* GB785628 (A)

Description: GB785628 (A) ? 1957-10-30

Improvements in or relating to the production of skeletal muscle relaxantcomprising5-chlorobenzoxazoles

Description of GB785628 (A) Translate this text into Tooltip

[75][(1)__Select language] Translate this text into

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.

COMPLETE SPECIFICATION Improvements in or relating to the production of Skeletal Muscle Relaxant comprising 5-Chlorobenzoxazoles We, MCNEIL LABORATORIES, INCORPOR ATED, a corporation organised under the laws of the State of Pennsylvania, United States of America, of 2900 N, 17th Street, Philadelphia 32, Pennsylvania, 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 : The present invention relates to the production of new compositions useful as skeletal muscle relaxants. Spasticity is an uncontrolled, involuntary, excessive contraction of one or more skeletal muscles and is a major component of many common disease conditions. It has been difficult if not impossible to relieve clinically. The manifestations of spasticity range in severity from those observed in minor transient injuries to localized areas, such as sprains and strains, through more serious conditions, such as chronic low back pain (lumbago), rheumatoid arthritis and rheumatoid spondylitis to the very severe incapacitating neurological diseases,

such as multiple sclerosis, Parkinson's disease, and cerebral palsy. Mephenesin is known to relieve, in animals, experimentally induced spasticity, that is, to produce relaxation of the skeletal muscles, by a mechanism involving the depression of the polysynaptic pathways of the central nervous system. The activity of this compound is so low and the duration so brief, that it is not feasible to employ this material clinically for the relief of spasticity. In addition, as is known, the administration of this material produces undesirable side effects, such as initial excitement, salivation, nausea and vomiting. There are also certain other compounds, discussed in the literature, which are stated to possess this ability to relax skeletal muscles. These compounds include 2-aminobenzoxazole, 2-amino-5-chlorobenzothiazole and 2-amino6-methylbenzothiazole. However, these compounds also produce the undesirable effects mentioned above even at the dose levels insufficient to produce muscular relaxation. According to the present invention, there is provided a skeletal muscle relaxant comprising a 5-chlorobenzoxazole represented by the following general formula: <img class="EMIRef" id="026447534-00010001" /> where R is an amino or a hydroxy group, or a salt thereof. The invention also includes a medical preparation for the relief of spasticity comprising such 5-chlorobenzoxazole or a salt thereof together with a pharmaceutical carrier. The compositions of the present invention have been found to produce relaxation of the skeletal muscles by a mechanism involving the depression of the polysynaptic pathways of the central nervous system. That is to say, the compositions prevent or overcome hypertonia and hyperflexia by selective depression of subcortical and spinal polysynaptic pathways. Compared to mephenesin, the present compositions are at least four times as active in producing relaxation when given orally, have an exceptionally long duration of action (up to 24 hours in therapeutic doses), have a wide safety margin between effective dose and lethal dose, and lack any significant side effects, including initial excitement, salivation, nausea or vomiting. The compositions may therefore be readily employed for the relief of spasticity in animals and man. Of special importance is the fact that the compositions are highly effective orally, and the preferred compositions are, therefore, adapted for oral administration such as in the form of suspension, capsule or tablet dosage form. As will appear hereinafter, numerous tests have been made using compositions of the invention in various species of animals and in man from which it is evident that the compositions are highly effective in the relaxation of the

skeletal muscles and are safe. In accordance with the invention, the 2amino-5-chlorobenzoxazole and its salts may be prepared by heating 5-chloro-2-hydroxyphenylthiourea to remove hydrogen sulfide therefrom and, if desired, converting the resulting 2-amino-5-chlorobenzoxazole to its acid salt. This reaction is illustrated by the following equation: <img class="EMIRef" id="026447534-00020001" /> As will appear hereinafter, the removal of hydrogen sulfide and hence the reaction is facilitated by maintaining the reaction medium on the alkaline side of neutrality and/or by including in the reaction -medium a a metal compound forming a sulfide insoluble in the reaction medium. It has been found that the removal of hydrogen sulfide from 5-chloro-2-hydroxy- phenylthiourea results in the completion of the benzoxazole ring to provide 5-chloro-2-amino- benzoxazole. This can be done simply by heating the 5chloro-2-hydroxyphenylthiourea. This reaction preferably takes place in a liquid medium in which the thiourea is at least somewhat soluble, such as hot water. The temperature of heating will depend in part upon the nature of the liquid medium, and the temperature may go as high as 100 :, in die case of water, or even higher in the case of other, higher boiling liquids. In this embodiment the thiourea compound is heated generally to at least about 50"C. A specific example of preparing the 2amino-5-chloro-benzoxazole by simply heating a 5-chloro-2-hydroxyphenylthiourea is as follows: EXAMPLE A A solution of 2-hydroxy-5-chlorophenyltllio- urea in hot water is boiled for 6 hours, and then cooled. The resulting precipitate is collected by filtration and extracted with dilute hydrochloric acid. Neutralization of the hydrochloric acid extract with ammonium hydroxide results in precipitation of a solid. This solid is recovered and purified by crystallization from a mixture of acetone and benzene. The resulting product, 2-amino-S- chlorobenzoxazole, has a melting point of 185-1860C. An ultraviolet spectrum of a solution of 2 milligrams of the product in 100 milliliters of methanol show peaks at 244 and 285 mu. The removal of the hydrogen sulfide is facilitated by maintaining the medium on the alkaline side of neutrality during the heating operation as by including in the medium a base soluble therein. Any base may be used for this purpose including the alkali metal hydroxides, the alkaline earth metal hydroxides, basic salts of alkali metals and of alkaline earth metals, and ammonia. A specific example illustrating the preparation of

2-amino-5-chlorobenzoxazole by the removal of hydrogen sulfide from the thiourea in alkaline medium is set forth below. EXAMPLE B A suspension of 2-hydrol;y-5-chlorophenyl- thiourea is prepared in water. One equivalent of sodium hydroxide, in aqueous solution, is added to the suspension. The resulting solution is heated at the boling point for three hours, and then cooled. The precipitate is filtered from the mixture, and purified by crystallization from a mixture of acetone and benzene. The crystalline product, 2-amino-5-cbloro- benzoxazole, has a melting point of 1S5- 186"C. An ultraviolet spectrum of a solution of 2 milligrams of the product in 100 milliliters of methanol shows peaks at 244 and 285 mu. The calculated nitrogen content for 2amino-5-chlorobenzoxazole is 16.6, that found in the product is 16. 8. The removal of hydrogen sulfide from the 2-hydroxy - S - chlorophenylthiourea is is also facilitated by including in the reaction medium a metal compound forming a sulfide insoluble in the medium in accordance with the following equation: <img class="EMIRef" id="026447534-00020002" /> /oN metal ~ /o'c-NH of ll + compound 11a sulfide + antorL Ci\'i\iHCSi\iH, C1\N cornon Metals which form insoluble sulfides include lead, copper, iron, nickel, cobalt, silver, mercurt, uranium, tin, and gold. The metal compound included in the reaction mixture may be an oxide or hydroxide or a suitable salt, such as a chloride, acetate. or sulfate, of one or more of the stated metals. The compound selected should be sufficiently soluble in the reaction medium to permit formation of the corresponding sulfide. Lead compounds, particularly lead oxide, copper compounds, particularly cupric chloride, and iron compounds, particularly ferric chloride, have been found to be especially suitable. Where a metal salt, e.g. a chloride, acetate, or sulfate, is employed, sufficient base will be added to the medium to neutralize the acid, e.g. hydrochloric, acetic, or, sulfuric acid formed during the reaction. The base employed for this purpose may be one of those mentioned hereinabove. The amount of metal compound employed will be at least that sufficient to combine with the hydrogen sulfide liberated. Preferably some excess of the metal compound is employed and the excess may go up to as high as 50100% in excess of that theoretically required. The amount preferably used is between 10 and about 30% in excess of that

