Reactions tribromide

The conversion of an aliphatic carboxylic acid into the a-bromo- (or a-chloro ) acid by treatment with bromine (or chlorine) in the presence of a catal3rtic amount of phosphorus tribromide (or trichloride) or of red phosphorus is known as the Hell-Volhard-Zelinsky reaction. The procedure probably involves the intermediate formation of the acyl halide, since it is known that halogens react more rapidly with acyl haUdes than with the acids themselves ... 

The most suitable synthetic method for these products is the heterocyc-lization reaction of N-thioacyl derivatives of amino acids (202) with phosphorus tribromide (378, 442-450, 559, 560) or anhydrous trifluoroacetic acid (448, 449, 451, 452) (Scheme 103). Treatment of N-thioacyl amino acids with acetic anhydride leads directly to the thiazolylacetate without isolation of an intermediate thiazolinone (365. 452). 2-Alkoxy-derivatives of A-2-thiazoline-5-one, however, can be obtained without acetylation by this method (453, 454). 

Carbon disulfide readily reacts with a-aminonitriles giving 2-mercapto-5-aminothiazoles (213), (271, 293) which can be converted to 5-aminothiazoles unsubstituted in the 2-position (Scheme 110 and Table II-34a). If this reaction is carried out in the presence of benzyl chloride in phosphorus tribromide, a 2-S-substituted thiazole derivative (214) is obtained in quantitative yield (Scheme 111), with R = hydrogen or phenyl (68, 304). 

Hydroxyalkylthiazoles are also obtained by cyclization or from alkoxyalkyl-thiazoles by hydrolysis (36, 44, 45, 52, 55-57) and by lithium aluminium hydride reduction of the esters of thiazolecarboxylic acids (58-60) or of the thiazoleacetic adds. The Cannizzaro reaction of 4-thiazolealdehyde gives 4-(hydroxymethyl)-thiazole (53). The main reactions of hydroxyalkyl thiazoles are the synthesis of halogenated derivatives by the action of hydrobroraic acid (55, 61-63), thionyl chloride (44, 45, 63-66), phosphoryl chloride (52, 62, 67), phosphorus penta-chloride (58), tribromide (38, 68), esterification (58, 68-71), and elimination that leads to the alkenylthiazoles (49, 72). 

Thionyl chloride and phosphorus tribromide are specialized reagents used to bring about particular functional group transformations For this reason we won t present the mechanisms by which they convert alcohols to alkyl halides but instead will limit our selves to those mechanisms that have broad applicability and enhance our knowledge of fundamental principles In those instances you will find that a mechanistic understand mg IS of great help m organizing the reaction types of organic chemistry... 

Reaction of alcohols with phosphorus tribromide (Section 4 13) As an alternative to converting alco hols to alkyl bromides with hydrogen bromide the inorganic reagent phosphorus tribromide is some times used... 

Reaction with phosphorus trihalides (Section 4 13) Phosphorus trichloride and phosphorus tribromide convert alcohols to alkyl halides... 

This method of a bromination of carboxylic acids is called the Hell-Volhard-Zelinsky reaction This reaction is sometimes carried out by using a small amount of phosphorus instead of phosphorus trichloride Phosphorus reacts with bromine to yield phosphorus tribromide as the active catalyst under these conditions... 

Ha.logena.tlon, 3-Chloroindole can be obtained by chlorination with either hypochlorite ion or with sulfuryl chloride. In the former case the reaction proceeds through a 1-chloroindole intermediate (13). 3-Chloroindole [16863-96-0] is quite unstable to acidic aqueous solution, in which it is hydroly2ed to oxindole. 3-Bromoindole [1484-27-1] has been obtained from indole using pytidinium tribromide as the source of electrophilic bromine. Indole reacts with iodine to give 3-iodoindole [26340-47-6]. Both the 3-bromo and 3-iodo compounds are susceptible to hydrolysis in acid but are relatively stable in base. 

Niobium Oxide Tribromide. Niobium oxide tribromide, NbOBr, is a yeUowbrown soHd which is readily hydrolyzed by moist air. It is prepared by reaction of bromine with a mixture of niobium pentoxide and carbon at 550°C. It decomposes in vacuum to the pentabromide and pentoxide at 320°C. 

Friedel-Crafts reaction, utilising phosphoms trichloride or phosphoms tribromide [7789-60-8] in place of an acyl haUde, can also be used for the preparation of many arylphosphoms compounds (8) (see Friedel-CRAFTS reactions). 

Hydroxyisoquinolines. Hydroxy groups in the 5-, 6-, 7-, and 8-position show phenoHc reactions for example, the Bucherer reaction leads to the corresponding anainoisoquinolines. Other typical reactions include the Mannich condensation, azo-coupling reactions, and nitrosation. Both 0-methyl and /V-methyl derivatives are obtained from the methylation of 1-hydroxyisoquinoline, indicating that both tautomeric forms are present. Distillation of various hydroxy compounds, eg, 1- and 4-hydroxyisoquinoline, with zinc dust removes the oxygen. Treatment of 1-isoquinolinol with phosphoms tribromide yields 1-bromoisoquinoline [1532-71 -4] (178). 

