Derivatives with Halogen

with MeMgBr - MesSnCHaCl + Me EtSnCHsCl + MeaSnCCH cDa + MeEtSnCCHaCl)  

Tris(pentafluorophenyl)tin Chloride (M-296) SnCiaClFis (C6F5)3SnCl 

By rxn. of SnCl and CePsMgBr (1 2.5) and vacutan sublimation without hydrolysis as by-prod. (II98). 

with SnCl4 (at 150 ) (C6F5)2SnCla (2 1) or CeFsSnCla-excess (II98). 

NHq [(C6F5)3Snl20 (77)-NaOH (CeF5)3Sn0H (II98). 

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Coordination Compounds of Thio- and Selenocarbonyl Derivatives with Halogens... 

Praefcke et al.47 and Boden et al.48 have both synthesized triphenylene derivatives with halogens attached to the core (46). It was assumed that the resulting chirality would express itself more strongly than chirality present in the side chains. These halogenated compounds could be readily modified to give the hepta-alkylated triphenylenes however, in spite of calculations which revealed that the triphenylene core indeed becomes helical, no expression of the helicity at the mesoscopic level could be achieved. 

Manoussakis et al,46 have synthesized a series of selenocarbamate six-coordinate complexes of arsenic (20 and Table 8 cf. As—S analogues). By reacting the piperidyl derivative with halogens dissolved in CCU a series of haloselenato carbamate complexes are produced which are probably pentacoordinate (equation 13). 

Chloropyrido[l,2-a]pyrimidin-4-ones 399 (R = Me, Cl R1 = 6-Me X = Cl) were prepared in excellent yields when 3-unsubstituted derivatives reacted with phosphorus pentachloride in phosphoryl chloride at 105-110°C for 1.5 hours (85JHC481). Other 3-bromo- and 3-chloro-2-(chloromethyl)-4//-pyrido[l,2-a]pyrimidin-4-ones were also prepared from 3-unsaturated derivatives with halogenation agents (e.g., with N-chlorosuccinimide (NCS) in a mixture of carbon tetrachloride and ethyl acetate) (83EUP81945). 

The cationic complexes [Ir(CO)2(SbPh3)3]+ and [Ir(CO)2(PR3)2]+ (R = Ph, C6Hn) have been synthesized from iridium carbonyl halide derivatives with halogen acceptors in the presence of CO.109... 

The cleavage of tetrahydrofuran and its alkylated derivatives with halogen acids is an excellent method for the preparation of, A-dihalo-alkanes.The reaction of tetrahydrofuran with the less-reactive hydrogen chloride stops at the chlorohydrin stage, whereas the reaction in the presence of zinc chloride catalyst leads to the formation of the dichloride. The crude reaction mixture containing the intermediate chlorohydrin may be treated directly with phosphorus tribromide, yielding tetramethylene chlorobromide. The preparation of dibromides can be accomplished easily with hydrogen bromide or phosphorus and bromine and diiodides, by the action of potassium iodide and orthophosphoric acid. ... 

Halotriazoles have been prepared by treatment of (122) and alkyl- or aryl-substituted derivatives with halogen acids (8ihc(37)1, p. 228). The preparation of 3-fluorotriazole required UV irradiation of (122 X = Bp4). Aminotriazolinones and 3,5-diaminotriazole are diazot-ized and tetrazotized, respectively, to afford 3-halo-l,2,4-triazolinones and 3,5-dihalotriazoles, respectively (65la(682)123, 67CB225o). 

Fig. 4-27. Reaction of metalated chiral ferrocene derivatives with halogenes, boron and carbon electrophiles.

Swithenbank et al. (1971) synthesised forty related benzamide derivatives to study the relationship between chemical structure and action. The herbicidal activity of N-alkyl-3,S-dichlorobenzamides was enhanced by, y-unsaturation, and activity was further improved by a,a-dimethyl groups. In the case of dimethylpro-pynyl nzamides, derivatives with halogen substituents on the aromatic ring are the most active, substitution in positions 3 and 5 being optimal. 

A review on the reaction of tervalent phosphorus acid derivatives with halogens has appeared. Alkylbis(diisopropyl-amino) phosphines (41) react with carbon tetrachloride or bromotrichloromethane to give the P-halogeno ylides (42) below 0 The ylides rearrange to the substituted phosphines (43)... 

Mo2(02CR)4]l3 Derivatives. The initial objective of work on the oxidation of Mo2(02CR)4 derivatives with halogens was to examine the possibility of achieving addition of halogen across the quadruple bond, as in the reaction ... 

Brown, H.C., C. Subrahmanyam, T. Hamaoka, N. Ravindran, D.H. Bowman, S. Misumi, M.K. Unni, V. Somayaji, N.G.J. Bhat. Vinylic Organoboranes. A Convenient Stereospacific Synthesis of (Z)-l-Halo-l-alkenes from l-AUqmes via (E)-TAlkenylborane Derivatives with Halogens, Org. Chem. 54 6068—6075 (1989). 

Scheme 91 Addition-rearrangement reactions of furan derivatives with halogenated thiophene 1,1-dioxides [101]...

Representative results of the hydroxytrifluoromethylation are summarized in Table 1. Styrene derivatives with halogen atoms, F (19b), Cl (19c), and Br (19d),... 

The compounds are listed in Table 276 derivatives with halogen and oxygen functions may be found in Table 27T-... 

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