cac g6c hidrocaebon va ten hidrua nen "diazen" (HN:::NH). Thi du :

Diphenyldiazen

(3-Clophenyl-4-clophenyl)diazen

C6HS-N=N-Q-S03H Pheny I( 4-s unfophenyl)d iazen

II ..... ~ -...J, A _ lflii' .. "'"..:.

II. KHAI NI~M VE MAU SAC, QUAN H~ GllIA CAU TRUC VA MAU SAC

1. Khili ni~m v~ trnlU s~c, chit mau va phfun nhuC}m

a) cam giac ve mau sac cua mot chat nao do d6i voi mat la ket qua cua su hap thu chon loc anh sang trang doi vao chat do nho co nguyen til hoac nhom nguyen til mang mau.

52

Anh sang trang la anh sang h6n hop gem nhieu tia don sac (gom bay mall co ban 13. tim, cham, xanh, luc, yang, da cam va do). Mat ngiroi chi co th~ phan biet diroc va quan sat duoc mall sac trong vung kha kien (tit 400 -)0 700 nm). Nell anh sang trang chieu vao mot chat nao do rna bi khuyech tan hoan toan hoac cho di qua hoan toan cac tia kha kien thl doi voi mat ta chat do co mall trang hoac khong mall. Nguoc lai, nell mot chat hap thu hoan toan tat cacac tia don sac thi mat ta tMY chat do c6 mall den. Nell S,! hap thu chi xay ra mot phan thl chat hap thu se co mall. Luc do mat chi cam nhan duoc nhirng tia con lai. Nhu vay mot chat hap thu mot tia mall nao do thl mat se cam nhan diroc mall phu cua mall do (xem bang XIII.5).

Bang XII/-5. Cae mall phI,! cua nhau

Buoc song (11m) Mau cua tia bj hap thu M au cua chat hdp thu
400 - 430 tim vang luc
431 - 490 xanh vang
491- 510 xanh luc daeam
511 - 530 luc do
531 - 560 yang luc tim
561 - 590 yang xanh
591 - 610 daeam xanh luc
610 -730 do hole Nhir vay, nell mot chat hap thu tia yang thl ta thay chat co mall phu cua mall yang la mall xanh, Ngiroc lai, mat ta thay mall yang thi chat hap thu tia xanh. Vang va xanh la hai mati phu cua nhau,

Mal nguoi khong the phan biet duoc mot each chinh xac sir hap thu nhir vay. Vi vay, muon nghien cuu dinh hrong ve mall sac can phai su dung quang ph6 h.ap thu electron rna dai hrong d~c trung la Amax va tmax• Amax dac tnrng cho su hap thu mall cua chat con Emax d~c tnmg cho cuong d¢ hap thu mall cua no.

Nghien ciru ve mall sac cua chat la nghien CUu su phu thuoc gitra A.max va Emax vito Call tnic cua no,

b) Mot chat ,huu co co the la chat mall, nhung chua phai Ia pham nhuom. Muon 06 tra thanh pham nhuorn thl Call 1'.l0 'cua chat mall phai dat hai yell Call sau day:

53

- Ch£lt mall phai co nhom mang mall hay goi la crornopho. Cac crornopho la nhirng nhom chirc khong no co kha nang hap thu rum sang lam cho chat co mall, co cac nhorn cromopho co ban nhu -N;::N-; -N;::Q; -7=0 ; 0- ; v.v ...

- Chat rnau phai co nhorn tro mau hay goi 13. auxocrom, la nhom co hieu ling lien hop dirong nba co cac cap electron n chua su dung, nhu -NH2' -NHR, -NR2, -OH,

- SH ... Cac nhorn nay lai co kha nang hoa muoi, Chat mau cang co nhieu nhom tro mau thi cang tham mall va cuong dQ mau cang 1&1, nghia 1a "'-max va Emax tang.

NglJ<;1C lai, mot s6 nhom khoa mal hoat dong cua nhorn tro mall lam mall nhat di.

Nho cac auxocrom co tinh axit hoac bazo hoac nhb luang tac hoa hoc nao do rna chat mall co the gAIl chat VaG vat lieu can nhuom,

Pham nhuom la cac chat mall co kha nang nhuom mau ben len cac v~t lieu, St,t tang "'-max cua phllm nhuom hay ciia chat mau ve phia hap thu cac tia co biroc song dai tit mau tim den mall do goi la su tharn mall batocrom. S1,1' giam "'-max goi 13. su nhat mau hay goi Ia su chuyen dich hipsocrom.

Su tang ctrong d¢ mau Emax goi la hieu ling hipecrom, con S1,1' giam Emax goi ia hieu irng hipocrom.

2. Quan he giita diu true cua cha't va mau s3c

, .

Mall sac cua chat htru co co m6i quan he chat che vai cau tnic cua no. a) SI! tang chieu dai mach lien hap ella eromopho :

Su tang chieu dai mach lien hop dan den su tham rnau (hieu ling batocrom) va tang cuong d¢ mall Emax (hieu ling hipecrom): xem bang XIII-6.

Bang XIII-6. SI! phu thuQc cua A.max• Emax vito chieu diti mach lien hc;1P

HQ]J chat S6' n61 o6i c=c us« sac A.rnall (nm) f:max .10-3
lien hQ]J
Hexa-l,3,5-trien 3 khong mau 258 35
. Vitamin A 5 vang 328 51
a-Caroten 10 yang cam 445 145
Licopen 11 do 472 170 S4

, b) Anh huang etta nh6m the

Cac nh6m the' a dau mach lien hop nell lam tang dQ phan cue ciia mach lien hop se gay hien nrong thAm mall va tang cuong dQ mall.

Thong thirong-cac nh6m auxocrom c6 tfnh day electron, nhu nh6m -OH, -NH2' -NHR, -NR2 •.. hoac nhom hut electron (goi Hi anti auxocrom) nhu nh6m -N02, >C=O ... thi lam cho eha:t tham mau nhanh va ctrong dQ mau ciing tang nhanh. Thi du :

eJult

C6HS - N = N -C6HS

Ho-<Q)--N =N ":'C6HS (CH3)z~=N-@-N02

Amax (nm) I Emax

318/21380 349/26300 478/33110

e) linh huiJng eua sf! ion hOG phdn tU

Sl! ion hoa phan tir do me dung v6i axit hoac bazo lam thay dOi su phan cue cua phan ui.

Neu SI! ion hoa Hun tang dQ phan eire hoa cua eromopho thl se e6 hien nrong tham mall va tang cuong dQ mau.

Nguoc lai, su jon hoa lam giam dQ phan eire cua cromopho gay hien tuong nhat mall. Thi du : metyl da cam

HO NaOH

yang dacam

trong moi tnrong bern, Arnax = 460 nm (503 lam giam d~ phan eire)

do (trong moi tnrong axit) pH < 3,2 ; Arnax: = 520 nm

+

( N H lam tang d~ phan eire)

d) Anh huang cua kh6ng gian

Mau sac cua chat con phu thuoc vao cau tnic kh6ng gian, Hieu Ung khong gian loai II lam giam su lien hop cua eromopho. Auxocrom gay hien nrong giam mau va lam giam cuong dQ mau. D6 la do cac nhom the co hieu irng kh6ng gian IOn da lam giam tinh dong phang cua h~ lien hop eromopho va auxocrom. Neu nhom the' kich thu6c cang 1611 cang lam nhat mau va cirong dQ mau dog giam, Thi du :

55

Nh6m the' R

H CH3 (CH3)zCH

Amnx n.rn I emnx 10-3 478/32 438/22 420/18,6

e) Anh huang eua qua trinh tao phuc viti ion kim loai

SJ,( tao phirc cua cromopho voi ion kim loai tlurong lam chuyen mau v6 phfa tham mall do su tao phirc cua kim loai da: dung cham den trang thai electron cua cromopho.

~ J . ."1 ~

III. MQT SO lO~1 PHAM NHUQM QUAN TRQNG

Nguoi ta c6 the phan loai pham nhuom thea hai each :

Cach 1 : Dua vao Call true hoa hoc cua pham nhuom. each 2 : Theo phuong phap su dung phdm nhuom.

1. Phan Ioai ph3m nhuym theo ca'"u triac eua eromopho a) Phdm nhuom azo : Co y nghia thirc te to Ian.

Pham nhuorn azo chua nh6m azo -N=N- trong phan tu va cac nh6m tro mall tuy theo d~c tinh cua nh6m tro mall. Nell nh6rn tro mall mang tinh bazo c6 cac nhom dAy electron manh nhu -NH2• -NR2 ... goi 1a pharn nhuom azo-bazo, Thi du :

C6H5-N::::N~H2

p- Aminobenzen

Crezodin

Nell nhom tro mall co tinh axit do cac nhom the -OH. -COOH. -S03H goi lit pham nhuorn azo-axit. Thi du :

¢NSOH

S03H

a-Naphtol da cam

(de nhuom to lua hoac len da)

Do nitranilin (M nhuom sci bong)

56

Do Conggo la chili mau tlm ra som nhat, dung de nhuorn viii, to, soi, len.

MQt s6 pham nhuom 4.0 huyen phu khong tan trong mroc dung de nhuom to soi tOng hop nhu soi poliamit, sci axetat, polieste. Thi du :

CH3 0

Cl-@-NH-~~. H Cl

o N=N--@

o .

mau Yang

maude.

