Bromine analysis

To determine the distribution of lignin from bromine analysis, it is essential to know the reactivity of bromine toward lignin in different morphological regions. For black spruce (Picea mariana), Douglas-fir (Pseudotsuga menziesii) and loblolly pine (Pinus taeda), the lignin in the secondary wall of tracheids is 1.7... 

Preparation of Macromolecular Dioxolenium Salts. Living polystyrene prepared by the polymerization of styrene in THF with a-methylstyrene tetramer dianion reacted with a 2.1-molar amount of ethylene oxide for three hours at room temperature a 6.6-molar amount of adipoyl chloride was added, and the mixture was stirred for 20 horns a 20-molar amount of ethylenebromohydrin was added. This mixture was stirred for 44 hours. The bromoethylated polystyrene was precipitated in excess methanol and freeze-dried from benzene in a vacuum system. A 1-nitropropane solution of polystyrene dioxolenium salt was prepared by reaction of bromoethylated polystyrene with silver perchlorate in 1-nitropropane. Silver bromide was removed from the reaction mixture by filtration. Molecular weight of the product was measured by a vapor-pressure osmometer it was 1910 for living polystyrene and 5190 for the bromoethylated polystyrene. Bromine analysis of the bromoethylated polystyrene showed 67.9% of the calculated value. 

Technetium tetrabromide, TcBr4, was synthesized analogously to rhenium tetrabromide [107] by reduction of pertechnetic acid with a 46 % solution of hydrobromic acid. This procedure was repeated four times. An unstable brown-red compound was obtained which rapidly hydrolyzed in moist air. The bromine analysis was always low due to slow spontaneous loss of bromine. TcBr4 dissolves in ethanol and acetone and forms complexes with 1,2-bis(diphenyl-phosphino)ethane and triphenylphosphine [89]. 

Evaporation of the benzene in a rotary evaporator yields 4.75 g of additional product melting at 222-224°C. Sublimation at a pressure of 10 to 10 torr and between 40 and 78°C results in a loss of weight of only 0.1 g, and the melting point of the product is 228-230°C. The combined product yield of 13.83 g is 89.3% of the theoretical yield of 15.48 g. Analysis of the bromine content in the product yields 76.51% compared to the theorefacal 77.42%. Recrystallization from a dichloromethane-hexane mixture does not change the melting point or bromine analysis results for the product. 

Methyl brominated polymers (II) were prepared for comparison with the ring brominated materials. Under the conditions used (NBS, light, CCI4 at reflux, 3 hrs) with 0.5 mole NBS/repeating unit, the product contained 0.41 Br/unit by bromine analysis. A four hour reaction with 1.0 NBS/unit introduced 0.88 Br/unit. 

The Wurtz-Fittig reaction of bis(dibromomethyl)arenes yields high polymer (S6). The formulas are idealized since double-bond contents and bromine analysis indicated that the polymers were not fully conjugated. Both polymers [63] and [65] had ordered structures (X-ray diffraction) and showed good thermal stability. 

In product mixture as determined by bromine analysis RsSn——... 

Kinetic data are available for the nitration of a series of p-alkylphenyl trimethylammonium ions over a range of acidities in sulphuric acid. - The following table shows how p-methyl and p-tert-h xty augment the reactivity of the position ortho to them. Comparison with table 9.1 shows how very much more powerfully both the methyl and the tert-butyl group assist substitution into these strongly deactivated cations than they do at the o-positions in toluene and ferf-butylbenzene. Analysis of these results, and comparison with those for chlorination and bromination, shows that even in these highly deactivated cations, as in the nitration of alkylbenzenes ( 9.1.1), the alkyl groups still release electrons in the inductive order. In view of the comparisons just... 

Chlorine and bromine add vigorously, giving, with proper control, high yields of 1,2-dihaloethyl ethers (224). In the presence of an alcohol, halogens add as hypohaUtes, which give 2-haloacetals (225,226). With methanol and iodine this is used as a method of quantitative analysis, titrating unconsumed iodine with standard thiosulfate solution (227). 

Bromine ttifluoride is commercially available at a minimum purity of 98% (108). Free Br2 is maintained at less than 2%. Other minor impurities are HF and BrF. Free Br2 content estimates are based on color, with material containing less than 0.5% Br2 having a straw color, and ca 2% Br2 an amber-red color. Fluoride content can be obtained by controlled hydrolysis of a sample and standard analysis for fluorine content. Bromine ttifluoride is too high boiling and reactive for gas chromatographic analysis. It is shipped as a Hquid in steel cylinders in quantities of 91 kg or less. The cylinders are fitted with either a valve or plug to faciUtate insertion of a dip tube. Bromine ttifluoride is classified as an oxidizer and poison by DOT. 

