Bromo toluene

Aryloxy- 3,5-Dinitro- 1-Naphthyl p-Toluene- Bromo-Benzoate acetic acid benzoate carbamate sulphonate derivative... 

It is very simple to trade in a bromine atom against an iodine atom by the consecutive treatment of the bromo compound with -butyllithium and molecular iodine. Such an exchange may offer practical advantages as only the derivatives of the heaviest halogen undergo halogen/metal permutations very rapidly even at -100 °C and in poorly polar solvents such as toluene. Bromo analogs react several powers of ten more slowly. 

Bromo-4-aminotoluene, Suspend the hydrochloride in 400 ml, of water in a 1-Utre beaker equipped with a mechanical stirrer. Add a solution of 70 g. of sodium hydroxide in 350 ml. of water. The free base separates as a dark heavy oil. After cooUng to 15-20°, transfer the mixture to a separatory funnel and run off the crude 3-bromo-4-amino-toluene. This weighs 125 g. and can be used directly in the next step (3). 

Equip a 1 litre three-necked flask wdth a reflux condenser, a mechanical stirrer, and a cork carrying a dropping funnel and a thermometer which reaches nearly to the bottom of the flask connect the upper end of the condenser to an absorption trap (Fig. II, 8, 1). Place 100 g. of p-bromo-toluene (Section IV.62) in the flask and immerse the latter in an oil bath (colourless oil in a large beaker). Heat the bath until the temperature of the stirred p-broniotoluene reaches 105°. Illuminate the liquid with... 

In a 500 ml. bolt-head flask provided with a thermometer (reaching almost to the bottom) and a calcium chloride (or cotton wool) guard tube, place 100 g. of a-bromo-wo-valerj l bromide and 50 g. of dry, finely-divided urea. Start the reaction by warming the flask on a water bath the temperature soon rises to about 80°. Maintain this temperature for about 3 horns the mass will liquefy and then resolidify. Transfer the sticky reaction product to a large beaker containing saturated sodium bicarbonate solution, stir mechanically and add more saturated sodium bicarbonate solution in small quantities until effervescence ceases. Filter at the pump, suck as dry as possible and dry the crude bromural upon filter paper in the air. RecrystaUise the dry product from toluene. Alternatively, recrystaUise the moist product from hot water (ca. 700 ml.). The yield of pure brommal, m.p. 154-155°, is 28 g. 

First-order nitrations. The kinetics of nitrations in solutions of acetyl nitrate in acetic anhydride were first investigated by Wibaut. He obtained evidence for a second-order rate law, but this was subsequently disproved. A more detailed study was made using benzene, toluene, chloro- and bromo-benzene. The rate of nitration of benzene was found to be of the first order in the concentration of aromatic and third order in the concentration of acetyl nitrate the latter conclusion disagrees with later work (see below). Nitration in solutions containing similar concentrations of acetyl nitrate in acetic acid was too slow to measure, but was accelerated slightly by the addition of more acetic anhydride. Similar solutions in carbon tetrachloride nitrated benzene too quickly, and the concentration of acetyl nitrate had to be reduced from 0-7 to o-i mol 1 to permit the observation of a rate similar to that which the more concentrated solution yields in acetic anhydride. 

That aqueous layer that was saved can be removed of most of its water by vacuum distillation, allowed to cool slightly then extracted with hot toluene. When the toluene cools, a few hundred more grams of catechol will crystallize out but will be contaminated with some heavy red bromo compounds. The crystals are filtered and vacuum distilled such that the pyrocatechol will distill over first, leaving the higher boiling bromo compounds behind. Yield is about 80% or 600g of catechol. 

After the addition of 2 1. of water, the mixture is steam-distilled as long as any oil comes over. The crude, heavy, yellow oil is separated and washed with two 200-cc. portions of 10 per cent sodium hydroxide, once with 100 cc. of water, twice with 150-cc. portions of concentrated sulfuric acid, and finally with 100 cc. of 5 per cent, sodium carbonate solution. It is dried with about 5 g. of calcium chloride, filtered through glass wool, and distilled using a long air condenser. Most of the product boils at i8o-i83°/75o mm. The yield of pure colorless material, b.p. i83°/76o mm., is 125-135 g. (36-39 per cent of the theoretical amount, based on the amount of -toluidine originally used, or 54-59 per cent based on the amount of 3-bromo-4-amino-toluene). 

Bromural [A -(aminocarbonyl)-2-bromo-3-methylbutanamide, bromisovalum] [496-67-3] M 223.1, m 154-155 . Crystd from toluene, and air dried. 

Bromo atom of ethyl (3S)-10-bromo-3-methyl-7-oxo-2,3-dihydro-7//-pyrido[l,2,3- fe]-l,4-benzothiazine-6-carboxylate was change for hetaryl groups with tributylstannyl derivatives of heterocycles in the presence of (Ph3P)2Pd(II)Cl2 in boiling toluene (OOMIPIO). 7-Aryl-5-oxo-2,3-dihydro-5//-pyrido[l,2,3- fe]-l,4-benzothiazine-6-carboxylates, 6-carboxamides and their 1,1-dioxide derivatives were prepared from 7-chloro derivatives in the... 

