Khoa hoc TU nhien i
Ph6 ^H NMR cua day phu-c chit [PtCl(eugenol-lH)(amin)]
(amin: pyridin, 4-Me-pyridin, quinolin, p-cloanilin, p-toluidin)
TruoTig Thiiy HSng, Nguyen Thi Thanh Chi' Khoa Hoa hoc. Tnr&ng Dai hoc Sirphgm Ha Ngi
Ngay nhan bai 7/10/2019; ngay chuyen phan bien 10/10/2019: ngay nhan phan bien 8/11/2019; ngay ch5p nhan dang 12/11/2019
Pho 'H NMR cua nam phirc chat co cong thuc |PtCl(eugenol-lH)(amin)| [amin: pyridin (2), 4-Me-pyridln (3), quinolin (4), p-cloanilin (5), p-toluidin (6)] trong dung moi rf^-axeton va CDCI, da duffc nghien ciru. Kk qua cho thay, trong dung m6i rf,-cloroforni cac phirc chat 2-^-5 cho hai bd tin hieu on dinh theo thoi gian irng vol hai tu'OTig tac lien phan tu manh (hen kit hydro CI3C-H... ClPt(II) va liln ket halogen Cl3HC-CI...Pt(II)) d6i v ^ 2, 3, 4 va hai lien k^t hydro manh (liln kk noi phan tis NH,...Cl-Pt(II) va lien kk lien phan tu CljC-H.-.d-anilin) dSi vol phirc chat 5. Trong khi do, trong dung moi </^-axeton phuc chat 5 va 6 co chua cac dan xuat ciia anilin, xay ra sir dong phan hoa nhom amin chuyen tir vi tri cis sang vj tri trans so voi nhanh allyl cOa eugenol. Qua trinh chuyen doi nay dat den trang thai can hang sau 48 gicf.
Tie khoa: amin, eugenol, 'H NMR, lien ket halogen, phiic chat ciia platin(H).
Chi so phdn loai: 1.4
Mdd^u
Tir lau, platin va phiic chat ciia no dugc biet den voi nhieu irng dung quan trpng, dien hinh la xiic tac trong tong hop huu CO [1] va thuoc dieu tri ung thu trong y hoc [2, 3].
0 Viet Nam co nhieu loai cay cho tinh dau voi ham lupng arylolefin rat 1cm nhu tinh dau huong nhu chua khoang 70% eugenol (EugH)... Mot so dan xuat ciia no nhu metyleugenol, ankyl eugenoxyaxetat (ankyl la metyL etyl, n-propyl) dupc biet den la nhung hpp chat co cac boat tinh sinh hpc khac biet: dan du ruoi vang hai cam, kich thich sinh truong 6 thuc vat...[4]. G^n day, cac arylolefin nay da dupc hoat hoa lien ket C-H thom trong c§u ph6i tri ciia Pt(ll) duoi dang cac phiic chat khep vong hai nhan dang [PtCI(arylolefin-IH)]^ [5-7]. Phan ung giira phiic chSt khep vong hai nhan nay vai cac amin kliac nhau da tao ra mot s6 day phiic chat don nhan co cau tnic thii vi voi cong thiic chung [PtCl(arylolefin-]H)(amin)] [5-9]. Tuy nhien vai day phiic chat o do arylolefin ia eugenol co hien tupng bdt thuong, do la pho 'H NMR ciia mot so phuc chat trong chiing cho 1 bp tin hieu trong dung moi rf^-axeton, con trong CDCI3 iai cho 2 bp tin hieu [8]. Do vay, trong cong trinh nay chiing toi tap trung nghien cuu pho 'H NMR ciia 5 phiic chat [PtCl(Eug)(amin)] (amin: pyridin (2), 4-Me-pyridin (3), quinolin (4),/>-cloanilin (5), p-toluidin (6)) trong dung moi (s/^-cloroform va t/^-axeton de tim loi giai thich cho hien tupng bat thuong nay.
ThiA nghrem Hoa chat
Cac amin dupc su dung gom pyridin, 4-Me-pyridin, quinolin, p-cloanilin, p-toluidin ciia hang Sigma - Alrich.