theoretically required. In this procedure, where the metal compound is employed with the precipitation of a metal sulfide, the preferred reaction medium is an organic solvent in which the 2-amino-S- chlorobenzoxazole is soluble and in which the metal sulfide is insoluble. Examples of suitable organic solvents which may be employed are alcohols, such as methyl alcohol, ethyl alcohol, and isopropyl alcohol; ketones, such as acetone and methyl ethyl ketone; esters, such as ethyl acetate; and ethers, such as dibutyl ether. The preferred solvent media are the alcohols, especially methyl-, ethyl and isopropyl alcohol. In this procedure, the reaction temperature may vary from room temperature up to the boiling point of the solvent. Preferably the temperature employed is at least about 50"C. and is not substantially over about 100"C. During the reaction, agitation, although not necessary, is preferred as by stirring the reaction mixture. Examples of the preparation of the 2-amino5-chlorobenzoxazole in accordance with this procedure are set forth below: EXAMPLE C Sixty-one grams of 5-chloro-2-hydroxyphenylthiourea are mixed with 145 grams (0.65 mole) of yellow lead oxide and one liter of methanol. The mixture is refiuxed with stirring for three hours. The lead sulfide which is formed and the excess lead oxide are removed by filtration and washed with methanol. The methanol solutions are combined, and distillation of the methanol under vacuum, leaves, as residue, crude 2-amino-5-chlorobenzoxazole. Recrystallization several times from benzene results in white crystals melting at 185185.5"C. The calculated analysis for C7H5ClNO is C, 49.9; H, 3.0; C1, 21.0 and N, 16.6; that found is C, 49.5; H, 3.2; C1, 20.9 and N, 16.5. An ultraviolet spectrum of a solution of 2 milligrams of the compound per 100 milliliters of methanol shows peaks at 244 and 285 mu. The above compound is converted to a salt by adding to a solution thereof in methyl ethyl ketone a saturated solution of an equivalent of maleic acid in methyl ethyl ketone, and separating the resulting solid product by filtration. Recrystallization of the product from methyl ethyl ketone gives 2-amino-5-chlorobenzoxazole maleate melting at 159.5--160"C. The calculated N content for CllH9ClN2Os is 9.8; that found is 9.6. EXAMPLE D To a solution of 20 grams (0.1 mole) of 2hydroxy-5-chlorophenylthiourea in 50 ml. of methanol is added a solution of 17 grams (0.1 mole) of cupric chloride dihydrate in 50 ml.

of methanol. A brown precipitate results. Ammonium hydroxide (27 ml. of 28% solution, 0.2 mole) is then added, and the mixture is heated to boiling and filtered. The filtrate is poured into 500 ml. of water. The resulting precipitate is collected, dissolved in 25 ml. of acetone, and the resulting solution treated with activated charcoal. The addition of 50 ml. of benzene, evaporation to 35 ml. and cooling gives brown crystals melting at 178-1820C. Recrystallization of the crystals from benzene gives needles of 2-amino-5-chlorobenzoxazole melting at 185-1860C. An ultraviolet spectrum of a solution containing 2 milligrams of the crystals per 100 milliliters of methanol shows peaks at 245 and 286 mu. EXAMPLE E To a solution of 10 grams (0.05 mole) of 2-hydroxy-5-chlorophenylthiourea in 50 ml. of methanol is added a solution of 11 grams (0.04 mole) of ferric chloride hexahydrate in 50 ml. of methanol. The initial purple-red color changes in a few minutes to amber. After stirring for one half hour, the solution is treated with 16.5 ml. of 57% ammonium hydroxide solution (0.24 mole). A brown, flocculent precipitate of ferric sulfide appears. The mixture is then reflexed with stirring for one hour, cooled and centrifuged. The centrifugate is evaporated to dryness, and the residue is shaken with ether and water to separate the organic material from the ammonium chloride. The ether layer is extracted three times with 25 ml. portions of 1 N hydrochloric acid. The acid solution is then poured into excess ammonium hydroxide, and the resulting solid collected, washed with water and dried. This gives a light tan solid melting at 183--185"C. The material is then dissolved in 25 ml. of acetone and 50 ml. of benzene are added. After treatment of the solution with activated charcoal, the light yellow solution is evaporated to 25 ml. and cooled. The white crystals of 2-amino-5-chlorobenzoxazole which separate melt at 185--186"C. The 5-chloro-2-hydroxyphenylthiourea employed in the above-described procedure may be readily prepared by reacting 2-amino-4chlorophenol with a thiocyanate, such as ammonium thiocyanate, in aqueous medium containing one equivalent of acid. Further in accordance with the invention, the 2-amino-5-chlorobenzoxazole and its salts may be prepared by reacting, with an aminating agent, a 5-chlorobenzoxazole having, at the carbon atom at the number 2 position, an atom or group replaceable by an amino group. The reaction may be illustrated by the following equation :

<img class="EMIRef" id="026447534-00040001" /> wherein Y is hydrogen, a halogen, or a SOOH group, and Z is H (to provide ammonia) when Y is other than H or OH (to provide hydroxylamine) when Y is H. Amination of the carbon atom in the number 2 position may also be accomplished by other means, including two-stage reactions, for example, as by reaction of an appropriate 5- chlorobenzoxazole compound with an amine, which on hydrogenation readily releases the substituent group, such as benzylamine or hydrazine, followed by reduction of the resulting compound to provide the corresponding 2-amino-compound. In the foregoing equation, the reactant, Z-NII, when Y is hydrogen (H), may be, as stated, hydroxylamine. In such case the reaction will take place in an aqueous medium, either neutral or alkaline. Basic hydroxylamine may be employed as such or the hydroxylamine may be employed in the form of a salt, such as the hydrochloride, a base, such as sodium hydroxide, also being included in the reaction medium. In this procedure the temperature of the reaction may range from about room temperature to the boiling point, preferably just below the boiling point, as in a steam bath. Agitation is highly desirable, such as by stirring during the reaction. An example of this procedure is as follows: EXAMPLE F A mixture of 4.1 grams (0.027 mole) of 5chlorobenzoxazole and 1.85 grams (0.027 mole) of hydroxylamine hydrochloride is treated with a solution of 1.72 grams (0.043 mole) of sodium hydroxide in 25 ml. of water. Heating on the steam bath for 30 minutes and cooling gives crystals which are purified by recrystallization from aqueous methanol to give 2-amino-5-chlorobenzoxazole. In the foregoing equation, the aminating compound, Z Z--NH,, when Y is halogen or a SOOTH group, may be, as stated, a} ammonia. In such case, since acid is released during amination, it is desirable to employ an excess of the aminating compound, the excess combining with the acid being formed. In this procedure, the reaction may tale place in an aqueous medium or in an anhydrous medium such as in chloroform or in anhydrous liquid ammonia. Widely varying reaction temperatures may be employed, depending upon the reaction medium used, and temperatures ranging from as low as about 0 C, as in an ice bath, to the refluxing temperature of the reaction mixture may be employed. A specific example of the preparation of the compound in accordance with this procedure is as follows: EXAMPLE G