Pham nhuorn azo co thanh phan cau tao phan tir la cac nhom sau :

OH @-N=N- ;

OH

--@-OH

(-COOH)

SOH "

OH (-COOH,-COR)

deu co kha nang 4.0 phirc VOl ion kim loai,

b) Phdm nhu(Jm di- !loge triarylmetan

Loai pham nhuom chu yeu la nhirng san pham the cua diphenylmetan hoac triphenylmetan, trong do cac nhom hidroxyl, nhom amino hoac nhom diankylamino a vi trf para co the t<lO dl1qc quinoit, DAy 111. nhtrng cMI nam trong thanh phan co ban ella nh~eu thu6c nhuom, Loai chat nay tlurong it mau nhirng rat de bi oxi hoa 00i. oxi khong khf r6i rac dung vm axil hay bazo thich hqp I~O ra thu6c nhuom,

Auramin 0 ia chat mau diarylmetan dUQc t6ng hop tit N,N-dimetYlanilin diroc aryl hoa nhi'1 photzen co mat ZnC12 r6i dun nong san pham v6i NH40 va ZnCI2"

57

2(CH3. )2~J(5\ COCl2(ZnCI2l) (CH1),M'~C~N(CH3)2 +NH4C1(ZoCI2l ~

l~ -2HCI . ,l~lI~ -H20

o

r (OI,!, t<-@-~-Q N(CH,!, <--> (CH,!, N-\Q)-?O >1(01,), <---'>

l +NH2 NH2

<---'> (CH,), V ~(CH,),CI-l Aurarnin

NH2 J

Auramin la chat mau bazo, rnau vang dung M nhuom len, Iua, sqi bong va con duqc dung de nhuom da va giay.

Philm rnau xanh malachit duoc dieu ch€ bang each ngung tu N,N·dimetylanilin voi benzandehit co m.;tt H2SO4 darn d~c M hut mrcc hoac ZnCI2 sau d6 oxi hO<1, axit hoa.,

CHo-@+ 2(OI,!,N-@ ~5 > (OI'hN~-@-t«OI'),

Lenco bazo [QJ

Khi oxi hoa bazo leuco nay bang Pb02 trong rnoi tnrong axil roi dun len se cho mau xanh malach it

(co vong quinoit),

'* Phenolphtalein (chat ehi thi bazo) :

Phenolphtalein diroc dieu eh€ bang phan irng ngung tu giua phenol va anhidrit phtalic co mat H2S04 di.ie hoac ZnCl2 hut rnroc :

?

. ij"-o + 2HOJO' H1S04d(ZnCI:J rRr-' AQrOH

~(( . \::::!/ -H20 ~j'r"()1 2KOH/H'"

o H '~OH 2H20 o

Phenolphtalein (khong maul

o

II Ale-oK

~c_J=\,_O

~~

OK (do canh sen)

58

8HHIIiJlJC(l38

c) Phdm nhuom indizo

Loai chat mau nay c6 Call tao dua vao khung indigo, ttl'C la trong cromopho c6 nh6m lien hop ki~ll :

°

)~f

°

Indigo la chat rnau duoc tim thay a chau Au tir the ki 18. N6 dl1Q'C chiet tic cay Indigo/era tinctoria. D6 la mot glicozit cua indoxin, Ngiroi ta chiet va thuy phan glicozit nay thu diroc indoxin. Indoxin bi oxi khong khi oxi hoa tao ra indigo; khir indigo bang Na2Sz04 thu duoc indivai khong mau :

OH 0 co
OOOC6HlOOS +©r: > +°2
©Q ©(>
+ H20 _.... NH
• ..---
-C6H1206 -H2O
I I A
H H
Indoxin g1icozit Indoxin OH

Indivai (khong mau)

Ngay nay, nguoi ta t6ng hop chat mall indigo tir axit antranilic dung d~ nhuom val, len va lua. Trong vong ben zen co th~ co cac nguyen tu halogen nhu brom hay do a vi tri meta. Indigo la bot mall nau tham, a tren 392°C co th~ bi thang hoa tao ra hoi mall do, khong tan trong rnroc nong nhungco th~ ket tinh lai trong anilin hoac anhidrit phtalic. Trong cong nghiep, ngiroi ta hay SIl dung indigosol va dieu che no' bang each closunfo hoa indivai trong piridin roi sau d6 them xut vao :

OS03Na ~ NH~

OS03Na

Indigosol

2CI-SO)H -2HCl

+2NaOH

Indivai (khong mall)

59

Trong moi tnrong axit loang, indigosol hi thuy phan tao ra indivai va no lai hi oxi hoa trong khong khf tao ra mau vang cua indigo ham tren sci vai,

d) Phdm nhuom antraquinon

Trong phan tit co bo khung antraquinon. Pham nhuom nay chua cromopho quinoit co the tao mu6i co mau,

Thi du _: Alizarin, alizarin saphirol B dieu ch€ tir 1,5-dihidroxyantraquinon qua phan ung sunfo hoa, nitro hoa roi khir ...

l-Amino-4-( 4- hidroxiphenylamino-antraquinon

(rnau xanh)

Hoac chat mau phirc tap co nhan antraquinon thu diroc do dun v6i kiem chay cua

~OH ~

o

Alizarin

l-Amino-d-hidroxi-antraquinon (mau tim do)

2-aminoantraquinon:

o

-~

~N~

o

Alizarinsaphirol

-4H

®NH ON~

o 0 Xanh indanthren

+

o H2N~

~

o

2-Aminoantraquinon

Yang flavanthron

o

Ngoai ra con nhieu loai phdm nhuom phenoxazin, phenothiazin, phenazin ...

2. Phan lo~i ph~m nhu{)m thea phltdng phap sit d-..ng

Trong ki thuat nhuom, nguoi ta phai co cac bien phap ki thuat de cho. pham nhuorn bam chac, tham sau, di van phia trong cua vat lieu can nhuorn nhu loai soi len. soi vii, sci t6ng hop ... va phai dam bao yeu cau ben mau, khong bi mroc cu6n mau di. Vi vay,

60

trong ki nghe nhuom nguoi ta con phan loai pham nhuom theo phuang phap sir dung, Sau day Ia mot so Ioai pham nhuom,

a) Phdm nhuom true tilp

Day Hl IOl:1i pham nhuorn nhuom true tiep len sqi vii bang dung dich pham nhuorn trong ruroc, LOl:1i thu6c nhuom nay tlurong d~ nhuom len, sci to tam. Trong IOl:1i pham nhuorn nay thuong co cac nhom amino, sunfonic (pham azo axit, azo bazo) co kha nang lam tang tinh ben mau d6i v(ri qua trinh gi~t, tily rira vi cac 10Zti thuoc nhuorn nay nrong tac voi cac nh6m phan eire, nhu -NH.:.., -COOH, trong soi polipeptit,

Sqi bong co thti nhuom true tiep bang do Conggo vi cac nhom amino (-NH2) va nhorn sunfonic (-S03H) phan cue c6 thi tao b tren soi vii nhfrng lien ket hidro vOi cac nhorn hidroxyl va ete cua xenlulo, Di~u nay lam giam bot sl,l hoa tan mau trong nuoc.

b) Phdm nhuom cdm mau (gian tiep)

LOl:1i pham nhuorn nay dtroc gan gian tiep len soi vii qua chat cam rnau. Ngiroi ta thuong sit dung cac hidroxit kim IOl:1i nhu nhom axetat, sat axetat dt lien ket giiJ'a soi vai va phAm nhuom, Pham nhuom co chat cam mau thirong d~ nhuorn bong, len, to lua, Qua trlnh nhuorn kha phirc tap, Dau tien v8i sci duec xit If bang dung dich mu6i va kiem yeu. Ltic d6 cation kim loai tao phuc vdi. sei vai ; Sau d6 thuoc nhuom se tac dung voi mu6i phirc khong tan hlnh thanh trong sci.

Thi du dung alizarin (l,2-dihidroxiantraquinon) nhuom soi bong thanh mall do tuoi. Khi nhuom c6 dung AI(OHh hoac Fe(OHh lam chat cam mau, Luc nay alizarin tac dung vCri nhom hidroxit gao tren soi vai.

~sqib()ng

o 0

'-./

Al

.. ' I

«XfH

o

Pham nhuom cam rnau thtrong c6 g6c phenol mang tfnh axit yell va mot vai nhom hut electron nhu nh6m cacboxyl (-eOOH).

c) Phdm nhuom hoan nguyen (hay gQi ta phdm nhuom thung)

Loai pham nhuom nay thuong khong tan. Ngiroi ta phai chuyen n6 thanh dang tan bang each dung chat khir tham vao soi vai, roi tai sinh phdrn nhuom bam chac vao s¢ viti bang each oxi hoa chung trong khong khi.

61

Nhuom sci bong bang pham mall indigo la mQt thi du v~ pham nhuom hoan nguyen. Ngiroi ta dung chat khir la natri thiosunfit Na2Sz04' indigo khong tan tao thanh leueo khong rnau tan duoc trong mroc. Hop chat leuco tham VaG trong sci bong, sci viii. Sau do oxi khong khf se oxi hoa leuco thanh indigo co mau xanh tren soi vai, Loai thuoc nhuorn hoan nguyen rat ben mau :

o

(i~N

o Indigo

2NaOH

OH Luico indigo khong mau tan trong nuoc

0- Indigo trang tan tren soi vlri

Indigo trang -----+- tren soi vlti dir kiern

nra kiern

Indigo trdng 02 (khong khO

dll sach kiern

Indigo mall xanh gao chat tren soi

d) Phdm nhuom phdn tan

Do Ia loai pham nhuorn khong tan trong mroc, co th~ phan bin trong soi, diroc dung d~ nhuom rat t6t cac Ioai soi co dQ phan eire trung blnh hoac kern. Ngiroi ta dung pham nhuom dmri dang huyen phu. Khi nhuorn viii, d~ tang qua trinh hap phu thu6c nhuom VaG soi viii thi phai nhuom a nhiet dQ cao hoac tang ap suat,

Thi du : l-Arnino~-hidroxiantraquinon

~2 ~

° OH

e) Phdm nhuom phdt trie'n (phdm nhuom hien mau]

D~ thu duoc san pham nhuom dep, mau ben nhieu 11k ngiroi ta dieu ch€ thu6c nhuorn ngay tren soi bang phan irng ghep (diazo hoa).

