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VO NHM CHC
NI DUNG
1. Kim nghim hydrocarbon v dn cht halogen
y H2S
2
xC
H2O c xc nh do to thnh cc git nc trn thnh ng nghim. CO2 to thnh c xc nh bng phn ng to ta vi dung dch calci hydroxyd:
CO2
+
Ca(OH) 2
CaCO3 + H2O
H2S
Pb(CH3COO)2
PbS + 2CH3COOH
AgNO3
AgX
NO3+ 2H2O
Ag X
+ 2NH4OH
[Ag(NH3)2]Cl
phn bit cc halogen, da vo hnh dng v mu ta to thnh: Ta AgCl trng xm, vn Ta AgBr mu hi vng Ta AgI mu vng.
Tip
Tuy nhin, xc nh chc chn l halogenid no, phi da vo th oxy ha kh ca chng. Cho vo dung dch cha ion halogenid nc clo (dung dch clorua vi, dung dch cloramin...) v cloroform th: Nu trong dung dch cha ion clo: Mu khng i Nu cha ion brrom, lp cloroform c mu vng. Nu cha ion iodid, lp cloroform c mu nu
Cl2
Cl-
AgNO3
AgX
NO3-
Xc nh im kt thc bng o in th hoc ch th mu Trong trng hp dng ch th mu, tu pH mi trng m dng ch th mu thch hp. Nu pH t 7 n 10, dng phng php Mohr (ch th Kali cromat:
AgNO3d-
KCrO4
AgCrO4
KNO3
Trong trng hp ny, nu pH > 10 s to ta Ag2O; nu pH < 7 s to Cr2O72- v Ag2Cr2O7 tan trong mi trng acid
Nu mi trng acid, phi dng phng php Volhard, ch th phn st amoni, cht chun amoni sufocyanid:
AgNO3
+
SCN-
AgSCN
NO3-
SCN
Fe
3+
Fe(SCN)
2+
Trong phng php ny, nu nh lng ion clorid th phi thm vi ml nitrobenzen vi mc ch bao ly ta AgCl khng cho chng tan ra v tch s tan ca AgCl ln hn AgSCN.
Phng php Fajans: Phng php ny dng ch th hp ph.
Nguyn tc l ngay sau im tng ng, ta AgCl mang in tch dng (d Ag+) trn b mt ta. Mt anion hu c mang mu thm vo s lin kt trn b mt ta, mu thay i.
Tu theo mc lin kt ca halogen vo carbon m c th bin chng sang dng ion bng cc thuc th khc nhau:
nh hng ca halogen ln bn ca lin kt C X: Nu lin kt trn cng 1C v cng chu nh hng ging nhau ca cc nhm th bn cnh th bn ca lin kt gim dn t F > Cl > Br > I (do bn knh tng dn
nh hng ca gc hydrocarbon: bn gim dn t vng thm, mch vng, mch h
S lng halogen trn C: Nu s lng tng, bn lin kt tng (do km phn cc) nh hng ca nhm th khc: Cc nhm th m in ni chung lm gim bn ca lin kt Sau y l mt s phn ng hay dng: 1. un si vi dung dch KOH trong ethanol
++ t RX KOH K X + ROH Phn ng ny p dng cho tt c cc hp cht hu c cha halogen, tr halogen gng vo nhn thm m v tr ortho hoc para khng c nhm th m in +
0
AX + NaI Na X + RI Phn ng ny dng xc nh clo v brom. Ta NaI khng tan trong aceton
++
RX + Na2CO3
NaX + CO2
H2O
i vi tt c cc hp cht gn iod, tr gn vo nhn thm, ch cn un nng, gii phng hi iod mu tm i vi hp cht gn iod vo nhn thm, cn thm acid sulfuric v un nng (levothyroxin)
i vi hp cht gn fluoro, lin kt cng ha tr rt bn vi carbon. bin sang dng ion fluorid, phi un ch phm vi kim loi kim.
2.1. ALCOL
2.1. ALCOL
Alcol l nhng hp cht, trong phn t cha 1 hay nhiu nhm OH lin kt vi carbon mch h, mch vng hoc mch nhnh ca hydrocarbon thm.
