HA HC D VNG

N
S

DANH PHP CC HP CHT

D VNG

Heterocyclic Chemistry
GVC. : PGS. TS. NG VN HOI

DANH PHP CC HP CHT D VNG

C 3 h thng tn hp cht d vng:
1) Tn thng thng: din t mt t hoc khng c
thng tin v cu trc, nhng vn c dng rng ri.
2) The Hantzsch-Widman (IUPAC hoc h thng)
phng php cho bit tn c th suy lun ra (deduce)
cu trc ca hp cht.
3) Phng php thay th

GVC. : PGS. TS. NG VN HOI

I- Danh Php thng thng

1)

Cn thuc tn thng thng. Tn thng thng thng

bt ngun t hp cht ln u c iu ch hoc t tnh

cht c bit ca n.

2) Nu c nhiu hn mt d t ging nhau, nh s bt

u t mt d t c bo ha, v d: imidazole.
N3

5
1

N
H
GVC. : PGS. TS. NG VN HOI

Danh Php thng thng

3) Nu c nhiu hn mt loi d t khc nhau, vng
c nh s bt u t d t u tin hn (O>S>N) v
nh s tip tc theo hng d t khc c s ch v tr
nh c th.
Br
4

5
H 2N

3
1
O

GVC. : PGS. TS. NG VN HOI

Danh Php thng thng

4) Nu c nhng nhm th, v tr nhm th nn
c xc nh bng s ca nguyn t mang
chng v c sp xp theo th t alphabet.

Br
4

5
H 2N

3
1
O

5 -A m ino -4 -b ro m o isox a zole

GVC. : PGS. TS. NG VN HOI

Danh Php thng thng

5) Nhng t dihydro, hoc trihydro, hoc tetrahydro
c dng nu 2 hoc 3 hoc 4 nguyn t c bo
ha. Nhng t ny c t trc bi cc s ch v tr
nguyn t bo ha nh c th, v c theo sau bng
tn thng thng khng bo ha y .
H
N

1 ,2 - D i h y d r o - p y r i d i n e
GVC. : PGS. TS. NG VN HOI

Tn thng thng
1) D vng 5 cnh vi 1 hoc 2 d t

2) D vng 6 cnh vi 1 hoc 2 d t

Common azines-six-membered aromatic nitorgrn heterocycles
N

N
O
2H-Pyran

O
4H-Pyran

These are tautomers

Both are not aromatic

N
Pyridine

Pyridazine

N
Pyrimidine

N
Pyrazine

DNA/RNA bases

GVC. : PGS. TS. NG VN HOI

Tn thng thng
3) Nhng d vng ngng t
O
N
N

NH
N
Guanine

GVC. : PGS. TS. NG VN HOI

NH2

Tn thng thng

Coumarine
Chromen-2-one

1
2

Ph

Flavone

Chromen-4-one

7
2
8

9
N

6
5

10
N
4
H

9,10-Dihydro-acridine
9H-Carbazole

GVC. : PGS. TS. NG VN HOI

Tn thng thng
4) Cc d vng bo ha

Bi tp :
Cho tn thng thng ca cc hp cht sau y:
N
O

H2N

CH3

H
N

NH

GVC. : PGS. TS. NG VN HOI

II-Danh Php thay th

Trong danh php thay th, tn ca d vng c t tng ng vi
vng carbon v mt tip u ng ca tn nguyn t d vng (nu c
hn 1 d t th c lit k theo th t u tin xem (table 1). Theo
danh php ny, tetrahydrofuran, chng hn, c c l
oxacyclopentane.

Table
1
Atom
O
Se

Prefix
oxa

u tin gim dn

selena

thia

aza

phospha

GVC. : PGS. TS. NG VN HOI

Tn ca hp cht sau, t theo phng php thay th?:

1) Tn tng ng ca vng carbon?