Viii soi dtroc tam dung dich (3-naphtol trong kiem ; sau do nhung sci VaG dung dich p-rutrobenzendiazoni clorua a nhiet dQ lanh 0 - SoC; mau do tren vai soi xuat hien do phan ling diazo hoa,

OH

00- N = N -@- NO! + NaCl

Maudo

62

§6. sa urqc VE H(J'P CHAT NITRO

.. ~ ""

I. so LUQC VE CAC HQP CHAT NITRO

1. Cc1u tao cua hQp chat nitro

Hop chat nitro la dan xuat the mot hay nhieu nguyen til H hidro trong phan til hidrocacbon bang cac nhom nitro -N02.

Cau true electron cua nhom nitro duoc mo ta nhu sau :

4'0 R-N ..,....____.... ~O

Hai lien ker N-O trong nhom nay 1a nhu nhau.

Cac hop chat nitro cua ankan, xicloankan, aren v.v ... d6u co ten la nitro kern thea 56 chi vi tri ella nhom nitro.

Nitrometan

1 ,3-Dini tropropan

2- Nitronaphtalen

3. Tinh chat v~t Ii

Cac hop chat nitroankan noi chung ta cac chat long khong mau, co rnui de chin nhimg doc, Chung hoan roan khong tan trong nuoc nhtrng tan t6t trong nhieu dung rnoi hiiu ca. Cac nitroaren thuong co mau vang hoac doi khi co nhii'ng chat ket tinh mall vang ... Khi dun nang cac hop chat nitro d6i khi co 51! phan huy hoac su n6.

4. Phuong philp di~u che'

aJ Nitro hod ankan

Cac ankan diroc nitro hoa b tuong khi, cr nhiet d¢ 400°C bang axil nitric. Phafi ling xay ra theo co ch€ gee.

Giai doan khoi mao:

HON02 ~ HO· + NOz

63

Giai doan phat trien mach :

OH + RH ----7 H20 + R'

R' + HON02 ----7 RN02 + HO'

o day, ngiroi ta se thu duoc hOn hop cac nitroankan, ngoai ra con thu duoc san pham oxi hoa cat mach lien ket C-C, Thi du :

CH3-CH2-CH2-N02 I-Nitropropan

-tCH3 -CH-CH3

CH3-CH2-CH3 H~03) ~02

-7 CH 3CH2 N02

---) CH3N02

2-Nitropropan

Nitroetan

Nitrometan

b) Nitro hod aren

Ole aren se duoc nitro hoa bang axit RN03 d~e b6e kh6i hay hOn hop nitro hoa (axit nitric d~e va axit H2S04 d~e) hoac axit RN03 va axit axetie. Phan rmg nitro hoa +

cac aren xay ra thea co ch€ the electrophin (ion nitroni NOz Ia tac nhan), Thi du :

5. Tinh chit hoil hoc

a) Tautome hod va tao mu6'i

Ole nitroankan bac I va bac 2 (e6 nguyen tit hidro ex) thuong tao ra hien nrong tautome, Cac nitroankan (dang pscudo-axijthirong nam iJ dang can bang nrong U"ng v6i dang axi, nhirng can bang chu yeu nam phia trai. Do hieu ling -I ella nhom.nitro rna cac nitro ankan bac 1, bac 2 co C-H axit nen tan ducc trong kiem d~ tao mu6i. Anion nrong ung se diroc Mn hoa nho sl! mezomeri.

64

Khi axit hoa thi dilu tien tao ra dang ax i-nitro tan trong nuoc r6i sau do tautome hoa tao nitroankan khong tan trong mroc,

b) Phdn itng khit

Phan irng khir nitroankan phu thuoc van pH va tac nhan khir, Neu cho nitrobenzen trong dung moi axit co mat cua Fe. Zn hay ZnQ2 thl nhat dinh se tao ra cac san pham trung gian khong the tach duoc la nitrozobenzen va N-phenylhidroxylamin, anilin. Trong rnoi tnrong trung tinh, neu dung chat khir la Zn trong NH4Cl thi co the dieu che' ducc N-phenylhidroxylamin (tnc 81°C).

@-N=O +2H

I

@-NHOH

I

r -HzO @-N=N-@~@-N=N-@~@-NH-NH-@ ~

0- Azoxibenzen

Hidrazobenzen

Trong dung dich kiem (thi du Zn trong NaOH) thl nitrobenzen se bi khir thanh hidrazobenzen. Qua trmh nay t'.1O fa san pham trung gian lit nitrozobenzen va N-phenylhidroxylamin t6i cluing se ngung tu voi nhau tao thanh azoxibenzen. sau do azoxibenzen chuyen thanh hidrazobenzen. Azobcnzen va azoxibenzen deu co the dieu ch€ tu nitrobenzen trong dieu kien em diu nay:

c) Su ngung tu vai hap chat cacbonyl

ve nguyen rae, hop chat nitro bac 1 va bac 2 se tham gia phan trng cong andol hoa voi andehit va xeton, sau do tach mroc, Thi du :

9HHHiJUCOlA

65

-- <Q)-~H-CH2-N02 OH

A J J

II~ MQT SO HQP CHAT NITRO QUAN TRQNG

1. Nitrometan

Nitrometan co thi diroc dieu che thea phirong phap Kolbe bang each eho axil cloaxetie rae dung voi natri nitrit. Tnroc tien la tao ra axit nitroaxetie roi nho hieu ling -I cua nhom -N02, hop chat nay rat de bi deeaeboxyl hoa :

HOOC-CH2 -Cl

-+ HGNG2 ) CH -COOH

-NaCl I 2

N02

Axit nitroaxetic

Trong cong nghiep, ngiroi ta dieu che nitrometan bang each nitro hoa rnetan va no diroc sir dung nhu mot dung moi. Khi do hoa metan se xuat hien clopickin :

Clopickin

2. Nitrobenzen

Nitrobenzen diroc dieu che bang each nitro hoa benzen. N6 la chat long khong mau, co vi dang, khong tan trong nuoc va de bi hoi nuoc cuon thea. Nitrobenzen la mot chat dQC, pha hoai hong cau cua mall. C6 the su dung n6 nhu mot dung moi trong phan ling Fridel-Crafts (tac nhan oxi hoa), hoac la san pham trung gian de dieu che anilin, benzidin va 4-aminophenol.

3. 2,4-Dinitrotoluen va 2,6-dinitrotoluen

2,3-Dinitrotoluen va 2.6-diaminotolllen la mot h6n hop duoc dieu che tir toluen va axit nitric. Chung co y nghia rat 160 VI Ut nhtrng chat dau de dieu che diazoxianat cho tong hop poliuretan.

66

4. 27476. Trinitrotoluen (TNT)

TNT thu diroc bang each nitro hoa toluen boi axit nitric b6c kh6i va axit H2SO4 b6c khoi, Phan trng dieu ch€ xay ra nhanh han khi tao thanh trinitrobenzen tir benzen VI nhorn metyl lam de dang cho phan trng the electrophin.

CHr<Q)

+ 3HN01 b6c kh6i

. ,

TNT la mot chat n6~ N6 se nO khi dot chay hoac khoi mao.

Mot s6 nitroaren nhu 5-tert-butyl-l,3-dimetyl-2,4,6-trinitrobenzen duoc si'r dung nhu chat co mui thorn xa huang nhan tao trong cong nghiep huang lieu,

5. Axit picric (2,4,6-trinitrophenol)

Axit pirie thu duoc ve mat nguyen uk tu phenol qua axit phenol-2-sunfonic va axit phenol-4-sunfonie hoac til 2,4-dinitrophenol.

Axil picric la hop chat co rnau yang ket tinh, vi dang. No la axit manh, tao mu6i voi amin, kho tan, co th~ dinh tinh bang diem nong chay, c6 the tao phirc chuyen dich dien tfch voi nhieu aren. Co the dieu che axit picric thea sa d6 sau :

OH OH
©,SO,H o,VSO,H
+HN03
OH OH
© +~S04 N02 +HNOJ O,N*No,
OH OH
c¢J +HN03 O'VNO, N02
Axit picric
S03H S03H OH

~NO'

N02

67

6. Cloramphenicol

La chat ket tinh mau vang (tnc =150oC), diroc tach tit actinomycen nam 1947. No HI. chat khang sinh rat manh dung chua benh nhiem trung vi khuan, virut. Clorarnphenicol 13. mot amit cua hop chat nitro tim diroc trong tl! nhien, dong thai la khang sinh dau tien co the tdng hop diroc (narn 1949).

OH CH20H ~-II ?2N~CH-CH-NH-CO-CHC12

Cloramphenicol

cau hoi an t(ip

1. Viet phuong tlinh hoa hoc th1/c hi~n cac chuyen hoa sau day: a) Ancol etylic ~ etylamin (cac phuong phap) metyl-sec-butylamin

b) Xiclohexanol ----- 1,4-butandiamin

c) Toluen

----- axit o,m,p-aminobenzoic

d) p- Toludin ~ axit p-brombenzoic 4-metyl-2-aminophenol .

e) m-Nitroal"\ilin~ m-cloiotbenzen m-nitroanizol

2. Tlr benzen, ancol etylic va cac chat vo co tuy chon, thiet I~p so d6 tong hop "metyl do".

(CH3hN-@-N=~ GOOH

Trang ba nguyen tCr nita, nguyen tCr nao c6 tfnh bazo rnanh nhat ? Giai thfch.

3. Hay sap xep thee th(r t1/ tang dan pKb cua cac chat trong day sau va giai thich ngan 9<;>n.

a) C2H5NH2, {C6H5hNH, NH3, C6H5NH2' (G2H5hNH.

b) p-toludin, anilin, p-nitroanilin, m-toludin.

68

I

4. Cho etyl bromua tac dl;mg voi amoniac. Vi6t c6ng tMc cau tao cua cac san ph~m hrru co co the tao ra :

- Neu cac phuong phap hoa h9C de tach rieng cac san ph~m do.

- Muon co riling cac san ph~m tren rna khOng Ian thi can phai dung phuong phap nao ?