A slurry of 2 grams of 2, 5-dichlorobenz- oxazole in 20 ml. of 28% aqueous ammonia is shaken vigorously for about an hour until all the dichloro compound has reacted. The solid 2-amino-5-chlorobenzoxazole is then filtered off and washed with water. To hasten the reaction, the mixture may be heated gently under a reflux condenser during the stirring period, the heating not being sufficient to drive off substantial amounts of ammonia before the reaction is completed. Crystallization of the solid product from benzene gives 2-amino-S- chlorobenzoxazole melting at 185--186"C. Ultraviolet spectrum analysis in methanol shows peaks at 245 and 286 mu. According to the invention, the 2-hydroxy5-chlorobenzoxazole and its salts may be prepared by hydrolysis of 2-amino-5-chlorobenzoxazole and, if desired, converting the resulting 2-hydroxy-5-chlorobenzoxazole to its salt. A specific example of the preparation of 2hydroxy-5-chlorobenzoxazole in accordance with this procedure is as follows: EXAMPLE H A solution of 16.9 g. (0.1 mole) of 2-amino5-chlorobenzoxazole in 200 ml. of 1 N HC1 is refluxed until precipitation is complete. The resulting solid is collected by filtration, dissolved in 200 ml. of 1 N NaOH and the solution extracted with 50 ml. of ether. Acidification of the alkaline solution gives a precipitate which is purified by crystallization from acetone to give 2-hydroxy-5-chlorobenzoxazole melting at 191--191.5"C. The calculated N content for C7H4ClN02 is 8.26; that found is S. 1. The 2-hydroxy-5-chlorobenzoxazole and its salts may also be prepared in accordance with the invention by heating 2-hydroxy-5-chlorophenylurea or 2-hydroxy-5-chlorophenylthiourea in acid solution and, if desired, converting the resulting 2-hydroxy-5-chlorobenz oxazole to its salt. A specific example of this procedure is as follows: EXAMPLE I 9.8 g. (0.05 mole) of N-(5-chloro-2hydroxyphenyl) urea, 4.1 ml. (0.05 mole) of concentrated HCl and 50 ml. of water are refluxed for 3 hours. After 30 minutes needles begin to separate. At the end of reflexing the hot mixture is filtered. The solid is dissolved in sodium hydroxide solution and the solution is extracted with ether. Acidification of the alkaline layer gives 2-hydroxy-5-chlorobenzoxazole. The 2-amino-5-chloro-benzoxazole possesses basic properties enabling it to form addition salts with acids. Hence this compound may be employed either as the base or as a salt. The acid forming salt may be any inorganic or organic acid producing a pharmaceutically acceptable

salt, for example, hydrochloric, hydrobromic, hydroiodic, nitric, sulfuric, or phosphoric acid; acetic, propionic, caproic, stearic, and other acids of this series; crotonic, fumaric, oleic, citric, tartaric, lactic, benzoic, naphthoic, salicylic, methane sulphonic, and camphor suiphonic. The 2-hydroxy-5-chlorobenzoxazole, on the other hand, possesses acidic properties enabling it to form salts with bases and this compound may be employed as the acid or as a salt. These salts can readily be prepared by reaction between the 2-hydroxy-5-chlorobenzoxazole and an equivalent amount of a compound containing the desired cation, and the salts formed may be the alkali metal salts, alkaline earth metal salts, ammonium salts, or substituted ammonium salts, such as those of ethanolamine and ethylenediamine. If a salt is employed, the salt will be pharmaceutically acceptable and any toxicity or other undesirable effects which may be imparted should be taken into consideration as well known in the art. Pharmaceutically useful salts should not be substantially more toxic than the compound itself and should be able to be incorporated in liquid or solid pharmaceutical media for the preparation of therapeutically useful compositions. In preparing the compositions of the present invention the benzoxazole compound may be combined with a significant amount of a pharmaceutical carrier. The carrier may take a wide variety of forms depending upon the form of the preparation desired for administration. For parenteral injection the carrier may be sterile water with suitable adjustment of the pH to insure solution of the benzoxazole compound. For example, the compounds not in salt form are practically insoluble in water while the salts vary in solubility, and in some cases the solubility of a salt is not sufficient to provide the desired concentration. In this case the pH may be further adjusted. Thus when using the hydrochloride, for instance, in water, the pH will be further adjusted by the addition of acid to maintain the compound in solution. As stated, the preferred form of administration of the present composition is oral, and the oral dosage may be in the form of a suspension, powder adapted for suspension in liquid media, tablet or capsule. In preparing the compositions in oral dosage form any of the usual pharmaceutical carrier media may be employed, such as gelatin, in the case of capsules; sterile water, glycols, oils or alcohols, in the case of suspensions; starches, sugars, kaolin, salts, lubricants, or binders in the case of powders and tablets. Tablets represent the most advantageous oral dosage form. The amount of the composition administered and the amount of benzoxazole compound in the composition may vary somewhat depending

upon the severity of the spasticity and upon the species being treated. As far as administration is concerned, the amount of composition administered may range from that providing as little as about 2 milligrams of the benzoxazole compound per kilogram of body weight to that providing as high as about 100 milligrams per kilogram, preferably in the case of humans, that providing between about 5 and about 40 milligrams of benzoxazole compound per kilogram of body weight. In the composition, the concentration of the benzoxazole compound should be at least 1% by weight, preferably at least 2%. The concentration of the benzoxazole compound may vary widely above these figures depending upon the form the composition takes, and in some cases the concentration of the benzoxazole compound may go as high as about 8090%. Depending also upon the severity of the spasticity and upon the species being treated, as stated, the amount of benzoxazole compound per dosage unit form may also vary widely. Generally, the compositions per dosage unit will contain at least 25 milligrams of the benzoxazole compound, and in some cases such as in compositions for the treatment of large domestic animals, like horses, the amount per dosage unit may reach as high as about 10,000 milligrams. In the case of compositions adapted for human administration, the amount will generally range between 100 and 1000 milligrams of benzoxazole compound per dosage unit. The compositions of the present invention will be more readily appreciated from a consideration of the following specific examples which are given for the purpose of illustration and are not intended to limit the scope of the invention in any way. In these examples, as is customary in pharmacological investigations, albino mice of a uniform age and weight and from a standard strain are used as a primary test object since they are readily available and since the relative activity of depressant drugs in these animals as compared to useful drug actions in man is well known. The results have also been confirmed by repetition in higher animal species including rats, hamsters, dogs, cats and guinea pigs and this is referred to in examples below. Finally, as also pointed out in certain of the examples, the results have been confirmed in man. The primary criterion used for the presence of skeletal muscular relaxation in animals, especially the smaller animals, is the inability of the animal to roll over when placed flat upon its back. This is a convenient end point for the experimental observer, but is far in excess of the amount of skeletal muscular relaxation desired in man. Much of the following data are based on this observation although numerous concurrent confirmatory observations of skeletal muscular relaxation were made.

