MANITSHEMA

manitshp01@gmail.com THIAGARAJAR COLLEGE

EXPERIMENTS

Experimental methods Purification of Solvents:

Diethylether (Glaxo), was refluxed over sodium metal pieces for 3-4h then benzophenone was added refluxed till blue color persisted.The fraction distillating at 34-35C was stored in a well stoppered bottle. Chloroform (E.Merck),was distilled over phosphorous pentoxide.The fraction distillating at 60-62 C was collected. Petroleum ether(BDH),was kept overnight over phosphorous pentoxide.After decantation it was refluxed over sodium metal piecesfor 3-4 h.The fraction distilling between 40-60C was stored in a well stoppered bottle. Benzene (E.Merck),was refluxed with freshly cut pieces of sodium metal for 6-8 h and then benzophenone was added and refluxed till blue color persists. The fraction distilling at 79-80C was collected. Diethylamine (BDH), was kept over potassium hydroxide pellets for 24 h and then distilled. The fraction distilling at 55C was collected. Ethanol (Zhuhai Hongtu Industries Corporation), was kept over sulphate overnight. The liquid was filtered anhydrous copper and distilled over sodium metal pieces. The fraction distilling at 78C was collected. Dichloromethane (E.Merck) ,was distilled over phnosphorous pentoxide.The fraction distilling 39-40C was collected. Methanol (E.Merck), was refluxed over sodium metal species for 3-4 h. The fraction distilling at 72-74C was collected. Tetrahydrofuran (E.Merck), was refluxed over sodium metal piecesfor 3-4 h. Benzophenone was added and reflued till blue color persists.The fraction distilling at 65-66C was collected for use.

Preparation of anhydrous metal chlorides

Anhydrous metal(II) chlorides were prepared by treating powdered sample of the appropriate chloride with a large excess of thionyl chloride at room temperature.The contents were then refluxed on a water bath for another few hours till there was no evoluation of SO2 gas.The anhydrous metal (II) chlorides was then filtered in a dry atmosphere and washed with distilled petroleum ether and dried under vaccum. N,N-diisopropylisonicotinamide(L): Step I: Isonicotinic(20 g) was refluxed with thionyl chloride (50-60mL) in the presence of a few drops of dimethylformamide over a low flame till the acid was distilled.The excess of thionyl chloride was removed azeotropically with benzene using Dean Stark apparatus to give pure isonicotinyl chloride(m.p.155-160) Step II: Isionicotinyl chloride 6.82 g (0.038mol) was suspended in a mixture of 50mL dry benzene and 6.12mL(0.076mL) of pyridine;13.4mL(0.095mol0 of diisopropylamine was added. The mixture was added.The mixture was refluxed for refluxed for half-an-hour and then was allowed to stand at roonm temperature overnight.The solid which separated out was removed and washed with benzene.The combined benzene filtered out wasd removed and washed with benzene. The combined benzene filterate and washings were chilled in an icebath and treated with an excess of 50% aqueous sodium hydroxide.The benzene layer was separated and the alkaline solution was extracted with ether. The combined benzene and ether layers were dried over sodium sulphate and the solvents were removed by distillation.The yellow distillate was solidified on cooling.Recrystallisation from water containing a little methanol gave the precipitates.Recrystallisation of this material from about 20mL of heptanes gave large crystals of yellowish-brown color.

Characterization: color:Yellowish-brown Melting point:97-98C Elemental analysis:(Found):C,69.23;H,8.94;N,13.14(%) (calculated):C,69.90;H,8.74;N,13.59(%) IR(cm-1):co:1600;pyridine vib.:1595,1540,995,602 and 403
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H NMR: 8.580 (2H, dd, J=6, 1.5 Hz, Py), 7.130 (2H, dd, J=6, 1.5 Hz, Py), 3.621, 3.471 (broad singlets,1H each,-CH), 1.465,1.083 (broad singlets, 6H each,-CH3). Preparation of N,N-Diisobutylisonicotinamide(L): N,N- Diisobutylisonicotinamide but diisobutylamine was used in place of diisopropylamine.

Characterisation:

Color:yellowish-brown Melting Point:54-56C

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H NMR (CDCl3): (0.693) (d,6H,CH3); (0.905) (d,6H, CH3); (1.785) (m,1H,CH); (2.08) (m,1H,CH); (2.941) (d,2H,CH2); (3.276) (d,2H,CH2); (7.17) (q,2H,py); (8.594) (d,2H,py). IR(cm-1): co 1670;pyridine vib.:1590,1540,990,600

Preparation of complexes of N,N-dialkylisonicotinamide: (1)[Co(BF4 )2 .6H 2O(diisobutylisonicotinamide)]: This complex was prepared from a reaction mixture containing equimolar amounts of Co(BF4 )2 .6H 2O(437.5mg) and diisobutylisonicotinamide (601.14mg) dissolved in about 25mL of isopropylalcohol.The contents were refluxed for 6 h which on keeping into refrigerator for overnight.After cooling there were no crystals out.So the minute amount of contents of filtered using with whattmann filter paper.Then the filterate was cooled at 4 in a refrigerator for overnight.And also the filter paper was kept in desiccators which is filled with CaCl2. After 2-3 days,pink coloured fine crystals appeared in the flask.The mother liquor was kept as decanted and the crystalline solid was dried.The mother liquor was again kept in the fridge for further crystalline. Yield: Colour: Solubility: Melting point:

(2) [Co(BF4 )2 .6H 2O(diisopropylisonicotinic acid)]: This complex was prepared from a reaction mixture containing equimolar amounts of Co(BF4 )2 .6H 2O(489.3mg) and diisopropylisonicotinamide (591.84mg) dissolved in about 25mL of isopropylalcohol.The contents were refluxed for 6 h which on keeping into refrigerator for overnight.After cooling there were no crystals out.So the minute amount of contents of filtered using with whattmann filter paper.Then the filterate was cooled at 4C in a refrigerator for overnight.And also the filter paper was kept in desiccators which is filled with CaCl2. Yield: Colour: Solubility: Melting point: (3)[Ni(NO3)2 6H2O(diisopropylisonicotinamide)]: This complex was prepared from a reaction mixture containing equimolar amounts of Ni(NO3 )2 .6H 2O(594.7mg,2mmol) and diisopropylisonicotinamide (834.4mg,4mmol) dissolved in about 25mL of acetonitrile.The contents were refluxed for 6 h which on keeping into refrigerator for overnight.After cooling there were glassy layer was formed.Then it is dissolved in 5 ml of acetonitrile. Then it was covered by the aluminium foil and allow to evaporate followed by cool.So the minute amount of crystals (pale green colour) formed. Yield: Colour: Solubility: Melting point:

(4)[CoI2 . 6H2O(diisopropylisonicotinamide)]: Firstly,we take small amount of KI and put into oven for drying purpose. The next day we add CoCl2 6H2O with KI inti the round bottom flask then we add the 25ml of acetonitrile and then it stirred for overnight. So the CoI2 6H2O is obtained.Then it is treated with diisopropylisonicotinamide dissolved in about 25mL of acetonitrile. The contents were refluxed for 6 h which on keeping into refrigerator for overnight. Yield: Colour: Solubility: Melting point: