Mixtures browning

Parallel reactions of the Schemes VI and VII type have attracted much interest because of their analytical utility. If a mixture of two or three reactants can be arranged to undergo parallel reactions, with appropriate rate constant ratios, it may be possible to determine the composition of the initial mixture. Brown and Fletcher introduced the extrapolation technique discussed above for this purpose, and many modifications of the approach have since been made. ... 

When the green iodide product is recrystallized (as above) from an ethanol-dimethylformamide mixture, brown crystals are obtained. These crystals, which analyze for Crl2-4py, are filtered off and dried under vacuum. Anal. Calcd. for Crl2-4py Cr, 8.4 I, 40.8 C, 38.6 H, 3.2. Found Cr, 8.3 I, 40.6 C, 38.6 H, 3.2. 

After addition of 2 g of Cu(OAc)2, the solution of R 2NCH2OH (half the amount of that prepared in exp. 1.1 is used) is brought 10 70 C, then the reactive acetylenic compound (0.55 mol) is added over - 20 min. while keeping the temperature between 70 and 80 C. Tie conversion is terminated by heating the mixture (brown suspension) for an additional half hour at 90"G after which it is cooled to room temperature. 

Fig, 2-16. Critical loci of binary n-paraffin mixtures. (Brown et al., Natural Gas and the Volatile Hydrocarbons, NGAA, 1947, 4, with permission.)... 

In a medium bowl, combine the egg yolks, ground almonds, cooled chocolate mixture, brown sugar, and vanilla extract, whisking to combine. Set aside. 

The second evidence confirming the structure of the pyrolysis product was furnished shortly after publication of the above results. The pyrolysis of p -xylene yields, in addition to the poly-p -xylelene, some minor products. From their mixture Brown and Farthing isolated an interesting hydrocarbon and identified this product by x-ray analysis as paracyclophane,... 

Table 1 indicates that the enthalpy of mixing in the liquid phase is not important when calculating enthalpies of vaporization, even though for this system, the enthalpy of mixing is large (Brown, 1964) when compared to other enthalpies of mixing for typical mixtures of nonelectrolytes. 

Crum Brown s rule A guide to substitution in benzene derivatives. This rule states that a substance C Hj A yields the meia disubstituied product if the compound HA can be oxidized directly to HOA otherwise a mixture of the o-and p-compounds will be obtained. Not universally applicable.. Sec Hammick and Illingworth s rules. 

By warming either copper(I) oxide or a mixture of copper(II) chloride and copper with concentrated hydrochloric acid, until a deep brown solution is formed ... 

The plate is removed from the tank, the position of the solvent front marked, and the solvent allowed to evaporate from the plate. If the components of the mixture are coloured, the separation is obvious if colourless, they must be located either by viewing under U.. or by standing the plate in a closed dry tank containing crystals of iodine, whose vapour makes brown spots show i p. 

Add 2 -3 drops of phenylhydrazine to about 2 ml. of Fehling s solution in a test-tube and shake the mixture vigorously nitrogen is evolved and reddish-brown cuprous oxide is precipitated. The reaction proceeds rapidly on gentle warming, more slowly in the cold. 

Assemble in a fume-cupboard the apparatus shown in Fig. 67(A). Place 15 g. of 3,5-dinitrobenzoic acid and 17 g. of phosphorus pentachloride in the flask C, and heat the mixture in an oil-bath for hours. Then reverse the condenser as shown in Fig. 67(B), but replace the calcium chloride tube by a tube leading to a water-pump, the neck of the reaction-flask C being closed with a rubber stopper. Now distil off the phosphorus oxychloride under reduced pressure by heating the flask C in an oil-bath initially at 25-30, increasing this temperature ultimately to 110°. Then cool the flask, when the crude 3,5-dinitro-benzoyl chloride will solidify to a brown crystalline mass. Yield, 16 g., i.e,y almost theoretical. Recrystallise from caibon tetrachloride. The chloride is obtained as colourless crystals, m.p. 66-68°, Yield, 13 g Further recrystallisation of small quantities can be performed using petrol (b.p. 40-60°). The chloride is stable almost indefinitely if kept in a calcium chloride desiccator. 

Now cork the flask securely, and shake it vigorously for about 5 minutes the solution should now have only a faint brown colour due to unchanged iodine. Cool the mixture in ice-water, pour it into a separating-funnel, and extract it twice with water to remove sodium iodide and most of the ethanol. Then shake the residual ethereal solution with a dilute aqueoussolution of sodium thiosulphate the excess of iodine is thus removed and the... 

