IL27482A - Process for the preparation of nitrosyl hydrogen pyrosulphate - Google Patents

Description

PATENT ATTORNEYS D 1 REINHOLD COHN PATENTS AND DESIGNS ORDINANCE SPECIFICATION Process for the preparation of hydrogen pyrosulphate an Italian of Buonaparte do hereby declare the nature of this invention and in what manner the same is to be to be particularly described and ascertained in and by the following hydrogen It is known that nitrosyl hydrogen pyrosuipnate is a reactant useful in processes that exploit the reactivity of the and that can thus be advantageously used in processes involve reactions such as for instance in the cesses for the production of Nitrosyl hydrogen pyrosuipnate has shown itself particularly useful in processes for the preparation of lactams by way of reaction with cycloalkanecarboxylic The high yields attainable and the easy trol of the course of the reaction malce this process very attractive from the industrial point of Nitrosyl hydrogen shows a high thermal stability and be used advantageously under particularly severe reaction conditions for at high temperature or in the presence of substances that do not allow the use of more easily decomposable compounds containing the Ν As a matter of fact nitrosyl hydrogen pyro sulphate may be heated up to temperatures of almost without appreciable It is known to produce nitrosyl hydrogen pyro sulphate by reacting nitrosyl hydrogen sulphate with sulphuric anhydride or chlcrosulphonie according to this it is necessary to nitrosyl hydrogen a product not easily on the market and must therefore often be It is an object of this invention to provide a process for the preparation of nitrosyl hydrogen pyro in ready supply and largely available the According to this nitrosyl hydrogen pyro sulphate is obtained by reacting nitrosyl nitrosulphuric anhydride or nitrous anhydride with sulphuric acid and sulphur The process according to the invention be represented by the following 2 A mixture constituted by sulphuric acid and sulphur trioxide may be obtained by dissolving the quantity of sulphur trioxide required by the stoichiometry of the reaction in a suitable quantity of sulphuric but it is also and generally to use when commercial oleum is its content will have to be adjusted in such a way that the molar ratio between sulphuric acid and sulphuric anhydride corresponds broadly to the molar ratio required by the stoichiometry of the Instead of sulphur trioxide ay be used which liberate sulphur trioxide under the conditions of for instance chlorosulphonic acid may be It possible to react a mixture of sulphuric acid and chlorosulphonic acid with the above mentioned compounds containing the in order to obtain the desired nitrosyl hydrogen pyro It may be convenient to substitute only a part of the sulphur trioxide by this the above mentioned pounds the axe reacted with a constituted by y e quan y o c on c ac use eren quan es o chloride will be produced as When such ternary mixture is e process according to this invention may be represented by the following H H H HCI 2HC1 The following summary equation represents a substitution of this in the case when equal molar proportions are SC HCI in general the process according to this invention prises reacting the above mentioned compounds containing an with sulphuric acid and sulphur other compounds acting as a source of sulphur According to an alternative form of the the process be carried out in successive that the ing the be first reacted with sulphur as such or using acting as a source of sulphur under the reaction and subsequently with sulphuric This alternative technique is particularly convenient during the first stage ox the well defined and stable products are which may be separated from the reaction ally purified and then subjected to the second stage of the This alternative technique may be exemplified by the following schemes V KC1 Equations and snow the formation ox as the reaction product of the first stage of the HC1 Equatio shows the second stage of the reaction in which the nitrosyl chlorosulphonate is reacted with sulphuric acid order to obtain the nitrosyl hydrogen Another of process of the conducted in two successive may be represented as 2 the irst represented by equation there occurs the of the intermediate product second starting this one obtains the desired nitrosyl hydrogen pyrosulphate In the above cited the intermediate nitrosyl chlorosulphonate and dinitrosyltrisulphate and are known and their characteristics are described in the technical they may be purified by crystallization or by washing with solvents and thereupon reacted wit sulphuric acid in order to obtain the desired In the process of this invention the quantity of reactants that are to react correspond substantially to the stoichiometric ratios of the reactions which take It preferred to operate with a slight excess the compound containing the EXAMPLE is gr of of to moles of and to moles o are made to absorb 8 of nitrosyl The solution thus obtained then heated under up to order to facilitate the removal the hydrogen chloride that had as a as well as the excess of nitrosyl The heating under vacuum was carried on until the crystalline mass that had formed showed a constant 20 gr of nitrosyl hydrogen sulphate were obtained with a point of The yield with respect to the oleum used was EXAMPLE To 8 of liquid nitrosyl cooled down to a mixture of gr of chiorosulphonic acid and of sulphuric acid at was The solution thus obtained was heated under vacuum up to hydrogen chloride the excess of nitrosyl The heating under vacuum was maintained until the white crystalline formed attained a constant this way gr of nitrosyl hydrogen pyrosulpliate were obtained having a melting o of 115 The yield calculated with respect to the sulphuric acid amounted to EXAMPLE A mixture of gr of anhydride as described in 1952 and gr of oleum at SC to moles of and to moles of was heated u 150 C until a solution was formed which was then left to cool A crystalline mass of gr of nitrosyl hydrogen having a melting point of EXAMPLE A mixture of gr of acid gr sulphuric acid was added of gr nitrosyl sulphuric This was then stirred at room temperature until dissolution was and was then heated up to in order to remove the hydrogen The white crystalline mass obtained was heated under until a weight was In way gr nitrosyl hydrogen were obtained a melting point of and a yield of in respect to EXAMPLE 5s To a constituted by gr of oleum at of to moles of and to of and by gr of chlorosulphonic were added gr of liquid nitrous The solution thus obtained was heated up to under in order to the removal of the hydrogen The white crystalline obtained was further heated under vacuum until attaining a constant Thereby of nitrosyl hydroge pyro sulphate were obtained having a melting point of with a substantially quantitative EXAMPLE 6s A consisting of gr of nitrosyl chlorosulphonate prepared according to known 157 and of gr of sulphuric was slowly heated until The solution obtained was then heated under at in order to facilitate tl e removal of the hydrogen chloride which was forming A white crystalline separated which was subjected to heating under vacuum until a weight of the mass was 20 gr of nitrosyl pyro obtained which corresponded to a of calculated with respect to the sulphuric A of gr oi trisuiphate prepared to 1951 C 65 of sulphuric was to complete The solution then left to cooi down and white crystalline of nitrosyl o hydrogen obtained with a point Ufa The yield insufficientOCRQuality

Claims (1)

1. particularly described and ascertained the nature of our said invention and in what manner the same is declare that a we claim is A process for ci nitrosyl hydrogen pyrosulphate reacting nitrosyl nitrous or sulphuric anhydride and sulphur simultaneously or A process according to in w is used as in source of sulphuric A process according to 1 or in which nitrosyl chloride is first reacted with sulphur to give nitrosyl clilorosulphonate and in this latter is then reacted with sulphuric process according to Claim 1 or in nitrous anhydride is reacted with sulphur trioxide to give dinitrosyl trisulphate and ia v hich latter is then reacted with sulphuric A process for fee production of nitrosyl hydrogen pyrosulphate substantially as described in any of the foregoing Nitrosyl hydrogen pyrosulphate when obtained according to any ci the Dated this 23rd day of insufficientOCRQuality