Reflux distillation procedure

By far the best method I have tried to produce benzodioxole in terms of yields and simplicity. In comparison to other processes, this is in fact quite fun and I ll explain It in a fashion that can be followed by a complete novice, like I was when I started a while ago. What we do is react and reflux the ingredients first, then use a simple distillation procedure to extract the product with water as an azeotrope. Once extracted we wash until the product is clear, and then separate. From start to finish it will take about six hours. 

Dehydration by total reflux distillation This technique is suitable for warm services (100 to 200°F) and is similar to liquid circulation but at the same time, water is stripped from the liquid. Similar to dehydration by liquid circulation, this operation needs to be performed at a positive pressure. This dehydration procedure can be slow and tedious. Further details are discussed in Sec. 12.8... 

The first important step in this systematic procedure is to analyse the number of degrees of freedom (DOF) for the system. For the integrated prefractionator arrangement there are eleven DOF, when assuming a fixed feedrate. These are the boilup in the HP column, the condensation rate in the HP column, reflux, distillate and bottom flowrate from both columns, sidestream flowrate in the LP column, boilup in the IP column and condensation rate in the LP column (see Figure 1). 

Such one-step reactions are the exception rather than the rule. More commonly, it is necessary to carry out a series of successive reactions and procedures, such as refluxing, distilling, crystallization, filtration and washing in an inert atmosphere. The most evident way of doing this is to work in an inert-atmosphere filled glove box using conventional apparatus. This is both... 

If preferred, the following alternative procedure may be adopted. The absolute alcohol is placed in a 1 5 or 2 litre three-necked flask equipped with a double surface reflux condenser and a mercury-sealed mechanical stirrqr the third neck is closed with a dry stopper. The sodium is introduced and, when it has reacted completely, the ester is added and the mixture is gently refluxed for 2 hours. The reflux condenser is then rapidly disconnected and arranged for downward distillation with the aid of a short still head or knee tube. The other experimental details are as above except that the mixture is stirred during the distillation bumping is thus reduced to a minimum. 

Allyl Chloride. Comparatively poor yields are obtained by the zinc chloride - hydrochloric acid method, but the following procedure, which employs cuprous chloride as a catalyst, gives a yield of over 90 per cent. Place 100 ml. of allyl alcohol (Section 111,140), 150 ml. of concentrated hydrochloric acid and 2 g. of freshly prepared cuprous chloride (Section II,50,i one tenth scale) in a 750 ml. round-bottomed flask equipped with a reflux condenser. Cool the flask in ice and add 50 ml. of concen trated sulphuric acid dropwise through the condenser with frequent shaking of the flask. A little hydrogen chloride may be evolved towards the end of the reaction. Allow the turbid liquid to stand for 30 minutes in order to complete the separation of the allyl chloride. Remove the upper layer, wash it with twice its volume of water, and dry over anhydrous calcium chloride. Distil the allyl chloride passes over at 46-47°. 

For water insoluble aldehydes or ketones, the following alternative procedure may be used. Reflux a mixture of 0-6 g. of the aldehyde or ketone, 0 5 g. of hydroxylamine hydrochloride, 5 ml. of ethanol and 0 5 ml. of pyridine on a water bath for 15-60 minutes. Remove the alcohol either by distillation (water bath) or by evaporation of the hot solution in a stream of air (water pump). Add 5 ml. of water to the cooled residue, cool in an ice bath and stir until the oxime crystallises Filter off the solid, wash it with a little water and dry. Recrystallise from alcohol (95 per cent, or more dilute), benzene, or benzene - light petroleum (b.p. 60-80°). 

Suberic acid. Prepare hexamethylene dibromide from hexamethy-lene glycol (Section 111,15) according to the procedure described in Section 111,35). Convert the 1 6-dibromohexane, b.p. H4r-115°/12 mm., into hexamethylene dicyanide, b.p. 178-180°/15 mm., by refluxing it with a 20-25 per eent. excess of aqueous - alcoholic sodium cyanide solution (compare Section 111,114), distilling off the hquid under diminished... 

The purified commercial di-n-butyl d-tartrate, m.p. 22°, may be used. It may be prepared by using the procedure described under i o-propyl lactate (Section 111,102). Place a mixture of 75 g. of d-tartaric acid, 10 g. of Zeo-Karb 225/H, 110 g. (136 ml.) of redistilled n-butyl alcohol and 150 ml. of sodium-dried benzene in a 1-litre three-necked flask equipped with a mercury-sealed stirrer, a double surface condenser and an automatic water separator (see Fig. Ill, 126,1). Reflux the mixture with stirring for 10 hours about 21 ml. of water collect in the water separator. FUter off the ion-exchange resin at the pump and wash it with two 30-40 ml. portions of hot benzene. Wash the combined filtrate and washings with two 75 ml. portions of saturated sodium bicarbonate solution, followed by lOu ml. of water, and dry over anhydrous magnesium sulphate. Remove the benzene by distillation under reduced pressure (water pump) and finally distil the residue. Collect the di-n-butyl d-tartrate at 150°/1 5 mm. The yield is 90 g. 