Cac dung moi axeton, etanol ciia Trung Quoc.
Tong hop cdcphuv chdt
Cac phiic chat 2-^ dupc tong hop tu phirc chat dau [PtCI(Eug)]j (1) dua theo phuang phap dupc mo ta trong tai lieu [8] nhu sau: nlio tir tir dung dich chiia 0,2 mmol amin vao 0,1 mmol phuc chat 1. Phan irng dugc thuc hien trong axeton (4) hoac hon hpp hai dung moi axeton - etanol (2, 3, 5, 6) a nhiet do phong. Sau 2 gio phan ling Ipc thu dupc san pham ket tua doi voi 2 hoac thu dupc dung dich ciia cac phii'c chat 3-^6. Bay hoi cham dung moi ciia dung dich thu dupc cac chat ran 3-^6, rira san pham bang HCI, etanol lanh va say kho. Cac phiic chat thu dupc co mau vang vai sac do khac nhau voi hieu su4t cao 81 % (2), 92% (3), 95% (4), 50% (5), 83% (6)
Phu'Ong phdp nghien ciru cdu tnic
Pho cong huong tir hat nhan cua cac phiic chat dugc do tren may Bruker AVANCE (500 MHz) voi chk chuSn ta TMS trong cac dung moi thich hop tai Vien Hoa hoc thuoc Vien Han lam Khoa hpc va Cong nghe Viet Nam.
*Tdc gid lien he chin!I@hni
InMGNGHEViNam'
^H NMR spectra of a series of complexes [PtCl(Eugenol- lH)(amine)] (amine: pyridine,
4-Me-pyridine, quinoline, p-cloaniline, p-toluidine)
Thuy Hang Truong, Thi Thanh Chi Nguyen*
Faculty of Chemistry, Hanoi National Umversiiy of Education Received 7 October 2019; accepted 12 November 2019 Abstract:
The 'H NMR spectra of five complexes of the genenal formula [PtCI(eugenol-lH)(amine)l (amine: pyridine (2), 4-Me-pyridine (3), quinoline (4), p-cloanlline (5), p-toluidine (6)) in rf^-acetone and CDClj solvents were studied. The result showed that in </,-chloroform, Complexes 2-^5 gave t>vo stable over time sets of signals which corresponded with two existence forms of the complexes in the solution: two strong intermolecular interactions (Cl3C-H...CIPt(II) hydrogen bond and CljHC-Cl...Pt(H) halogen bond) for 2, 3, 4; and two strong hydrogen bonds (NHj...CI-Pt(II) intramolecular bond and CljC-H.-.d-aniline intermolecular bond) for 5. Meanwhile, in f/^-acetone solvent, complexes containing aniline derivatives, 5 and 6, revealed an isomerization, that was, the amine group transferred from cis position to trans position compared with the ally! group of eugenol. This conversion process reached an equilibrium after 48 hours.
^^vwords: amine, eugenol, halogen bond, 'H NMR, piatJnum(II) complexes.
^Classification number: 1.4
Ket qua va thao luan
Viec thay M etylen trong mu6i Zeise K[PtCL(C,H^)]
bang eugenol (EugH) da tao ra phirc chdt K[PlCl3(EugH)].
Phirc chat nay co the dl dang chuygn thanh phiic chat kliep vong hai nhan [PtCl(Eug}], (1) trong dilu kien em diu [8].
Trong nghien ciru nay, phiic chit 1 tuong tdc voi cac amin dl vong khac nhau trong cac di6u kien thich hpp (de cap a phan T6ng hap cac phiic ch4t) da thu dupc cac phirc chat trung hoa don nhan 2-^6 nhu dupc chi ra trong hinh 1.
