Chloro bromide

Cyclobutanedicarboxylic acid has been prepared by hydrolysis of the ethyl ester,1 or of the half nitrile, 1-cyano-l-car-boxycyclobutane.2 The ethyl ester has been prepared by condensation of ethyl malonate with trimethylene bromide1 or chloro-bromide.3 The half nitrile has been prepared by condensation of trimethylene bromide with ethyl cyanoacetate followed by hydrolysis of the ester to the acid.2... 

The ease with which selenium combines with many other elements to form binary compounds has already been mentioned (p. 299). Only one compound with hydrogen is known, but a series of polyselenides of the alkali metals corresponding to the polysulphides has been obtained. Selenium forms a hexafluoride, SeFG, but no other hexalialide has been isolated. The tetrahalides arc the most stable, and mixed chloro-bromides of quadrivalent selenium, SeCl Br, are known. Selenium monochloride, SeaCla, and selenium monobromide, Se2Br2, also exist as comparatively stable liquids at ordinary temperatures. No compound of selenium and iodine is known. Selenium oxychloride, SeOCl2, and the oxybromide, SeOBr2, are extremely reactive and useful compounds. 

Ferrous chloride unites with bromine to yield an unstable chloro-bromide, FeCl2Br (see p. 106). 

Bromine, however, forms no additive compound. By treatment of phenyl dichloroarsine with excess of bromine, the molecule is decomposed with formation of dibromobenzene, arsenic chloro-bromide and hydrobromic acid, as follows ... 

Much remains to be done in the fleld of complexes of mixed ligands. All the ruthenium (III) 12) and rhodium (III) 126) chloro-aqua complexes have been separated by ion-exchange techniques, and the mixed complexes, OsClaBr6 a and IrClaBr6 a S by electrophoresis (7, 88). Labile mixed complexes such as bismuth (III) 78) and uranium (IV) 38) chloro-bromides have been studied by spectrophotometry, but the conclusions are obviously more difficult to obtain. 

Intercalated reagent. Melin and Herold have reported the preparation of C24SbCls as black platelets with considerable stability to air. Kagan et al. find that intercalated SbCls differs considerably in reactivity from ordinary SbCls. It reacts with alkyl bromides, iodides, and tosylates to give the corresponding alkyl chlorides. It does not effect aromatic chlorination. In contrast, ordinary SbCls reacts with alkyl bromides to give a-chloro bromides and readily chlorinates aromatic compounds. 

SYNONYMS bromochlororaethane, fluorocarbon 1011, halon 1011, methylene chloro-bromide. 

The spectra obtained are exactly analogous to those of binary mixtures of stannic halides (2), where analogous labile mixed molecules are formed. Each of the five species present is unmistakably characterised by an intense polarized Raman line of different frequency. Table I shows the close analogy between the chloro-bromo complexes of Ga " and the stannic chloro-bromides. 

Oxidative cleavage of the complex 549 with CuCri affords 2,3-bis(chloro-methyl)-1,3-butadiene (550) and regenerates PdCri. Thus the preparation of this interesting dimerization product 550 can be carried out with a catalytic amount of PdCl2 and two equivalents of CuCb in MeCN[495], Similarly, treatment of allene with PdBr2 affords the dimeric complex 551. Treatment of this complex with 2 equiv, of bromine yields the dibromide 552. The tetra-bromide 553 is obtained by the reaction of an excess of bromine[496]. Similarly,... 

Bromination of isoprene using Br2 at —5 ° C in chloroform yields only /n j -l,4-dibromo-2-methyl-2-butene (59). Dry hydrogen chloride reacts with one-third excess of isoprene at —15 ° C to form the 1,2-addition product, 2-chloro-2-methyl-3-butene (60). When an equimolar amount of HCl is used, the principal product is the 1,4-addition product, l-chloro-3-methyl-2-butene (61). The mechanism of addition is essentially all 1,2 with a subsequent isomerization step which is catalyzed by HCl and is responsible for the formation of the 1,4-product (60). The 3,4-product, 3-bromo-2-methyl-1-butene, is obtained by the reaction of isoprene with 50% HBr in the presence of cuprous bromide (59). Isoprene reacts with the reactive halogen of 3-chlorocyclopentene (62). 