Because of the foregoing and because of expected differences in the relative responsiveness of man and animal to drugs of this type, much of the following data are based on doses that produce effects that could be considered excessive for ordinary clinical use. EXAMPLES I-XII In these examples 2-amino-5-chlorobenzoxazole is made up into a 2% aqueous solution with sufficient hydrochloric acid to provide a pH of 1.3. This solution is administered by intra-peritoneal injection into twelve groups (designated Groups I through XII) of five albino mice, weighing between 19 and 20 grams each, in doses set forth in the following Table A. In each case, with a minor exception noted below, the mice show skeletal muscular relaxation as evidenced by uncomplicated loss of the righting reflex within 1-2 minutes after injection, and lasting for the time listed in Table A. Recovery of the righting reflex is uneventful unless othenvise indicated in the table. No preliminary excitement or any tremor, running movements or twitching that would indicate undesirable side effects are observed. TABLE A Group Dose mg./kg. Duration ofeffect (min.) I 75 7* II 100 47.6 III 125 84.6 IV 150 71.2 V 175 140.4 VI and VII 200 92.8, 127.6 VIII 225 151.8 IX and X 250 172.6, 209.8 XI 300 321.6 XII 350 385** *This figure is the average duration of the loss of righting reflex for the three mice that do lose their righting reflex. Two mice do not lose this reflex. This dose is the minimally active dose in mice. **Three of the five mice are so intensely paralyzed that death results from inadequate respiration. Consequently higher doses are not used in this series of examples. EXAMPLES XIII-XXIV In these examples 2-amino-5-chlorobenz- oxazole is made up into a 2% suspension in a solution containing 8.6% polyethylene glycol 300, 0.5% sodium carboxymethyl cellulose and the remainder water. In making up this suspension, the 2-amino-5-chlorobenzoxazole is first dissolved in

the polyethylene glycol, and the resulting solution is diluted slowly, with constant stirring, with a 0. 5% aqueous solution of sodium carboxymethyl cellulose. This suspension is injected intraperitoneally into six groups (designated Groups XIII through XVIII) of 10 to 30 young adult albino mice weighing 15.2 to 21.6 grams. Approximately half of the mice are males and half females. At the same time, six groups (designated Groups XIX through XXIV) of 10 to 20 mice of a similar type receive oral administrations of the suspension. The dosage amounts are set forth in the following Table B. In each case, unless otherwise specified, the mice show skeletal muscular relaxation as evidenced by uncomplicated loss of righting reflex, within 1-2 minutes after injection and within 2-10 minutes after oral administration, and lasting for the time set forth in Table B. Recovery of the righting reflex is uneventful unless otherwise noted. No preliminary excitement or any tremor, running movements or twitching that would indicate undesirable side effects are observed. TABLE B No. of mice Dose Duration of Group in group Route mg./kg. effect (min.) XIII 10 intraperitoneally 75 18.4* XIV <RTI ID= TABLE C No. animals Dose Duration of Group in group Route mg./kg. Effect (min.) XXV 4 intraperitoneally 75 25* XXVI 4 ,, 100 54 XXVII 4 ,, 150 155 XXVIII 4 ,, 200 165-240 XXIX 4 ,, 250 108** XXX 24 orally 100 60-140 XXXI 20 20 ,, 200 240-410 XXXII 16 ,, 300 28-1380 XXXIII 4 ,, 400 420-1080** XXXIV 8 ,, 500 1440** *This figure is the average duration of the loss of righting reflex for the two rats that do lose their righting reflex. This is the minimally active dose in rats. **This figure is the range of duration for the animals that survive which are two, two and one for Groups XXIX, XXXIII and XXXIV, respectively. The time until respiratory paralysis occurs in the remainder of the animals is 42, 60 and 115 minutes,

respectively, for these groups. EXAMPLES XXXV-XLIII In these examples the procedure of Examples XXV-XXXIV is followed in nine groups (designated Groups XXXV through XLIII) of 2-16 hamsters weighing 62-102 grams with comparable results. The data are tabulated as follows: TABLE D No. animals Dose Duration of Group in group Route mg./kg. effect (min.) XXXV 5 intraperitoneally 75 25 XXXVI 7 ,, 100 53 XXXVII 2 ,, 150 31 XXXVIII 4 ,, 250 150 XXXIX 2 ,, 300 96 XL 16 orally 300 102 XLI 10 ,, 400 170 XLII 4 ,, 500 240* XLIII 10 ,, 600 300* *This figure is the average duration for the animals that survive which are three and eight for Groups XLII and XLII I, respectively. The time until respiratory paralysis occurs in the remaining animals in these groups is 180 and 193 minutes, respectively. EXAMPLES XLIV-XLVIII In these examples a 2% suspension of 2amino- 5- chlorobenzoxazole is prepared as in Examples XIII-XXIV and sufficient hydrochloric acid is added to provide a pH of 1.82.1 thereby forming a solution of the benzoxazole. This solution is injected intravenously into five groups (designated Groups XLIV through XLVIII) of 2-5 albino rabbits whose age and weight vary as set forth in Table E. The dosages are set forth in Table E below. The pattern of onset is very characteristic in the rabbits for this type of muscular relaxant; there is immediate weakness in the hindquarters followed by weakness of the forelegs with inability to walk or right, and finally relaxation of the neck muscles so that the rabbit is unable to hold up its head. In order that the data be comparable with that given above, the loss of the righting reflex is given in Table E. The other signs of skeletal muscular relaxation occur before the loss of this reflex and are still present after its return for an appreciable length of time. TABLE E No. animals Weight Dose Duration of Group in group Age (kilo) Route mg./kg. effect (min.)

XLIV 2 young 2 intravenously 20 35 XLV 2 ,, 2 ,, 25 50 XLVI 2 ,, 2 ,, 45 105 XLVII 2 adult 3.4 ,, 50 27 XLVIII 2 mature 4.4 ,, 80 12.5 Higher doses than those listed for the young rabbits are lethal. Lower doses for those listed for the mature rabbits are ineffective. This decrease in activity with increasing age is of minor importance in all other animal species tested. EXAMPLE XLIX Oral preparations of 2-amino-5-chlorobenzoxazole are given to 43 dogs in dosages ranging from 25 to 362.5 mg./kg. of body weight, and the following typical results are obtained: Capsules containing 2-amino-5-chlorobenzoxazole and imbedded in raw liver are given to a dog (male) weighing 11.6 kg. in an amount to provide 250 mg. of drug per kilogram of body weight. Within 50 minutes the dog shows slight ataxia and incoordination. This initial sign of skeletal muscular relaxation increases in intensity until the animal can no longer stand at 95 minutes. The intensity of this effect is strictly equivalent to the loss of righting reflex described above for the smaller animals. However, it continues to increase until the animal is no longer able to swallow or to move its tongue although respiration appears normal or only slightly depressed at 160 minutes. After this maximal effect is reached it is maintained for an indefinite period, but slowly diminishes in intensity until the animal is able to walk six hours later. At this time the animal appears and acts approximately normal. In another dog (female) weighing 5.6 kilograms the same dose of 2-ariino-5-chlorobenz- oxazole is given but in the form of the suspension employed in Examples XIII-XXIV by stomach tube. The results are qualitatively identical with those of the above dog, with the onset of the inability to stand occurring at 75 minutes, the maximal effect at about 90 minutes and the inability to stand lasting for 390 minutes. With all the dogs tested, no serious druginduced side effects are observed following the administration of doses as high as 362.5 mg./ kg. or as many as ninety-seven daily doses of from 25 to 115 mg per dose per day per kilogram of body weight. Representative animals upon sacrifice show no indication of pathological change on gross or microscopic examination. Periodic blood studies show no signs of deleterious effects. Confirming this, concurrent tests in rats, in which the drug is administered orally, daily in the food, at dose levels of 50-200 mg./kg. of body weight do not show any signs of drug toxicity.