Alternatively, use the following procedure in which triethylamine replaces potassium acetate as the basic catalyst. Place 2 1 g. (2-0 ml.) of purified benzaldehyde, 2 0 ml. of anhydrous triethylamine and 5 0 ml. of A.R. acetic anhydride in a 200 ml. round-bottomed flask, equipped with a short reflux condenser and a calcium chloride drying tube. Boil the solution gently for 24 hours—heating may be interrupted. Incorporate a steam distillation apparatus in the flask and steam distil until the distillate is no longer cloudy (about 100 ml.) and then collect a further 50 ml. of the distillate di ard the steam distillate. Transfer the residue in the flask to a 400 ml. beaker, add water until the vplume is about 200 ml., then 0 2 g. of decolourising carbon, and boil for a few minutes. Filter the hot solution, and acidify the hot filtrate with 1 1 hydrochlorioiaoid... 

This is a way to do this procedure without having to use one of those crazy tube furnaces stuffed with thorium oxide or manganous oxide catalyst [21]. The key here is to use an excess of acetic anhydride. Using even more than the amount specified will insure that the reaction proceeds in the right direction and the bad side reaction formation of dibenzylketone will be minimalized (don t ask). 18g piperonylic acid or 13.6g phenylacetic acid, 50mL acetic anhydride and 50mU pyridine are refluxed for 6 hours and the solvent removed by vacuum distillation. The remaining residue is taken up in benzene or ether, washed with 10% NaOH solution (discard the water layer), and vacuum distilled to get 8g P2P (56%). 

To a mixture of O.BB mol of anhydrous lithium chloride and 100 ml of OMSO was added a solution of 0.40 mol of the acetylenic tosylate (for a general procedure concerning the preparation of acetylenic tosylates, see Chapter VllI-3, Exp. 3) in IBO ml of DMSO. The flask was equipped for vacuum distillation (see Fig. 5). Between the receiver, which was cooled at -75°C, and the water-pump was placed a tube filled with KOH pellets. The apparatus was evacuated (10-20 mmHg) and the flask gradually heated until DMSO began to reflux in the column. The contents of... 

Medium Boiling Esters. Esterificatioa of ethyl and propyl alcohols, ethylene glycol, and glycerol with various acids, eg, chloro- or bromoacetic, or pymvic, by the use of a third component such as bensene, toluene, hexane, cyclohexane, or carbon tetrachloride to remove the water produced is quite common. Bensene has been used as a co-solvent ia the preparatioa of methyl pymvate from pymvic acid (101). The preparatioa of ethyl lactate is described as an example of the general procedure (102). A mixture of 1 mol 80% lactic acid and 2.3 mol 95% ethyl alcohol is added to a volume of benzene equal to half that of the alcohol (ca 43 mL), and the resulting mixture is refluxed for several hours. When distilled, the overhead condensate separates iato layers. The lower layer is extracted to recover the benzene and alcohol, and the water is discarded. The upper layer is returned to the column for reflux. After all the water is removed from the reaction mixture, the excess of alcohol and benzene is removed by distillation, and the ester is fractionated to isolate the pure ester. 

Regardless of the procedure used, certain initial steps must be taken for the determination or specification of certain product properties and yields based on the TBP distillation curve of the column feed, method of providing column reflux, column-operating pressure, type of condenser, and type of side-cut strippers ana stripping requirements. These steps are developed and ilhistrated with several detailed examples by Watkins (op. cit.). Only one example, modified from one given by Watkins, is considered briefly here to indicate the approach taken during the initial steps. 

Other control methods. A cychng procedure can be used to set the pattern for column operation. The unit operates at total reflux until equilibrium is established. Distillate is then taken as total draw-... 

In Distefano s method, Eqs. (13-149) to (13-161) are solved with an initial condition of total reflux at Lq equal to D R + 1) from the specifications. At t = 0, Lq is reduced so as to begin distillate withdrawal. The computational procedure is then as follows ... 

For a second run the distillate is placed in a i-l. flask with 4 cc. of water, 25 g. of the azlactone, and 20 g. of red phosphorus. The mixture is refluxed for three to four hours and treated according to the above procedure. The yield is practically the same as in the first case. 

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