Vi6t phrronq trinh phan (rng dieu che cac san ph§m do.

5. Bon amin dong phan A, B, C, 0 co c6ng thUc phan t(r C3H9N. Khi cho phan (rng vOi NaN02 va HCI thi A va C gia.i ph6ng khf nita va tao san p~~m cO c6ng thUc phan tu C3H80 con 0 kh6ng cho dau hi~u gl : B cho san ph~m rnau vang a di,mg dau. San ph~m hrru co cua A (C3H80) cO phan (rng iodofom (iot trong mOi truang kiem). Tim cOng thuc cau tao cua bon amino vi6t phuong trlnh minh hoa va gQi ten b6n amin do.

6. Dun nang nhe dung dich benzendiazoni clorua trong nuoc thu duc;rc hal san ph~m hll'u co la CsHsO (A). CsHsCI (B) va khf nita. N6u cho tMm NaCI vao thi toc dq phan (rng khOng thay dOl nhllng luqng B tang manh, Giai thich hi~n tuqng tren.

7. a) Hay phan bi~1 cac khai ni~m sau day va minh hoa bang thf du ~ the: - CM:t mau va ph~m nhuom.

- Cromopho va auxocrom.

- Ph~m nhuqm azo va cac loai ph~m nhu¢m khac.

b) Mau sac cua mQt chat phu thuQc vao cac yeu to nao ? Cho Ihf du C\l the.

69

ChU?ngXIV

,. ~ ...

CAC HQP CHAT DJ VONG

§1. MOT SO KHAI NI~M CHUNG

I. D!NH NGHiA

Nguyen tir cua cac nguyen to khong phai la cacbon co trong bQ khung cua phan nr chat hUU co goi Ia cac di 16: Thi du : oxi, luu huynh, nita, ...

Mach phan nr chat htru co co chua cac di t6 goi la di mach. Thi du :

-CH2 -CH2 -O-CH2 -CH2 -0- ... ,

-N-[CH21s -C- N-[CH21s -C-

I II I II

o H 0

Mach yang kin cua phan ttt chat hiiu co co chua cac di t6 goi la di vong. Thi du :

N-

I ~o , ...

Hap chdt di vong fa hap chat lulu CC/ ma pluin lir cua cluing co cdu tao vong kin va trong vong co chua mot hay nhieu di 16~

Hop chat d] yang kin rna trong yang chi chua cac di t6 Ia cac hop chat Yang vo co.

Thi du :

Borazole

70

Mot s6 hop chat di yang dircc hlnh thanh til cac hop chat hiru co da chirc hoac tap chirc lai khong ben virng, de bi va yang nen tlurong duoc coi HI. cac dan xuat cua cac hop chat da chirc hoac tap chirc tren,

TId du :

CH2-COOH I CH2-COOH

Axit sucxinic

Anhidrit sucxinic

~O ~If-H

s-Caprolactam

Axil e-arninocaproic

II. PHAN lO~1

Cac hop chat di yang duoc chia thanh hai Ioai chinh : di yang thom va di yang khong thorn. Trang di yang khong thorn co di yang no va khong no.

Trong moi loai di yang thorn hoac khong thorn lai diroc phan loai theo di t6 (0, S, N ... ), s6 di 16 (1,2,3 ... ), s6 canh ella yang (3, 4,5, 6 ... canh), don yang va da yang.

Thi du :

Hap chat

L d

Ten

T huoc loai

Don yang, di yang no, ba canh, chua mot di t6 O.

Ox iran

Thietan·

Dan yang, di yang no, b6n canh, chua mot di t6 S.

Dioxan

Don yang, di vong no, sau canh, chua hai di t6 O.

Furan

Don yang, di yang khong no, sau canh, chua mot di t6 O.

Dan yang, di vong thorn, 5 canh, chua mot di t6 O.

y-Piran

r7'N ~"j

N

Pirimidin

Don veng, di yang thorn, 6 canh, chua hai di t6 N.

71

6-0xaspiro- Da vong, di vong no kieu spiro, chua mot di t6 O. -[4,5]decan

N N

rr J

N0N

Quinolin Da vong, di vong thorn ngirng tu mot di vong, chua mot di t6 N va vong benzen.

Pteridin Da d] vong thorn ngung tu, chua bon di t6 N.

,. _.....; J

III. CACH GQI TEN VA OANH SO

Ten cua cac hop chit di vong diroc goi theo b6n each :

- Ten he th6ng thee Hanso - Vitman (Hantzch-Widman).

- Ten trao d6i.

- Ten thuong va ban he thong.

- Ten dung hop va ten cong.

1. Ten he thang theo Hansd - Vitman

a) Cac di vong dan vong voi so' cank khong qua 10 chua mot hay nhieu di t6 diroc goi ten bang each ghep lit ca siJ noi len so' canh cua vong viii phdn tie'n 16 noi ten so' luang cung len cac di ttf va phdn hdu t6' noi len muc d¢ bdo hoa etta vong,

Cac tien to chi cac di t6 co duoi -a (xem bang XIV -1)

Bang XIV-1. Cae win to eua mqt so d! to

SIT Dj t6' HoG. tri Tien (6- SIT Di t6' Hoa tri tu; t6'
I Oxi II Oxa 5 Photpho III Photpha
2 Luu huynh II Thia 6 Asen III Asa
3 Selen II Selena 7 Silic IV Sila
4 Nita III Aza 8 Bo III Bora Khi co nhieu di t6 cling loai trong mot di vong thi dung them cac tien t6 ve d¢ boi.

Thi du : dioxa (2 oxi). triaza (3 nita), ... Khi co cac di t6 khac nhau trong mot di vong thl phai dung t6 hop cac tien to (chi di to) thea thtr ttl uu tien nhir trong bang XIV -1, nghia 13. M.t dau tir di t66 nh6m cao nhat trong bang he thong tuan holm cac nguyen t6 va co s6 nguyen t6 nho nhat trong nhom ay. Khi t6 hop cac tien t6 nhu vay can luoc bat

72

nguyen am ella tien t6, uu tien hon neu co 2 nguyen am di lien voi nhau. Thi du : oxaza(1 oxi va 1 nito, bo i ella oxi), thiaza- (1 hru huynh va 1 nito, bo a ella thia), tetroxoean (4 oxi trong vong no 8 canh, bo a ella tetra, bo i ella oxi), ...

Cac tit eC1 so va hau t6 ella d] yang diroc ghi trong bang XIV -2.

Bang XIV-2. Tu co so va h~u to cua dl vang

St/ Til co sa + Juju /6"
qlllh Tu V ong chua nita V ong khong chua nita
cua coso
vong * Bao hoa Khong bdo hoa Bao hoa
Khong bdo hoa
3 - IT- - irin - iridin - uen - iran
4 - et - - ete - etidin - ete - etan
5 - 01- - ole - olidin - ole - olan
6 - Ill- -Ill ** -m - an
7 - ep- - epin ** - epin - epan
8 - oe- -oem ** -oem - oean
9 -·on - - onin ** - onin -onan
to - ee- - eein ** - eelO -eean * Yang khong bao hoa la vong khong no hoac thorn.

** Them perhidro van ten cua vong khong baa hoa nrong lIng.

Viec danh ·so diroc bat d~u tlr di t6. Khi trong yang co nhieu di t6 khac nhau phai bat dau tiT di t6 co de:) uu tien cao han nhu trong.cach goi ten.

Sau day Ia mot so thi du v~ each goi ten h~ thong nay.

¥ H
I *1 NI 2 Sl
0 N 4Cyl 0 502 S03 .,(1,
/"'\_ /"'\_ 502
7 _ 4
3 2 4 3 4 3 6 5 54N
Oxiran Aziridin Oxetan Oxolan Azole Azocin 1,4- Thiazepin b) Ten cua cac g6c di vong diroc hinh thanh tir len cua di vong ghep voi hau to -yl, -diyl, ... kern theo chi so chi vi trl, Thi du ;

H

s<r4)jH

10HHIlWC03II

73

2. Ten trao d6i

a) Ten trao d6i cua di yang duoc hinh thanh bang each them cac tien t6 cua di t6 (bang XIV -1) kern thee chi s6 chi vi trf cua cluing vao ten cua hidrocacbon mach vong tUC1Tlg irng, Viec danh s6 a cac hop chill dC1Tl yang duoc bat d~u tir di t6. Viec danh s6 a cac hop chill da yang tuan theo quy lac danh s6 cua hidrocacbon da vong urong irng sao cho t6ng cac chi s6 chi Y~ trf cua cac di t6la nho nhat. Thi du :

9

7 Nb=bN2

6 S 4 3

Silaxiclopentan (Silolan)

1- Azabixic1o- [2.2.1 }heptan

6 1

'm2

9 to 4 3

6-0xaspiro- [4.5]decan

2.7,9- Triazaphenantren

b) Ten trao d6i cua cac g6c di yang duoc hinh thanh luang tl,1' ten g6e hidroeaebon nrong irng, Thi du :

Silaxiclopent-2-yl

I

N

6(7\'i- 5l,]/h

4

6

8r~fl2

\.___/s\_.J 3

9 10 4

1- Azabixiclo-[2.2.1 }hept-2-yl

6-0xaspiro[4.5}dex - 2- Y I

3. Ten thudng va ten nita h~ thang

a) Khoang tren 60 hop chat di yang (dan yang, da yang ngirng 1\1) co ten thuong hoac ten nira he thong va diroc dung ra't ph6 bien, Sau day la mot s6 thi du (co ghi ca each danh so).

