Bi tp mn hc Chuyn Ha hc V c

Nguyn Th Huyn Trang-K61CLC Page 1

CHNG 3. KT QU V THO LUN
3.1. IU KIN TNG HP CC PHC CHT
Cc phc cht Na
2
[PtCl
6
], Na
2
[PtCl
4
], [Pt(NH
3
)
4
]Cl
2
l cc phc
cht truyn thng, c nhm nghin cu phc Platin(II) trng i hc S
Phm H Ni tng hp nhiu ln theo phng php c tnh n nh cao, hiu sut
cao. Do chng ti tng hp cc phc cht ny theo cc ti liu [34], [35].
3.1.1. Tng hp H2[PtCl6], Na2[PtCl6] v mui Xayze
Cc cht u H
2
[PtCl
6
], Na
2
[PtCl
6
] v mui Xayze c tng hp theo
phng php m t trong cc ti liu chuyn kho theo cc phng trnh phn ng
sau:
3Pt + 18HCl + 4HNO
3
3H
2
[PtCl
6
] + 4NO + 8 H
2
O
H
2
[PtCl
6
] + 2NaCl Na
2
[PtCl
6
] + 2HCl
Na
2
[PtCl
6
] + C
2
H
5
OH H[PtCl
3
(C
2
H
4
)] + 2NaCl + CH
3
CHO + HCl
H[PtCl
3
(C
2
H
4
)] + KCl K[PtCl
3
(C
2
H
4
)] + HCl
3.1.2. Tng hp phc cht natri tricloroeugenolplatinat(I I ) (P1)
Phc cht P1

ln u tin c tc gi [14] thm d tng hp nm 2009. Sau
khong 30 th nghim khc nhau, c 1 th nghim duy nht tc gi tng hp c
phc vi hiu sut 4%. Nm 2010, bng phng php c o l s dng phn ng
d th ca eugenol v mui Xayze vi t l mol Xayze : eugenol l 1 : 1,2 trong
vng 1h nhit phng, tc gi thu c sn phm P1 vi hiu sut rt cao.
V vy, chng ti cng tin hnh tng hp phc cht P1

theo phng php ca tc
gi khng nh tnh n nh ca phng php ng thi thu c sn phm P1

.
Phng trnh tng hp:
K[PtCl
3
(C
2
H
4
)] + Eug K[PtCl
3
(Eug)] + C
2
H
4

Bi tp mn hc Chuyn Ha hc V c
Nguyn Th Huyn Trang-K61CLC Page 2

Theo phng php ny, nhiu ln chng ti tng hp c phc cht P1 vi
hiu sut khong 90%. iu ny khng nh y l phng php thch hp
tng hp phc cht ny.
Ngoi ra, trong qu trnh tng hp P1,

chng ti cn rt ra nhng ch sau:
- Nu mui Xayze t s lm tng kh nng oxi ha eugenol lm sn phm
khng sch, do thng phi kt tinh li nhiu ln dn n gim hiu sut.
- thu c phc cht P2 sch cn kt tinh li. Dung mi ph hp l hn
hp etanol- axeton vi t l th tch 1:1, cn t l ln hn 1 thu c sn phm c
mu vng nu v nh hn 1 thng kh tch c sn phm.
3.1.3. Nghin cu s to thnh phc cht P2 t phc cht P1
xy ra qu trnh ng vng th mt Cl
-
phi tr phi tch ra cng vi mt
H ca eugenol. Chnh t gi thit , chng ti t ra hng nghin cu: Th nht
phi dng cc tc nhn xc tin cho s tch Cl
-
nh Ag
+
...
u tin chng ti nghin cu tng tc ca phc cht P1 vi AgNO
3

trong dung mi ru nc. Cc th nghim nghin cu c lit k bng 3.1.
Nh bit, AgCl l hp cht rt t tan, ru etylic c tnh baz yu. V vy khi
cho dung dch AgNO
3
tng tc vi phc cht P1, ion Ag
+
v ru etylic xc
tin rt nhanh cho qu trnh tch 2Cl phi t v mt H ca eugenol dn n s to
thnh phc cht khp vng P2.







Bi tp mn hc Chuyn Ha hc V c
Nguyn Th Huyn Trang-K61CLC Page 3

Bng 3.1. Cc th nghim nghin cu s to thnh phc cht [Pt
2
Cl
2
(Eug-
1H)
2
] (P2) do tng tc ca P1 vi AgNO
3
Stt
tn
T l
Eug:Ag
NO
3

Dung
mi
nc:r
u
(th tch)
Nng

dung
dch
AgNO
3

Nhit

(
o
C)
Thi
gian
khuy
(h)
c im
ca sn
phm
Hiu
sut
(%)
1 1:2 7:1 0,12 30 2 Vng nht
2 1:1,1 10:1 0,12 30 2 Vng nht