'•y'" " ^ "QQ" " ^ '
Hinh 1. So- do tong ho-p cac phirc chat 2 - 6 va cau true ciia cac amin (s6 chi vi tri trong Eug va amin dung cho viec phan tich pho ' H NMR)-
Cia triic cua cac phiic chat 2-^6 da dupc chung minh bang phan tich nguyen t6, ph6 IR, ESI-MS, 'H NMR va phuang phap XRD (doi vai 2, 3, 6) trong tai Heu [8]. Kel qua cho thdy, trong cac phirc chat nay, Eug phoi tri vai Pt(ll) qua Cg=C cua nhanh allyl va C5 ciia vong benzen, amin phoi tri voi Pt(ll) quaN va o vi tri c/5 so voi nhanh allyl nhu o hinh 1. Tuy nhien, dieu dac biet la tren pho 'H NMR, bon phirc chat 2-^5 cho hai bp tin hieu khi do trong CDCIjVa cho mot bp trong is'^-axeton, trong khi 6 cho mot bp khi do trong ca CDCL va <:/_j-axeton. Su bat thudng nay buoc dau dupc ly giai CO the do trong dung moi CDCL ton tai 2 tuong tac lien phan til' hydro va halogen manh giiJa dung moi va phuc chat nen 2-^5 ton tai dual 2 dang trong dung dich [8]. De lam ro van de nay, truoc het chung toi quy ket, phan tich pho do trong CDCL tai thai diem moi pha cua 2-^6 (pho cua chung trong axeton da dupc phan tich [8]). Cac tin hieu proton cua Eug va amin trong cac phirc chat 2-^6 dugc liet ke a bang I.
Hinh 2 dan ra mot phan pho cua 5 trong dung moi CDCl^ va
£/,-axeton lam vi du.
(A) (B) Hinli 2. Mot phan pho ^H NIMR cua 5 do trong CDCI^ (A) va trong
dj-axeton (B)
(dau • la tin hieu v^ linh do '-^Pt gay tach).
IHSSJIdSiViNam^^'^'^-^''^"
Khoa hoc TU nhien i
Bang 1. Tin hieu ^H NIVIR cua 2 ^ do trong CDCI3 5 (ppm), J^^ (Hz).
H3 H3 H6 H7 OH
HSa
H8b
H9
HlO/roni
HlOcu HI2 HI3 HI4 HI5 HI6 HI7
Hkhac Eugenol (EugH) 19|
6,78 d 6.63 dd 6.76 d 3,81s 7,30 5
3,29 d
5.94 m
5,05 dd
4,99 d
|PtCI(Eue) (Py)l (2b/2a) I n t l / l 6,57s/6,64s
5,8lsV^45/7,12sV„„4:^
3,80s/3,Sls 5.26 s/5.27 s 2.65 dVp„ 109/
2.82 d V ^ 104 3,86dd/3,86dd 4,65 oW 5,56my^,72 3,97dVp,p73/
4,16 d y ^ 65 3,65d-Jp^,71/4.63ov 8,81 dd/8,71 dd 7,49ov/7.47ov 7,94tt/7,83t[
7,49 ov/7,47 ov 8,81 dd/8,71 dd
|PtCI(Eug) (4MePy)| (3b/3a) I n t 1.3/1
6,64s/6,57s
5,82 sVp,„ 45/7,12 sVp,, 3,81 s/3,79 s 5,28 s/5,26 s
2,82 d V ^ , 90/2,63 d V ^
3,85ov/3.8ov
5,52 mVp^, 72/4,62 mUj
4,13dUp^68/3,94d'4
4,59dV^7l/3,63d=J„, 8,62 d/8,53 d 7,27 d/7,25 d
7,27 d/7,25 d S,62 d/8,55 d 2,43 $12,4\ s
,45
,90
J2
,68
f™
[PtCI(Eug) (Qui)I (4b/4a) I n t 2/1 6.61 E/6,63 S
7,25 E/7,22 S
3,82s/3,77s 5,29s/5,29s
2,66 dVp^ 95/2.90 dVp^, 95
3.91 dd/4,(l4 ov
4,57 m ^,,^,,70
3,57ovy,,,i,71/4,86ov
3,72dy^75/5,14ov 9,O5dd/7,90dd 7,53 dd/7,49 br g,34d/S,3ld 7,54d/7,99br 7,68 ni/7,74 br 7,91 ov HIS; 9,21 br/7,99br
[PtCKEug) (p-CIAni)l (5b/Sa) Inf. 1/1
6,48 s/6.53 s
7,I4br/7,l5br 3,76 s/3.77 s 6,80 br/6,82 br
2 . 4 2 d \ „ l 0 2 / 2 , 5 7 d ' i ^ l 0 2
3,59 dd/3,72 dd
4 , 1 4 r D \ , | 7 5 /
3,96;d^J„„7l/3,49;d
3,39 d'l,^, 75/4,28 d^lp^ 75 6,99 d 7,31 d
7,31 d 6,99 d
H'(N) 4,59 d/4,86 d H W 4 . 8 6 d / 5 . 0 8 d
IPtCi(Eug) {p-To[)| (6)
6,49 s
7,03s'Jp,j,4l 3,76 s 5,25 s
2,42d=]^,ll0
3,44 dd
4 , t l n i \ J 5
3,67 d
3,41d-Jp,„75 6,91 d 7,14 d
7,14 d 6,9! d 2,34 s HtN). 4,35 d H'(N), 4,68 d
Jnl: ty le cirang do ciia 2 bg tin hieu.