H H H H
~I 01 $1 I ~1 r4
NI N
502 502 502 502 50N2 0 U
4 3 4 3 4 3 4 3 4 3
Pirate Furan Thiophen Pirolidin Pirazole Piridin Piperidin
H
/ 8 I
NI 60J 8 NI 8 1 2 N N
602 7eer 7 CON 7()CY
S ~ I ;} 2 6~ I "':::::3
S ...:;:;N 6~ ...::::: 3 6::::-" ..-::::N 3
4 3 4 3 S 4 5 4 . sN 4
Pirimidin Indole Quinolin Isoquinolin Pteridin
74 1 G HHH\JtJOJ:Jj H

1 6 I

N~N7

2~j_>8

N4N 3 9

Purin9

H I

8 9N I

7rYY~2

6~3

5 4

8 9 I

7~2 6~O~3

5 10 4

8 9 I

1~2 6~~~3

5 N 4 10

Acridin

hoac

Cacbazole

Phenantridin

Viec danh s6 (] day tuan thea quy luat chung nhu (] phan ten trao d6i (muc 2), co ngoai le (] vong purin. Cac vi trl ghep n6i diroc danh s6 thea hai each : danh s6 tiep theo chieu da danh s6 hoac mang s6 ella nguyen tiI dirng tnroc kern thea chtr cai a, b ...

Thi du :

boac

M~t s6 di vong mot di t6 con diroc danh s6 bang ehu cai Hi Lap a, p, y. Thi du :

o «'0«

p'. j}

N

a'oa

w~ I~

"f

H I

r-7YNila ~~

b) Ten ella cac g6c di vong diroc hinh thanh bang each them vao ten di vong nhimg hau t6 nhu -yl, -diyl, -yliden .... kern thea chi s6 vi tri, Thi du :

H

r!p

50!

4 3

8 Nl

~~

6~3

S 4

Pirole-2-yl

Pirimidin-2-yl

Quinolin- 2,6-diyl

Mot s6 g6c sau day co ten rieng :

01

sa-

4 3 2-Furyl (va 3-)

Nl

6(~ 5V3

4

2-Piridyl (va 3-, 4-)

sl

5a-

4 3

2-Thienyl (va 3-)

Furfuryl

Thenyl

H

I Nl

6('f

5l.._)3

4

2-Piperidyl (va 3-, 4-)

. N

~~ ~

2-Quinolyl (va 3-, 4-, 5-, 6-, 7-, 8-)

75

4. Ten c9n9 va ten dung hC1P

Ten cong va ten dung hop duoc hinh thanh til ten thirong va ban he thong cua di yang.

a) Ten cong diroc hlnh thanh chu yeu bang thao Hie cong hop phan nao do vao ten di yang. T hi du :

Tetrahidrofuran

Tetrahidrothiophen

1

60° 2

5 3

4

Tetrahidropiran

b) Ten dung JU;p diroc dung cho h~ d] yang ngirng tu,

De goi ten dung hop he di vong ngung tu, can phai chon yang co sa va kf hieu vi tri ghep noi.

Vong co sa duoc chon la : d] vong, di yang Ian han, di yang co nhieu di to han vadi yang co di to iru tien han.

Ki hieu vi tri ghep nei : dung chu cai a, b, c ... ki hieu cho canh cua di yang co sa va s6 1,2,3 (de a trong vong, neu can) ki hieu cho nguyen tir cua yang ghep noi. Trong truong hop dan gian co the bo.

Viec danh s6 chung cac vi tri cua yang van thea quy luat nlnr a phan ten trao d6i (de a ngoai yang).

Trong ten dung hop thi ten cua yang co sa diroc giG' nguyen, con ten cua yang ghep vao duoc d6i duoi thanh "0". Thi du :

4 4 4 5
SOJ3 SOn 3 3N~6 4 3
Ib 1 ~ db k';: 7 5l~J
6:::::"" 2 6:::::"" 2
7 ° N ~l 2 N N S 0 2
1 7 1 8 6 1
H
Benzo[b ]furan Pirolo[2 ,3w b ]piridin Pirido[2,3wd]w Thienol Z.S> b ]furan
(Benzofuran) -pirirnidin 7 1

6of' N)[)O 2

1 3,1 e 3 1

5 h 3

o N

4 8

8 1

N 0

hoac 7(]f]f. j:

6 0 N

5 4

Dibenzo[ d: b [thiophen (Dibenzothiophen)

Difuro[2,3wb:2' . 3' -e ]pirazin

76

§2. Hf1P CHAr DI VDNG KHONG THaM

I. PHUONG PHAP rONG HQP

Cac hop chat di yang khong thorn thuong diroc t6ng hop thee hai phirong phap chung III yang hoa cac hop chat mach ha ya khl'r cac hop chat di yang thom.

1. Phttdng phap vong hoa cac help chitt mach hif

a) T 6ng hap cae di vong 3 canh tt't anken va a-aminoancol

CH3

I

CH3CH2CH2C=CH2

2-Metylpent-l-en

Br2 + H20) RCH -CH2Br

-HBr I

OH

NaOH) -NaBr

2-Ankyloxiran

OH I

C6H5 -CHCH2NH2

-___"".,--=--+) C6 H5 -CH - CH 2 (90%)

-NaHS04 V

I H

Cacbetoxinitren

2-Phenylaziridin :r~'~N-roOC2H5 ~7

5

7-(Etylcacboxylato )-7 -azabixiclo] 4 .. l.Olheptan

b) T dng hap cae di vong 4 canh tit cdc hap chdt co hai nhom chuc J vi tri J,3 tuang ung hoac tit xeten

o + 2NaCI (20-30%) Thietan

77

BrCH2CH2CH2NHCH3

KOH50%. 100° C ) 0 -KBr.-H20

N-CH3

(80%)

1 ~ Metylazetidin

Diphenylxeten

P6H52

CoHsIT

C6H5 4 N -C6HS

I

2~Oxo~ 1.3.3,4~tetraphenylazetidin

ete

2

CH2 ~C~O + CH2 ~O ZnCi,.1O"C ao (88%) I

Xeten 2~Oxooxetan ([3-Propiolacton)

c) T 6ng hap cac di vong 5 ho(ic 6 canli tir cac hap chat co hai nhom chuc a vi tri 1,4 hoac 1,5 hay khit cac hap chdt dj vong tham tuang ung

BrCH2CH2CH2CH2Br + C6H5NH2 + 2KOH ~ 0 +2KBr + 2H20 (100%) N

I

C6H5

1- Phenylazolidin

(1- Pheny Ipirolidin)

BrCH2CH2CH2CH2CH-COOH + Na2S ~ UCOOH + 2NaBr

BI S

r

Axit thian-2-cacboxylic

2. C{)ng hidro vito cac di vang thom

Ni,50°C

Q

Furan

Tetrahidrofuran (fHF)

o

N

Pt.HO.25°C,latm

o

I

H

Piperidin

Piridin

78

II. TiNH CHAT HOA HQC

Cac hop chat di vong khong thom co tinh chat cua hop chat co nhom chirc mach ho nrong ling va tinh chat rna vong.

1. Tinh eha't eua hdp eha't co nhom chirc

Cac hop chat di vong khong thorn chua oxi co tinh chat cua ete, chua luu huynh co tinh chat cua thioete, chira nita co tinh chat cua amin bac hai.

2. Tinh chilt mil vong

Tinh chat rna vong la tinh chat quan trong cua cac hop chat di vong khong thom, nhat Ht cac hop chat di yang 3, 4 canh ...

a) Cdc hap chd: di vong 3, 4 canb di tham gia phdn ung cong rna vong WYi nuac, ancol (co mat axit hoac bazo), vai hidro halogenua hodc viii tdc nhdn nucleophin (nhu thioancolat) :

HOCH2CH20H Etylen glicol

Ox iran

(58%)

3-Etoxipropan-l-ol

H I N

1\

Cl

I +

+ 2HCI ~ C6HSCHCHZNH3Cl-

2-Phenylaziridin

2-Clo-2-phenyletan amoniclorua

Q

100°C

C6HSCH2SCH2CH2CH20H + NaOH 3-Benzylthiopropan-l-ol (63%)

Thietan

b) M9t s6' hap chat di vong kh6ng tham 6, 7 cank co thi ma vong bang phdn {mg trung hap khi co cau tCJO va dieu kien thick hap.

Thi du :

BF3 (hay tia y)

Trioxan

Polifomandehit

79

Vet Hio,250"C

)

tNH-[CH2]4 -8)n

Pol icaproam it

s-Ca prolactam (2-0xoazepan)

III. SO LUQC VE cAc O! VONG 6 C~NH CHUA OXI KHONG THOM

Cac di vong 6 canh khong thorn chua mot oxi g6m eo:

10 101 10 0 0
0 0 0
a-Piran y-Piran 2,3 -Dihidro- 2, 3-Dih idro- Tetrahidropiran
-v-piran -u-piran Ole dan xuat eaebonyl cua piran la pi ron : o

('~o I()

u-Piron

v-Piron

Cac di vong ngirng tu ciia piron (benzopiron)

5 ,4

6~1 "'<::::33 7~_~

8 0 0 1

6~3 7~_jJ2

8 0 I

Cumarin

Cromon

Flavon

Xanthon

Die di vong 6 canh no clura hai di t6 oxi g6m co:

o

(J

CO)

° l,4-Dioxan

1,2-Dioxan

1,3-Dioxan

1. Cac piran

rx-Pi ran la chat it duoc biet den, chi biet cac dAn xuat cua n6.

y-Piran e6 th~ duoc tong hop, nhirng eire ki kh6ng ben, bi phan huy trong kh6ng khi a -80°C.

EO

Dihidropiran la dang khir cua piran dl1<;1C biet den nhieu han. Do lil mot ete vong khong no nen rat d~ tham gia phan ling cong electrophin.

Tetrahidropiran la ete vong, d~ bi rna yang khi g~p axit.