2) Tip u ng ca d t (hp cht c O= oxa

N=aza)

Oxa aza cyclopentadiene

3) S ca tt c d t v lin kt i

GVC. : PGS. TS. NG VN HOI

GVC. : PGS. TS. NG VN HOI

II-- Danh Php thay th

II

GVC. : PGS. TS. NG VN HOI

II-- Replacement nomenclature

II
Thiacyclohexane

cyclohexane
S
8
7
6

8a

4a

1
2

1
2

naphthalene

4H-4a-azanaphthalene

4a 4

1,4-dithianaphthalene

naphthalene
S
2 1

cyclododecadiene

N O
O N
7

1,7-Dioxa-2,8-diazacyclododeca-2,8-diene

GVC. : PGS. TS. NG VN HOI

III-- Danh Php Hantzsch

III
Hantzsch--Widman (IUPAC
(IUPAC)
)
Danh Php Hantzsch-Widman c t tn sau khi hai nh
ha hc ngi c Hantzsch v Oskar Widman, xut
cc phng php ging nhau t tn h thng tng
ng cho cc hp cht d vng vo nm 1887 v 1888.
Theo h thng ny nhng vng t 3 n 10 nguyn t
c t tn bng cch kt hp prefix thch hp (hoc
prefixes) m biu th (denotes) loi v v tr ca s c mt
d t trong vng vi suffix xc nh va kch thc vng
(ty thuc tng s cc nguyn t trong vng) v mc
cha bo ha (lu rng bo ha y v cha bo ha
y c nhng quy tc nht nh cho danh php trong
khi s cha bo ha tng phn s c ch nh trong
nhng cch nht nh). Hn na, suffixes phn bit gia d
vng c nitrogen-N v d vng khng c nitrogen
Tn IUPAC = locants +Prefix + suffix

GVC. : PGS. TS. NG VN HOI

Quy tc Hantzsch
Hantzsch--Widman i vi cc d vng bo ha
hon ton hoc cha bo ha hon ton
1) Xc nh d t c mt trong vng v chn t (table 1
slide 11) tng ng vi prefix (v d: thia cho sulfur, aza
cho nitrogen v oxa cho oxygen).
2) V tr ca mt d t ring l quy nh s trong hp cht c 1
vng. D t lun lun c nh s 1 v nu cc nhm th
c mt trong vng s c nh s theo cch sao cho v tr
nhm th nh c th.
v d:
4

N1
2

CH3
GVC. : PGS. TS. NG VN HOI

Quy tc Hantzsch
Hantzsch--Widman
3)

Mt tip u ng (A multiplicative prefix: di, tri, ect.) v

locants c dng khi hai hay nhiu d t ging nhau
trong vng ( hai nitrogen l diaza) v nh s bt u
t nguyn t bo ha hn h nguyn t cha bo ha,
nh c m t (depicted) trong v d: 1,3-diaza.
4

2
1

N
H

4) Nu nhiu hn mt loi d t c mt trong vng th tn

s bao gm nhiu hn 1 prefix vi locants xc nh v tr
ca cc d t.
Prefixes nguyn t nguyn t c th t u tin nghim
ngt theo th t c lit k. V d:,Oxa(i vi
oxygen) lun lun ng trc aza (i vi nitrogen)
(xem table 1).
Khi kt hp nhiu prefixes (v d: oxa v aza) hai nguyn
m i cng nhau, th nguyn m ca prefix u c b i
(oxaza).
GVC. : PGS. TS. NG VN HOI

Quy tc Hantzsch
Hantzsch--Widman
nh s bt u t d t u tin cao nht ri tip tc theo
vng n cc d t khc sao cho s nh c th (cc nhm
th khng lin quan). V d prefix tng ng i vi hp
cht sau 4-Methyl-1,3-Thiaza.
4

N3

2
1

5)

Chn suffix thch hp t (table 2) ty thuc cho d khng

c mt nitrogen trong vng, kch thc vng v s c
hoc khng c lin kt i

6)

Kt hp prefix(s) v suffix cng nhau v b nguyn m

u nu hai nguyn m cnh nhau.
GVC. : PGS. TS. NG VN HOI

Quy Tc Hantzsch
Hantzsch--Widman
Table 2
Ring size

N-present

N-absent

Unsat

sat

Unsat

sat

irine

iridine

irene

irane

ete

etidine

ete

etane

ole

olidine

ole

olane

ine

in

ane

epine

ocine

onine

10

ecine

epin

epane

ocin

ocane

onin

onane

ecin

ecane

GVC. : PGS.
TS. NG
a: means use the prefix perhydro followed
by the
fullyVN HOI
unsaturated name

Quy Tc Hantzsch
Hantzsch--Widman
V d
H
N

Vng c nitrogen (N)

Prefix l aza
Vng 3-membered v bo ha
suffix l iridine
Kt hp prefix v suffix, hai nguyn m (azairidine), v
th nguyn m ca prefix b b i. Tn ng s l:
Aziridine