Bang I cho thay, 6 chi cho 1 bp tin hieu trong khi 2-5 cho 2 bp dupc ky hieu la a va b, so lupng cung nhu hinh dang cac tin hieu a 2 bp la nhu nhau. Tin hieu cong huong ciia cac proton trong 2-^ do trong CDCl^ co dac diem tuang tu nhu do trong i^'^-axeton. Cu the ia, hai proton H8 a eugenol tir do von la mot van doi a 3,29 ppm nhung tren pho 'H NMR ciia cac phii'c chat, chung the hien bai hai tin hieu rieng biet dupc gpi la HSa co dang van doi o 2,42-^2,90 ppm va H8b CO dang van doi-doi o 3,44-^4,04 ppm. Ben canh do, so voi EugH tu do tin hieu cong huong ciia cac proton H9, HI Qcis, H10/ra«5 deu thay doi ca ve do chuyen dich hoa hpc (giam manh vol AS = 0,38-^1,83 ppm) va hinh dang (xuat hien tin hieu ve tinh voi gia tri -Jp,^, = 65-73 Hz). Dieu nay cho thiy Eug da ph6i tri voi Pt(II) qua C=C^|,^|. Su ph6i tri cua Eug voi Pt(n) qua C5 dupc the hien ro 6 su vang tin hieu cua H5 tren pho ciia 2-^6, dong thoi H3 va H6 deu co dang van dan trong khi a dang tu do chiing co dang van doi, con H5 co dang van doi-doi. Dac biet o tin hieu ciia H6 con quan sat thay tin hieu ve tinh do '^^Pt tach voi J =; 43 Hz phii hpp voi
gia tri ^1^,^,. Su thay doi tin hieu cong huong cua cac proton nhanh allyl va tham cua Eug trong 2-^6 so vai a phoi tir tu do cung tuong tu nhu a cac phuc chat co cau tnic tuong dong, [PtCl(arylolefin-H)(amin)] [5-9].
Bang 1 con cho thay xuat hien day dii tin hieu cong huong proton cua cac amin trong cau phoi tri ciia 2-^6 va chiing deu co dp chuyen dich hoa hoc thay doi so vai a cac ammtudo. Dieu nay chiing to cac amin da phoi tri vai Pt(II) trong cac phirc chat. Nhu vay 6 phiic chat 6 cQng nhu o hai dang a va b ciia cac phirc chat 2-^5, eugenol deu phoi tri voi Pt(II) qua C=C^||^| va C5, amin ph6i tri voi Pt(n) qua N.
De khang dmh cau tnic khong gian ciia cac phiic chat 2^6, tiic la khang dinh amin o vi tri cis hay trans so vai nhanh allyl, chiing toi lua chpn do pho NOESY cua 3 trong c/^-axeton va 4, 6 trong CDCL (cac chal co do tan tot hon ca). Tuy nhien, cac chat van co dp tan vira phai trong dung moi do pho nen cac pic giao irng voi bo co cuong dp nho hon ciia 4 trong CDCI^ kho quan sat. Bang 2 liet ke cac pic giao giira tin hieu cong huong ciia Eug va amin tren pho
KHOA HOC
l&NGNGHE
M lam 62(3) 3.2020
NOESY ciia cac pMvc chat va hinh 3 din ra mot phjn ph6 cua 4 trong CDCUam vi du.
ph6 NOE^SY c i a a ^ ' J V " '"^" " ' " ^ ^"""^ "" ^"^ "' ""'" " ™
Pic giao giira Eug v^ a.