L tnh: Tt c cc alcol (tr enol) u l nhng hp cht trung tnh; c nhit si rt cao (do lin kt hydro). Monoalcol vi C < 11 l nhng cht lng, nh hn nc tan: T C1 n C3 trn ln vi nc mi t l. Polyalcol l cht lng nht hoc cht rn, v ngt
2.1. ALCOL
Ho tnh:
- D xy ra theo th t: Bc nht > bc hai > bc 3. - Th nhm OH trong lin kt C OH theo chiu ngc l Oxy ho alcol bc 1 v 2 thnh aldehyd v ceton:
R CH2OH
+
(R)2 CO
2.1. ALCOL
Phn ng ny khng xy ra vi alcol khng no do s oxy ho s xy ra ti lin kt khng no ny. Phn ng acyl ho (to ester): Thng dng l phn ng to acetat hoc benzoat
-Tc dng vi acid acetic khan hoc natri acetat trong v acid sulfuric c:
R CH2OH + CH3COOH RCH2OOCCH3 H2O RCH2OH + C6H5COCl C6H5COOCH2R + H2O nh tnh, cc acetat ca alcol thp c mi thm; cc benzoat ca alcol khng tan trong nc. nh lng bng cch xc nh ch s acetyl ho
2.1. ALCOL
Cho vo ch phm 1 lng d anhydrid acetic acetyl ho, tch sn phm acetyl ho ri nh lng bng pp tha tr. Phn ng Xantogenic: Tc dng vi carbon sulfid trong mi trng kim, thm mui ng (II) to ta mu nu
R1 R1 C O
H2N NH2
R1 R2 C N NH2
H2O
R1 R2 C O + H2N NH C NH2
S R1 R2 C N NH C NH2+ H2O
R1 R2 C O
O2N H2N HN
NO2 R R C N NH
O2N NO2
3.1. ALDEHYD
L tnh: L nhng cht c tnh trung tnh. Formaldehyd v acetaldehyd l nhng cht kh c mi c bit. Cc aldehyd mch h vi s carbon trung bnh l nhng cht lng linh ng n snh nh du, c mi d chu. Cc aldehyd thm l nhng cht lng hoc rn. Ho tnh: Tnh kh v tham gia phn ng cng Tc dng vi bc nitrat trong amoniac (phn ng Tollen) to ta bc kim loi, vi thuc th Fehling to ta , vi thuc th Nessle to ta nu en ca thu ngn kim loi
O R C H
+ 2[Ag(NH3)2]NO3 + H2O
ALDEHYD
O R C H + K2[HgI4] +3KOH RCOOH
+ Hg + 4KI + 2H2 O
O R C H
Cu2O + RCOOH
Cc polyphenol, aminophenol v cc - hydroxyceton (cc ng n, cortison...) v mt s hp cht khc cng cho phn ng tng t. Tuy nhin, phn bit, dng thm phn ng ngng t nu trn. Cc aldehyd thm khng cho phn ng vi thuc th Fehling
ALDEHYD
Phn ng vi natri bisulfit hoc thuc th Schiff: Tc dng vi thuc th Schiff (dung dch Fuchsin lm mt mu bng kh sulfur (SO2): To mu hng n mu . C ch phc tp, bn cht phn ng cng. Tc dng natri bisulfit to ta. Cho ta tc dng vi dung dch kim hoc acid s gii phng tr li aldehyd.
O R C H
+
NaHSO3
R CH
OH SO3Na
V vy, ngoi vic dng nh tnh cc aldehyd, thuc th ny cn c dng phn lp cc aldehyd.
3.2. CC CETON
L tnh: Cc ceton l nhng cht trung tnh. Cc ceton c t carbon l nhng cht lng nng, linh ng, c mi ether; tan trong nc v ether. Cc ceton cha nhiu carbon l nhng cht lng snh nh du hoc cht rn.
Ho tnh: Khng c tnh kh. Song di tc dng ca nhm carbonyl lm cho hydro gn vo cc nguyn t carbon bn cnh tr nn linh ng v c mt s phn ng sau. Tuy nhin, do cc phn ng ny khng c hiu nn trc khi tin hnh cc phn ng ny, cn tin hnh trc cc phn ng: Xc nh nhm carbonyl bng phn ng ngng t Dng phn ng vi natri hydrosulfit tch aldehyd
CC CETON
1. Phn ng Legal: Tc dng vi natri nitrofrussiat (Na2[Fe(CN)5NO] trong mi trng kim to mu khc nhau. Mu khng bn, acid ha bng acid acetic thng chuyn sang mu xanh. C ch cha xc nh.
Cc ceton mch h, mch vng, cc aldehyd, 1,3-diceton (enol), -cetoester, ester ca acid malonic u cho phn ng ny. Cc hp cht khng ln phn ng l benzophenon, benzaldehyd v formaldehyd.
2. Phn ng vi meta-dinitrobenzen: Tc dng vi meta dinitrobenzen trong cn v kim ha to sn phm c mu vng m. Cc hp cht to mu
vi trong phn ng Legal cng to mu trong phn ng ny.