In further experiments, the activity of 2amino-5-chlorobenzoxazole as a 0. 5% solution in H,SO,; 1% solution in hydrochloric acid or as the suspension employed in Examples XIII -XXIV has been demonstrated following intravenous injection into thirteen cats, intraperitoneal injections into three cats, oral administration into ten cats, intraperitoneal injections into twenty-six guinea pigs and intravenous injections into a monkey. EXAMPLES L-LI In these examples is used a 2% suspension of 2-hydroxy-5-chlorobenzoxazole in an aqueous solution consisting of 8.60,10 polyethylene glycol 300, 0.5% sodium carboxymethylcellulose and the remainder water. Two albino mice, designated L and LI, respectively, receive oral administrations of this suspension in an amount of 333 and 1000 mg of the benzoxazole per kilogram of body weight, respectively. Mouse L shows skeletal muscular relaxation for 1-2 hours, but does not lose the righting reflex. Mouse LI loses the righting reflex in 2 minutes and respiratory failure occurs in 38 minutes. EXAMPLES LII--LVI In these examples3 five groups (designated Groups LII through LVI) of 2-7 albino mice receive intraperitoneal injections of a 1 solution of 2-hydroxy-5-chlorobenzoxazole in water containing sufficient sodium hydroxide to provide a pH of 11. In all cases within a few minutes loss of righting reflex occurs and the duration of this effect is noted and set forth in Table F. The doses in terms of mg of benzoxazole per kilogram of body weight, are also set forth in Table F. TABLE F No. animals Dose Group in group mg./kg. Duration of effect (min.) LII 2 75 4.5 LIII 4 100 19 LIV 2 150 36.5 LV 7 200 94 LVI 5 225 89* *This figure is for the three mice that survive. In the other two respiratory failure occurs in 10 minutes. EXAMPLES LVII-LIX In these examples, three groups (designated Groups LVII through LIX) of two albino rats are given oral administrations of a 2% solution of 2-hydroxy-5-chlorobenzoxazole in water containing suflicient sodium hydroxide to provide a pH of 11. Group LVII receives 400 mg of the benzoxazole per kilogram of body

weight. One rat loses the righting reflex in 20 minutes for a period of 44 minutes. The other doesn't fully lose the righting reflex. Group LVIII receives 600 mg./kg. In 4 minutes, the righting reflex is lost for 110 minutes. Group LIX receives 800 mg./kg. In 3 minutes loss of the righting reflex occurs and this progresses to respiratory failure in 30 minutes. EXAMPLES LX-LXIII In these examples four groups (designated Groups LX through LXIII) of two hamsters receive oral administrations of the solution emplayed in Examples LVII--LIX. Group LX receives 300 mg. of the benzoxazole per kilogram of body weight, and loses the righting reflex in two minutes for a period of 4 minutes. Group LXI receives 400 mg./kg. The righting reflex is lost in 3 minutes for a period of 29 minutes. Group LXII receives 500 mg./kg. The righting reflex in this group is also lost in 3 minutes for a period of 29 minutes. Group LXIII receives 600 mg./kg. One animal loses its righting reflex in 2 minutes for 83 minutes. Respiratory collapse occurs in the other after 4 minutes. The 2-hydroxy-5-chlorobenzoxazole is very close to 2-amino-5-chlorobenzoxazole in terms of potency and duration of action. With this compound no indications of side effects or of potential hazards in higher animals are observed. The following examples illustrate the preparation of typical compositions of the present invention in oral dosage unit form. EXAMPLE LXIV The following formula is for preparing 8000 tablets (10 grain) each containing 250 mg. of 2-amino-5-chlorobenzoxazole : g. 2-amino-5-chlorobenzoxazole 2000 milk sugar 800 dibasic calcium phosphate U.S.P. 1527.2 starch (filler and disintegrating agent) 1799.3 calcium stearate 56.7 gelatin solution 1.5 pounds per gallon In place of the milk sugar, dibasic calcium phosphate and the portion of the starch making up the filler, there may be used sucrose, polyethylene glycol 4000, mannitol and/or calcium carbonate in various combinations and proportions. Starch paste, acacia solution, glucose solution, carboxymethyl-cellulose solution, or shellac may be used in place of gelatin solution as granulating agent. Calcium stearate is employed as lubricating agent and may be replaced by magnesium stearate, stearic acid, or talc. EXAMPLE LXV The following formula may be employed for preparing 10,000 tablets

(11.25 grains) each containing 500 mg. of 2-amino-5-chlorobenzoxazole: 2-amino-5-chlorobenzoxazole 11 libs., 162 grains milk sugar 1 Ib., 13 oz., 96 gr. starch (filler) 1 lb., 13 oz., 96 gr. polyethylene glycol 4000 7 oz., 24 gr. starch (disintegrating agent) 13 oz., 340 gr. calcium stearate 1 oz., 180 gr. gelatin solution 1.5 pounds per gallon EXAMPLE LXVI The following formula may be employed to make 1000 #3 capsules each containing 100 mg. of 2-amino-5-chlorobenzoxazole : 2-amino-5-chlorobenzoxazole 100 g. milk sugar 150 g. fill weight 250 mg. In place of or in addition to the milk sugar may be used sucrose, dicalcium phosphate, calcium carbonate, kaolin, mannitol and/or starch. EXAMPLE LXVII The following formula may be employed for preparing a suspension containing 250 mg. of 2-amino-5-chlorobenzoxazole per 5 cc.: 2-amino-5-chlorobenzoxazole (200 mesh) 51.5 g. propylene glycol 50 g. 70% sorbitol solution 250 g. alcohol (7.7%) 77 cc. carboxymethyl cellulose (low viscosity, type 70) 10 g. granulated sugar 375 g. methyl ester of parahydroxy benzoic acid 1.5 g. propyl ester of parahydroxybenzoic acid 0.3 g. polyoxyethylene sorbitan monooleate 0.5 cc. flavoring 3 cc. citric acid 1.5 g. water q.s.a.d. 1000 cc. In place of the propylene glycol may be used polyethylene glycol and/or glycerine. The carboxymethyl cellulose may be replaced by any one of the natural gums used as suspending agents. The parahydroxybenzoic acid esters may be replaced by any commonly used bacteriostatic agent, and other commonly used surface agents may be used in place of the polyoxyethylene sorbitan monooleate. EXAMPLE LXVIII The following formula illustrates the preparation of a suspension containing 500 mg. per 5 cc. of 2-amino-5-chlorobenzoxazole : 2-amino-5-chlorobenzoxazole 103 g. carboxymethyl cellulose (low viscosity, type 70) 20 g. 70% sorbitol solution 250 g. granulated sugar 375 g. propylene glycol 50 g. methyl ester of parahydroxybenzoic acid 1.5 g. propyl ester of parahydroxybenzoic acid 0.3 g. polyoxyethylene sorbitan monooleate 0.5 g. methyl

salicylate 2.5 cc. water q.s.a.d. 1000 cc. In the formulation of Examples LXIV- LXVIII, the 2-amino-5-chlorobenzoxazole may be replaced by a like amount of 2hydroxy-5-chlorobenzoxazole. Compositions of the type illustrated in Examples LXIV-LXVIII have been administered, by the present time, to well over 200 patients. The periods of administration have been as long as eight weeks, and doses as large as 6 grams of benzoxazole a day have been used. Most patients received 500 mg. or more three or four times a day. The administration of these compositions has been found to produce a significant degree of relief from muscle stiffness, spasm and pain in patients with the fibrositic type of arthritic involvement and in rheumatoid spondylitis. The compositions also produce prompt symtomatic relief of a moderate to a marked degree from low back pain and muscle spasm, and have been shown to produce some relief of spasticity in severe neurological disorders. What we claim is: - 1. A skeletal muscle relaxant comprising a 5-chlorobenzoxazole having the general formula I or a salt thereof. 2. A skeletal muscle relaxant substantially as hereinbefore described with reference to and as illustrated in Examples A to I. 3. A medical preparation for the relief of spasticity comprising a 5-chlorobenzoxazole having the general formula I or a salt thereof, together with a pharmaceutical carrier.

* Sitemap * Accessibility * Legal notice * Terms of use * Last updated: 08.04.2015 * Worldwide Database * 5.8.23.4; 93p

* GB785629 (A)

Description: GB785629 (A) ? 1957-10-30

Process for the production of phthalocyanine dyestuffs

Description of GB785629 (A)

Translate this text into Tooltip

[75][(1)__Select language] Translate this text into

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 785629 Date of Application and filing Complete Specification Sept 27, 1955. No 275061/55. Application made in Germany on Sept 28, 1954. Complete Specification Published: Oct 30, 1957. Index at acceptance:-Classes 2 ( 3), C 2 D 20; and 2 ( 4), D 1 T. International Classification:-CO 7 c 5 C 09 b. COMPLETE SPECIFICATION Process for the production of Phthalocyanine Dyestuffs SPECIFICATION NO 785,629 The Inventors of this Invention In the sense of being the actual devisers thereof within the meaning of Section 16 of the Patents Act, 1949, are Berthold Bienert, of 9 Karl Krekelerstrasse 9, Leverkusen-Bayerwerk, Germany, Fritz Baumann, of 65 Christian Hess-Strasse, Leverkusen-Bayerwerk, Gernany, and Manfred Groll, of 6, Hahnenweg, Xolk-Starrmnhelm, Germany, all German citizens. THE PATENT OFFICE, 20th November, 1957 1) pntnaliocyanme Suipancinuriuczs a 1 c scabs. with aminosalicylic acid (see Specification No. 520,199). It has now been found that particularly valuable dyestuffs of the phthalocyanine series which may be used as chrome dyes can be obtained if phthalocyanine sulphochlorides are reacted with aminoalkyl aminosalicylic acid derivatives of the general formula ti -OH. in which X represents hydrogen or a sulpho group, R hydrogen, a monovalent metal, alkyl, cycloalkyl, aryl or aralkyl, R' hydrogen or alkyl and R' a primary or secondary amino-substituted alkyl group or, in the case where R' is hydrogen, a tertiary aminosubstituted alkyl group. The phthalocyanine sulphochlorides containing the central atoms usually employed, for example cobalt, nickel or copper, are suitable for the process Qf the present invenDB 00816/1 ( 5)/3605 100 11/57 R 6 LU Up OA V A r 2 hydroxy 5 N (/3-aminoethyl)-amino-3sulphobenzoic acid

and 2-hydroxy-5-N-(/3aminoethyl) N methylamino 3 sulphobenzoic acid. The aminoalkyl-amino-o-hydroxycarboxy 55 lic acids can be used in the form of their salts or esters for the reaction with the phthalocyanine sulphochlorides. The reaction of the aforementioned aminoalkyl aminosalicylic acids with the phthalo 60 cyanine sulphochlorides takes place very readily and most easily in water In order to fix the acid which is liberated, acid-fixing substances, for example sodium hydroxide solution or sodium bicarbonate, are preferably 65 added It is possible to convert all or if desired only some of the sulphochloride groups into the corresponding amides. If the solubility of the phthalocyanine dyestuffs obtained is not satisfactory, it can be 70 improved by subsequent after-sulphonation, for example with chlorosulphonic acid. The phthalocyanine dyestuffs which can be obtained by the process of the invention are characterised by their clear colour shade, their 75 very good light-fastness properties and their excellent dyeing properties They are taken up as chrome dyes The colours of the finally dyed or printed fabrics are very uniform, very fast to rubbing and are often fast to finishing 80 operations, lPrice 3 s 6 d l PATENT SPECIFICATION 7859629 Date of Application and filing Complete Specification: Sept 27, 1955. No 27506/55. Application made in Germany on Sept 28, 1954. Complete Specification Published: Oct 30, 1957. Index at acceptance:-Classes 2 ( 3), C 2 D 20; and 2 ( 4), D 1 T. International Classification:-CO 7 c 5 C 09 b. COMPLETE SPECIFICATION Process for the production of Phthalocyanine Dyestuffs We, FARBENFABRIKEN BAYER Ax TIENGESELLSCHAFT, of Leverkusen Bayerwerk, Germany, a body corporate organised under the laws of 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 relates to novel phthalocyanine dyestuffs and to a process for their production. It is known that chrome dyes of the phthalocyanine series can be obtained if phthalocyanine sulphochlorides are reacted with aminosalicylic acid (see Specification No. 520,199). It has now been found that particularly valuable dyestuffs of the phthalocyanine series which may be used as chrome dyes can be obtained if phthalocyanine sulphochlorides are reacted with aminoalkyl

aminosalicylic acid derivatives of the general formula /o -OH in which X represents hydrogen or a sulpho group, R hydrogen, a monovalent metal, alkyl, cycloalkyl, aryl or aralkyl, RI hydrogen or alkyl and RI' a primary or secondary amino-substituted alkyl group or, in the case where RI is hydrogen, a tertiary aminosubstituted alkyl group. The phthalocyanine sulphochlorides containing the central atoms usually employed, for example cobalt, nickel or copper, are suitable for the process of the present invenlPnice 3 s 6 d l tion The sulphochloride groups may be either directly on the benzene ring in the 3-position or 4-position or on a side chain They are introduced into the phthalocyanine molecule by known methods, for example with chlorosulphonic acid. The aminoalkyl aminosalicylic acids used for the process of the invention are obtained, for example, by reacting aromatic amino-ohydroxycarboxylic acids with the corresponding halogen alkyl amines In order that the final products should be sufficiently soluble, it is advisable to use aromatic amino-ohydroxycarboxylic acids which contain sulpho groups Examples of such compounds are 2 hydroxy 5 N (B 8-aminoethyl)-amino-3sulphobenzoic acid and 2-hydroxy-5-N-(,8aminoethyl) N methylamino 3 sulphobenzoic acid. The aminoalkyl-amino-o-hydroxycarboxylic acids can be used in the form of their salts or esters for the reaction with the phthalocyanine sulphochlorides. The reaction of the aforementioned aminoalkyl aminosalicylic acids with the phthalocyanine sulphochlorides takes place very readily and most easily in water In order to fix the acid which is liberated, acid-fixing substances, for example sodium hydroxide solution or sodium bicarbonate, are preferably added It is possible to convert all or if desired only some of the sulphochloride groups into the corresponding amides. If the solubility of the phthalocyanine dyestuffs obtained is not satisfactory, it can be improved by subsequent after-sulphonation, for example with chlorosulphonic acid. The phthalocyanine dyestuffs which can be obtained by the process of the invention are characterised by their clear colour shade, their very good light-fastness properties and their excellent dyeing properties They are taken up as chrome dyes The colours of the finally dyed or printed fabrics are very uniform, very fast to rubbing and are often fast to finishing operations, t 2 L 111 EXAMPLE 1. 15.3 Parts by weight of 100 % ( = 31 7 parts by weight of 48 3 %) sodium salt of Cuphthalocyanine 4,41411,4111 tetrasulphonic acid (from the sodium salt of 4-sulphophthalic acid) are introduced slowly while stirring into parts by weight of chlorosulphonic acid and heated to 60-70 C At this temperature, 25 8 parts by weight of pure thionyl