This reaction gives fair-to-good yields of monoorganotin tribromides and trichlorides when quaternary ammonium or phosphonium catalysts are used (149). Better yields are obtained with organic bromides and staimous bromide than with the chlorides. This reaction is also catalyzed by tri alkyl antimony compounds at 100—160°C, bromides are more reactive than chlorides in this preparation (150,151). a,C0-Dihaloalkanes also react in good yield giving CO-haloalkyltin trihaHdes when catalyzed by organoantimony compounds (152). 

Titanium Dibromide. Titanium dibromide [13873-04-5] a black crystalline soHd, density 4310 kg/m, mp 1025°C, has a cadmium iodide-type stmcture and is readily oxidized to trivalent titanium by water. Spontaneously flammable in air (142), it can be prepared by direct synthesis from the elements, by reaction of the tetrabromide with titanium, or by thermal decomposition of titanium tribromide. This last reaction must be carried out either at or below 400°C, because at higher temperatures the dibromide itself disproportionates. 

Titanium Tribromide. Titanium tribromide [13135-31 ] crystaUizes in two different habits hexagonal plates or blue-black needles. It can be prepared by the reaction of TiBr with either titanium or hydrogen. 

Bromides and Iodides. The red-brown tribromide, UBr [13470-19-4], and the black tniodide, Ul [13775-18-3], may both be prepared by direct interaction of the elements, ie, uranium metal with X2 (X = Br, I). The tribromide has also been prepared by interaction of UH and HBr, producing H2 as a reaction product. The tribromide and tniodide complexes are both polymeric soflds with a local bicapped trigonal prismatic coordination geometry. The tribromide is soluble in H2O and decomposes in alcohols. 

Both antimony tribromide and antimony ttiiodide are prepared by reaction of the elements. Their chemistry is similar to that of SbCl in that they readily hydroly2e, form complex haUde ions, and form a wide variety of adducts with ethers, aldehydes, mercaptans, etc. They are soluble in carbon disulfide, acetone, and chloroform. There has been considerable interest in the compounds antimony bromide sulfide [14794-85-5] antimony iodide sulfide [13868-38-1] ISSb, and antimony iodide selenide [15513-79-8] with respect to their soHd-state properties, ferroelectricity, pyroelectricity, photoconduction, and dielectric polarization. 

Halobismuthines, Dihalobismuthines, and Related Compounds. Chloro-, dichloro-, bromo-, and dibromobismuthines are best prepared by the reaction of a tertiary bismuthine and bismuth trichloride or tribromide (7,43,45,46,104—107) ... 

The reaction is irreversible and can be used to synthesize aUphatic and aromatic esters. In addition, there are no complications involving water removal or azeotrope formation. Boron tribromide can be used ia place of boron trichloride, but the bromide has a stronger tendency to halogenate the alkyl group of the alcohol (26). Boron tritiuoride does not give the ester, but gives either a complex or dehydrated product. 

Reaction of etiianol witii phosphoms ttichlotide produces mainly ttiethyl phosphite ethyl biomide is the ptincipal product of reaction with phosphoms tribromide. However, reaction conditions strongly affect the composition of reaction products. 

Ethylene bromohydrin has been prepared by the reaction between ethylene glycol and hydrobromic acid and phosphorus tribromide. It has also been prepared by the direct addition of hypobromous acid to ethylene, and by the reaction between ethylene and dilute bromine water. With ethylene oxide now available at a reasonable price, the method described is probably the best because of the high yields and the convenience of reaction. 

Boron tribromide replaces fluonne with bromine on tertiary or secondary carbons however, trifluoromethyl groups are inert in this reaction [70] (equation 57). 

Many reactions of fluorinated organics with metal halides result in the replacement of fluorine with halogen A general route to 1,1,1-trichloro- or tribromo-fluoroalkanes involves treating primary fluoroalkyl iodides with aluminum trichloride or aluminum tribromide [74], Benzylic [75, 76] or vinylic [72] fluorine can be exchanged for chlorine when treated with aluminum trichloride... 

The reaction of a-aminonitriles and carbon disulphide was stated by Cook and Heilbron to give 5-amino-2-mercaptothiazoles however, they later found that the same reaction with aminoacetonitrile was more complex. When aminoacetonitrile sulphate in ethanolic solution was treated with carbon disulphide, the dithiodicarbamate 9 was formed. Benzylation was then carried out treatment of the resulting ester 10 with phosphorus tribromide with subsequent loss of water gave 5-amino-2-benzylthiothiazole 11 in a quantitative fashion. The rapid reaction was thought to be the first example of the formation of a 5-aminothiazole from an a-aminoamide. 

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