Hydrochloric acid catalyst

This appears to be a main constituent of commercial cyclohexanone peroxide together with the bis(hydroperoxy) peroxide (below), and is also known to be hazardous [1], Prepared from cyclohexanone and 30% hydrogen peroxide in presence of hydrochloric acid catalyst, it must be kept moist after isolation as it may explode on drying out [2],... 

C. Usually the polymerisation is carried out in the presence of Ziegler-Natta catalysts based on titanium tetrachloride and aluminium alkyl. The catalyst may be either prepared or formed in the reactor. Usually, the polymerisation is carried out in presence of a hydrocarbon solvent. The polymer is insoluble in the solvent. The reaction is terminated by addition of an alcohol and catalyst extracted with alcoholic hydrochloric acid. Catalyst removal is important for electrical insolution used. The Polymer chain obtained by this process is essentially linear. 

The older Bechamp method for iron oxide pigment production gives aniline as a co-product and is operated by Bayer in West Virginia. Nitrobenzene is reduced by reaction with iron filings in the presence of a hydrochloric acid catalyst. The iron is oxidized to the ferrous or ferric state, and the aniline-water mixture is separated from the iron-hydroxide sludge. The heavier aniline layer is removed and vacuum distilled to yield pure aniline. The yield is 90% to 95% of theoretical. The reactions are represented as follows138,255 ... 

Aniline can also be made by two other methods. In the first, nitrobenzene is reduced by reaction with scrap iron in the presence of a hydrochloric acid catalyst. The iron is oxidized to the ferrous state, and the coproduct aniline is separated. This route accounts for less than 5 percent of the current aniline production. The other process avoids nitrobenzene entirely and involves the vapor-phase ammonolysis of phenol, using an alumina catalyst. Aniline is formed with dipheny-lamine as a by-product. About 20 percent of the aniline is produced by this route. 

The variables affecting the product distribution are aniline concentration, hydrochloric acid concentration, and temperature. The higher the excess of aniline, the higher is the diamine concentration. Higher hydrochloric acid concentration and lower initial temperature favor the formation of 4,4 -MDA. Attempts were made over the years to replace the aqueous hydrochloric acid catalyst with slower reacting solid acidic clay catalysts, but the obtained product distribution was different, and therefore this approach was never used. 

Hoesch synthesis A variation of the Gattermann synthesis of hydroxy-aldehydes, this reaction has been widely applied to the synthesis of anthocyanidins. It consists of the condensation of polyhydric phenols with nitriles by the action of hydrochloric acid (with or without ZnCl2 as a catalyst). This gives an iminehydrochloride which on hydrolysis with water gives the hydroxy-ketone. 

Uses of hydrogen chloride—Hydrogen chloride is sometimes used in the preparation of an ester, for example ethyl benzoate, where it acts as both an acid catalyst and a dehydrating agent. Hydrochloric acid is used primarily to produce chlorides, for example ammonium chloride. It is extensively used in the manufacture of anilme dyes, and for cleaning iron before galvanising and tin-plating. 

For this reaction, charcoal is a catalyst if this is omitted and hydrogen peroxide is used as the oxidant, a red aquopentammino-cobalt(lll) chloride, [Co(NH3)jH20]Cl3, is formed and treatment of this with concentrated hydrochloric acid gives the red chloro-p0itatnmino-coba. t(lll) chloride, [Co(NH3)5Cl]Cl2. In these latter two compounds, one ammonia ligand is replaced by one water molecule or one chloride ion it is a peculiarity of cobalt that these replacements are so easy and the pure products so readily isolated. In the examples quoted, the complex cobalt(III) state is easily obtained by oxidation of cobalt(II) in presence of ammonia, since... 

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°. 

C. Fumaric acid from furfural. Place in a 1-litre three-necked flask, fitted with a reflux condenser, a mechanical stirrer and a thermometer, 112 5 g. of sodium chlorate, 250 ml. of water and 0 -5 g. of vanadium pentoxide catalyst (1), Set the stirrer in motion, heat the flask on an asbestos-centred wire gauze to 70-75°, and add 4 ml. of 50 g. (43 ml.) of technical furfural. As soon as the vigorous reaction commences (2) bvi not before, add the remainder of the furfural through a dropping funnel, inserted into the top of the condenser by means of a grooved cork, at such a rate that the vigorous reaction is maintained (25-30 minutes). Then heat the reaction mixture at 70-75° for 5-6 hours (3) and allow to stand overnight at the laboratory temperature. Filter the crystalline fumaric acid with suction, and wash it with a little cold water (4). Recrystallise the crude fumaric acid from about 300 ml. of iif-hydrochloric acid, and dry the crystals (26 g.) at 100°. The m.p. in a sealed capillary tube is 282-284°. A further recrystaUisation raises the m.p. to 286-287°. 

The vanadium pentoxide catalyst Is prepared as follows Suspend 5 g. of pure ammonium vanadate in 50 ml. of water and add slowly 7 5 ml. of pure concentrated hydrochloric acid. Allow the reddish-brown, semi-colloidal precipitate to settle (preferably overnight), decant the supernatant solution, and wash the precipitate several times by decantation. Finally, suspend the precipitate in 76 ml. of water and allow it to stand for 3 days. This treatment renders the precipitate granular and easy to 6lter. Filter the precipitate with suction, wash it several times with cold 5 p>er cent, sodium chloride solution to remove hydrochloric acid. Dry the product at 120° for 12 hours, grind it in a mortar to a fine powder, and heat again at 120° for 12 hours. The yield of catalyst is about 3 - 5 g. 