2. Cac piron

V& mat cau tao co the xern a-piron la a-lacton cua axil 5-hidroxipenta-2,4-dienoic va y-piron til ete cua 1,5-dihidroxipenta-l,4-dien-3-on_ y-Piron lil bazo yell (pKa = 0,3) ; a-piron la bazo yell ban y-piron. Khi tac dung voi axit manh, chung dell cho mu6i hidroxyli co CAll true cong huong voi ion piryli. Tid du :

2,6-Dimety l-y-piron

Ion hidroxyli

Ion piryli

Khi tac dung voi cac tac nhan electrophin, piron.bi the nhu mot hop chat thorn. Thi du :

A + CH3N02 02N~ +

Il.r.~ + N02BE4" Il",A + HBF4 (35%)

o 0 0 0

5- Nitro-u-piron

VOi cac tac nhan nucleophin (nhir NH3, RNH2), nguyen llt oxi trong vong piron de bi the boi nguyen tir nita. Thi du :

o

Il) + H20

N

I CH3

N ~ Metyl-y-piridon

Dac bier a-piron duoc coi lil hop phan 1,3-dien de thuc hien phan ling cong Dinxo-Andc, Thi du :

-C02

Diphenylaxetilen

5 ,6-Dipheny 1- 2-0xa-bixiclo[2.2.2]octa-

-5,7-dien-3-_on

o-Diphenyl benzen

! 1 HHHiJUCOlA

81

3. cse benzopiron

Cac benzopiron co tinh bazo yeu, trong do cromon va xanthon co d(> bazo IOn han, can cumarin co dQ bazo yeu nhat, co the: sap xep dQ bazo ella chung nhu sau :

Cumarin < flavon < cromon - xanthon

1,3

2,0

Tinh chat hoa hoc dang chii y a cac benzopiron i<\ phan irng the electrophin (SE) dien ra & phia vong benzen, can khi nrong tac voi tac nhan nucleophin thi vong piron de bi vts.

Nhieu dan xuat cua cac benzopiron la cac hop chat thien nhien quan trong.

a) Cac dan xuat cua cumarin co ph6 bien trong cac cay thuoc nhu umbeliferon (I) co trong cay tien h6 ... c6 tac dung dan dong mach vanh, chong co that.

b) Nhieu dan xuat cua cromon la cac chat rnau thuc vat, tao ra mau sac da dang cua cac loai hoa qua. Khenlin co trong ho cay hoa tan co tac dung dan mach va tro tim.

c) HQ chat flavon goi chung la flavonoit co trong nhieu loai cay, co nhieu tac dung : la chat chong oxi hoa, chong chat doc cua cay, ire che, kich thich sinh tnrong,

a)

HO 0 0

(I) Umbeliferon

Khenlin

tao mau sac, bao v¢ cay. Trong y hoc, cac flavonoit co

t.inh khang khuan, chong khoi u, nang cao tinh ben cua thanh mach mau, Tieu bicu cho loai nay la rutin co trong cay hoa hoe thuoc nhorn vitamin P. Rutin c6 ten khoa hoc iiI. 30- [6- (~- L- ramnozido) 1a- D- gl ucozidoq uexeti n hay q uexetinruti nozo,

Rutin

Q

00

d) Trong tu nhien can ton tai nh6m hop chat cua croman (benzn[b }dihidropiran), lieu bieu la a-tocopherol (C2<)Hso02), trong y hoc goi lil vitamin E, c6 trong mam hat lua mach, lua mi, ng6 va nhieu loai rau xanh :

82

1 It ,HHc'l)C036

Croman

Vitamin E co tac dung chong thoai hoa nen con goi la "thuoc tre lau", Ngoai a-tocopherol con co p-tocopherol (~8H4802) thieu di nhom CH3 i:J vi tri 7. y-tocopherol (C2gH4802) thieu di nh6m 5-CH3 va 8-tocopherol (C27H4602) thieu di 2 nhom 5-CH3 va 7-CH3.

e) Khi decacbonyl hoa xanthon ta duoc xanthen. Hop chat quan trong cua xanthen la chat chi thi axit - bazo fluorexein :

~ ~O~

ao

eOOH

OR

HO

(kh6ng mau) Xanthen

(do nau)

(vang xanh hay xanh 13. rna)

Fluorexein

4. Dioxan

Dioxan la cac hop chat di vong no 6 canh chua hai nguyen ttt oxi a trong vong, Co ba dong phan dioxan :

o

(J

1,3-Dioxan

CO)

° 1,4-Dioxan

1,2-Dioxan

a) l,2-Dioxan (la chat long)

1,2-Dioxan duoc dieu che' tir butan-I ,4-diylbismetylsunfonat va hidro peroxit :

(30%)

1,2~Dioxan khong ben, d~ bi va vong khi hidro hoa hoac khi co (ac dong cua axil, bazo:

HOCH2CH2CH2CH20H Butan-1,4-diol \

4- Hidroxibu tanal

83

b) Ll-Dioxan (la chat long; tnc =~42°C, ts = 106°C) 1,3-Dioxan la axetal vong cua fomandehit va trimetylen glicol :

<OH /H

+ O=C""

~OH H

CO J

+ H20

1,3-Dioxan bieu hien tinh chat cua axetal, dum tac dung cua axit no bi thuy phan thanh chat ban dau la hop chat 1,3-diol va fomandehit.

OH

< + O=CH2 ~OH

Phan irng nay khong xay ra trong dung dich kiem lanh. Khi bi hidro hoa, vong 1 ,3-dioxan bi va cho ancol nrong iing va metanol :

Q+2H2 C6Hs CH3

c) 1.4-Dioxan, con goi 13 dioxan, diety len ete hay dietylen oxit (la chat long ; tnc=1l,3°C; ts =101,4°C)

Dioxan diroc dieu che bang each dun etilen glicol voi H2SO4 4% hay voi FeS04 khan :

(0)

+ 2H20

°

Ve nhieu mat dioxan gi6ng ete, ben voi chat oxi hoa thong thirong, bazo va axit yeu, D~c biet, dioxan co th~ ket hop voi Br2' 12"" van di t6 oxi thrum san pham ben. Thi du : r=.

Br.O O.Br \._/

O,O-Dibromdioxan

san phdm ket hop nay diroc dung lam tac nhan brom hoa nhe nhang.

Dioxan duoc dung lam dung rnoi cho cac loai polime, rna, sap, dung moi pha san, chiet, tach. H6n hop dioxan va dimetyl, dietyldioxan duoc dung lam chat chong oxi hoa cho xang. San pham ket hop voi clo cua dioxan 13. chat Ol!C chien tranh.

r=.

CI.O O.C!

\._/

O,O-Diclodioxan

84

§3. HI1P CHAT DI VONG THam 5 C4NH 1 DI TO

Cac hop chat di vong thorn 5 canh 1 di t6 quan trong nhat la furan, pirole va thiophen:

Furan

(W)4 3(~)

(a')S02(a)

~l H

Pi role

(W)4 J(~)

(a')S0 2(a) S

1

(jJ')4 J(~)

(a')S02{a) o

1

Thiophen

Pirole va thiophen duoc hlnh thanh khi chung cat than da trong 10 c6c, dan xuat cua furan la furfural duoc hlnh thanh khi thuy phan pentozan trong vo trau, 15i ngo, ba mia.

, _,

I. PHUONG PHAP TONG HOP

1. Di~u che trong cong nghi~p

a) Furan duac dieu cht being each decacbonyl hod furfural tach duac tt't pentozan co trong VG trdu, fiJi ngo, btl mia ...

nQ-CHO

4000C -nCO

Pentozan

Pentozo

Furfural

b) Pirole duac tong hap tu axetilen va fomandehit

HOCH2-C=C-CH20H

NH,.p,t". -2-H20 )

o

N I H

Pirole co the thu diroc khi dun nong furan voi amoniac tren nhom oxit a 400 - 450°C theo phirong phap Iurep (Iurev) :

o

o

+ NH3

o

N I H

+ H20

c) T hiophen duoc tdng hap ttl bulan viii luu huynh bot

600"C

o +3H2S S

85

2. Tang hqp Pan-Kno [Paal-Knorr]

Tong hop Pan-Kno III plurong phap chung nhat d~ dieu che' furan, pirate, thiophen hoac dan xuat the cua cluing tir hop chat l,4-dicacbonyl voi cac hop chat chua cac di t6 thfch hop co kha nang loai mroc. TId du :

CH3, /CH2-CH2, ~H3

C C

II II

o 0

(Hexa-2,5-dion)

(2.5-Dimetylfuran )

(2,5-Dimetylpirole)

(2,5-Dimetylthiophen)

3. T 6ng hqp dan xufi't the' ella furan va pirol tit p-xetoeste a) Phdn ung Fai-Benari (Feist-Benari)

Cho ~-xetoeste phan img voi a-halogencacbonyl trong piridin diroc furan the:

CH3 ~COOC2H5

.. l(O>---'CH3 + H20 + HCI

Piridin, 25°C

Etyl-Bvxetobutirat Cloaxeton,

2 ,4-Dimety 1- 3 -( etoxicacbony l)furan

b) Phdn l~ng Hansa (Hantzsch)

Khi cho ~-xetoeste phan img vai a-halogencacbonyl va amoniac thu duoc pi rote the:

CH3

OOC2Hs

CH3COCH2COOC2H5 + CICH2COCH3 + NH3 -- + 2HzO + HCI

H3

I

H

2,4-Dimety 1- 3-( etoxicac bony 1 )pirol

c) Phon ung Kno (Knorr)

DO'la phan img ella ~-xetoeste voi a-aminocaebonyl trong axit axetic thanh pirol the:

. CH~OOC2H5 C2H500C~r-CH3

H

3,5-D ietoxicacbon yl-2,4-dimetylpirole

Etyl-u-amino- p- xetobutirat

86

4. T5ng hc;lp thiophen thea Hinxbec (Hinsberg)

Phan irng dien ra gicta cac a-dieaebonyl va dietyl este ella axit thiodiaxetic co mat natri ancolat trong ancol ;

2 ,5-Dicac boxi - 3 ,4-dipheny lthiophen

, J A ;

II. TINH CHAT V~T II

1. Tinh chAt v~t li thong thu'ong

Ba di vong furan, pirole, thiophen dell 13. cac chat long co nhiet dQ sci va nhiet d¢ n6ng chay khac nhau lien quan voi phan tll kh6i va d¢ phan eire cua phan tir. Ti kh6i va chiet suat ella chung tang dan ttl furan qua pirole den thiophen (bang XIV ~3)

Bang X/v·3. MQt s6 hang s6 v~t Ii cua furan, pirol, thiophen

Cllitt t, ({ley tn~ (0 C) J.l (D) diD nbo
Furan 32 - 30 0,7 0,9366 1,4216
Pi role 130 - 1,81 0,9480 1,5035
Thiophen 84 -40 0,51 1,0644 1,5287 2. Tinh chat ph6

Furan, pirole, thiophen co cac van plio dac tnrng :

a) Phd IR (ern") : > 3000 (vCH thorn), - 1600 (vc=c thorn), 3400 (vNH pirole)

b) Pho UV O"max (nm) / E) : c6 cac van pho dac tnrng cho Sl! chuyen-rrurc rt ---+ n* va n ---+ n* (xem bang XIV-4).

e) Pho NMR (ppm) : the hien ro nhirng cap hat nhan tirong dirong : CO'-Cu' • Cp-Cp. , Ha-HO'. , Hf3-Hp' (xem bang XIV-4).