Isoprene reacts with a-chloroalkyl ethers in the presence of ZnCl in diethyl ether from 0—10°C. For example,a-chloromethyl methyl ether at 10°C gives a 6 1 ratio of the 1,4-adduct, (F)4-chloro-l-methoxy-2-methyl-2-butene, to the 1,2-adduct, 2-chloro-l-methoxy-2-methyl-3-butene. Other a-chloroalkyl ethers react in a similar manner to give predominately the 1,4-addition product. A wide variety of aHyUc chlorides and bromides and a-chloroethers and esters add primarily 1,4- to isoprene in the presence of acid catalysts (8). 

Substitution reactions on dialkyl peroxides without concurrent peroxide cleavage have been reported, eg, the nitration of dicumyl peroxide (44), and the chlorination of di-/ fZ-butyl peroxide (77). Bromination by nucleophilic displacement on a-chloro- or a-hydroxyalkyl peroxides with hydrogen bromide produces a-bromoalkyl peroxides (78). 

Binary Compounds. The mthenium fluorides are RuF [51621 -05-7] RuF [71500-16-8] tetrameric (RuF ) [14521 -18-7] (15), and RuF [13693-087-8]. The chlorides of mthenium are RUCI2 [13465-51-5] an insoluble RuCl [10049-08-8] which exists in an a- and p-form, mthenium trichloride ttihydrate [13815-94-6], RuCl3-3H2 0, and RuCl [13465-52-6]. Commercial RuCl3-3H2 0 has a variable composition, consisting of a mixture of chloro, 0x0, hydroxo, and often nitrosyl complexes. The overall mthenium oxidation state is closer to +4 than +3. It is a water-soluble source of mthenium, and is used widely as a starting material. Ruthenium forms bromides, RuBr2 [59201-36-4] and RuBr [14014-88-1], and an iodide, Rul [13896-65-6]. 

Halogen donors are chemicals that release active chlorine or bromine when dissolved in water. After release, the halogen reaction is similar to that of chlorine or bromide from other sources. SoHd halogen donors commonly used in cooling water systems include l-bromo-3-chloro-5,5-dimethyIhydantoin, l,3-dichloro-5,5-dimethyIhydantoin, and sodium dichloroisocyanurate. 

Metalation. Benzene reacts with alkaH metal derivatives such as methyl or ethyUithium ia hydrocarbon solvents to produce phenyUithium [591 -51 -5], CgH Li, and methane or ethane. Chloro-, bromo-, or iodobenzene will react with magnesium metal ia ethereal solvents to produce phenyHnagnesium chloride [100-59-4], C H MgCl, bromide, oriodide (Grignard reagents) (32). 

Hydrogen hahdes normally add to form 1,2-dihaLides, though an abnormal addition of hydrogen bromide is known, leading to 3-bromo-l-chloropropane [109-70-6], the reaction is beUeved to proceed by a free-radical mechanism. Water can be added by treatment with sulfuric acid at ambient or lower temperatures, followed by dilution with water. The product is l-chloro-2-propanol [127-00-4]. 

Fig. 8. Sensitizing dyes of the cyanine class. K. = N — alkyl or chalcogens (O, S, Se, Te) R = chloro, phenyl, or additional benzene ring R = methyl, ethyl, or hydrogen n = 0, 1, 2 and RPRIME, R " = alkyl or sulfoalkyl. Solubihty in methanol for a carbocyanine dye n = 1 X = S R = Cl R = ethyl. Cationic dye (R" = R " = ethyl anion = bromide) 9.5 mmol/T. neutral dye (R" = ethyl R " = sulfopropyl) 3.6 mmol/L anionic dye (R" = R = sulfopropyl ...

In view of the high price and other difficulties associated with the use of phosphoryl bromide, the transhalogenation of 2-chloro- and 2-chloro-4,6-dimethyl-pyrimidine (919) by treatment with inexpensive phosphorus tribromide to give their bromo analogues in >50% yield, assumes potential importance as a general method (67JCS(C)1204). 

Additional pyrimido[4,5-f ]quinoline syntheses include one involving the action of cyanogen bromide on 2-chloro-3-cyanoquinoline similar to that described for pyridines (Section 2.15.5.5.1) (78JHC877), and a synthesis of pyrimido[4,5-fe]quinoline-2-carboxylic... 

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