H9/HI2(4,76/8,60ppm) H10c«/H12 (3,75/8,60 ppm) H9/H12 (4,54/9,05 ppm) H10c«/H12 (3,72/9,05 ppm) HI Oli-ans/H'(t^ (3,96/4,35 ppm)
Bang 2 cho thay giua cac tin hieu cong huong cua Eug va amin, chi co pic giao giifa tin hieu H9, HlOc/5 ciia Eug vai H12 cua 4MePy trang 3 va HI2 ciia Qui trong 4 (pic giao A va B trong hinh 3), con vai phirc chat 6 chi co pic giao cua
\i\Qlrans voi ff(N) ma khong quan sat thay pic giao nao khac. Ket qua nay cho thiy, trong dung dich do phd, amin khong phai o vi tn trans so voi nhanh allyl trong cac phiic chat ma phai 6 vi tri cis giong nhu cau tnic o dang ran ciia chiing da dupc xac dinh biing phuong phap nhilu xa tia X don tinh thi [8] nhu chi ra o hinh 1.
9 , S 9 , 0 8 , 5 B , 0 7 , 5 Hinh 3. Mot phin pho NOESY ciia 4 {CDCg.
Nhir vay, qua phan tich tren cho thay trong tat ca cac phirc chat 2-6, Eug dgu phoi tri vai Pt(II) qua C^C^,,^,, va C5, amin phfii tri voi Pt(n) qua N va d vj tri cis so vdi nhanh allyl trong ca dung moi CDCI3 hay a'^-axeton. Vay tai sao khi do trong CDCI, 2-5 deu cho hai bp tin hieu, con 6 chi cho mot bo tin iiieu duy nhit? Phan tich gin 2000 du tnic co chira CHC! hoac C H p , trong Cambridge Structural Database (CSD) Alien va'dSng nghiep [10] da chi ra r§ng, C-H ciia cloroform va diclorometan tao hen ket hydro voi N, O, S, haloeen trong gan 200 du true. Ngoai ra, hen ket halogen Sphirc cliltloai ™-[PtX,{Alk,N-CN)J (X = Cl, Br) voi CHI'cung da ditpc phat hien trong [11]- Bai vay, co the giai
thich hien tuang 2 bp tin hieu cua cac phiic chat nhu sau:
voi phirc chSt 2-^4, cloroform da sii dung proton dc U"^ '^'S"
kgt hydro vdi phdi tii C! trong phiic chdt, sau 60 no cung tao lien kk halogen vdi ion Pt(II). Do do, trong cloroform chung ton tai d hai dang nhu dupc mo ta dai die" '^''"^ P"'^'^
3 d hinh 4 Hai dang cua phiic chat 5 lai kliac, dang 5a chiia lien kit hydro npi phan tii' giiia ph6i tii Cl vdi proton ciia nhdm NH^, con dang 5b chua lien kit hydro Cl. .H-C gifta nguyen tir Cl ciia p-cloanilin va H ciia dung mdi (hinh 4). Sd dTphircchatfichicho mot bp tin hieu !a do chi tao duoc lien ket hydro npi phan gidng nhu cua 5a ma khdng tao dupc kieu gidng 5b do khdng cd nguyen tir Cl nao khac niia trong phan tir.
De tim hieu rd han ve qua trinh hinh thanh 2 dang a va b ciia 2-=-6, chiing tdi tien hanh do phd ciia chiing trong CDCI3 theo thdi gian. Kit qua cho thiy phd ciia cluing dhu khdng ddi sau 24 gia. Dieu nay cho thay qua trinh thiet lap 2 dang cua cac phirc chat 2-^5 dien ra nhanh va cac Hen ket hydro, halogen dupc hinh thanh kha ben va dn dinh trong dung dich.
Trong dung mdi c/^-axeton 2-^6 tai thdi diem mai pha mau chi cho 1 bp tin hieu, nhung heu theo thdi gian chiing cd bien ddi khdng? DS tra ldi cau hdi nay, chiing tdi cung tien hanh do phd ciia chiing trong ci^^-axeton Iheo thdi gian.