87

Bang XIV-4. Ph5 UV va NMR cua turan, pirote, thiophen

Phd Di;ic trung Furan Pirole Thiophen
Chuyen mire 1t ~ n '" 200/1000 210/15000
UV -
""max (om) 1 E Chuyen mire 0 ~ 1t '" 250/1 350nOO 235/4500
Co: va Co:' 143,0 ll8,O 124,0
CI3 vaCI3' 109.9 107,7 126,4 ,
NMR(ppm) n, va Ho:, 7,4 6,6 7,2
H!3va H!3' 6,3 6,1 7,0
N-H 9 - 11 J , ..... ,

III. CAU TRUC PHAN TU

1. Cac du kien

a) Neu dira vao·eong tlnrc cau 4.0 0 (Z = 0, NH, S) thi furan, pirole va

Z

thiophen phai eo tinh chat di~n hlnh ella dien lien hop va tinh chat ella ete, amin bac hai

va thioete, Thirc te cac hop chat tren eo bieu hien tinh chat ella dien lien hop nhung lai khong bieu hien nhirng tinh dien hlnh ella ete (khong bi phan cat ,bdi axit d~e rna hi polime hoa trong dieu kien do), cua amin bac hai (tinh bazo rat yeu, K~ ella pirole = 2,5,10-14), ella thioete (khong bi oxi hoa thanh sunfoxit nhu thioete thirong), Mat khac, cac hop chat di vong nay tham gia phan ling the electrophin rat' thuan loi (von la phan irng dien hinh cua cac hidrocaebon thorn).

b) V e mat nang hrong, ngiroi ta thay rang noi nang ella furan, pi role va thiophen do duoc bang phuong phap thieu nhiet nho hon nQi nang ella oxa-, aza- va thiaxiclopenta-2,4-dien Ian hrot la 22, 24 va 28 keal/mol theo each tinh nang hrong cac lien ket, Hieu so nang hrong ay chinh Iii nang hrong 6n dinh hay nang luong thorn.

c) V6 mat kich thuoc, nho nhieu xa tia X ngiroi ta do diroc :

- D¢ dill cac lien ket C-C trong cac di vong tren nam trong khoang tit 135 den 144 pm, dell dai hem lien ket doi C=C (134 pm) va dell ngan hem lien ket don C-C (154 pm).

- D¢ dai cac lien ket C-Z (Z : cac di t6) trong cac di vong tren deli ngan hem dQ dai cac lien ket C-Z tuong irng trong cac hop chat mach ho. Thi du ; D¢ dili lien ket C-N

88

trong pirole (142 pm) nho hem d¢ dai lien ket C-N trong amin (147 pm). D¢ dai lien ket C-O trong furan (141 pm) nho hem d¢ dai lien ket C-O trong ete (143 pm). D¢ dai lien ket C-S trong thiophen (174 pm) nho hem d¢ dai lien ket C-S trong thioete (182 pm).

- Cac goc hoa tri trong cac di yang furan, pirole va thiophen dao dong trong khoang til 910 den 1 130, gAn voi cac goc hoa tq cua xi clopentadien (tit 101 den 110°).

Tift ca cac dfr kien tren cho thay cac di yang furan, pirole va thiophen CO cau true dac biet CLIa hop chat thorn,

2. C~u true phan tll'

Cac hop chat di yang furan, pirole, thiophen co cau true yang 5 canh phang, cac nguyen tir cacbon va di t6 Mu a trang thai lai hoa sp2. M6i nguyen tu cacbon cua vong co mot lien ket sp2 -s voi hidro va hai lien ket sp2 _sp2 voi hai nguyen Iii ben canh. Moi di t6 co hai lien ket sp2 _sp2 voi hai nguyen tii cacbon ben canh va mot obitan Sp2 chua hai electron khong lien ket (voi oxi va luu huynh) hoac mot lien ket sp2 -s voi hidro (lien ket N-H). Moi nguyen Ill' cacbon con co mot obitan p chua mot electron va rnoi di 16 con co hai electron tren obitan p. Nam obitan nay xen ~!tu voi nhau tao nen obitan phan tiI cac electron p nhu hai dam may electron nam a phia tren va phia diroi mat phang vong. Obitan phan tir nay la h¢ lien hop khep kin co 6 electron, thoa man quy tac Hucken (Huckel) 4n+2 (xern hlnh XIV.1 va XIV.2). Nhu vay, furan, pirole va th~ophen Iii. cac hop chat thorn, thuoc loai di vong thorn 5 canh. Cong tlurc call 40 cua cluing co tM viet:

o

o

hay (Q) o

o

N I

H

hay @ N

I

H

Hinh XIV .1. Ou true obitan ella furan

12HHH iJIJC03A

89

Q

hay @ S

Hinh XTV.2. atu true obitan cua pirole

; J ;

IV. TINH CHAT HOA HQC

Lit cac hop chat thorn nen furan, pirole va thiophen bieu hien truce het la tinh thorn. Tfnh thom diroc bieu hien 0 nang hrong 6n dinh (nang hrong thorn). Nang hrong 6n dinh phu thuoc VaG sl! 6n dinh cua cac cau tnic cong hirong sau :

[Q.-+ -9

+

+

9]

(I)

(II)

(Ill)

(IV)

(V)

Cac cau true cong huang nay mo ta SI! mat dinh cu cua cap electron 0 di t6, trong do cac cau true II va III 6n dinh han cac cau true IV va V VI hai dien tfeh trai dau a gan nhau. SI! m[(t dinh cu cua cap electron a di t6 phu thuoc vao d¢ am dien cua di t6. D¢ am dien cua cac di t6 thay d6i nhu sau : 0 > N > S, vi v~y chung dong gop VaG su 6n dinh cua cac eau true tir II den v cua cac di vong, su dong gop do thay d6i thee day:

furan < pi rote < thiophen

Chfnh VI the, nang hrong 6n dinh cua furan < pirole < thiophen :

22 24 hay 92,4 109,2

28 (kcal/mol) 130,2 (kl/mol)

va d¢ thorn cua cluing duoc xep nhu sau : furan < pirole < thiophen.

Tinh thorn cua furan, pirole, thiophen bieu hien a chb cluing tham gia phan (rug the electrophin rat de, luang duong voi phenol va ani tin. Ben canh do, furan va pirole eon tham gia phan iing cong va khir,

90

La hop chat di vong nen furan, pirole, thiophen con th€ hien mot so tfnh chat khac nhau nhu tinh axit - bazo, thay the' d] to, ...

1. Phim itng the' electrophin, SE

Furan, pirole va thiophen nhay cam voi cac tac nhan electrophin hon benzen, VI mat dQ electron tren cac nguyen tit eaebon cua cac di vong nay Ian hen tren cac nguyen nr eaebon cua vong benzen. Kh3. nang the' eleetrophin giam d&1 til furan den pirole roi thiophen. Thi du khi nitro hoa cac hop chat di vong tren bang axetyl nitrat (CH3COON02 - mot anhidrit hen tap) phai tien hanh a nhiet d¢ khac nhau tit thap den eao. Ttrong tv nhu vay voi phan Ung sunfo hoa bang piridin s unfotrioxit (xem cac sa do phan Ung XIV. I, XIV.2 va XIV.5).

Phan ung the eleetrophin vao furan, pirole, thiophen au tien a vi tri so 2 (a), eel che phan img nrong tv co che the vao vong benzen :

ffP + E+ ~ ~ ----J-

phUc 0'

Giai thfch Inrong au tien the thea thuyet cong hucng nhu sau :

E+ tan cong vao vi trl s6 2 [~-+~ +-+ ~]

Q (I) (II) (III)
E+ t;in cong vao '1 trl s6 3 [Q; 9]
+-+
(IV) (V) S1,I' tan cong vao vi trf so 2 eho hai cong thuc gioi han II va III urong tv nhu hai cong tlurc gioi han IV va V cua su tan cong vao vi trf so 3, ngoai ra con them cong thirc gioi han I rai 6n dinh, Cac cong tlnrc gioi han I, II, III bieu dien Sl,l giiii toa di~n tfeh rong rai han khi E+ tan cong vao vi trf so 2 so voi vao vi tri so 3.

Sau day la cac sa do phan irng XIV. 1. XIV.2 va XIV.3 bieu dien mot so phan irng the eleetrophin tieu bieu cua furan, pirole va thiophen.

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Sa d6 XIV. 1. MQt s6 phan ling the electrophin cua furan.

