Điều chế một số chất lỏng ion đặc nhiệm tetrafloborat 1-xyanoalkyl-3-metylimidazol trong điều kiện hóa học xanh

[Nghien CLfu oc ml%m<br /> <br /> <br /> Dieu che mot so chat long ion dac nhiem Tetrafloborat<br /> 1-(xyanoall(yl)-3-metylimidazol trong dieu kien<br /> <br /> hoa hoc xanh<br /> yP I H I MY LOC, LE NGOC THA^ canh do, chung tdi eung tien hanh phan uYig bang cac phffdng<br /> Bo mon Hoa hoc hu'u cd, Khoa Hoa hoc, Dai hgc Khoa hoc phap dun khuay tff, khuay tff d nhiet do phdng trong cung<br /> tii nhien, Dai hoc Quoc gia Tp. Ho ChfMinh dieu kien, nham muc dich so sanh hieu qua cua cac phUdng<br /> phap kich hoat khac nhau.<br /> Nhffng chat Idng ion clo 1- (xyanoalkyi)- 3- melyimidazol<br /> 1. G I 6 I THIEU vdi eae nhdm the alkil chi phffdng (lan Iffdt la metyl, propyl,<br /> LTng dung cua chat Idng ion (ionic liquid - IL) trong tdng butyl) dffdc dieu ehe trffdc va dffdc xem nhU chat nen de dieu<br /> hdp hull cd cung nhU nhieu ITnh vffc khac dang thu hut nhieu che tetrafloborat 1- (xyanoalkyi)- 3- melyimidazol.<br /> sff chu y. Mdl Irong eac dac diem Ihu hut nhat ciia IL la ca<br /> cation va anion deu cd the Ihay ddi de cho Ihfeh hdp vdi mpt 2. T H U C NGHIEM<br /> nhiem vu dac biet nao dd. Trong nhting nam gan day, viec phat 2.1. Hoa chat: N-Metilimidazol (MI), cloroaetonitryl, 4-<br /> Irien gan cac nhdm dinh chffc thich hdp vao phan Iff chat Idng clorobulyronilril, 5-clorovaleronilril, NaBF4 cua Aldrich. Tatea<br /> ion de lam lang linh cd dinh xuc lac hay lang kha nang ly trich deu dffdc dung trffc liep khdng tinh che.<br /> da lao ra mpl ITnh vffc nghien cuXi mdi [1]. 2.2. Thiet bi: Phan ffng dffdc thffc hien dffdi sff chieu xa<br /> Thuat ngff "chat Idng ion dac nhiem" (task-specific ionic vi sdng va sieu am lan Iffdt trong Id vi sdng chuyen dung Dis-<br /> liquid, TSIL) da dffdc gidi thieu nham md ta cac mudi ndng cover CEM, bdn sieu am Power Sonic 405, va thanh sieu am<br /> chay mang nhdm dinh chffc vdi nhffng tfnh chat 6ddc dff doan CE model GE 130. Cd cau cua cac san pha'm dffdc xac djnh<br /> trffdc [2]. Mdl loal cac nhdm djnh chffc cd the gan vao cation bang phd IR (Equino X55) va phd 'H, "C NMR (Broker 500<br /> cua IL nhff: hydroxyl, carboxyl hda, hydogen sulfonic, amin, MHz). Chi sd khdc xa dffdc do tren khue xa ke WYA-S.<br /> amid, ete, carbonxylic, ure, lioure, day fluoro, day glicidil, 2.3. Thu'c hanh tong quat<br /> alkenil, alkinil, phosphoril, nilril, tiol. Ngoai ra, cung cd vai IL 2.3.1. Dieu che [CNCnMIJCI<br /> mang nhdm dinh chffc tren anion nhU anion thu tinh, carbonyl<br /> 2.3.1.1. Phu'dng phap chieu xa vi sdng; Can 10 mmol MI<br /> kim loai, alkylselenit, boral mang nhdm dinh chde, hydrosul-<br /> va 10 mmol CN(CH2)nCI Iffdng ffng vao dng nghiem thuy tinh<br /> fal, hydropholphat [3].<br /> diing cho Id vi sdng chuyen dung, day kin nap va dat vao Id,<br /> Trong dd, TSIL imidazo mang nhdm dinh chffc nilryl la mpl Ihiel lap cac thdng sd can khao sat.