The palladium may be recovered by heating the spent catalyst to redness in order to remove organic impurities this treatment may reduce some of the barium sulphate to barium sulphide, which acts as a catalytic poison. The palladium is then dissolved out with aqua regia and the solution evaporated the residue is dissolved in hot water and hydrochloric acid to form palladium chloride. 

An important general method of preparing indoles, known as the Fischer Indole synthesis, consists in heating the phenylhydrazone of an aldehyde, ketone or keto-acld in the presence of a catalyst such as zinc chloride, hydrochloric acid or glacial acetic acid. Thus acrtophenone phenylhydrazone (I) gives 2-phenyllndole (I V). The synthesis involves an intramolecular condensation with the elimination of ammonia. The following is a plausible mechanism of the reaction ... 

Hydrolysis of the azlactone leads to the acylaminooinnamic acid the latter may be be reduced catal3rtlcally (Adams PtOj catalyst 40 lb. p.s.i.) and then hydrolysed by hydrochloric acid to the amino acid. Alternatively, the azlactone (say, of a-benzylaminocinnamic acid) may undergo reduction and cleavage with phosphorus, hydriodic acid and acetic anhydride directly to the a-amino acid (d/ p phenylalanine). 

Method A. Cool a solution of the nitrate-free dichloride, prepared from or equivalent to 5 0 g. of palladium or platinum, in 50 ml. of water and 5 ml. of concentrated hydrochloric acid in a freezing mixture, and treat it with 50 ml. of formahn (40 per cent, formaldehyde) and 11 g. of the carrier (charcoal or asbestos). Stir the mixture mechanically and add a solution of 50 g. of potassium hydroxide in 50 ml. of water, keeping the temperature below 5°. When the addition is complete, raise the temperature to 60° for 15 minutes. Wash the catalyst thoroughly by decantation with water and finally with dilute acetic acid, collect on a suction filter, and wash with hot water until free from chloride or alkali. Dry at 100° and store in a desiccator. 

C. Palladium on carbon catalyst (5 per cent. Pd). Suspend 41-5 g. of nitric acid - washed activated carbon in 600 ml. of water in a 2-litre beaker and heat to 80°. Add a solution of 4 1 g. of anhydrous palladium chloride (1) in 10 ml. of concentrated hydrochloric acid and 25 ml. of water (prepared as in A), followed by 4 ml. of 37 per cent, formaldehyde solution. Stir the suspension mechanically, render it alkaUne to litmus with 30 per cent, sodium hydroxide solution and continue the stirring for a further 5 minutes. Filter off the catalyst on a Buchner funnel, wash it ten times with 125 ml. portions of water, and dry and store as in B. The yield is 46 g. 

Nitriles react with ammonia, or primary or secondary amines in the presence of an acid catalyst to give amidines (Scheme 26) (75, 77, 81). The catalysts used are hydrochloric acid and aluminium chloride. The amidines are anthelmintics for animals such as sheep, goats, cattle, horses, and Swine. 

Polymerization. Paraldehyde, 2,4,6-trimethyl-1,3-5-trioxane [123-63-7] a cycHc trimer of acetaldehyde, is formed when a mineral acid, such as sulfuric, phosphoric, or hydrochloric acid, is added to acetaldehyde (45). Paraldehyde can also be formed continuously by feeding Hquid acetaldehyde at 15—20°C over an acid ion-exchange resin (46). Depolymerization of paraldehyde occurs in the presence of acid catalysts (47) after neutralization with sodium acetate, acetaldehyde and paraldehyde are recovered by distillation. Paraldehyde is a colorless Hquid, boiling at 125.35°C at 101 kPa (1 atm). 

Uncatalyzed addition of hydrochloric acid is accompanied by replacement of one hydroxyl group, giving high yields of 2,4-dichloro-2-buten-l-ol (58) with mercuric or cupric salt catalysts, addition occurs without substitution (59,60). 

Heating with cuprous chloride in aqueous hydrochloric acid isomerizes 2-butene-l,4-diol to 3-butene-l,2-diol (98)] Various hydrogen-transfer catalysts isomerize it to 4-hydroxybutyraldehyde [25714-71-0] (99), acetals of which are found as impurities in commercial butanediol and... 

With a nickel carbonyl catalyst, hydrochloric acid, and an alcohol the initially formed aHenic ester cyclizes on distillation (198). 

The reaction occurs bypassing HCN and a 10 1 excess of acetylene into dilute hydrochloric acid at 80°C in the presence of cuprous chloride as the catalyst. 

HF is used as a source of fluorine for production of all the various fluorocarbon products. HF reacts in the presence of a suitable catalyst and under the appropriate temperature and pressure conditions with various organic chemicals to yield a family of products. A by-product stream of hydrochloric acid may be co-produced. 

Most phenohc foams are produced from resoles and acid catalyst suitable water-soluble acid catalysts are mineral acids (such as hydrochloric acid or sulfuric acid) and aromatic sulfonic acids (63). Phenohc foams can be produced from novolacs but with more difficulty than from resoles (59). Novolacs are thermoplastic and require a source of methylene group to permit cure. This is usually suppHed by hexamethylenetetramine (64). 

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