CC CETON
Do nhy ca phn ng cao nn hay c dng nh lng cc hp cht ceton khi hm lng thp (dch sinh hc) 3. Phn ng to iodoform: Cc methylceton v acetaldehyd (nhm CO lin kt vi H hoc C) khi tc dng vi iod trong mi trng kim to iodoform I2 + 2NaOH NaOI + NaI + H2O
CH3 CO R
+ 3NaOI
CI3CO R+ 3NaOH
CI3CO R + NaOH
CHI3 + R COONa
CC CETON
Phn ng ny khng xy ra vi acid acetoacetic, song mt s hp cht trong iu kin phn ng s b thy phn hoc oxy ha thnh nhm chc methylceton hoc acetaldehyd gy phn ng. Mt s v d:
3.3. CC ENOL
Enol l ng phn ca 1,3-diceton hoc l - cetoester v lun tn ti di dng h bin ceto-enol
R C CH2 CO R O R C CH2 COO R O Ha tnh: R C CH CO R OH R C CH COOR OH
Tnh acid ca nhm OH (to mu vi Fe3+ hoc Cu2+) Ha tnh nhm carbonyl (ngng t) Ha tnh ca lin kt i (phn ng cng) Ha tnh nhm methylen hot ng
3.4. CC QUINON
Quinon l nhng hp cht, trong phn t cha nhm C= O lin kt trc tip vo nhn thm Tnh cht: L nhng cht rn. D b kh thnh hydroquinon; mt s cht khng cho phn ng ngng t vi hydrazin. Ngoi ra, cc quinon cho phn ng c trng to quinhydron c mu khi tc dng vi phenol
OH O O HO
3.5. CC NG N
1. L tnh: L nhng cht rn, trung tnh, v ngt 2. Ha tnh: Ha tnh ca polyalcol Ha tnh ca nhm aldehyd (tnh kh) k c ng -hydroxyceton. Phn ng ngng t (to osazon)
R C O + R NH NH 2 HC OH 3 R' R C N NH R + R NH2+ NH3 C N NH R R'
3.6. NH LNG
i a s hp cht cha nhm carbonyl, nh lng da vo phn ng ngng t. Ring aldehyd, cn da vo tnh kh v tham gia phn ng cng 1. Phn ng vi hydroxylamin Thm mt lng d hydroxylamin, nh lng hydroxylamin d bng phng php o acid. Nu dng hydroxylamin hydroclorid: Acid gii phng c nh lng bng phng php o kim. 2. Dng 2,4-dinitrophenylhydrazin: Phn ng xy ra hon ton. nh lng sn phm bng phng php cn ta, cc ph hoc chun oxy ha kh, ph hp th kh kin trong mi trng kim
R O R' + HI
RI + R'OH
Phn ng ny xy ra vi ether bo, ether va bo va thom Trong trng hp R > R' th s to R'I + ROH
ArOH + R'I
O R' + AlCl3
Al(ArO)3+ 3R'Cl
Ca
2+
COO COO
Ca
Cu2+
R CH C H2N Cu
2
O O
Cu2+
COOH
N O Cu O
2
RCOOH + SOCl
Cc acid c phn t lng thp, phn ng xy ra nhit thng; cc acid c phn t lng cao phi un nng. Pht hin SO2 bng giy tm KIO3 v h tinh bt, clorid acid bng phn ng to hydroxamat. Cc acid khng thm gia phn ng gm acid oxalic, acid oaminobenzoic, meta v para hydroxybenzoic...
NaOH + H2N OH
O R C NH OH + NaCl H O 2
O 3+ R C NH OH + Fe
O Fe (R C NH O) 3 + 3H+
Phn ng decarboxy ha: Nu cnh nhm carboxylic c nhm th m in hoc dy ni i, khi un nng d dng gii phng kh CO2.
COOH COOH
C6H5 CH CHCOOH
COOH 0 t OH
CO2
O O HO OH O
COO
OH
nh lng: Phng php o kim: i a s acid hu c l cc acid yu nn mi trng cn - nc, ch th thymolphtalein hoc phenolphtalein. Cc acid rt yu phi chun trong mi trng khan (dung mi dimethylformamid, ethylendiamin, n-butylamin, cht chun methylat natri, tetrabutylamoni OH.
Thy phn: Phn ng xy ra trong mi trng acid cng nh mi trng kim R C OR' + NaOH R COONa + R'OH O nh tnh, xc nh acid hoc alcol to thnh. nh lng, dng kim d v chun li bng acid
- i vi cc ester kh thy phn nh ester phn t lng cao th phi un si lu hoc dng dung mi l alcol hoc ethylenglycol. - Cc ester ca alcol bc 3, ester thm m v tr O c nhm th th phi thy phn bng cch un si vi HCl 15%.
Phn ng to hydroxamat st: C ch phn ng nh clorid acid. Phn ng vi amoniac to amid: Phn ng ny xy ra vi ester c phn t lng thp
R C OR'+ NH3 O
R C NH2+ R'OH O
R1 NH2 ; R1 NH R2 ; R1 N R2 R3 Ty thuc nhm amin gn vo carbon m phn bit amin bc nht, nh, ba v amin thm
Tnh cht chung ca cc amin l tnh base v gim dn theo th t: Bc 3 > bc nh > bc nht > NH3 > thm v phn ng chung l to mui khi tc dng vi acid. Trong kim nghim, thng dng phn ng to mui kt ta nh picrat, acid ptl ln (silicovolframic...)
