Reflux inlet

B. (3-Bromo-3,3-difluoropropyl)trimethylsilane. A 1-L, four-necked flask is equipped with a mechanical stirrer, thermometer, Claisen adapter, septum inlet, reflux condenser (the top of which is connected to a calcium chloride drying tube), and a solid addition funnel. The flask is charged with (1,3-dibromo-3,3-difluoropropyl)trimethylsilane (78.3 g, 0.25 mol), and anhydrous dimethyl sulfoxide (200 mL), and the solid addition funnel is charged with sodium borohydride (11.5 g, 0.30 mol) (Notes 7 and 8). The stirred solution is warmed to 80°C, and sodium borohydride is added at a rate sufficient to maintain a reaction temperature of 80-90°C (Note 9). Toward the end of the addition, an additional portion of dimethyl sulfoxide (200 mL) is added via syringe to lower the viscosity of the reaction mixture. After the addition is complete, the mixture is cooled in an ice-water bath, diluted with 100 mL of pentane, and cautiously quenched with 12 M hydrochloric acid until no further gas evolution occurs. The mixture is transferred to a separatory funnel and washed with three, 100-mL portions of 5% brine. The pentane extract is dried over calcium chloride and the solvent removed through a 15-cm Vigreux column. Further fractionation yields 41.5 g (72%) of 3-bromo-3,3-difluoropropyltrimethylsilane, bp 139-141 °C (Note 10). 

Add [bis(trimethylsilyl)methyl]dichlorophosphine (17 g, 65 mmol) and dry diethyl ether (100 mL) to a three-necked round-bottomed (500 mL) flask with argon inlet, reflux condenser with blubber, magnetic stirrer bar and pressure-equalizing dropping funnel. 

A dry 50-mL flask equipped with septum inlet, reflux condenser, and magnetic stirrer is flushed with N2. The flask is charged with 12 mL of DME and 12 mmol of dich]oro[(lS,2S)-2-methylcyclopentyl]borane-dimethyl sulfide complex. The solution is heated to 60 °C and attached to a gas burette. Then, 1.4 g (13 mmol) of cyclopentyl azide is added dropwise (ca. 2 h) and the evolved N2 is measured. After the addition is complete, the solution is stirred for an additional 30 min. Gas evolution has ceased at this point. The solution iscooled toO°C and very carefully hydrolyzed by slowly adding 10 mL of H,0 (exothermic ). Then the mixture is made strongly basic with 40% KOH. The liberated amine is extracted with Et20. The ether solution is dried over anhyd K2C03 and the solvent is removed at reduced pressure. On distillation, 1.2 g (72%) of the amine are collected, bp 100 CC/15 Torr. The amine is further purified as its hydrochloride salt, mp 159-160 aC [a] 3 +39.13 (c = 10, CH3OH). 

A solution of 2.9 g (7.3 mmol) MnBr(CO)5 and 2.9 mL (3.4 g, 8.4 mmol) Sn(SC6H5)(n-C4H<,)3 in 40 mL of THF in a 100-mL round-bottom flask (Nz inlet, reflux condenser) is heated at reflux for 6 hr. The solution is allowed to cool. Solvent volume is reduced to 5 mL in vacuum cooling at -15° causes the orange crystalline product to precipitate from solution. This species is separated by filtration and air dried, yield 1.7 g, 93%. Recrystallization can be carried out using hexane. 

All manipulations must be carried out in an inert atmosphere using degassed solvents.9 To a 25-mL, round-bottom flask fitted with a nitrogen inlet, reflux condenser, and magnetic stirring bar is added the di-chloro(rj6-hexamethyl-benzene)ruthenium dimer (0.2 g, 0.3 mmole). Under a counterstream of ethylene, anhydrous sodium carbonate (0.2 g) and ethanol (15 mL) are added. The mixture is stirred and heated under reflux under a slow flow of ethylene for 2 hours the solution initially turns deep red and finally becomes brown. After cooling to room temperature, solvent is stripped in vacuo and the residue is extracted with four 5 mL portions of hexane. The filtered extract is concen-... 

A 1-1. three-necked flask is fitted with a nitrogen inlet, reflux condenser, and stirrer. After flushing the apparatus Anderson Chemical Co., Weston, Mich. 

The synthesis of the dimer is carried out in a 2-1. threenecked flask equipped with a nitrogen inlet, reflux condenser, and thermometer well. The reaction is conducted under nitrogen. During the heating period the temperature should never be allowed to exceed 140 . If this occurs, extensive decomposition will result and little or no product will be obtained. 

Preparation of the solution of bis(cyclopentadienyl)cobalt is best carried out in a 2-1. three-necked flask equipped with a nitrogen inlet, reflux condenser, stirrer, and dropping funnel. A solution of cyclopentadienylsodium in 1 1. of redistilled tetrahydrofuran is prepared from 40 g. (1.74 mols) of sodium metal and about 200 ml. (160 g. 2.4 mols) of freshly cracked cyclopentadiene. This solution is then treated with 110 g. (0.85 mol) of anhydrous cobalt(II) chloride, and the mixture is stirred for at least 2 hours at room temperature. 

A hot solution of triphenylphosphine (12 g, 46 mmol) in ethanol (350 mL) was added to a solution of rhodium(III) chloride trihydrate (2.0 g, 7.6 mmol) in 95% ethanol (70 mL) in a 500-mL, round-bottomed flask fitted with nitrogen inlet, reflux condenser, and a gas exit bubbler. After heating the solution at reflux for 2 h, the hot solution was filtered to give the crystalline product, which was washed with anhydrous ether and dried under vacuum to yield RhCl(PPh3)3 (6.25 g, 88% based on Rh) as an orange-red solid. ... 

L roimd-bottom three-necked flask, dropping funnel, nitrogen inlet, reflux condenser with nitrogen outlet, magnetic stirrer, safety glasses, laboratory coat, protective shield, and protective... 

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