5731 5735.output

* GB786139 (A)

Description: GB786139 (A) ? 1957-11-13

Purification of concentrated solutions of salts

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The EPO does not accept any responsibility for the accuracy of data and information originating from other authorities than the EPO; in particular, the EPO does not guarantee that they are complete, up-to-date or fit for specific purposes.

PATENT SPECIFICATION Inventor: CLYDE WEBSTER DAVIS Date of Application and filing Complete Specification Feb. 786,139 16, 1956. a i No 4910/56. Complete Specification Published Nov 13, 1957. Index at Acceptanoe:-Classes 1 ( 3), AID 210, A 1 (G 39 D 1 O: G 47 D 10: G 48 D 10); and 2 ( 6), P 8 D 3 A, P 8 P( 2 X: 6 X). International Classification: -C Oif, g CO 8 f. COMPLETE SPECIFICATION Purification of Concentrated Solutions of Salts We, THE Dow CHEMICAL COMPANY, a Corporation organized and existing under the laws of the State of Delaware, United States of America, of Midland, County of Midland, State of Michigan, United States of America, do hereby declare the invention for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement: - This invention relates to a method for removing impurities from concentrated aqueous solutions of inorganic salts It relates in particular to a method for removing iron, manganese, copper, chromium, lead, nickel and molybdenum ions from concentrated aqueous solutions

of zinc chloride, calcium chloride or magnesium chloride. There are many uses for concentrated salt solutions in which the presence of trace amounts of impurities is undesirable, even though much larger amounts of impurities may be tolerated in other fields of use of such solutions Concentrated aqueous solutions of zinc chloride may be used as a solvent medium for the polymerization of acrylonitrile, but many of the other metal chlorides which may be present affect the polymerization rate, or the chain length of the polymer obtained, or they confer undesirable colour upon fibres of the polymer spun from the solution Even the minutest detectable amounts of copper salts in a zinc chloride solution adversely affect the polymerization of acrylonitrile in such solutions In other fields of use, concentrated salt solutions are used to coagulate latex or polymer emulsions In many such cases it is desirable to avoid contaminating the coagulum with some of the salts which may be present with the coagulant Again, in certain extraction processes, high molecular weight materials of polymeric or complex structure are dispersed or dissolved in zinc chloride solutions, or in mixtures of zinc chloride with calcium chloride lNw or magnesium chloride to provide colloidal dispersions or solutions from which the polymer may be recovered, and the presence of iron, copper, nickel, cobalt, manganese, molybdenum, lead or various other ions in the solution may result in undesired contamination or discoloration of the colloid. Some of the methods proposed heretofore for the purification of colourless salt solutions, intended to free them from potential discolouring salts, have involved simply a change in valence of the metal ions of the impurities without actual removal of those ions Other methods have merely involved conversion of the impurities to a more soluble condition. Some of the prior methods have provided means for removing iron, but have had no significant effect on other impurities which may be equally troublesome. In the course of studies on the use of concentrated solutions of zinc chloride, or of its mixtures with calcium or magnesium chlorides, as media for the polymerization of acrylonitrile and as spinning solutions for converting the polymer to fibre form, it has become apparent that much more effective means are required to remove the above-noted cations from the solution without significant loss of zinc, calcium or magnesium Such method should be inexpensive, manipulatively simple, and unfailingly reliable It is the object of this invention to provide such a method. It has been found that the desired results can be obtained, and that iron, copper, manganese, and other ions which may discolour an acrylonitrile polymer or affect its molecular weight may be removed

from solutions in water of zinc chloride, calcium chloride or magnesium chloride, or mixtures thereof. According to the present invention there is provided a method for removing impurities from concentrated aqueous solutions which comprises adding to a water solution of at least 40 per cent salt concentration (and preferably at least 60 per cent) wherein' the principal solute consists of zinc chloride, calcium chloride or magnesium chloride or mixtures of two or all three of such substances, and contains trace amounts of the oxide of the principal cation present and trace amounts of at least iron and copper salts as impurities, an excess of a water soluble persulphate over the amount equivalent to the said iron and other cationic impurities present, at a temperature of at least 500 C (and preferably at least 1000 C) to form a precipitate by reaction between the persulphate and some of the said impurities; filtering to remove the precipitate; boiling the filtrate to decompose remaining persulphate; adding zinc dust to the hot solution; cooling the solution; and removing the remaining zinc dust together with the copper which has plated out thereon. The resulting solution is free from all of the metal salts which would have been troublesome in the polymerization of acrylonitrile The solution is of sufficient purity for use whenever freedom from the suggested cations is desirable. Following is a description by way of example of one method of carrying the invention into effect. EXAMPLE To 454 pounds of water in a glass-lined kettle was added 1146 pounds of zinc chloride (" technical'" grade, about 95 per cent zinc chloride) The resulting solution, of about 68 per cent zinc chloride content, was heated to 1250 C, and 8 16 pounds of potassium persulplate was added A brown, gelatinous precipitate was formed and was separated from the solution by filtration The precipitate contained 17 1 per cent calcium, 3 2 per cent aluminium, 1 3 per cent iron and 5 1 per cent manganese The clear filtrate was heated to boiling in a glass-lined kettle,, with stirring, to decompose residual persulphate A water slurry of 1 09 pounds of zinc dust was added to the boiling solution Boiling and stirring were continued for about an hour, then the solution was cooled and filtered to remove the zinc dust which had become plated with copper The filtrate was a clear, water-white solution of zinc chloride, containing not over 0 01 parts per million of copper The solution was neutralized carefully with hydrochloric acid, to convert zinc oxide to zinc chloride The resulting clear solution was used as a solvent medium for the polymerization of acrylonitrile, and the polymer products obtained in several batches made under similar conditions were consistent as to

molecular weight and gave strong fibres with good physical properties In contrast, when acrylonitrile was polymerized in some of the initial crude 68 per cent solution of zinc chloride, widely varying but generally low molecular weight polymers were formed, from which relatively weak fibres were made under the same conditions. When it was attempted to purify the same crude solution by procedures known in the art, inferior results were obtained Thus, chlorine was bubbled into a sample of the solution, but the impurities did not precipitate This is 70 believed to be due to conversion of zinc oxide to zinc chloride, and zinc oxide is believed to be necessary at this stage to buffer the solution so that some of the impurities can coagulate. The chlorinated solution was discoloured 75 Similarly, other samples were treated with hydrogen peroxide, and others with zinc peroxide In these cases, iron impurities were precipitated, but manganese remained in solution Such solutions could be used in poly 80 merization of acrylonitrile only with catalysts such as hydrogen peroxide or zinc peroxide or organic peroxides, which do not oxidize manganese salts to a coloured condition and do nor precipitate manganese dioxide, and when 85 using such catalysts, large amounts were required to obtain practical conversion of monomer to polymer. While many ions may discolour the polymer product, not all impurities in the salt solution 90 are -equally objectionable during polymerization Copper should be eliminated, if possible. Lead and nickel salts adversely affect polymerization at concentrations well within their limits of solubility in concentrated zinc 95 chloride solutions Iron salts can be tolerated at higher levels, and manganese salts at levels nearly 50 times as great as copper, if polymerization rate and molecular weight only are concerned, but, for colourless polymer pro 10 ducts, these salts should be removed The present procedure effectively accomplishes the desired result, while no known prior procedure does so to a comparable extent and with a satisfactory degree of consistency 10, The invention has been illustrated with reference to the purification of zinc chloride solutions It is applicable as well to the purification -of calcium chloride and magnesium chloride solutions, in which cases the presence 11 i of small amounts of calcium oxide or magnesium oxide is necessary to buffer the solution until after decomposition of the persulphate The temperature at which the persulphate treatment occurs in each case is not 11 ' critical except as it affects the quality of the precipitated sludge Thus, the higher the temperature, the more granular is the precipitate, and the easier is the subsequent filtration. The term " water-soluble persulphate " 121 employed in this

specification is intended to include ammonium sodium and potassium peroxy-disulphates, and such other peroxydisulphates as have at least 1 per cent solubility in water While zinc " dust " is the preferred 12 reducing and copper collecting agent, other forms of zinc having large surface relative to mass may be used, such as mossy zinc, and this is to be understood in the appended claims.

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* GB786140 (A)

Description: GB786140 (A) ? 1957-11-13

Improvements in and relating to devices for transmitting indications of ameasuring apparatus to a distance

Description of GB786140 (A)

PATENT, SPECIFICATION Date of Application and filing Complete Specification: Feb 27, 1956. 786, P 4 i N 6957156. ( O Application made in Belgium on March 4, 1955. Complete Specification Published: Nov 13, 1957. Index at acceptance:-Class 106 ( 1), D 1 B 3. International Classification:-GO 1 ql COMPLETE SPECIFICATION Improvements in and relating to Devices for Transmitting Indications of a Measuring Apparatus to a Distance We, COMPAGNIE CONTINENTALE D'APPAREILS DE MESURE, 53, rue de Birmingham, Brussels, Belgium, a Body Corporate under Belgian law, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be partieularly described in and by the following statement:- The present invention relates to a device which enables the indication

of' measurin g apparatus such as a gas meter to be transmitted and registered at a distance. Such a device is particularly useful in blocks of flats in order that the indications may be made visible upon a display located at an easily accessible point near the entrance to the building, for example of the gas consumption of the different tenants, without the meter reading having to obtain access to the meters themselves in the cellars or distributed over the different floors of the building. Devices enabling such remote transmission of meter readings to be effected already exist One such known device operates as follows. The meter is provided with an electric contact which is closed for an instant, for example when each cubic metre of gas is consumed The contact applies a voltage to a receiver or repeater located at a distance This receiver comprises an electromagnet, the movable armature of which through a pawl and ratchet wheel device operates numbered rollers which reproduce the readings of the meter. This system has several disadvantages. First, the energy necessary for the transmission of the readings is not provided by the meter itself, and a source of electric current must be available The device is therefore not self-contained Further. sparks may be produced at the closing and opening of the contacts which may be a lPrice 3/6 l source of danger. A device is also known in which the transmission of the readings is effected pneumatically This system does not present the above-mentioned disadvantages 50 of the electrical device But it requires conduits which are difficult to install, burdensome and of which the gas tightness is difficult to ensure. An object of the present invention is 55 to provide a device for reproducing meter readings at a distance which avoids the disadvantages of the systems known hitherto. The apparatus according to the present 60 invention comprises means for storing energy supplied by the measuring apparatus, means actuated by the measuring apparatus for releasing the stored energy periodically and means including 65 a magnet and an armature winding actuated by the released energy thereby to generate a voltage which can be transmitted to a remote receiver incorporating counting mechanism which reproduces the 70 reading of the measuring apparatus. Some different possible embodiments of the devices according to the present invention are described below with reference to the accompanying diagrammatic drawings 75 in which Figs 1 to 4 each show a different embodiment. As shown in Fig 1 the device comprises a transmitter 1 attached to the meter and a receiver or repeater 2 located at a 80 distance The receiver 2 and the transmitter 1 are connected by electric conductors

3 Similar provision is made in the other embodiments but is not shown in the drawings 85 In this case, in the transmitter 1 the movement of the counter-mechanism is transmitted by a reducing gear 4 of suitable ratio to a shaft 5 The ratio of the gear 4 may, for example be such 90 >that the shaft a makes one half revolution for each cubic metre of gas registered by the meter. In Fig 1 the shaft 5 winds up a spiral spring 6 connected to a shaft 7 having an arm which is held back by a detent S This shaft 7 carries a permanent magnet 9 of bar form At a certain point in its rotation a lever or cam 10 fast on the shaft 5 lifts the detent 8 and the shaft 7 is released -Under the torque of the spring 6 it makes a half revolution after which it is again held back by another detent 8 ' until after another half turn of the shaft 5 the lever or cam 10 lifts the detent 8 ' and the shaft 7 again makes a sudden half turn This sequence is then repeated as the shaft 5 continues to turn. The magnet 9 fast to the shaft 7 is located between pole pieces of an armature 11 of ferro-magnetic material which carries a winding 12 Thus, the magnetic flux of the magnet 9 links with the winding 12 At each half turn the flux varies suddenly and an impulse of voltage is induced in the winding The windincg 12 is connected to the receiver 2 by the conductors 3 above mentioned The receiver 2 comprises an electromagnet 13 The armature 14 of this electromagnet is urged away by a spring 15 At each voltage impulse induced in the transmitter, the armature 14 is attracted and by means of a pawl 17 it rotates a ratchet wheel 16 through a fraction of revolution In its movement the wheel 16 drives a series of -numbered drums 18 or needles which reproduce the readings of the meter. It is to be noted that the production and transmission of movement within the receiver 2 can be efected in other ways. The principle of this receiver ineluding the counter-mechanism is already known in itself and used for example in telephone meters. Figs 2 to 4 show possible modifications of the transmitter without exhausting the possibilities. As shown in Fig 2 the spiral spring 6 of Fig 1 can be replaced lv a blade spring or by a helical spring 19 acting by tension In this modification, the shaft 5 to which the movement of the meter mechanism is transmitted by the gearing 4 has an arm 20 The shaft 7 of the magnet 9 carries a crank 21 which is normally maintained in the position a. by the spring 19 Prom the instant when the arm 20 occupies the position a the crank 21 will be engaged by the arm 20 and the spring 19 will be progressively stretched The magnet 9 will turn but as the rotation is very slow the voltage indneed in the winding 12 will he insufficient to cause actuation of the receiver From the instant the

parts 20, 21, pass beyond the position b shown in chain lines, which is the position of unstable equilibrium of the crank 21 and spring 19, the crank 21 will return 70 suddenly to the position a of stable equilibrium, rapidly rotating the magnet 9 in so doing During this instant a voltage will be induced in the winding 12 sufficient to actuate the receiver 75 The springs 6 and 19 respectivelk of Figs 1 and 2 can le dispensed with and replaced by the magnetic attraction of the magnet 9 itself Fig 3 shows one such possibility 80 In Fig, there is again tooth gearing 4 transmitting movement from the meter to the shaft 5 which carries an arm 20, while the shaft 7 carrying the malnet again has a crank 21 as in Fig, 2 Inl this 85 example the ferro-inagnetie armature which carries the winding 12 is marked 22 As long as the magnet is not subjected to any force or couple it tends to align itself along axis AA of the poles of 90 the armature 22, the pole pieces being shaped to ensure a stable line of mag Retie attraction along the axis AA The magnet will therefore have two positions of stable equilibrium when the maonetic axis of 95 the magnet coincides with the axis AA In these positions the magnetic flux linking with the wrinding 12 is a maximum In addition, the magnet will have two positions of unstable equililbrinm whell the 100 marnetic axis NS is perpendicular to the axis A;\ In these twvo unstable positions the flux linking with the winding 12 is zero At the start, the magnet occupies the equilibrium position a, and the arm of 105 the shaft 20 occupies some position out of contact with the crank 21 From the instant when the arm 20 reaches the position a it will engage and carry with it the crank 21 and the magnet 9 The 110 flux linking with the winding 12 will progressively decrease. However, the variation of flux being very slow, the voltage induced in the winding 12 will be too low to actuate the 115 receiver At the instant when the magnet 9 and cranlk 21 reach the position b of unstable equilibrium the flux will be zero. Once the position b has been passed the 120 magnet 9 will roel suddenly under the action of magnetic attraction and will take the chain line position a' The flux linking with the lw Minding 12 will therefore suddenly ehanie -from zero to maximum 125 and a voltage will be indueed in the winding 12 sufficient to actuate the receiver. It is olbvio Lus that there will he no cliange in principle if in the above examples the magnet 9 instead of being 130 786,140 786,140 bipolar comprises more than one pair of poles It would also be possible to make the magnet stationary and move the armature and winding in relation to the magnet. Instead of giving the magnet or armature a rotational movement the movement can be rectilinear as in Fig 4. In this figure, the magnet 23 arranged between the pole pieces of the

armature 24 carrying a winding 25 is supported by a rod 26 sliding in guides 27, this rod being connected by a connecting rod 28 to a crank pin 29 on a crank disc 30 mounted through a free wheel mechanism not shown upon a shaft 31 driven by the mechanism of the meter A return spring 32 causes the disc 30 to overtake the shaft with a sudden displacement of the magnet 2023 between the pole pieces each time the crank pin 29 has passed its position of unstable equilibrium Obviously, an inverse arrangement is possible, the magnet remaining stationary while the magnetic armature is made movable. The springs could be replaced by weights which would be rewound by the mechanism of the meter Such weights could be constituted by the magnet itself or by the magnetic armature.


* GB786141 (A)

Description: GB786141 (A) ? 1957-11-13

N,n-diguanidino diimides of quinone-diolefin adducts




COMPLETE SPECIFICATION N,N1-Diguanidino Diimides of Quinone-Diolefin Adducts

We, FARBENFABRIKEN BAYER AKTIENGESELL SCHAFT, a body corporate organised under the laws of Germany, of Leverkusen, Germany, do hereby declare the invention, for which we pray that a patent may be granted to us and the method by which it b to be performed, to be particularly described in and by the following statement: This invention comprises new compounds which are N.N1-diguanidino diimides of quinone-diolefim adducts. They are valuable pharmaceutical products showing activity against streptococci and pneumonococci, and extremely effective activity against diphtheria bacilli. Due to the strong bacteriostatic effect of the new compounds against diphtheria bacilli, they are very effective as a mouth disinfectant for diphtheria carriers. The new compounds have the structure of an adduct of p-benaoquinone or p-naphthoquinone with a conjugated diolefin in which both oxygen atoms of the quinone nucleus are replaced by nitrogen atoms substituted with a guanidino or substituted guanidino radical. The invention also comprises a process for producing the new compounds which is by reacting a quinone-diolefin adduct with aminoguanidine or a substituted aminoguanidine still containing a free NH2-N group in the molar ratio of 1:2. The starting quinone-diolefin adducts are Diels-Alder adducts formed by the addition of a conjugated olefin to, penzoquinone or p-naphthoquinone in the molar ratio of 1:1. These Diels-Alder adducts are described, for example, on pages 136-192 of the book "Organic Reactions", Volume 5, 1949, published by John Wiley & Sons in New York. Any of the known conjugated diolefins which will form an adduct with quinone may be used as the starting diolefin for the formation of the adduct. Examples of such diolefins include butadiene, isoprene, 2.3-dimethylbutadiene, 2-chlorobutadiene, cyclopentadiene and cyclohexadiene. Examples of the starting aminoguanidines which may be used include aminoguanidine itself and 2-hydrazino-2-imidazoline. The reaction is effected with the aminoguanidines in the form of their salts and is preferably carried out in an aqueous or an aqueous-alceholic solution. The reaction will proceed under relatively mild conditions as, for example, at temperatures between about 0 and 60 C. The diguanidino diamides of the adducts used are directly formed in the reaction period. Though it is also possible to form mono derivatives, the same are generally obtained with greater difficulty and generally in an impure form. The formation of the dicompounds in accordance with the invention is rather surprising since, as is well known, other hydrazine derivatives such as semicarbazides generally

yield the mono-derivatives with the di-derivatives seldom being obtained in a pure form. The compounds of the invention are generally obtained in the form of their salts as, for example, the di-nitrate salt and the di-hydrochloride salt The compounds may be used in the form of these salts or the free bases may be recovered with the use of a weak alkali such as ammonia. The reaction, in accordance with the invention, may be illustrated for example by the reaction between aminoguanidine and the adduct of p-benzoquinone and cyclopentadiene which proceeds as follows: <img class="EMIRef" id="026473758-00010001" /> The adduct between the p-benzoquinone and cyclopentadiene may be designated as cyclopentadienequinone or in accordance with the systematic chemical abstracts nomenclature, as 1,4,4a,8a-tetrahydro-1,4-methanonaphthalene-5,8-dione. The diguanidino-diimide formed by the reaction may be designated N,N1-diguanidino-1,4,4a,8a-tetrahydro1,4-methanonaphthalene-5,8-diimid e. This compound is particularly active against diphtheria bacilli and may be used in the form of its salt, as for example tit dinitrate salt. The following Examples are given for the purpose of illustrating the invention: EXAMPLE 1. Sixty-eight grams (1/2 mol) of amino' guanidine - bicarbonate with 40 cc of concentrated nitric acid (d 1.5) are dissolved with 300 cc of warm water. The mixture is cooled to 30 C. and 34.8 grams, (2/10 mol) af the cyclopentadiene-quinone adduct, dissolved in 200 cc of methanol, are added. After a short period the dinitrate salt of N,N1-diguanidino1,4,4a,8a - tetrahydro - 1,4 - methanonaphthalene-5,8-diimide separates in yellow crystals with slight exothermic reaction. The mixture is stirred for 2 hours, the precipitate separated by suction filtration and the new compound is washed with methanol and ether. In order to avoid discolouration it is preferably dried at low temperatures. The yield obtained is 73.5 grams. The compound discolours in the melting point tube without showing a defined point of decomposition. The compound has the formula: <img class="EMIRef" id="026473758-00020001" /> and can be recrystallised by dissolving in three times the amount of dimethylformamide at 40 C. and adding six times the amount of water. The compound slowly crystallises out in a refrigerator. Under similar conditions the corresponding sulphate may be obtained with aminoguanidine sulphate. This salt decomposes at about 230 with evolution of gas.

EXAMPLE 2. Sixty-eight grams (1/2 mol) of aminog;uan idine bicarbonate are dissolved in a mixture of 40 cc concentrated hydrochloric acid and 125 cc of water. Thereupon 34.8 grams (2/10 mol) of the cyclopentadiene-quinone adduct in 200 cc of methanol are added and the temperature is kept at 15 C. The solution remains clear. Only after the addition of 50 cc of concentrated hydrochloric acid, diluted with 200 cc of water, the dihydrochloride dihydrate crystallises slowly within a few hours in a yield of 66 grams. The compound dissolves in hot water with yellow colour. After the addition of hydrochloric acid the colour becomes lighter. Beautiful rhombic greenish-white crystals separate. The analytical values correspond to the formula: <img class="EMIRef" id="026473758-00020002" /> The compound does not show any m.p. For the production of the free base 9 grams of the' hydrochloride described are heated in 150 cc of semi-diluted methanol to boiling and 100 cc of concentrated ammonium solution are added. A clear yellow solution is obtained from which yellowish, glittering and voluminous crystals separate upon cooling. Above 150 C, the compound becomes slowly orange-red and decomposes at about 238 with evolution of gas. EXAMPLE 3 Seventeen and two-tenths grams of the eyelopantadieno-quinonlo adduct in 100 ce of alcohol are dropped within half an hour into a solution of 38 grams of 2-hydrazino-imidazoline hydrobromide having the formula: <img class="EMIRef" id="026473758-00020003" /> in 200 cc of water and 20 cc of concentrated hydrochloric acid. The mixture is kept at 40 C. for a further hour. Upon cooling and rubbing 45 grams of yellowish crystals scparate. These are dissolved again in 150 cc of warm water. After the addition of 50 cc of concentrated hydrochloric acid the di-hydrochloride of N,N1-di-[1-(2-imidazolinyl)amino]-1,4,4a, 8a-tetrahydro - 1,4 - methanonaphthalene - 5,8diimide separates with a light yellow colour. The compound contains 4 mci of crystal water, decomposes at about 258 C. and has the formula: <img class="EMIRef" id="026473758-00020004" /> EXAMPLE 4. A boiling hot solution of 37.6 grams (2/10 mol) of 6,7 - dimethyl - 4a,5,8,8a - tetrahydronaphthalene-1,4-dione (adduct of 2,3-dimethyl butadiene and p-benzoquinone) in alcohol is slowly added to a solution of 1/2 mol of aminoguanidine hydrochloride obtainable according to

Example 2. The quinone addition product which precipitates at first dissolves clearly within 2 hours. Upon cooling some resin is obtained which is discarded. The alcohol is evaporated in vacuo and the desired compound crystallizes slowly in the form of hard yellowish crystals. These are dissolved in hot water. The dihydrochloride of N,N1 - diguanidino- 6,7 -dimethyl -4a,5,8,8atetrahydronaphthalene - 1,4 - diimide crystallizes again after the addition of hydrochloric acid. The product does not show any m.p. and has the formula: <img class="EMIRef" id="026473758-00030001" /> EXAMPLE 5. If the cyclopentadienequinone of Example 2 is replaced by the equivalent amount of 4a,5, 8,8a-tetrahydronaphthalene-1,4-dione (adduct of butadiene and 1,4-benzoquinone) and the same procedure is carried out, a compound is obtained which decomposes at about 228- 230 C. The analytical data corresponds to the formula: <img class="EMIRef" id="026473758-00030002" /> The compound may be designated dihydrochloride monohydrate of N,N1-diguanidino-4a, 5,8,8a-tetrahydronaphthalene-1,4-diimide. EXAMPLE 6. A solution of 30 grams of the cyclopentadiene-naphthoquinone adduct, 1,4,4a,8a-tetrahydro- 1,4 -methanoanthracene-9,10-dione, in alcohol is added at 40 C. to a hydrochloric acid solution of 1/2 mol of aminoguanidinehydrochloride. From the solution which is at first clear yellowish crystals separate after a few days which are recrystallised from methanol and are thus obtained nearly white. The compound has the formula: <img class="EMIRef" id="026473758-00030003" /> It decomposes slowly at 200 C. and with higher speed at 220 C., and is the dihydrochloride monohydrate of N,N1-diguanidino-1, 4,4a,8a tetrahydro- 1,4 - methanoanthracene9,10-diimide. What we claim is: 1. N,N1-diguanidino diimides of quinonediolefin adducts and salts thereof. 2. N,N1-diguanidino diimides of p-benzoquinone-diolefin adducts and salts thereof. 3. N,N1-diguanidino diimides of p-naphthoquinone-diolefin adducts and salts thereof. 4. N,N1-diguanidino diimides of quinonecyclopentadiene adducts and salts thereof. 5. N,N1-diguanidino diimides of p-benzoquinone-cyclopentadiene adducts and salts thereof. 6. N,N1-diguanidino diimides of p-naphthoquinone-cyclopentadiene

adducts and salts thereof. 7. N,N1 - diguanidino-1,4,4a,8a-tetrahydro1,4-methanonaphthalene-5,8-diimide and salts thereof. 8. The dinitrate salt of N,N1-diguanidino1,4,4a,8a - tetrahydro - 1,4 - methanonaphthalene-5,8-diimide. 9. The dihydrochloride salt of N,N1diguanidino - 1,4,4a,8a - tetrahydro- 1,4 -methanonaphthalene-5,8-diimide. 10. N,N1 - di - [1-(2-imidazolinyl)amino]1,4,4a,8a - tetrahydro - 1,4 - methanonaphthalene-5,8-diimide and salts thereof. 11. The dihydrochloride of N,N1-di-[1-(2imidazolinyl)amino] - 1,4,4a,8a - tetrahydro1,4-methanonaphthalene-5,8-diimide. 12. N,N1 - diguanidino - 6,7 - dimethyl4a,5,8,8a - tetrahydronaphthalene- 1,4 -diimide and salts thereof. 13. The dihydrochloride of N,N1 - diguanidino - 6,7 - dimethyl - 4a,5,8,8a - tetrahydronaphthalene-1,4-diimide. 14. N,N1 - diguanidino - 4a,5,8,8a - tetrahydronaphthalene - 1,4 - diimide and salts thereof. 15. The dihydrochloride salt of N,N1diguanidino - 4a,5,8,8a - tetrahydronaphthalene-1,4-diimide. 16. N,N1 - diguanidino - 1,4,4a,8a - tetrahydro - 1,4 - methanoanthracene-9,10-diimide and salts thereof. 17. The dihydrochloride salt of N,N1

* GB786142 (A)

Description: GB786142 (A) ? 1957-11-13

A process for the production of organosilicon compounds

Description of GB786142 (A)

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PATENT SPECIFICATION 786 A 142 Date of Application and filing Complete Specification: March 19, 1956. No 8518/56. Application made in United States of America on May 2, 1955. (Patent of Addition to No 766,528, dated March 30, 1955). Complete Specification Published: Nov 13, 1957. Index at acceptance: Classes 2 ( 6), P 2 D(IA: IX: 2 A: 3 A), P 2 FX, P 2 K( 7: 8: 11), P 2 P 1 D, P 2 P 1 E( 1:2:3:4:5), P 2 P( 3:5:6 D), P 2 T 2 X, P 4 D(IB:1 X: 3 A: 3 B 1), P 4 (FX:K 11), P 4 P 1 D, P 4 PIE( 1:2:3:4:5), P 4 P( 3:5:6 D), P 5 D( 1 X:2 A: 2 X), P 5 (FX: KI: PID), P 5 P 1 E( 1: 2: 3: 4: 5), P 5 P( 3: 5: 6 D), P 6 D( 2:3:4), P 6 (FX: K 1: PID), P 6 PE( 1: 2:3:4:5), P 6 P( 3: 5: 6 D), P 7 D( 2 A 1: 2 A 2 81: 3), P 7 FX, P 7 K( 2: 11), P 7 P 1 D, P 7 P 1 E( 1: 2: 3: 4: 5), P 7 P( 3: 5: 6 D), P 7 T 2 X P 8 D( 1 A: 1 B: IX: 2 A: 2 82: 3 A: 3 B: 4), P 8 FX, P 8 K( 2: 11), P 8 P 1 D, P 8 P 1 E( 1:2:3:4:5), P 8 P( 3:5:6 D), P 8 T 2 X, P 9 D 1 A( 1:2), P 9 (FX:K 11: P 1 D), P 9 Pl E( 1:2:3:4:5), P 9 P( 3:5:6 D), PIOD(l Al B:l X:2 A:3 X:4 A: 4 X), Pl O(FX: Kl: PID), P 1 O Pl E( 1:2:3:4:5), P 1 OP( 3:5:6 D), Pll(D 2 X: FX:Kll:PID), P 11 PIE( 1:2:3:4:5), Pll P( 3:5:66 D); and 2 ( 7), SI(A: C:D), 53 (A:B:C:D), S( 5:6), 57 (A:B:D), S( 8:9), T(IA:4:5), T 6 D(l A: l B: 2:4: 5: 10), T 6 F( 1: 2), T 6 G( 6: 7 B:I 7 C: 7 E: 7 F: 7 H). International Classification:-C 08 f, g. COMPLETE SPECIFICATION A Process for the Production of Organosilicon Compounds We, AMIDLAND SILICONES LIMITED, a British Company, of 19 Upper Brook Street, London, W 1, do hereby declare the invention, for which we pray that 'a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement: - This invention relates to a process for the production of organosilicon compounds and is concerned with an improvement in or

modification of the invention of our Specification No 9286/55 (Serial No 766,528). The said Specification No 9286/55 claims a process for the production of an organosilicon compound which comprises heating a mixture of ( 1) an organo-silicon compound having at least one alkyl radical per molecule, said radical having less than five carbon atoms therein, which organosilicon compound is substantially free from silicon-bonded hydrogen and substantially free from organic radicals having C= C linkages therein, ( 2) an olefinic compound 'and ( 3) ian aromatic acyl peroxide, at a temperature above that at which ithe peroxide forms free radicals The terms "olefinic compound " or "Colefin " as employed herein refer to a comnound containing C= C linkage. It has now been found according to this invention that certain other free radical generators may be used instead of the aromatic acyl peroxides employed in the process of Specification No 9286/55. In accordance with this invention a mixture of ( 1) an organosilicon compound having at least one silicon-bonded alkyl radical of less than 5 carbon atoms, per molecule, which organosilicon compound is substantially free from organic radicals having aliphatic unsaturation therein, ( 2) a substituted olefinic compound containing at least one aromatic hydro-carbon radical or iat least one atom other than carbon and hydrogen any remaining valencies being satisfied by hydrogen or carbon atoms and ( 3) 'a free radical generator which is an organic peroxide (other than an aromatic acyl peroxide) or an azo compound in which both nitrogen atoms of the azo linkage are attached to a tertiary carbon atom and the remaining valencies of said tertiary carbon atoms are satisfied by nitrile radicals, carboxyalkyl radicals, cycloalkylene radicals, alkyl radicals or radicals of the general formula YOOC in which Y is an alkyl radical, is heated at a temperature above that at which the free radical generator forms free radicals in contact with the organosilicon compound and the olefinic compound. When the above conditions are adhered to an addition of the olefinic compound to the alkyl radicals of the organosilicon compound takes place, isuch addition is hereinafter referred to as grafting The mechanism of this reaction is presumed to be a free radical mechanism, the first step of which is the extraction of a hydrogen atom from the alkyl radical on the silicon followed by an addition of the olefinic compound to the free radical thus generated It should be understood, of course, that this invention is not limited by the correctness of the above theory. The temperature at which the reaction is carried out is not critical except that it should be sufficiently high that the free radical generator will initiate the formation of free radicals This initiation

temperature will vary depending upon the free radical generator employed and depending -upon the reaction mixture employed In general, the reaction will take place above 1000 O although temperatures as low as 500 C or below may be employed In general, with the more reactive olefinic compounds, such as for example, acrylonitrile, temperatures of 50 to 750 C. are generally employed This is to minimise the intrapolymerisation of the olefin If, with such reactive materials, the reaction temperature is too high most of the olefin will form an intra-olymer rather than grafting onto the organosilicon compound On the other hand, with less reactive materials such as tetrafluoroethylene higher temperatures of the order of 1100 C to 150 C may be desirable. The concentration of the reactants in the process of this invention is not critical. Obviously, optimum yields will occur when the olefin is employed in amounts at least su Estantially equivalent to the number of alkyl groups in the organosilicon compound The amount of free radical generator catalyst is not critical although in general the amount of catalyst preferred is from 0 1 to 10 % by weight calculated on the weight of the organosilicon compound. This invention includes within its scope the use of any organosilicon compound which has at least one silicon-bonded alkyl radical of less than 5 carbon atoms, per molecule, and which organo silicon compound is substantially free from silicon bonded hydrogen and substantially free from radicals having aliphatic unsaturation therein All such compounds are operative in this invention It should be understood that the organosilicon compounds do not require to have one or more of the defined alkyl group attached to each silicon atom, but must have at least one such group per molecule Thus, hexamethyldisiloxane, pantaphenylmethyldisiloxane and copolymers of diphenylsiloxane and dimethylsiloxane are all operative herein. The term substantially free " as employed herein means that the compound may contain traces of the undesirable ingredients which are normallv present in commercially available organosilicon compounds For example, organosilicon resins and polymers often contain traces of silicon-bonded hydrogen as an impurity These trace amounts do not interfere with this reaction. The remaining valencies of the silicon atom can be satisfied by any other knownv type of group Specific examples of the types of compounds which are operative herein are organosilicon compounds of the general formula Ra R'b Si Xo O^_a-b-c, R:,Rl Si XRl -aie and R RW Xz Si(in which the Si is attached to one or more Si 70 atoms) In these compounds a has a value from 1 to 4, b has a value from 0 to 3, c has a value from O to 3, x has a value from 1 to 3, y has a value from 0

to 2, and z has a value from O to 2 R is an alkyl radical of less than 75 carbon atoms such as, for example, methyl, ethyl, propyl, isopropyl and butyl R' is any organic radical attached to the silicon by a silicon-carbon bond, which radical is free from aliphatic unsaturation such as for example, 80 higher alkyl radicals such as hexyl and octadecyl; cycloalkyl radicals such as cyclohexyl, and cyclopentyl, aryl hydrocarbon radicals such as phenyl, tolyl and xenyl; halogenated hydrocarbon radicals such as chlorocyclohexyl, 85 chlorooctadecyl, pentafluoroethyl, heptafluoropropyl, chlorophenyl, bromophenyl, chloroxenyl, and trifluorotolyl; and organofunctional radicals such as carboxyphenyl, gammahydroxy propyl, gamma-aminopropyl, penta 90 chlorophenoxymethyl lC C 15 OCH 2-l and any other hydrocarbon radical having aldehyde, ketone, nitrile, nitro, carboxyl, amide, hydrosulphide or other functional groups attached thereto RW' is any divalent hydro 95 carbon radical which is free from aliphatic unsaturation such as methylene, ethylene, propylene, phenylene, xenylerne or cyclohexylene. X is any hydrolysable or condensable group such as hyroxyl, amino, sulphide, halogen, or 100 OR 1 O groups where Rll' is a monovalent hydrocarbon radical free from aliphatic unsaturation such as methyl, ethyl, octadecyl, cyclohexyl, phenyl, tolyl, benzyl and naphthyl. Thus, is can be seen that for the purpose 105 of this invention the organosilicon compounds can be in the form of hydrolysable silanes, such as dimethyldichlorosilane, ethyltriisopropoxysilane, butyltrichlorosilane, phenylmethyldiphenoxysilane; non-hydrolysable silanes such 110 as tetramethylsilane, dimethyldiphenylsilane, ethylphenyldicyclohexylsilane; partially hydrolysed silanes containing residual hydrolysable groups; silazanes such as dimethylsilazane, phenylmethylsilazane and dimethyltetra 115 methyldisilazane; organosilicon sulphides; sillcarbanes; polysilanes; silanols; salts of silanols and both completely condensed and partially condensed polysiloxanes. Any monomeric substituted olefinic com 120 pound having at least one C= C linkage and any polymerised substituted olefin having substantial residual unsaturation such as poly786,142 polytetrafluoroethylene, polytrifluorochloroethylene or polyvinylchloride, for such polymers do not retain a substantial amount of olefinic unsaturation. The free radical generators which are in 70 cluded in this invention include organic peroxides (other than aromatic acyl peroxides) and the specified azo compounds These peroxides may be considered as derivatives of hydrogen peroxide in which one or both of the 75 hydrogen atoms has been replaced by an organic radical Thus, the peroxides employed in this invention can be compounds of the general formula ROOH (which are generally known as hydroperoxides or as peroxy

acids 80 depending upon the nature of the R group) and compounds of the general formula ROOR in which R is an organic radical These compounds are generally known as diorganoperoxides 85 Specific examples of peroxides which are operative in tthis invention are hydroperoxides such as methyl hydroperoxide, tertiary butyl hydroperoxide, trans-decalin hydroperoxide, 1-methyl cyclopentyl hydroperoxide, 3-methyl 90 3-hydroperoxy-1-butyne, 2-cyclohexen-1-yl hydroperoxide, cumene hydroperoxide, tetralin hydroperoxide, triphenylmethyl hydroperoxide, benzyl hydroperoxide, p-nitrophenyldiphenylmethyl hydroperoxide, -hydro 95 peroxy 'tetrahydrofuran and o-hydroperoxyethyl ethyl ether; peroxy acids such as peroxyacetic acid, peroxyisovaleric acid, peroxycrotonic acid, peroxytrichloroacetic acid, peroxylactic acid, peroxybenzoic acid, 100 monoperoxyphthalic acid, diperoxyphthalic acid, peroxycinnamic acid, p-methoxyperoxybenzoic acid, m-nitroperoxybenzoic acid and 2,4-dichloroperoxybenzoic acid; diorganoperoxides such as di-tertiarybutyl peroxide, 105 diethyl peroxide, tertiary butyl methyl peroxide, di-triphenylmethyl peroxide, ascaridole, 1,4-epydioxy-p-menthane, 1,4,2,3-diepoxy-p-menthane, diacetyl peroxide, dialkyl or diaryl peroxy dicarbonates of the general 110 formula ROOCOOCOOR in which R is methyl, ethyl, phenyl, or tolyl; ethyl peroxyacetate, tertiary butyl peroxybenzoate, di-tertiary butyl diperoxyphthalate, bis(l-hydroxycyclohexyl)-peroxide, 1-hydroxy-11-hydro 115 peroxycyclohexyl peroxide, bis(hydroperoxycyclohexyl)peroxide, trimeric cyclohexanone peroxide, bis(hydroxyethy 1)peroxide, his(phenylhydroxymethyl)-peroxide, trimeric acetone peroxide, methylhydroxymethyl peroxide 120 and (Me COO)2 C Me 2. The azo compounds which are operative in this invention are those containing tertiary carbon atoms (that is carbon atoms having no hydrogen attached thereto) attached to each 125 nitrogen atom of the azo linkage The remaining valences of the tertiary carbon are satisfied by nitrile radicals, carboxyalkyl radicals, cycloalkylene radicals, alkyl radicals and radicals of the general formula YOOC in 130 mers of perfluorobutadiene, chloroprene and co-polymers of butadiene and styrene is operative in the process of this invention The term "substituted olefin" means that the molecule contains at least one aromatic hydrocarbon radical or at least one atom other than carbon and hydrogen, for example oxygen, nitrogen, sulphur, halogen and phosphorus any remaining valencies being satisfied by hydrogen or carbon atoms Thus specific compounds which are operative are hydrocarbon olefins such as styrene, vinyltoluene, divinylbenzene and p-,phenylstyrene; halogenated olefins such as itetrafluoroethylene, vinyl chloride, allyl chloride, trifluorochloroethyllene,

hexafluorobutadiene, vinylidene chloride, dichloroethylene and chlorocyclohexene; unsaturated aldehydes such as crotonaldehyde, acrylic aldehyde and cinnamic aldehyde; unsaturated alcohols such as allyl alcohol, cyclohexenol, 4-methylpenten 3 ol-1, cinnamic alcohol and penten-4-ol-2, unsaturated acids such as acrylic acid, methacrylic acid, crotonic acid, vinylacetic acid, cinnamic acid, maleic acid and its equivalent maleic anhydride, dimethylmaleic acid, lauroleic acid, oleic acid, linoleic acid, and linolenic acid; unsaturated ethers such as diallyl ether, allylethyl ether; unsaturated esters such as methyl acrylate, methyl methacrylate, vinyl acetate and allyl acetate; unsaturated amides such as crotonamide, acrylamide and cinnanmamide; unsaturated nitriles such as acrylonitrile, methacrylonitrile and cinnamonitrile; unsaturated mercapitans such as allyl mercaptan; unsaturated amines such as allylamine, allylethylamine and vinyldimethylamine; unsaturated sulphides such as allyl sulphide and vinyl sulphide; unsaturated ketones such as methylvinyl ketone, allyl acetone, and benzalacetophenone; unsaturated isocyanates such as allyl isocyanate, cinnamyl isocyanate and compounds containing combinations of the above type functional groups. It has been found that whereas any of the above olefinic compounds are operative in this invention the best yields are obtained with those which are free from active hydrogen, that is, hydrogen which is attached directly to oxygen, nitrogen or sulphur atoms. Not only -are the above monomeric olefins operative herein but also polymeric olefins having substantial C=C residual unsaturation. Thus, polychloroprene, co-polymers of butadiene and styrene, co-polymers of butadiene and acrylonitrile, polyhexafluorobutadiene and similar compounds can be employed in this invention In general, it is preferred that these reactions be carried out in mutual solvents but this is not essential It can be seen that this invention not only applies to the modification of organosilicon compounds and polymers but also to the modification of olefinic polymers. This invention is not operative with polymers of olefins having only one C=C bond, such as 786,142 which Y is an alkyl radical Specific examples of such azo compounds are Me 2 (NC)CN NC(CN)Me 2, Me Et(NC)CN = NC(CN)Me Et, Et 2 (NC)CN=NC(CN)Et 2, Pr 2 (NC)CN=NC(CN)Pr 2, Am Me(NC)GN NC(CN)Me Am, (HOOCCH 2 CH 2)Me(NC)CN= NC(CN)Me(CH CH 2 COOH), (Me OOC)Me 2 CN = NC Me 2 (COO Me), (Eit OOG)Me 2 CN=NC Me 2 (COO Et) and H 2 CN H 2 N m H 2 QH H 2 H 2 The last compound is an example of a cycloalkylene substituted tertiary carbon atom The abbreviaitons "Me", "Et", "Pr" and "Am" represent methyl, ethyl, propyl and amyl respectively. The reaction of this invention can be carried out either at sub-atmospheric, atmospheric or super-atmospheric pressure The latter

is desirable when volatile reactants are employed If desired, the reaction can be carried out in ithe presence of inert hydrocarbon solvents such as benzene, toluene and petroleum ether. The products of this invention are useful as lubricants, surface active agents, hydraulic fluids, electrical insulating materials and for other uses in which organosilicon compounds are normally employed. The following examples illustrate;the invention:EXAMPLE 1 210 G of trifluorochloroethylene, 360 g of a trimethyl end-blocked dimethylpolysiloxane having a viscosity of 1,000 cs at 25 "C 5 of di-tertiary butyl peroxide and 2 g of Mg were heated in an atmosphere of nitrogen in an autoclave at a temperature of 131 'C for about 17 hours The reaction product was a gel containing 29 % of grafted trifluorochloroethylene This product was separated by extraction with toluene and there was obtained a soluble liquid containing 27 X% by weight of grafted trifluorochloroethylene. EXAMPLE 2 408 G of the siloxane of Example 1, 189 g. Of trifluorochloroethylene, 5 g of tertiary butyl hydroperoxide and 2 g of Mg O were heated under nitrogen in an autoclave at 139 "C for 16 5 hours The product was a grease-like material which was found to contain 24 2 i% by weight of grafted trifluorochloroethylene. EXAMPLE 3 334 G of the siloxane of Example 1, 192 g. of trifluorochloroethylene, 6 5 g of dilauroyl peroxide and 2 g of Mg O were heated in an autoclave for 17 hours at 111 VC After removing the unreacted materials 410 g of an oily product containing 13 4 per cent by weight of grafted trifluorochioroethylene was obtained. EXAMPLE 4 307 G of the siloxane of Example 1, 5 g. of succinic acid peroxide, 219 g of trifluorochloroethylene and 2 g of Mg O were heated for 18 5 hours at 112 'C in an autoclave The resulting product was centrifuged and there was obtained 322 g of an oil containing 10.5,% by weight of grafted trifluorochloroethylene. EXAMPLE 5 374 G of the siloxane of Example 1, 170 g. of trifluorochloroethylene, 4 g of perbenzoic acid and 2 g of Mg O were heated in an autoclave 16 hours at 97 "C The product was 361 g of an oil containing 7 2 per cent by weight of grafted trifluorochloroethylene. EXAMPLE 6 313 G of the siloxane of Example 1, 200 g. of trifiuorochloroethylene, 7 g of cumene hydroperoxide and 2 g of Mg O were heated in an autoclave for 17 hours at 113 'C The product amounted to 309 g of an oil containing 2 4 %, by weight of grafted

chlorotrifluoroethylene. EXAMPLE 7 304 G of the siloxane of Example 1, 178 g. of trifluorochloroethylene, 5 g of azo-bis-diisobutyrol-nitrile, F Men Me, I I _NCCN = NCCN_ were heated in an autoclave for 15 5 hours at 110 "C The resulting product amounted to 328 g of an oil containing grafted chlorotrifluoroethylene. EXAMPLE 8 Products similar to those of Example 7 were obtained when the following azo compounds were employed in the process of that example. 786,142 786,142 (HOOCC Ha CH 2)Me(NC)CN= NC(CN)Me(CH 2 CH 2 COOH) (Me OOC)Me 2 CN = NC Me 2 (COO Me) and H 2 N H 2 N H 2 s N X H 2 H 2


* GB786143 (A)

Description: GB786143 (A) ? 1957-11-13

Thiamin salts and process for preparing the same




COlv2LETE. SPECIFICATION Thiamin Sal s and for cress 2or preparing the same

We, FARBENFABRIKEN BAYER AllTIEit: GESELLSCHAFT, a body corporate organised under the laws of Germany, of Leverkusen, Germany, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement : - This invention comprises new difficultly water soluble crystalline salts of vitamin B which may be designated as reaction products of salts of this vitamin with certain hydroxybenzoic acid derivatives (hereinafter defined with reference to a formula), such as derivatives of salicylic acid carrying aliphatic or aromatic substituents within the benzene nucleus. The invention also comprises a process for the production of such salts. In contrast to the general class of difficultly water soluble salts of thiamin known heretofore, the compounds of the invention contain as acid components derivatives of salicylic acid. It is ncw well established that both thiamin and salicylic acid possess remarkable antineuralgic and anti-rheumatic activity although each functions on a different principle; the former acting within the oxidationreduction processes of the human body concerned in the utilization of carbohydrate to correct disturbances in carbohydrate metabolism and nerve function, and the latter through its analgesic action within the central nervous system. The compounds of the invention may be employed with particular advantage for antirheumatic applications by reason of the fact that both components of the novel salts are active for this purpose and exhibit synergy, or synergistic physiological activity, within the crystalline products of the invention. The compounds also possess utility for use in the recovery and purification of vitamin B1 from crude solutions or from molten liquors of crystallisaion, or they may be employed in the preparation of vitamin compositions of protracted activity and prolonged storage stability even in moist media, by reason~ of their favourable solubility characteristics for these purposes. Of course, it is expected that the products of the invention will also find utility in the conventional applications for known difficultly soluble salts of thiamin, such, for example, as additives or enriching agents for flour and other foodstuffs, and in particular, foodstuffs of the type which are prepared by cooking in water wherein the relatively water-solublc, labile salts of thiamin tend to lose their physiological activity. The new difficultly water soluble crystalline salts of vitamin B1 may be formed by reacting in aqueous solution, salts of vitamin B1 with salts of certain derivatives of hydroxybenzoic acid as defined hereinafter. In order to avoid partial precipitation of free acids which are difficultly soluble in water when strongly acid salts of

thiamin such as thiamin chloride hydrochloride are employed as starting materials in the process of the invention, it will be found advantageous to effect thereaction between salts at pH values within the range of pH 5.0to 7.0, and preferably at pH 6.0. This may be accomplished quite readily by adjusting the respective solutions of both components to the desired pH value before they are reacted. The acids which have been found to be capable of forming the difficultly water soluble crystallised salts of vitamin B1 in accordance with the invention are represented as a class by the following general formula: <img class="EMIRef" id="026700653-00010001" /> wherein R represents an aliphatic or aromatic hydrocarbon substituent including bicyclic fused or condensed aromatic substitution as in the homologous salicylic acid type de rivatives of the naphthalene series; and R represents hydrogen or methyl. In particular, the following acids among others of similar structural characteristics have been found to be effective in preparing the difficultly soluble compounds of the invention: <img class="EMIRef" id="026700653-00020001" /> ACID SOURCE 1). 5-isobutyl-2-hydroxybenzoic acid; Prepared by carboxylation of the (5-isobutyl-salicylic acid) corresponding phenol (J. Org. Chem. 19, 510, 1954); COOH P CH ' ONa aC 2). 5-isohexyl-2-hydroxybenzoic acid; Same; (5-isohexyl-salicylic acid) fzX NsC\ cHL)){0 \ CHirCHzCH M3C/ 3). 5-isoheptyl-2-hydroxybenzoic acid; Preparation by carboxylation of tbe (5-isohexyl-salicylic acid) corresponding phenol 19, Org. Chem. 19, 510, 1954); COON H3c OH "j:H-p

N8C 4). 5-isooctyl-2-hydroxybenzoic acid; Same; (5-isooctyl-salicylic acid) coos sCH(CH2)+CH2toH h IC/ 5). 5-cyclohexyl-2-hydroxybenzoic acid; (5-cyclohexyl-salicylic acid) COON X CHz t 13 OH Hzc/ =c CHa- CHa 6). 44sopropyl-3-methyl-2-hydroxy- Prepared by carboxylation of isothymol benzoic acid; (isothymotinic acid) by the method of J. Org. Chem., supra; CQOH ON CH cn(cN3) H3)a <img class="EMIRef" id="026700653-00030001" /> ACID SOURCE 7). 5-isobutyl-3-methyl-2-hydroxy Prepared from 4- isobutyl -2 - methyl benzoic acid; (isobutyl-o-cresotinic phenol by carboxylation, i.e., treating acid) a mixture of the phenol and anhy COON drous potassium carbonate with car bonic acid under pressure and at an HACKS NOW elevated temperature; Nsc/CN CHa CN3 8). 5-cyclohexyl-3-methyl-2-hydroxy- 1 Same procedure as described above benzoic acid; from 4-cyclohexyl-2,-methyl phenol (cyclohexyt-o-cresotinic acid) obtained by hydrolyzing 5-cyclo hexyl-2-amino-1-methyl benzene; COON s CHt CHy hOH NC CN CH3 9). 3-phenyl-2-hydroxybenzoic acid; Beilstein, 10 341;

(diphenyl-2-hydroxy-3 -carboxylic acid, COON OH /c=q

10). S-phenyl-2-hydroxybenzoic acid; Same; (diphenyl-4-hydroxy-3 -carb oxylic acid) COON MON 11). 1-l?droxy-2-naphthoic acid; (l-naphthol-2-carboxylic acid) Beilstein, 10, 331 ox COON Analytical investigation of the compounds of the invention indicates that the majority of the crystalline salts are obtained in a molar ratio of one mole of vitamin B1 base to one mole of acid even when a large excess of acid is employed. In one instance, however, namely the thiamin salt of cyclohexyl salicylic acid (5 above), it has been observed that the difficultly soluble crystalline salt con taias two moles of acid for each mole of vitamin B, base. While the compounds are difficultly soluble in water, they are very readily soluble in methanol and ethanol, substantially soluble in acetone and dioxan, but insoluble in ligroin. They may be recrystallized readily without change in composition. In their application to the recovery and purification of vitamin Bl the compounds of the invention are !superior to laaown diffi cultly soluble compounds of thiamin by reason of their unique overalI solubility characteristics. Thus, it is possible to precipitate thiamin from a thiamin-containing mother liquor as one of the difficultly soluble salts of the invention, separate it from the solution and thereafter dissolve the salt in methanol, whereby thiamin chloride hydrochloride may be recovered in almost quantitative yields by acidifying the methanolic solution with hydrochloric acid and adding acetone. Alternatively, thiamin chloride hydrochloride may be recovered from the difficultly soluble salts of the invention by acidifying their methanolic solutions with aqueous hydrochloric acid, evaporating the methanol and separating the hydroxybenzoic acid component which is insoluble in the aqueous solution, and thereafter recovering thiamin chloride hydrochloride from the aqueous solution The following Examples are provided for the purpose of illustrating the inention: - EXAMPLE I.

Thiamin chloride hydrochloride, in amount 10.11 grams, was dissolved in 30 cubic centimetres of water. The solution was cooled with ice-water and sodium bicarbonate solution added with continued cooling and stirring until the pH value was adjusted at 6.0. A solution of isobutyl sodium salicylate was prepared by suspending 7 grams (slight excess) of isobutylsalicylic acid (5-isobu-cyl-2- hydroxybenzoic acid) in 300 cubic centimetres of water and adding sodium hydroxide (20%) until the acid dissolved and the solution reached a pH of about 6.0. This solution was then added, by pouring, to the solution of thiamin chloride hydrochloride. By rubbing the wall of the reaction vessel with a glass rod, nuclei of crystallisation were obtained in the clear super-saturated solution and the mixture was then left standing with continued cooling. In a short time, a thick crystal slurry was formed consisting of fine needles which were recovered after 2 hours by suction filtration, washed with icecold water, and then dried The yield was 12 grams. The analysis of the recrystallised compound showed the composition to be one (1) mole of thiamin base and one (1) mole of isobutyl-salicylic acid (5-isobutyl -2- hydroxybenzoic acid). In exactly the same manner described above, thiamin compounds of the following acids were prepared in yields of 80 to 95 per cent of theoretical by employing in place of isobutyl sodium salicylate, the corresponding salts of these acids (in slight excess): (1) 5-isohexyl-2-hydroxybenzoic acid; (2) 5-isoheptyl-2-hydroxybenzoic acid; (3) 5-isooctyl-2-hydroxybenzoic acid; (4) 4- isopropyl - 3 - methyl - 2-hydroxy benzoic acid; (5) 3-phenyl-2-hydroxybenzoic acid; (6) 5-isobutyl - -methyl-2-hydroxybenzoic acid; and (7) 1-hydroxy-2-naphthoic acid. All compounds thus prepared analyzed one whereas it was found that in preparing the mole of acid for each mole of thiamin base, thiamin salt of 5-cyclohexyl - 2-hydroxybenzoic acid, as described in the following Example, the proportion of acid employed must be higher in order to obtain good yields since the compound contains two (2) moles of acid for each mole of thiamin base. EXAMPLE II. Cyclohexyl-salicylic acid (5-cyclohexyl-2- hydroxybeazoic acid), in amount 15 grams, was suspended in 60 cubic centimetres of water, and thereafter the acid was dissolved by the addition of sodium hydroxide (20%) and the solution adjusted to pH 6.0--6.2. A thiamin solution, obtained by dissolving 10.11 grams of thiamin chloride hydrochloride in 20 cubic centimetres of water and carefully neutralizing the

solution by the addition of sodium hydroxide (20%) with cooling and stirring to a pH of 6.0, was added to the solution of cyclohexyl-salicylic acid. After lightly rubbing the clear solution with a glass rod, needle-shaped crystals formed immediately and condensed to a thick precipitate upon standing for a short period. The precipitate was recovered by suction filtration after two (2) hours, washed with water, and then dried. The yield amounted to 18.5 grams. The analysis of the recrystallized compound showed the composition to be one (1) mole of titiamin base and two (2) moles of cyclohexyl-salicylic acid (5-cyclohexyl-2- hydroxybenzoic acid). In exactly the same manner, the thiamin salts of the following acids were prepared, but these analyzed one 11) mole of acid for each mole of thiamin base: (1) 5 - cyclohexyl - 3-methyl - 2-hydroxy benzoic acid; and (2) 5-phenyl-2-hydroxybenzoic acid. What we claim is: - 1. Thiamin salts of substituted hydroxybenzoic acids of the formula: <img class="EMIRef" id="026700653-00040001" /> wherein R is an aliphatic or aromatic hydrocarbon radical (including bicyclic fused or condensed aromatic substitution); and R1 is hydrogen or methyl. 2. The normal thiamin salt of 5-isobutyl2-hydroxybenzoic acid. 3. The normal thiamin salt of 5-isohexyl2-hydroxybenzoic acid. 4. The normal thiamin salt of 5-isoheptyl2-hydroxybenzoic acid. 5. The normal thiamin salt of 5-isooctyl2-hydroxybenzoic acid.

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