NH3
NH2
+
HNO2 t
OH
+
N2+ H2O
- Cc amin bc 2 (thng phi un nng, thm) to nitro samin mu vng, khng tan trong nc, tan trong ether
R1 NH R + HNO2
R1 N R + H2O N O
NH2
+
HNO2 t
OH
+
N2+ H2O
- Cc amin bc 2 (thng phi un nng, thm) to nitro samin mu vng, khng tan trong nc, tan trong ether
R1 NH R + HNO2
R1 N R + H2O N O
NH2
HNO2
HCl
N N . Cl
+ 2H2O
COOH
+
Cl
RNH2 (2R2 N)
Cl O NHR N(R2)
+
RNH (R)2N
Cc amino khc nhau c mu khc nhau. Cc amin mch h c hunh quang di n t ngoi. Cc nitril v cc amid cng cho phn ng ny.
(R)2NH + Cl CO R'
R NH2+ Cl SO2 CH3
CH3+ HCl
Vi amin bc nht, sn phm cn H nn c tnh acid, ta tan trong dd kim. Vi amin bc hai, sn phm khng cn tnh acid nn ta khng tan trong kim. Cc phn ng chn lc:
Phn ng to isonitril: Cc amin bc nht khi tc dng vi cloroform trong mi trng kim to isonitril c mi c trng
R NH2+ CHCl3 + KOH
+ + 3KCl + 3H2O R N C
Cc amin bc 1 v 2 (tr amin thm), khi tc dng vi CS2, thm ion nikel to mui, amin bc 1 mui tan, bc 2 khng tan trong nc; un si phn hy to mi c bit
R CS2 + R' NH
2+ + N R' 2+ N R' Ni .[R' NH2] [S C ] [ S C S ]2Ni S
2R
N S + H2S + NiS
Phn ng to mui bc 4: Cc amin bc ba v i a s amin d vng, khi tc dng vi methyl iodid hoc benzyl clorid s to methyl amoni iodid hoc benzylamoni clorid + R [R3 N CH3] . I R' N R''+ CH3I
N + CH3I
N CH3]+. I
SO3H
+ [CH 3 N R3 ] .X
HO O
CH N R3
+ H2O + SO2
Cc amin bc nht v cc cht c nhm methylen hot ng cng cho phn ng ny. Phn ng cng hp vi mui kim loi nng: i a s amin d vng v amin bc 3, khi tc dng vi mui kim loi nng to ta; thng dng thuc th HgCl2
Phng php trung ha: - o acid trc tip: p dng cho cc amin c tnh base mnh nh amin mch h. Ch th methyl hoc xanh bromocresol, dung mi cn-nc. - o acid mi trng khan: L phng php ph bin nht. Dung mi hay dng l acid acetic khan, ch tm kt tinh hoc o th, cht chun acid percloric
i vi cc mui ca amin c cc phng php sau:
- nh lng to cp ion: * To cp ion vi ch th acid - base, chit cp ion bng dung mi hu c. nh lng da vo hp th nh sng hoc nh lng trc tip bng cht chun ion.
* Khi thy phn bng acid: xc nh acid to thnh, ct (nu acid d bay hi); hoc chit bng ether ri dng cc phng php nh tnh, nh lng acid tch. xc nh amin, kim ha. Amin bay hi em ct, khng bay hi, chit bng dung mi hu c ri xc nh * Khi thy phn bng kim: Tch amin trc (ct hoc chit ring). Amin bay hi lm xanh qu , nh lng bng chun acid d trong bnh ct. Cc amid c tnh acid:
R NH2 + HONO
R OH + N2+ H2O
2R
Phn ng Biure: Cc hp cht c 2 nhm CONH2 nh sau, trong mi trng kim, tc dng vi mui ng to mui c mu
CONH2 H2NCONH2 ; H2C CONH 2 CONH2 ; HN CONH 2
CONH2 CONH2
O O C NH C
Ha tnh nhm chc imid tng t amid, song tnh acid mnh hn. Cc php th nh tnh, nh lng thng da vo tnh cht ny. V d:
CONHCO + AgNO3
CONAgCO
H2O2 + 2KI
+1 1 00 1
2HCl
+1
H O O H
O H)
Vy, 1 phn t H2O2, tng s oxy ha ca Oxy l - 2, sau phn ng bin thnh - 4, tc l cht nhn 2e (cht oxy ha.
CH2OH HO CH O HO OH
I2
CH2OH HO CHO O O
O+ I
HO C C OH O O
KMnO4
CO2 + Mn2+
HT