Q-

furan

1) CH3C02N02/(CH3COhO.-10"C

2) Piridin

-CH3COOH VN02

(2-Nitrofuran)

SDyfpiridin

(Axit 2-furylsunfonic)

(CH3COhOIBF3 -CH3COOH

(2- Axety lfuran)

1) HCNIHCI 2)H2D

(Furfural)

HgCliCH3COONa ~

(2-Furyl thuy ngan clorua)

-HCl HgCl

IV <, ='HgCI2

v-:::Hg CH3C~

~CI ~COCH3

'" Thirc chat day lit phan ling cong - tach:

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Sa d6 XIV.2. Mot s6 phan iing the electrophin cua pirole

Q

I H

Pirole

-CH3COOH_
S03,90oC
02N -0- N!Cl-
-HCI
CHCl1.3KOH
- 3KCl, - 2H2O
-
l.HCN, HCI ; 2.H2O
-HCI.-NH3
(CH3COhO, 250°C
-CH3COOH
48r2, C2HsOH
-4HBr
412, K.I -4ID

~S03H

a

Axit pirole-2-ylsunfonic

V-CHO I

H

2-Fomylpirole

V-CHO I

H 2-Fomylpirole

-V-C"'CH3

I II

H 0

2-Axetylpirole

Br Br

BlrJ.--Br

I H

2,3,4,5- Tetrabrompirole I I

I~I

I H

2,3,4,5- Tetraiotpirole

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So d6 XIV.3. MQt s6 phan irng the electrophin ella thiophen

~S03H

Axit 2~thienylsunfonic

CH)C02N02f(CH)COhO, ufc G

-CH)COOH S N02

2-Nitrothiophen

2Br2fC6l4. ~

t--..,-_-2-HB-r----+ B0s~Br

O 2,5-Dibromthiophen

S -

thiophen

~CH2C1 Theny 1 clorua

Trong cac phan ling the electrophin tren, dang ~hu y 13. phan tmg nitro hoa va sunfo hoi khong dung cac tac nhan thong thuong nhir voi benzen (RN03 darn dac va H2S04.S03) vi dQ axit cao cua moi tnrong se pha va he thong lien hqp vong thorn va nlura hoa cluing, d~c biet 0 furan va pirole (xem phan tinh axit - bazo),

VHgO

-HI

co I

~ :0 AICI)

~CO

~I

2-Iotthiophen

G~

S CC6H4C02H

Axit 2-(2-thlenocacbonyl)benzoic

2. Phcin itng the' nucleophin, SN va phan itng the' g5c, SR a) Phdn ung the' nucleophin, SN

Cac dan xuat halogen cua furan co nhom the hut electron manh nhu -N02• -COOH, -COOR co the tham gia phan ling the nucleophin. Thi du ;

Br -()- COOCH3 + CH30Na 2-Brom-5-(metylcacboxylat)furan

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CH30-()- COOCH3 + NaBr (42%) 2- Metoxi - 5-(metylcacboxilato )furan

Cac da.n xuat halogen cua thiophen khong e6 nh6m the hut electron va.n e6 the tham gia phan ling the nucleophin. Thi du :

n Piridin, t" soi ~

Br S CH3 + Cu2(CNh ------.. NC -'Z..~_)- CH3 + C~BrCN (73%)

S

2· Brom-5-metylthiophen

5- Metyl-2- xianothiophen

b) Phdn ling the' goc, SR

Pharr ling the goc thuong xiiy ra 0 vi tri c. Thi du :

p-Clophenyl diazonic1orua

a-fp-Oophenyl]furan (29%)

NO NO

Q + @- N - COCH3 ----+ Q-© + H~ - COCH3

I . I

COOC2Hs COOC2HS

N -(Ety lcacboxylato)-pirole

N-Axetyl-N-nitrozo· -anilin

l-(Ety lcacboxylato)- N -N itrozoaxetamit • 2·pheny lpirole

2-Nitrophenyl diazoniclorua

2-(2- Nitropheny1)thiophen

3. Phim .mg d)ng

Furan, pirole va thiophen co kha nang tharn gia pharr ling cong khac nhau, nhung nhin chung deu d~ han benzen. CO ba lnrong cong vao cac hop chat di vong thorn nay 130 : cong vao lien ket doi, cong mo vong va cong d6ng vong ki€u Dinxo-Ando,

a) Cong VaG lien kel doi

Furan va pirole c6 the cong hidro tren xuc tac di the (Ni chang han) tao ra cac hop chat di vong no nrong ling :

o +2H2 o

Ni,50°C

Q

Tetrahidrofuran (THF)

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o

N I H

+ 2H2

Ni, 200- 2500 C

Q

I

H

Pirolidin

Phan irng cua thiophen voi hidro tren xuc tac di th~ kh6ng thirc hien diroc VI '

thiophen diiu dQc xuc hie kim 10'.1i. Furan, pirole va thiophen cfing c6 th~ phan irng v6i. hidro rnoi sinh tao ra cac hop chat di vong khong no nrong ling. Thi du :

CH3DcH3 + 2NaCI N

I

H

2,5-Dimetyl-6? -pirolin

b) Cong rna vong

Phan ung cong mroc rna vong dac tnrng cho furan :

CH3 ~ CH3 + H20 H2S04 [CH3 A CH3] ----+ CHr .... C-cH2-CH2-C-CH3

~~ OH OH & &

Hexan-2.,5-dion (90%)

Pirole kh6 cong rna vong hon, nhung khi phan U'ng vai hidroxylamin clohidrat thi bi chuyen hoa :

o + 2H2NOH.HCI

~ ,

H

Sucxindiandoxim

Thiophen ben vung han furan va pirole trong pharr trng rna vong, Tuy nhien, khi dun soi thiophen Val hidro co Ni-Ranay (Raney) lam xuc tac thi khong c6 phan Ung hidro hoa rna la phan img hidro phan kern thea su desunfua hoa :

iO-CH(OC2HS)2 +4H2 Ni-Ranfty/ele, tOs6i CH3CH2CH2CH2CH(OC2H5 h +H2S i S

2-( I, I-Diemtoximetyl)thiophen

1 ,l-Dietoxipentan

c) Phdn ung cong dong vong

Furan tham gia phan irng cong hop dong vong Dinxo-Ande (Diels-Alder) : do la kieu cong 1,4 vao dien thea quy uk chong chat cue dai cac lien ket rt (hay quy uk cong end6), (hi du :

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Maleimit

Pirole tham gia phan ling voi dienophin nhu tren rat kh6 khan, nhirng pi role N-the lai cho phan img tirong tl! voi I-brom-2-flobenzen (voi dehidrobenzen hay aryn).

(35 - 41%)

N-(tert-Butoxicacbonyl)pirole

11- tert - Butoxicacbony 1 )-ll-azatrixic1o-[ 6.2.1.02,7]undeca-2(7),3,5,9-tetraen

Thiophen khong tham gia VaG phan (mg cong hop voi dienophin nhu tren.

4. Tinh axit - bazo

a) Ttnh axil

Furan va thiophen the hien tfnh axit rat yeu, chi co the lac dung voi bazo eire manh nhu hop chat co - kiem, Chang han, khi furan va thiophen phan ling voi n-butylliti cho ta 2-furylliti va 2-thienylliti :

5-Metyl-2-furylliti

5- Metoxi - 2-thien yl Uti

Pirole co tinh axit ro ret hen furan va thiophen nhung van yell. Pirole (K, = 10-15) la axit manh hen mroc (K, = 10-16), NH3 (K, = 10-35) va amino Vi vay, pirole co the phan img voi KOH va hop chat co-magic :

97

+KOH

Q

I

K Pirole-l- kali

Q

I H

Q

I MgBr

Pirole-l-magie bromua

b) Tinh baza

Tinh bam cua furan va pirole (K, = 10-14) nlt yeu, Trong nuoc, cluing tao ra cac ion oni kern 6n dinh so voi dang phan ti'r.

O +HO

o 2

----=::.. Q~

~ DOH-

I

H

Furan proton hoa

o

WOHI \

H H

Pirole proton hoa (pKa = 0,4)

Khi tac dung voi axit vo CO manh, cluing se bi polirne hoa :

O~O ~(J (f) Hf:J-C) I[)
-----+ .r 0 o .. . .. ~ Polifuran
o 0+ He) H 0 0
1- + +
H
Q 0 ~ Hf:JJ:) 0
H+ HDi
---=-+ -----+ A NH ~ NH. ... ~ Polipirole
N+ H N+ H N N+
I / -, I I I
N H H H H H
Thiophen khong co tinh bazc. 5. Phan itng ehuyfin hoa giii'a cac dj t6 thea Iurep (lOpLcn - Iurev) Phan irng chuycn hoa gifra cac di to cua cac di vong thorn 5 canh xay ra khi co xuc ttic Al203 a 300°C:

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,. #If'. A. J ,I A _ fI' "..."..

V. GIOI THI~U MQT SO HQP CHAT THIEN NHIEN PHUC T~P CHUA VONG PIRatE

1. Porphin

Hemoglobin (hong Call cua mall) va clorophin (chat diep h;IC cua cay xanh) co thanh phan co ban ta porphin. Porphin la bo khung g6m 4 vong pirole lien ket voi nhau boi cac call noi metin thanh vong 16 canh voi 18 electron p co Call tao phang va co tinh thorn,

Porphin chua cac nhom the khac nhau goi la porphirin,

a) Hemoglobin

Hemoglobin la mot protein phirc tap thuoc loai cromoprotein (protein mang mall). Thanh phan cua hemoglobin g6m 4 heme (chiern 4% khoi luqng) va globin (chiern 96% khoi hrong phan tir hemoglobin). Moi heme la mot phirc chat cua ion Fe2+ voi vong porphirin. Hemoglobin lam nhi~I? vu chuyen cho oxi tit phoi den te bao va chuyen cho khi thai (C02 chang han) tir te bao ve phoi de thai ra ngoai nho tao lien ket phoi tri cua cac khi nay vci ion Fe2+.

Porphin

Heme

b) Clorophin

Clorophin la phirc cua IDQt loai porphirin voi ion Mg2+. Do lit chat diep luc, dong vai tro quan trong trong qua trlnh quang hoa cua cay xanh.

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