chloride are added dropwise and the mixture is then heated for about 5 to 6 hours at 90 C. After cooling, the reaction mixture is mixed by stirring with iced water, the precipitated Cu-phthalocyanine ( 4)-tetrasulphochloride is filtered off and washed neutral with iced water The neutral paste of the sulphochloride is stirred with a small amount of iced water and introduced while stirring into a solution of 8 6 parts of 5-N-(l 3-aminoethyl) mino-2hydroxy-3-sulphobenzoic acid and 5 45 parts by weight of 45 % sodium hydroxide solution in 50 parts of water After stirring for two to three hours, another 13 85 parts of 45 % sodium hydroxide solution are added The mixture is thereafter stirred for 12 hours at room temperature, and is then heated for 1 hour at 60 C, 1000 parts of water are added and filtration carried out while hot with active carbon After the filtrate has been acidified with HI Cl, the dyestuff is salted out with sodium chloride and separated in the usual manner A good yield of a clear turquoise blue chrome dye is obtained. If the equivalent amount of 5-N-(f 3-aminoethyl) N-methyl-amino-2-hydroxy-3-sulphobenzoic acid is used instead of 5-N-( 13-aminoethyl)-amino-2-hydroxy-3-sulphobenzoic acid, a dyestuff with similar properties is obtained. The 5-N-(f-amin 6 ethyl)-amino-2-hydroxy3-sulphobenzoic acid can be obtained as follows: 233 Parts of 5-amino-2-hydr 6 Y y-3-sulphobenzoic acid are dissolved in 1400 parts of water and 178 parts of a 45 % sodium hydroxide solution, the reaction vessel being filled with nitrogen Thereafter, 118 parts of 1 amino -2 chloroethane hydrochloride are added and 266 parts of 45 % sodium hydroxide are slowly added dropwise to this mixture at 20 C Thereafter the reaction mixture is stirred for about 12 hours at room temperature and then for 1 to 2 hours at C Upon acidifying ther Yixture with hydrochloric acid (p HI= 1) it is stirred for some time while cooling The precipitated unreacted 5 amino 2 hydroxy-3-sulphonic benzoic acid is sucked off and washed 2 to 3 times with iced water The filtrate is brought to a p H of about 5 to 6 and saturated with sodium chloride The precipitated 5-N-(f Saminoethyl) amino 2 hydroxy 3-sulnhobenzoic acid is filtered off and recrvstallised from a small amount of water The acid obtained is readily soluble in water Therefore it is advantageously not isolated but used as aqueous solution for further reactions. In a similar manner 5-N-( 13-aminoethyl)-Nmethyl amino 2 hydroxy-3-sulphobenzoic acid can be obtained as follows: 310 5 Parts of 5 N methyl amino 2hydroxy-3-sulphobenzoic acid are dissolved in 1760 parts of water by adding 223 parts of a 45 % sodium hydroxide solution Then 148 5 parts of 1-amino-2-chloroethane hydrochloride are added and 335 parts of a 45 % sodium hydroxide

solution slowly added dropwise at a temperature of 205 C The pulpy mass obtained is diluted with 1250 parts of water and then stirred for 12 hours at room temperature and 1 to 2 hours at 600 C. The reaction mixture is thereafter made acid (p H= 1) by adding hydrochloric acid and the non-reacted 5-N-methyl-amino-2-hydroxy-3sulphobenzoic acid filtered off in the cold and the residue washed with a small amount of icy water The 5-N-( 13-aminoethyl-N-methylamino-2-hydroxy-3-sulphobenzoic acid is obtained by neutralising the filtrate with sodium hydroxide solution and saturating the mixture with sodium chloride Upon sucking off, the acid is recrystallised from 530 parts of water The acid thus obtained contains only small amounts of a compound containing more nitrogen, presumably 5-N-(Il-aminoethyl aminoethyl) N methyl-amino-2hydroxy-3-sulphobenzoic acid. Other salicylic acid derivatives can be obtained by starting from other halogen alkyl amines, for example 1-chloro-2-NN-diethylamino-ethane. EXAMPLE 2. 22.62 Parts of Cu-phthalocyanine are heated for 2 hours at 140 ' C in 226 parts of chlorosulphonic acid 15 Parts of thionyl chloride are slowly run into the solution when 105 it has cooled to 800 C and the temperature is then maintained at 90-95 C until a sample is insoluble in diethylamine solution. The reaction mixture is stirred while cold into ice, the precipitated sulphochloride is 110 filtered off and washed neutral with iced water The neutral paste is divided into two equal portions: a) The first portion of the sulphochloride is introduced into a cold solution of 8 6 parts 115 of 5 N ( 13-aminoethyl)-amino-2-hydroxy-3sulphobenzoic acid and 5 54 parts of 45 ' sodium hydroxide solution in 50 parts of water Another 13,85 parts of 45 % sodium hydroxide solution are added and the mixture 120 is worked up as described under b) below. b) The other portion of the sulphochloride is mixed by stirring with a cold solution of 15.4 parts of 5-N-( 3-arninoethyl)-amino-2hydroxy-3-sulphobenzoic acid and 9 9 parts 125 of 45 % / sodium hydroxide solution in 50 parts of water After adding another 5 54 parts of % sodium hydroxide solution, the mixture is stirred for a further 12 hours at room temperature and for one houlr at 600 C The 130 785,629 5.54 parts by weight of 45 % sodium hydroxide solution are similarly added to solution b). After stirring for 12 hours at room temperature, the mixture in each case is heated 70 for 1 hour at 600 C The dyestuff formed is salted out with sodium chloride, filtered with suction and if necessary dried In each case a clear bluish-green chrome dye is obtained in good yield

75 Dyes having a somewhat more yellowish shade are obtained if 27 36 parts of 4,41,411, 4 '11-tetraphenyl copper phthalocyanine are converted into the tetrasulphochloride by reaction with 274, parts of chlorosulphonic acid 80 and 15 parts of thionyl chloride at ordinary temperature and further processed as indicated above Particularly valuable chrome dyes are obtained from 4,41-diphenyl copper phthalocyanine-49 ',4-"-disulphonic acid 85 EXAMPLE 5. Parts of a copper-phthalocyanine containing four sulpho groups in the 4-positions, dissolved in 540 parts of chloro-sulphonic acid, are reacted with 78 parts of thionyl 90 chloride by heating for 6 hours at 90 to 950 C to obtain the sulphochloride The reaction mixture is poured on to ice and the precipitate filtered off and washed until neutral with iced water 95 The sulphochloride thus obtained is mixed with a small amount of iced water and then reacted with 38 2 parts of the disodium salt of 5 N (/ diethylamino ethyl) amino-2hydroxy-3-sulphobenzoic acid which has been 100 made alkaline to bicarbonate by stirring with about 11 5 parts of a 37 % hydrochloric acid and 9 35 parts of sodium bicarbonate Thereafter a further 29 1 parts of sodium bicarbonate are introduced and the mixture is then 105 stirred for 10 to 12 hours at room temperature After heating for 1 hour at 600 C, the dyestuff formed is salted out with sodium chloride, filtered off and washed with sodium chloride solution A clear turquoise chrome 110 dye is obtained which does not turn to green when treated with dilute acids. The 5-N-(,B-diethylamino-ethyl)-amino-2hydroxy-3-sulphobenzoic acid can be obtained as follows: 115 255 Parts of the sodium salt of 5-amino-2hydroxy-3-sulpho-benzoic acid are dissolved in 510 parts of water and 485 parts of a 33 % sodium hydroxide solution, the reaction vessel being filled with nitrogen 172 Parts of di 120 ethylamino-chloroethane hydrochloride dissolved in 350 parts of water are slowly added dropwise to the mixture within 4 to 5 hours at 55 to 600 C while stirring Thereafter, the reaction mixture is stirred for another 2 hours 125 at 55 C to 600 C and then for 12 hours at room temperature Upon addition of 91 parts of sodium chloride, 197 parts of a 37 % solution of hydrochloric acid are added to obtain a p H of 5 to 6 The reaction mixture is then 130 chrome dyes formed in good yield as described under a) and b) above are salted out with sodium chloride and separated in the usual manner. EXAMPLE 3. 6 Parts of niclkel-phthalocyanine are heated for 4-5 hours at 112-113 C in 60 parts of chlorosulphonic acid, cooled to 70-75 C and, after adding 7 25 parts of thionyl chloride, heated for approximately another 2 hours at 90-95 C until a sample is insoluble in diethylamine solution After cooling, the reaction mixture is mixed by stirring with

