Dichloromethyleneamino

The observation that l,3,5-trimethyl-2,4,6-trichloroborazine yields some dimeric (dichloromethyleneamino)dichloroborane upon photochemical chlorination 30> (c.f. Eq. (7)) prompted the synthesis of this compound by the reaction of BC13 with C1SNCC12 2I> (c.f. Eq. (7)) and also by the 1,2-addition of trichloroborane to chlorocyanide 23> as depicted in Eq. (15). 

Preparations of (dichloromethyleneamino)dichloroborane have been mentioned earlier (c.f. Eq. (7)). 

Replacement of halogen in dimeric iminoboranes containing tetracoordin-ated boron is not so readily accomplished. For example, bis[(dichloromethyl-eneamino)dichloroborane]reacts with C4H9MgCl in nonetheric solvents to yield dimeric (dichloromethyleneamino)butylchloroborane, whereas C4H9Ii replaces both boron-bonded chlorine atoms by butyl groups 25). 

Dichloromethyleneamino Tellurium Pentafluoride2 Equimolar quantities of tellurium chloride pentafluoride and cyanogen chloride are loaded into a 61 Pyrex flask to give a pressure of approximately 1 atm at 20°. This mixture is irradiated for 5 h with an internal low-pressure mercury lamp. The volatile products are distilled under vacuum through a series of traps at — 70°, — 110°, and —196°. The trap at — 70° contained the crude product. A series of photolysis reactions starting with 150.7 g of tellurium chloride pentafluoride yielded 82.3 g crude product that is distilled on a 100-cm spinning-band column at 76 torr yield 59.7 g (32%) b.p. 63-65776 torr. 

Mercury Bis[pentafluorotelluro trifluoromethylamide]3 14.2 g (44.6 mmol) of dichloromethyleneamino tellurium pentafluoride are condensed into a 100 ml stainless steel autoclave containing 48.0 g (201 mmol) of mercury (II) fluoride. The mixture is stirred and heated at 60° for4days. The autoclave is chilled to — 25° and any volatile materials removed at this temperature under vacuum. The remaining solid is sublimed at 60" onto a cold-finger at — 25° yield 17.8 g (98%) m.p. 67-68°. 

The chlorine atoms in dichloromethyleneamino tellurium pentafluoride were replaced by methoxide, when the tellurium compound and sodium methoxide in diethyl ether were kept at 20° for four days2. The products were dimethoxymethyleneamino and chloro(methoxy) methyleneamino tellurium pentafluoride. 

Dichloromethyleneamino tellurium pentafluoride was converted by excess hydrogen fluoride to trifluoromethylamino tellurium pentafluoride, by heating with cesium fluoride to cesium pentafluorotelluro(trifluoromethyl)amide, and by heating with mercury (II) fluoride to mercury bis pentqfluorotelluro trifluoromethylamide] . ... 

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