Ket qua rat bat ngd la phirc chat 2,3 (24 gid sau khi pha) va phiic chat 4 (48 gid sau khi pha) khdng ddi Cdn phirc chat 5 va 6 bi bien ddi tao 2 bd tin hieu ngay sau 6 gid pha mau, hinh dang cac tin hieu cung nhu ty le cudng dp 2 bp khdng ddi sau 48 gid. Hinh 4 dan ra mot phan phd chdng theo thdi gian cua 3 va 5 lam vi du.
Su bien ddi thanh 2 bd phd cua 5 va 6 cd the dupc giai thich do xay ra su ddng phan hda chuyen cau hinh tir cis (amin d vi tri cis so vdi nhanh ally]) sang trans (amin d vi tri Irans so vdi nhanh allyl) tuong tu nhu da xay ra d cac phuc chat dang c;5-[PtCl,(piperidin)(amin)] (amin: p-nitroanilin, p-iotamlin) khi do trong dung mdi rf^-axeton [12, 13], den 48 gid he dat trang thai can bang ciia 2 cau hinh cis - trans.
Cho den nay, trong nhieu cdng trinh nghien ciiu ve phiic chat ciia Pt(II) cho thay, qua trinh ddng phan hda kieu nay thudng xay ra vdi phuc chat chiia phdi tir la dan xuat cua anilin va dupc do trong dung mdi axeton [12, 13], DiSu nay cd the duoc ly giai do cac dan xuat cua anilin cd tinh baza yen, trong khi dd axeton lai la dung mdi cd kha nang tao phuc qua nhdm C=0. Do do, qua trinh chuyen ddi cdu hinh xay ra thdng qua san pham phiic chat trung gian phdi tri S [PtCl(Eug)(amin)(</^-axeton)]. Vdn de nay se duac lam sang td khi cd su bd trp sau rdng hon ciia cac nghien ciru vl tinh loan lupng hi'. Hinh 4, 5 thi hien cau tnic ciia phirc chat 3, 5 trong CDCI3 va phd chdng theo thdi gian ciia 3 (hmii A), 5 (hinh B) trong d^-axeton.
te»Nani"'^'"°"
Khoa hoc TU nhien i
Hinh 4. Cau true cua phuc chat 3, 5 trong CDCIj.
Hinh 5. Pho chdng theo thoi gian cua 3 (hinh A), 5 (hinh B) trong d^-axeton.
K6I luan
Trong bai bao nay, phd 'H NMR trong dung mdi d^- axeton va CDCl^ ciia nam phirc chat dang [PtCl(Eug) (amm)] ((amin: pyridin (2), 4-Me-pyridin (3), quinolin (4), /j-cloanihn (5), /)-toluidin (6)) da duoc nghien cim. Ket qua cho thay, trong dung mdi cloroform, cac phiic chat 2—5 deu cho 2 bd tin hieu khdng bien ddi theo thdi gian irng vdi 2 dang tdn tai cua mdi phiic chat trong dung dich. Dang 2a, 3a, 4a cd tuong tac hydro ngoai phan tu manh giiia proton ciia dung mdi va phdi tii Cl ciia phiic chit [Cl3C-H...ClPt(n)], dang 5a iai ung vdi lien ket hydro ndi phan tu manh giira proton nhdm NH, cua/j-cioanilin vdi phdi tir Cl [NH,...CI- Pt(n)]. Cdn 2b, 3b, 4b tdn tai tuong tac halogen ngoai phan tu manh giiia Cl cua dung mdi va ion Pt(II) [Cl^HC-CI...
Pt(n)], dang 5b ling voi lien ket hydro ngoai phan tii manh gifl'a Cl ciia p-cloanilin vdi H ciia dung mdi. Trong dung mdi axeton, phiic chat 5, 6 (chua dan xuat cua anilin) xay ra su ddng phan hda chuyen tir cau hinh d do amin d vi tri cis sang trans so vdi nhanh allyl, va 2 dang nay dat trang thai can bang sau 48 gid sau khi pha mau.
TAI l l | U THAM KHAO
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