<br /> trong cac TSIL da va dang Ihu hut sff chu y ciia cac nha khoa 2.3.1.2. Phu'dng phap chieu xa sieu am: Can 10 mmol MI<br /> hoc nhd cd kha nang thay Ihe dung mdi axelonitryl Irong long va 10 mmol CN(CH2)nCI vao dng nghiem, sau dd cho dng<br /> hdp hffu cd. TSIL imidazol mang nhdm dinh chffc nilryl il bay nghiem vao bon sieu am cd chffa nude va chat hoat ddng be<br /> hdi, bdl ddc hai vdi mdi trffdng, lam lang hoat linh va ludi thp mat, chinh thdi gian can khao sat. Khi phan iiTig vdi thanh sieu<br /> xuc lac, cd dinh xiic lac, va cd the tai sff dung nhieu lan van am thi dat thanh sieu am thang dffng vao dng nghiem, dau<br /> khdng giam hoai linh [4]. TSIL imidazol mang nhdm djnh chffc<br /> thanh nam d vi tri trung tam cua hon hdp phan uhg.<br /> nilryl cung gdp phan "xanh hda" phan ffng ghep cap cheo xuc<br /> 2.3.1.3. Phu'dng phap khuay tif; Can 10 mmol MI va 10<br /> lac paladi Heck, Negishi, Suzuki (Giai Nobel Hda hpc nam<br /> mmol CN(CH2)nCI vao binh cau 20 ml cd gan dng hoan Iffu<br /> 2010) khi dffdc sff dung lam mdi trffdng phan ffng, IL nay se<br /> dat vao bdn dau silicon da dieu chinh nhiel dp can Ihiet, chinh<br /> giff xuc tac paladi lai va tai sff dung ma hoat tfnh van giff<br /> tdc dp khuay ciia may khuay tff 500 vdng/phut. Khuay tff d<br /> nguyen, lam lang tinh kinh le eho phan uTig va ngan ngffa sff<br /> nhiet dp phdng thi khdng can dat binh eau vao bdn dau<br /> d nhiem ciia paladi [4b].<br /> silicon dieu nhiel. San pham dffdc ed lap bang each rffa hon<br /> Oun ndng hoan Iffu Iruyen thong Irong dung mdi la each hdp sau phan ffng vdi dietyl ete de loai chat nen va tac chat<br /> phd bien nhal de dieu che cac mudi imidazoli. So vdi quy Irinh dff. Cac chat nen clo cianoalkil rat d l loai bang dung mdi do<br /> mat thdi gian cua phffdng phap Iruyen thdng, phan ifng hda ehung cd ai Iffc kem vdi chat Idng ion. Rieng MI tffdng lac<br /> hpc cd ho trd vi sdng, sieu am da dffdc ap dung de tong hdp manh vdi IL nen rat khd loai, phai rffa nhieu lan bang dung<br /> chat Idng ion [5]. Trong khoang hai thap nien qua, viec sff<br /> mdi va thff nffdc rffa bang phffdng phap mau Holbrey [1,3d]<br /> dung vi sdng trong long hdp va phan tfch hda hpc da phat<br /> vdi thudc thff la CUCI2, MI se lao phffc [Cu(MI)4]2+ mau xanh<br /> trie'n nhd vao kha nang riil ngan thdi gian phan uTig, cai thien<br /> vdi thuoc thff nay. Neu nUdc rffa am linh vdi thudc thff CUCI2<br /> hieu sual, quy trinh ddn gian [6].<br /> tffc la da rffa hel MI cdn dff Irong san pha'm. Theo lac gia Hol-<br /> Viec dieu che chat Idng ion mang nhdm djnh chffc Irong brey, phffdng phap nay cho phep xac djnh MI hien dien d nong<br /> dieu kien khdng dung mdi chffa dffdc bao cao trffdc day. Vi dp rat thap. Rffa xong ed quay de thu hoi dung mdi, thu dffdc<br /> vay, trong pham vi de lai nay, chung ldi nghien cffu dieu che chat Idng set, cd mau vang nhal hoac chat ran tuy theo chat<br /> mpt sd chat Idng ion tetrafloborat 1- (xyanoalkyi)- 3- metyim-<br /> nen clo xyanoalkyi. Can va xae dinh hieu suat cd lap. Ghi pho<br /> idazol chffa nhdm djnh chffc nilryl trong dieu kien hda hoc<br /> IR va NMR de xac dinh cd eau.<br /> xanh nhff vi sdng, sieu am, khdng dung mdi, ti Iffdng. Ben<br /> 2.3.2. Oieu che [CNCfjMIJBF^: Sff dung 10 mmol<br /> <br /> 30 KHOA H