GVC. : PGS. TS. NG VN HOI

III-- Danh Php Hantzsch

III
Hantzsch--Widman (IUPAC)

V d 2:

Vng c nitrogen = azaV c oxygen = oxaVng 4-membered bo ha

Vng = -etidine
B nguyn m trong oxa & aza
Tn = 1,2-Oxazetidine
GVC. : PGS. TS. NG VN HOI

III-- Danh Php Hantzsch

III
Hantzsch--Widman (IUPAC)

V d 3:

Vng c nitrogen = azaVng c oxygen = oxaVng nm c nitrogen = ole

Oxygen u tin hn nitrogen, nn
Oxygen c s v tr l 1.
Hai nitrogens c v tr 2 v 5
Tn = 1,2,5-Oxadiazole
GVC. : PGS. TS. NG VN HOI

III-- Danh Php Hantzsch

III
Hantzsch--Widman (IUPAC)

V d 4:

Vng c sulphur= thiaVng c oxygen = oxaVng 5 bo ha, khng nitrogen = olane

Oxygen c u tin hn sulphur, do
Oxygen c nh s 1.
B nguyn m trong thia
Tn = 1,3-Oxathiolane
GVC. : PGS. TS. NG VN HOI

Quy Tc Hantzsch
Hantzsch--Widman

N
H

Vng 6-memberd, bo ha c nitrogen N

Prefix perhydro c theo sau bng tn ca vng 6-memberd cha
bo ha c nitrogen N
azine
V th, tn y l: perhydroazine

GVC. : PGS. TS. NG VN HOI

Quy Tc Hantzsch
Hantzsch--Widman
Bi tp:
Gii thch cch xc nh tn ca cc d vng sau:
Br
N
O
O

GVC. : PGS. TS. NG VN HOI

Quy Tc Hantzsch
Hantzsch--Widman i vi cc
d vng cha bo ha hon ton
S cha bo ha hon ton trong cc hp cht
d vng c th c xc nh bng 1 trong
nhng phng php sau:
a) V tr ca nitrogen hay carbon c cc nguyn t
hydrogen, phi c xc nh bng s v ch hoa
nghing H (v d: 1H, 2H, ...) theo sau l tn ca
vng cha bo ha hon ton.
4
5

3
2
O
1

2H, 3H-Oxole

1
N
H
1H-Azepine

3N 4
2S 1 5
O
5H-1,2,3-Oxathiazole

4
5
6

1
O

3
2

4H-Oxin

GVC. : PGS. TS. NG VN HOI

Quy Tc Hantzsch
Hantzsch--Widman i vi cc
d vng cha bo ha hon ton
b) Nhng t dihydro, hay trihydro, hay tetrahydro
c dng nu 2, 3 hay 4 nguyn t c bo ha.
Nhng t ny c ng trc l cc s ch v tr ca
nguyn t c bo ha, s nh c th, v c
theo sau l tn tng ng y theo quy tc
Hantzsch-Widman.
4
5

4
3

N
H

N
H

1,2-Dihydroazine

1,4-Dihydroazine

Isomers have the same M.F.

but differ in the position of
the double bond

2,3,4,5-Tetrahydroazine

2,3-Dihydrooxole

GVC. : PGS. TS. NG VN HOI

Quy Tc Hantzsch
Hantzsch--Widman i vi cc
d vng cha bo ha hon ton
c) Ngoi ra, nhng vng 4 v 5 cha bo ha
hon ton (ngha l: cc vng c 1 ni i)
c cho suffixes Hantzsch-Widman c bit
nh trong table 3 v lin kt i c quy nh
l 1, 2, 3, ... Ci m ch ra nguyn t 1 ; 2
v 3; c 1 lin kt i tng tng
(ngha l tn : x + Prefix + special suffix )
( x= v tr lin kt i)
Table 3
Ring size

With N

Without N

-etine

-etene

-oline

-olene

GVC. : PGS. TS. NG VN HOI

Quy Tc Hantzsch
Hantzsch--Widman i vi cc
d vng cha bo ha hon ton
V d

HN

2
1

HN

-Oxetene

-Azetine

N
H

-Azoline

2 -Oxolene

NH

4
2

5
1

S
4

-1,3-Thiazoline

5
1

N
H

2 -1,3-Diazoline

GVC. : PGS. TS. NG VN HOI