Quaternization of o-bromo-iv,iv-dimethyIbenzylamine with the p-toluene-sulfonate of ethanol affords bretylium tosylate (78), an antihypertensive agent acting by peripheral sympathetic blockade. 

A. Toluene diisocyates (TDI), xylene isocyanates, chloro-TDI, bromo-TDI, dichloro-TDI, and trichloro-TDI... 

Benzoic m-Toluic (Benzoic acid, 3-methyl-] p-Toluic [Benzoic acid, 4-methyl-J 3,5-Dimcthylbcnzoic [Benzoic acid, 3,5-dimcthyl-] p-Chlorobenzoic [Benzoic acid, 4-chloro-] p-Bromobenzoic [Benzoic acid, 4-bromo-J Phthalic [ 1,2-Bcnzcncdicarboxylic acid] Toluene [Benzene, methyl-] (78) m-Xylene [Benzene, 1,3-dimethyl-] (82) />-Xylene [Benzene, 1,4-dimethyl-] (74) Mesitylene [Benzene, 1,3,5-trimethyl-] (82) p-Chlorotolueno [Benzene, l-ehloro-4-methyl-] (94) p-Bromotolucnc [Benzene, l-bromo-4-methyl-] (94) o-Xylene [Benzene, 1,2-dimethyl-] (64)... 

Propargyl Bromide (3-Bromo-l-propyne). HC=CCH2Br mw 118.97 colorl to faintly brownish liq mp 24.4° bp 88—90° d 1.52 g/cc RI 1.4320 at 20°. Sol in ale, eth, benz chlf. Flammable flash pt 10° (closed), 18° (open) ignition temp 328° lower flammable limit 3.0%. It can be decompd by mild shock. When heated under confinement, it decomps with expl violence and may detonate. When suitably diluted, as with 20—30% by wt of toluene, its expl properties are practically eliminated (Ref 4)... 

Stock and Baker2 5 9 measured the relative rates of chlorination of a number of halogenated aromatics in acetic acid containing 20.8 M H20 and 1.2 M HC1 at 25 °C and the values of the second-order rate coefficients (103Ar2) are as follows p-xylene (11,450), benzene (4.98), fluorobenzene (3.68), chlorobenzene (0.489), bromobenzene (0.362), 2-chlorotoluene (3.43), 3-chlorotoluene (191), 4-chloro-toluene (2.47), 4-fluorotoluene (9.70), 4-bromotoluene (2.47). Increasing the concentration of the aromatic, however, caused, in some cases, a decrease in the rate coefficients thus an increase in the concentration of chlorobenzene from 0.1 M to 0.2 M caused a 20 % decrease in rate coefficient, whereas with 4-chloro-and 4-bromo-toluene, no such change was observed. 

Thiophenol, lithium salt [Benzenethiol, lithium salt], 55, 122 Toluene, 4-bromo- [Benzene, 1 bromo 4 methyl-], 55, 49... 

Benzene, bromo, 55, 51 Benzene, 1 -bromo4-chloro, 55, 51 Benzene, 4-bromo-l,2-dimethyl-, 55, 51 Benzene, l-bromo-4-fluoio-, 55, 51 Benzene, l-bromo-4-methoxy-, 55, 51 Benzene, 1-bromo-3-methyl-, 55, 51 Benzene, l-bromo-4-methyl- [Toluene, 4-bromo-], 55, 49... 

Heteropolycyclic compounds were obtained [29] by treating bromo furylethers with tris-(trimethylsilyl)silane (TTMSS) in hot toluene containing a catalytic amount of AIBN (Equation 1.12). 

Rapid aminations of 1-bromonaphthalenes with piperidine under microwave irradiation were reported by Hamann using Pd2(dba)3/rac. PPFA (N,N-dimethyl-1-[2-(diphenylphosphanyl)ferrocenyl]ethylamine) precatalyst in combination with NaO-t-Bu in toluene at 120 °C (Scheme 92) [97]. Typically, reactions performed under conventional heating at 120 °C (oil bath) were still progressing after 16 h and were essentially complete by 24 h, whereas the microwave reactions appeared to be finished after 10 min. The same reaction conditions were also useful to functionalize 5- and 8-bromoquinolines with anilines and aliphatic amines (Schemes 93 and 94). Remarkably, no product formation was observed with 5-bromo-8-cyanoquinoline and 5-bromo-8-methoxyquinoline under conventional heating for 24 h at the same temperature, while the desired 5-aminoquinolines were smoothly obtained under microwave irradiation in a reaction time of only 10 min. 

The reaction of 1-haIo 3-bromo propane with the phenol gives the halo-propoxy derivatives 8a (X=C1) and 8h (X=Br). The reaction proceeds in DMF, MEK or toluene at reflux in the presence of potassium carbonate but also at room temperature in DMSO (eqn. 6). 

---