To a few drops of the ester, add 0 2 g. of hydroxylamine hydrochloride and about 5 ml. of 10% NaOH solution and gently boil the mixture for 1-2 minutes. Cool and acidify with HCl, cool again and then add a few drops of FeClj solution. A violet or deep red-brown colour develops immediately. 

Action of sodium hydroxide. Boil about 0 2 g. of glucose with 5 of 10% NaOH solution the mixture turns yellow, then brown, and emits the odour of caramel. Fructose, maltose, lactose and soluble starch behave similarly sucrose and ordinary starch do not give colorations. 

I. Oxidation to benzoic acid. Boil a mixture of i ml. of benzyl chloride, 50 ml. of saturated aqueous KMn04 solution and 2 g. of anhydrous Na.jCOj under reflux for 30 minutes. Acidify with cone. HCl and then add 25% Na SOj solution until the brown precipitate of MnOj has dissolved. On cooling, benzoic acid crystallises out. Filter through a small Buchner funnel, wash with water and identify (P 347) When recrystallised from water, benzoic acid has m.p. 121 . 

Place 10 ml. of 1% starch solution (prepared as described above) in a boiling-tube, add 2 ml. of 1% sodium chloride solution and place the tube in a water-bath maintained at 38-40 . Place about 5 ml. of water in a series of test-tubes and to each add a few drops of 1% iodine solution. Now add 4 ml. of the diluted saliva solution to the starch solution, mix well and note the time. At intervals of about 30 seconds transfer 2 drops of the reacting mixture, by means of a dropping tube, to one of the test-tubes, mix and note the colour. As in the previous experiment, the colour, which is blue at first, changes to blue-violet, red-violet, red-brown, pale brown, and finally disappears at this stage the solution will reduce Fehling s solution. If the reaction proceeds too quickly for the colour changes to be observed, the saliva solution should be diluted. 

Hydrobromic acid. Method 1 (from bromine and sulphur dioxide). A mixture of 600 g. (or 188-6 ml.) of bromine, 250 ml. of water and 760 g. of crushed ice is placed in a 1 6 litre round-bottomed flask and a rapid stream of sulphur dioxide (from a siphon of the liquefied gas) is passed into the flask, care being taken that the outlet of the gas-delivery tube is below the surface of the bromine layer. The rate of flow of the gas is adjusted so that it is completely absorbed. It is advisable to cool the flask in ice and also to shake the contents from time to time. The reduction is complete when the mixture assumes a uniform yellowish-brown or yellow colour, which is unaffected by further introduction of sulphur dioxide excess of the latter gas should be avoided as it will be... 

In a 1-litre three-necked flask, fitted with a mechanical stirrer, reflux condenser and a thermometer, place 200 g. of iodoform and half of a sodium arsenite solution, prepared from 54-5 g. of A.R. arsenious oxide, 107 g. of A.R. sodium hydroxide and 520 ml. of water. Start the stirrer and heat the flask until the thermometer reads 60-65° maintain the mixture at this temperature during the whole reaction (1). Run in the remainder of the sodium arsenite solution during the course of 15 minutes, and keep the reaction mixture at 60-65° for 1 hour in order to complete the reaction. AUow to cool to about 40-45° (2) and filter with suction from the small amount of solid impurities. Separate the lower layer from the filtrate, dry it with anhydrous calcium chloride, and distil the crude methylene iodide (131 g. this crude product is satisfactory for most purposes) under diminished pressure. Practically all passes over as a light straw-coloured (sometimes brown) liquid at 80°/25 mm. it melts at 6°. Some of the colour may be removed by shaking with silver powder. The small dark residue in the flask solidifies on cooling. 

In a 200 ml. distilling flask place 64 g. (50 ml.) of dry n-butyl bromide and 80 g. of dry silver nitrite (1). Insert a reflux condenser, carrying a cotton wool (or calcium chloride) guard tube, into the mouth of the flask and close the side arm with a small stopper. Allow the mixture to stand for 2 hours heat on a steam bath for 4 hours (some brown fumes are evolved), followed by 8 hours in an oil bath at 110°. Distil the mixture and collect the fraction of b.p. 149-151° as pure 1-nitro-n-butane (18 g.). A further small quantity may be obtained by distilling the fractions of low boihng point from a Widmer flask. 

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