Mt vn t ra l phi loi AgCl sinh ra c ln trong sn phm. V sn
phm rt t tan trong CHCl
3
, t tan trong axeton. Cn AgCl khng tan trong CHCl
3

v axeton. Chnh v th, chng ti tm c h dung mi tch AgCl l clorofom.
Sn phm tan trong h dung mi chn, tuy nhin rt km v phi dng lng
ln dung mi ho tan sn phm. AgCl mt phn tch ra lng xung, cn mt
phn dng l lng. em li tm hn hp tc 4000 vng/pht trong 30 pht.
Sau em lc thng, dung dch thu c c mu vng xanh. Kt lun AgCl
c loi ht.
3.1.4. Nghin cu tng tc gia P2 vi 8HOQ
Ha 0,05 g (0,06 mmol) hai nhn vo 5ml axeton. (1)
Ha tan 19,14 mg 8-HOQ ( 0,132 mmol) vo 3 ml axeton (2)
Nh t t (2) vo (1) thy cht rn trong dung dch (1) tan dn to ra dung
dch mu trong sut mu vng cam.
Sau 15 pht, phi t c nh xong. Khuy 2h na. t lnh 2h thy xut
hin tinh th vng cam. Lc, ra bng dung dch axit clohiric long v ancol lnh.
Sn phn thu c k hiu P3. Hiu sut 60%. Sn phm tan tt trong clorofom v
axeton).
Bi tp mn hc Chuyn Ha hc V c
Nguyn Th Huyn Trang-K61CLC Page 4


3.2. NGHIN CU THNH PHN CA PHC CHT.
3.2.1. Phng php ph hng ngoi
Chng ti o ph IR ca tt c cc phc cht nghin cu. quy kt ph
IR, chng ti da vo ti liu tham kho.
Hnh 4. Kt qu o ph

IR ca phc cht P3.



Bng 3.3: Cc vn hp th chnh trn ph IR ca cc phc cht (
1
cm

)
K
hiu

OH

NH

CH
(thm,
anken)

CH
(bo)

NH,

C=C

2
CH no

C-O,
C-C, C-N

CH
thm

Pt-
N

Pt-
C=C

P7

3363 - 3065
2937
2845
1580

1495
1464
1275;
1148
1047
826
534
640
456
Bi tp mn hc Chuyn Ha hc V c
Nguyn Th Huyn Trang-K61CLC Page 5


Xut hin mt tn hiu 3363 cm
-1
c trng cho dao ng ha tr ca nhm
OH. y c th l OH ca eugenol hoc ca 8- hidroxylquinolin hoc ca c hai
phi t.
P3 cha amin d vng nn khng xut hin vn c trng cho dao ng NH,
Tuy nhin s xut hin vn hp th trong vng 534640 cm
-1
c trng cho dao
ng ha tr ca lin kt Pt-N, l du hiu cho thy, cc phc cht ny phi t
amin phi tr vi Pt(II) qua N.
Vn hp th yu tn s 3000 3077 cm
-1
ng ha tr ca
CH (thm)
v
CH
(anken)
. Tuy nhin, vic qui kt rch ri ngun gc cc vn hp th l rt kh v
dao ng ha tr CH thm v CH anken thng th hin vi cng rt yu, c
tn s khc nhau t, chng li d b che lp bi bi cc vn c cng mnh bn
cnh
Vn hp th c cng trung bnh 2834 2960 cm
-1
c trng cho dao
ng
CH (no)
ca eugenol hoc metyleugenol trong cc phc cht
Vn hp th c trng cho dao ng ha tr C=C ca nhnh anlyl Eug t
do th hin tn s khong 1620 1670 cm
-1
. Trn ph IR ca cc phc cht u
khng thy xut hin vn c trng C=C ca nhnh anlyl tn s ny m thay vo
l 1 vn vi cng mnh tn s thp hn, 1580 cm
-1
. Vn hp th ny
trng vi vn hp th
C=C
ca vng benzen (16001500 cm
-1
) . V th, vic qui
kt ring r
C=C thm
v
C=Canken
l kh khn nhng r rng s gim tn s ca lin
kt C=C ca nhnh anlyl so vi dng t do chng t Eug phi tr vi Pt(II)
qua lin kt i C=C ca allyl trong phc cht P3.
Vn hp th vi cng mnh 1464 1495 cm
-1
v mt vn yu tn s
khong 1376 cm
-1
. y l cc vn dao ng bin dng ca nhm CH
2
no v CH
3
.
Bi tp mn hc Chuyn Ha hc V c
Nguyn Th Huyn Trang-K61CLC Page 6

Vng ph 1025 1281 cm
-1
xut hin mt vi vn hp th c cng
mnh c trng cho dao ng ha tr ca lin kt n C-C, C-O, C-N ca Eug v
amin. Tuy nhin chng ti khng ch r c tn s no ng vi tng loi lin kt,
bi tn s c trng cho cc lin kt C-C, C-O, C-N bin i mnh v khc nhau
khng nhiu.
tn s thp hn khong 422 - 505 cm
-1
c vn hp th trung bnh c
trng cho dao ng ha tr ca lin kt Pt-(C = C). Nh vy s xut hin cc vn
hp th ny mt ln na chng t s to phc ca platin(II) vi ni i C = C
nhnh anlyl.
3.3.2. Phng php ph cng hng t proton (
1
H NMR):
Ph cng hng t ht nhn l phng php hu hiu nghin cu cu trc
ca cc phc cht. Chng ti o ph
1
H NMR ca phc cht P3.
Hnh 4. Kt qu o ph
1
H NMR ca phc cht P3
Bi tp mn hc Chuyn Ha hc V c
Nguyn Th Huyn Trang-K61CLC Page 7


tin qui kt tn hiu cng hng ca cc proton, chng ti k hiu cc
proton ca Eug nh sau:


Bng 3.4: Tn hiu cc proton ca eugenol dng t do v phi tr trong phc cht
nghin cu (ppm); J(Hz).
Cht
H8a
H8b
H9 H10trans H10cis OH H3 H5 H6
H7a
H7b
Bi tp mn hc Chuyn Ha hc V c
Nguyn Th Huyn Trang-K61CLC Page 8

Eug

3,29

5,94

5,05


4,99

7,30 6,78 6,63 6,76 3,81
P3

3,33

5,31


4,09


4,06

Cha
r
8,98 7,61 7,56 4,21

H9 do tng tc spin spin vi H8a, H8b, H0cis, H10trans nn tn hiu ca
n theo l thuyt l 16 hp phn. Trn ph
1
H NMR ca Eug t do n th hin
5,94 ppm, cn trong P3 n th hin 5,31 ppm.
H10cis v H10trans do khc nhau v tnh cht t nn khc nhau v chuyn dch
ha hc. phn bit c chng, chng ti da vo tng tc spin- spin, c
trans > cis: Trn ph ca Eug t do H10cis l vn i c dch chuyn ha hc
( ) th hin 4,99ppm H10trans th hin l vn i i 5,05ppm. phc cht
P3, tn hiu H10cis l mt vn i 4,06ppm v H10trans l vn i 4,09 ppm.
Hai nguyn t H8 trong Eug tng ng nhau, chng tng tc spin-spin
vi H9 nn H8 th hin l mt vn i 3,29ppm , trong phc P3 th hai nguyn t
H8 cho tn hiu ca H8 l vn i i 3,33ppm
Qua bng 3.4 cho thy, i vi phc cht cha Eug (P3), chuyn dch ha
hc ca H9 khi to phc gim t 5,94 ppm xung cn 5,05 5,6 ppm v chuyn
dch ha hc ca H10cis v H10trans t do ln lt l 4,99 v 5,05 ppm gim
xung. iu ny chng t Pt tham gia phi tr vi lin kt i C=C ca nhm
allyl.
phn t eugenol c mt nhm OH, do proton ca nhm ny gn vi O c
m in ln v khng tng tc vi bt k proton no nn trn ph ca Eug t
Bi tp mn hc Chuyn Ha hc V c
Nguyn Th Huyn Trang-K61CLC Page 9

do n th hin l mt vn n vi kh ln 7,30ppm. phc cht P3 cha phi
t l 8- hidroxylqiunolin nn y cng c th l nhm OH ca 8- hidroxylqiunolin.
Proton H7 do khng tng tc spin - spin vi proton no nn d dng nhn ra tn hiu
ca n l mt vn n, cng ng vi 3H.
Proton H3 tng tc vi H5 nn tn hiu ca H3 c dng mt vn i vi hai
nh rt gn nhau trong phc cht P3, H3 l vn i th hin 8,98ppm.
Trn ph ca P3 tn hiu ca H5 l vn i i 7,61
T bng 3.4, chng ti nhn thy khi phi tr vi Pt(II) th chuyn dch
ha hc ca H3, H5, H6 ca eugenol tng ln ng k. eugenol t do,
H3
>
H6
>

H5
, cn tt c cc phc cht u c s o v tr cng hng
H3
>
H5
>
H6
.
Nguyn nhn l khi phi tr vi platin(II), electron chuyn dch mnh v pha platin
lm cho nhnh anlyl tr thnh nhm ht electron khi vng thm, do mt
electron u gim tt c cc v tr trong vng thm, trong v tr 6 gim t hn
v tr 5.
3.3.3. Ph
13
CNMR cua cc phc cht


Bng 3.6: Tn hiu
13
C NMR ca eugenol trong cc phc cht (ppm)
Cht C1 C2 C3 C4 C5 C6 C7 C8 C9 C10
P3

146,03 146,79 114,51 131,43 122,83 115,30 55,94 38,15 109,21 80,34

KT LUN
Sau mt thi gian nghin cu chng ti t c mt s kt qu nh sau:
tng quan c tnh hnh tng hp, nghin cu cu to, tnh cht ca
phc Pt(II) cha phi t eugenol v 8-HOQ
Bi tp mn hc Chuyn Ha hc V c
Nguyn Th Huyn Trang-K61CLC Page 10

Tng hp cc phc cht K
2
[PtCl
6
], K
2
[PtCl
4
], [Pt(NH
3
)
4
]Cl
2
sch vi
hiu sut cao
Bng thc nghim khng nh rng, s dng phn ng d th ca eugenol
v mui Xayze l phng php c tnh n nh v thch hp tng hp
phc cht K[PtCl(Eug)].