CC PHNG PHP TNG HP IMIDACLOPRID

Tm tt: bi qu trnh oxy ha, acyl ha, clo ha, ngng t bn bc phn ng Imidacloprid, tng hiu sut t 55. 2%. . Cc sn phm c c trng bi phn tch nguyn t, IR v H NMR c tnh. Cc cch gim chi ph, ci thin tc phn ng v n gin ha cc bc tch, gim tiu th nng lng v nhim, v do sn xut sch hn sn phm ph hp cho sn xut cng nghip, v c nng sut cao, hm lng cao v chi ph thp. T kha: 3-metyl pyridin (3 ); Imidacloprid (); tng hp (); clorua ( ). Imidacloprid l thuc tr su mi, hiu qu cao, c tnh thp, c tn thng thng l Imidacloprid, tn ha hc l 1-[(6-chloro-3- pyridinyl) methyl]-N-nitro-2-imidazolidinimine) C cu trc ha hc: CTPT: C9H10ClN5O2

Mt cht trung gian quan trng cn trong vic tng hp nhng thuc tr su ny l 2Chloro-5-clometyl-pyridin. Trong nhng nm gn y, mt s phng php tng hp cht ny c bo co ch yu l tng hp trc tip 3-methyl-pyridin natri [1~2]. Phng php ny ch t tng hiu sut khong 18% khi sa dng Acid Nicotinic l nguyn liu th. [3,4] Qu trnh phn ng 5 bc nng sut ln n 50%, nhng tn thi gian v thit b cng knh.. Hin nay, cc phng php hay c s dng nhiu hn l clo ha 2-chloro-5methylpyridine [5~7] thng s dng clo lm cht kh clo, tc nhn phn ng l cc gc t do? () , kt qu l cho cc sn phm: 2.-cloro-5-chloromethyl pyridin; 2-chloro-5-(dichloromethyl) pyridin; 2-clo-5-(trichloromethyl) pyridin v hp cht vng 2-clo-5-methyl-pyridin. Hn hp clorua trong sn phm gy kh khn ln trong vic tch sn phm.

2-clo-5-chloromethyl pyridine c th tng hp theo nhiu cch nh sau: (1) S dng 2-amino-5-metyl pyridin lm nguyn liu:

(2) S dng N-benzyl-N-acetamit propenyl lm nguyn liu:

(3) S dng 3-metyl pyridin lm nguyn liu:

(4) S dng niacin (axit nicotinic) lm nguyn liu:

Tng hp Imidacloprid theo cc con ng sau y: (1) Phng php ngng t trc tip:

(2) Nitrat ha:

(3) Phng php kim ha:

(4) Phng php dng Nitroguanidin:

I.

Phn thc nghim. I.1. Ha cht v dng c.

Thit b o im nng chy, my o quang ph NMR, HNMR Brucker Avance 500DMX, (tiu chun TMS, dung mi CDCl3); IR s dng FT-8000 mu bn ngoi my quang ph? (Bng KBr)? ( I R F T - 8 0 0 0 ( K B r ) ); phn tch t ng loi PE-2400. 3-methyl pyridin; tert-butyl hypochlorite (t-butyl hypochlorite, ); axit phosphomolybdic ( ); phthaloyl dicloride ( ) , 2-nitroimino imidazolidine (2 ); kali cacbonat khan ( ) ; cesi clorua ( ); aceton nitril ( ); cloroform (); thuc th phn tch hoc tinh khit v mt ha hc.

I.2.

Phng php tng hp.

I.3.

Cc bc tin hnh. I.3.1. Tng hp 3-methyl pyridin N-oxide. (Oxi ha)

Bnh 3 c c gn nhit k, sinh hn, my khuy. Ln lt cho vo trong bnh cu 3 c 4.6 ml H2O; 0.16 mol (14.88g) 3-methyl pyridin (3 ) ; 51.8 ml CHCl3 v 0.93 g axit photphomolybdic. Tng nhit n 75C, sau thm nh git 31.4 g H2O2 30%., tip tc nh git trong 3h cho n khi ht, phn ng thm 6h na, sn phm thu c c mu nu nht trong sut. un nng, benzen c chng ct di p sut thp, loi nc, sau thm 35ml CHCl3, lc b cc cht xc tc rn, dch lc thu c em lc chn khng cho mt cht lng mu nu, sau lm ngui 20C thu c cht rn mu nu nht, nng 16.4g (0.147mol), tinh khit 97.3%, hiu sut 91.7%.

I.3.2. Tng hp 2-clo-5-methyl pyridin (Acyl ha) 500ml trong bnh 3 c c thm 0.147 mol N-oxy-3-methyl pyridin; 0.22 mol Et3N (trietyl amin) v 147ml CH2Cl2 (diclo metan_DCM), phthaloyl diclorid c nh git b sung vo khi c kh N2, sau tip tc trong 2 gi. Ht lc cn vi 29.2 ml CH2Cl2, ra lc loi dung mi, thu c cht lng nht mu nu nht. Lm mt iu chnh pH ca cht lng duy tr trong khong 6. Lp du thu c trong sn phm em chng ct, lp nc c tch ra v chit vi 176ml CH2Cl2. Kt hp lp du vi lp du thu c phn chit, em lm khan bng MgSO4, sau khi lm khan c nn di p sut thp n cht lng du mu vng nht nng 15.2g (0.114 mol), tinh khit 95.7%, hiu sut 77.8%.

I.3.3. Tng hp 2-chlo-5-clometyl pyridin (Clorin ha) Tert-butyl hypochlorite c tng hp theo cc ti liu [9]. 0.114 mol ( 12g ) 2-clo-5methyl-pyridin v 0.057 mol (6.19g ) t-butyl chloroformate c thm cng lc vo bnh 3 c 500 ml. Nhit duy tr 30-40 C, chiu x bng nh sng mt tri hoc tia cc tm, un trong 20-30 pht th ngng li. trong qu trnh phn ng, dung dch chuyn t mu vng sang mu xanh l cy. Chng p sut kh quyn loi b t-butanol, v sau chng chn khng thu hi nguyn liu khng phn ng ( 43C/200 Pa ). Sn phm th cn li em tinh ch thu c nhiu hn 70-80C, 200 Pa. Hiu sut t 82.6%. I.3.4. Tng hp Imidacloprid. (Ngng t) Thit b gm 1 nhit k, sinh hn hi lu, my khuy. Rt t phu 40 vo 1 l cha sn 14ml acetonitril, N-nitroimino-imidazolidin-2-ylamin 0.21 mol; Kalicacbonat 10.6g; v 1 cht CsCl.. 2-clo-5-clometyl pyridin c nh git thm vo ng thi khuy u ha tan 0.148 mol acetonitrile. un hi lu trong 5 gi, sau lc cn v ra sch vi? loi b dung mi acetonitrile, gom dch lc thu c kt hp vi lc gim p sut thu c 1 cht rn mu nu, c tinh ch bng sc k ct silica gel. Thu c 37.5 g sn phm, c tinh khit 95.3% v hiu sut 93.7%.

2 - 5 - pp ny

2- - 5- s tbi