Bismuth Tribromide. Bismuth(III) bromide is a hygroscopic, golden-yeUow, crystalline soHd made up of pyramidal molecules. X-ray analysis has shown that the three bromines are 0.263 0.002 nm from the bismuth and the Br—Bi—Br angles are 100 4°. More recent nqr experiments indicate that the bromines are not equivalent (20). The soHd has a density of 5.72 g/mL and that of the Hquid is 4.572 g/mL at 271.5°C. 

Bromine is used as an analytical reagent to determine the amount of unsaturation in organic compounds because carbon—carbon double bonds add bromine quantitatively, and for phenols which add bromine in the ortho and para positions. Standard bromine is added in excess and the amount unreacted is deterrnined by an indirect iodine titration. Bromine is also used to oxidize several elements, such as T1(I) to T1(III). Excess bromine is removed by adding phenol. Bromine plus an acid, such as nitric and/or hydrochloric, provides an oxidizing acid mixture usefiil in dissolving metal or mineral samples prior to analysis for sulfur. 

Analysis. Butenes are best characterized by their property of decolorizing both a solution of bromine in carbon tetrachloride and a cold, dilute, neutral permanganate solution (the Baeyer test). A solution of bromine in carbon tetrachloride is red the dihaUde, like the butenes, are colorless. Decoloration of the bromine solution is rapid. In the Baeyer test, a purple color is replaced by brown manganese oxide (a precipitate) and a colorless diol. These tests apply to all alkenes. 

When simple Hquids like naphtha are cracked, it may be possible to determine the feed components by gas chromatography combined with mass spectrometry (gc/ms) (30). However, when gas oil is cracked, complete analysis of the feed may not be possible. Therefore, some simple definitions are used to characterize the feed. When available, paraffins, olefins, naphthenes, and aromatics (PONA) content serves as a key property. When PONA is not available, the Bureau of Mines Correlation Index (BMCI) is used. Other properties like specific gravity, ASTM distillation, viscosity, refractive index. Conradson Carbon, and Bromine Number are also used to characterize the feed. In recent years even nuclear magnetic resonance spectroscopy has been... 

Benz[e][ 1,2]azaborine, 1,2-dihydro-2-methyl-halogenation, 1, 656 Benz[6]- 1-azafulvenes dimerization, 4, 309 Benz[c]-2-azafulvenes dimerization, 4, 309 Benzazatropolone X-ray analysis, 7, 494 1 -Benzazepine, N-acetyl-6-hydroxy-bromination, 7, 528... 

X-RAY FLUORESCENCE ANALYSIS OE ORGANIC COMPOUNDS CONTAINING BROMINE USING QUASI-SOLID SPECIMENS... 

The optical rotatory dispersion curves of steroidal ketones permit a distinction to be made between the conformations, and assignment of configuration is possible without resorting to chemical methods (see, e.g. ref. 36) which are often tedious. The axial halo ketone rule and, in the more general form, the octant rule summarize this principle and have revealed examples inconsistent with the theory of invariable axial attack in ketone bromination. 2-Methyl-3-ketones have been subjected to a particularly detailed analysis. There are a considerable number of examples where the products isolated from kinetically controlled brominations have the equatorial orientation. These results have been interpreted in terms of direct equatorial attack rather than initial formation of the axial boat form. 

An important series of reactions, which illustrates the diversity of behaviour to be expected, is the comproportionation of halates and halides. Bromides are oxidized quantitatively to bromine and iodides to iodine, this latter reaction being much used in volumetric analysis ... 

Repeat this analysis for the bromine addition and substitution reactions of benzene leading to trans-5,6-dibromo-l,3-cyclohexadiene and phenyl bromide, respectively. Do your thermochemical results account for the experimental observations ... 

Bromination of substituted biphenyls is more complicated since bromination of each ring may lead to different products. Repeat the analysis described above for each of the following reactions. 

The solid disulfide reacts explosively with chlorine or bromine. At low temperatures in certain non-aqueous solvents, e.g. chloroform, CISCSN3 and BrSCSN3 are probably formed, but the extreme instability of these compounds has precluded their exact analysis and description. However, the reaction between cyanogen bromide and the potassium salt of the thiol yields the well-defined cyanide NCSCSN3,... 

---