ice, the precipitated sulphol 5 chloride is filtered with suction and washed neutral with iced water The sulphochloride paste is introduced into a solution of 3 78 parts of 5 N (j aminoethyl) amino 2hydroxy-3-sulphobenzoic acid and 2 76 parts of 45 % sodium hydroxide solution in 30 parts of water The mixture is then stirred for 3 to 4 hours while adding 5 2 parts of 45 % sodium hydroxide solution and for a further 12 hours at room temperature After heating for 1 hour at 600 C, the dyestuff formed is precipitated by being stirred into a solution of hydrochloric acid and sodium chloride and recovered by filtration It constitutes a valuable, clear, greenish-blue chrome dye. EXAMPLE 4. 22.6 Parts of 4,41-diphenyl-copper phthalocyanine prepared from 2 mols of 3,4-dicyandiphenyl and 2 mols of phthalodinitrile are heated for 2 hours at 1400 C in 226 parts of chlorosulphonic acid The mixture is then allowed to cool to 800 C and 15 parts of thionyl chloride are slowly run in at this temperature The mixture is then heated to 90-95 C until a sample is insoluble in diethylamine solution The reaction mixture is stirred while cold into ice, the precipitated sulphochloride is filtered with suction, washed neutral with iced water and divided into two portions. One half of the sulphochloride paste is introduced into a solution of: a) 869 parts by weight of 2-hydroxy-5-N(,B-aminoethyl)-amino-3-sulphobenzoic acid, and 5 54 parts by weight of a 45 % sodium hydroxide solution in 50 parts by weight of water, and the other half introduced into a solution of b) 15 4 parts by weight of 2-hydroxy-5-N( 13-aminoethyl)-amino-3-sulphobenzoic acid and 9.90 parts by weight of 45 % sodium hydroxide solution in 50 parts by weight of water. After the sulphochloride paste has been added, each of these mixtures is stirred for about 1 hour, and then another 13 85 parts by weight of 45 % sodium hydroxide solution are slowly added dropwise to solution a) and 785,629 4 785,629 stirred for some time while being kept ice cold The precipitate so formed is sucked off and washed twice with ice cold sodium chloride solution The residue is then dispersed with about 1500 parts of a 5 ' sodium chloride solution and hydrochloric acid is added until a strong Congo-acid reaction is obtained The undissolved 5 amino 2hydroxy-3-sulphobenzoic acid is filtered off and the 5-N-( 3-diethylamino-ethyl-amino-2hydroxy-3-sulphobenzoic acid obtained from the filtrate by adding sodium chloride, while maintaining the solution at a p H of 8 to 8 5. The 5 N (fl diethylarino ethyl-amino-2hydroxy 3 sulphobenzoic acid is readily soluble in water and therefore is preferably not isolated but used as aqueous solution for further reactions. In contrast to the 5-amino-2-hydroxy-3sulphobenzoic acid or the

5-methylamino-2hydroxy-3-sulphobenzoic acid the reaction products of these acids with chloroethylamine, or diethylamino-chloroethane are readily soluble in hydrochloric acid containing sodium chloride. EXAMPLE 6. 37.8 Parts of copper-phthalocyanine dissolved in 340 parts of chlorosulphonic acid are heated for 4 to 5 hours to 112 to 1130 C. until a sample is soluble in a 10 ' pyridine/ water mixture Thereafter, 24 parts of thionyl chloride are added dropwise at 60 to 700 C. The mixture is then heated to 90 to 950 C. until a worked up sample is insoluble in diethylamine/water. The sulphochloride formed is then poured on to ice and used in the same manner as described in Example 5 Thus, a greenishblue chrome dye is obtained. EXAMPLE 7. Parts of the sodium salt of 4-phenylcopper-phthalocyanine 41, 411, 4 "'-trisulphonic acid, obtained as an easily soluble compound from 3,-dicyanodiphenyl and the sodium salt of 4-sulphophthalic acid by using a urea melt, are slowly introduced into 300 parts of chlorosulphonic acid Thereafter, 16 4 parts of thionyl chloride are added dropwise while stirring, the stirring being continued for 5 to 6 hours at 75 to 80 C until a worked up sample is insoluble in diethylamine/water. The reaction mixture is poured on to ice, the precipitated sulphochloride sucked off and washed neutral with iced water. To the sulphochloride which is mixed with a small amount of iced water, an aqueous solution containing 18 3 parts of the disodium salt of 5-N-(i,-diethylamino-ethyl)-amino-2hydroxy-3-sulphobenzoic acid which has been brought to a p H of about 11-12, are added. Then 26 55 parts of a 33 % sodium hydroxide solution, diluted with 265 parts of water are slowly added dropwise while stirring The reaction mixture is stirred for about 10 to 12 hours and then neutralised with acetic acid. Upon adding sodium chloride, a clear bluishgreen dyestuff is obtained which can be purified by dissolving in 1500 parts of water which contain 25 parts of glacial acetic acid and salting out again by adding 250 parts of sodium chloride.

* Sitemap * Accessibility * Legal notice * Terms of use * Last updated: 08.04.2015 * Worldwide Database

* 5.8.23.4; 93p

* GB785630 (A)

Description: GB785630 (A) ? 1957-10-30

Apparatus for bending and dishing the edges of sheet metal blanks ofcircular, oval and other shape

Description of GB785630 (A)

PATENT SPECIFICATION Date of Application and filing Complete Specification: Oct 10, 1955 No 28847/55. Application made in Germany on June 13, 1955. Complete Specification Published: Oct 30, 1957. Indexatacceptance:-Class 83 ( 4), E( 1 EX: 1 J 3: 1 JX: 4 A: 4 F: 713: SC: 12), H( 2 E 1: 4 LX: 19). International Classification:-B 23 j, k. COMPLETE SPECIFICATION Apparatus for Bending and Dishing the Edges of Sheet Metal Blanks of Circular, Oval and other Shape I, WALTER ECOLD, of German Nationality, of Sperrluttertal 540, St Andreasberg/ Oberharz, Western Germany, do hereby declare the invention, for which I pray that a patent may be granted to me, and the method by which it is to be performed, to be particularly described in and by the following statement: - The invention relates to apparatus for bending and dishing the edges of sheet metal blanks of circular, oval and other shape. The purpose of the invention is to provide apparatus which will make it possible to perform satisfactorily, and at an economical cost, thickening and stretching operations on the edges of individual blanks or of small batches, which do not justify the considerable outlay for special presses and drawing machines. The apparatus as proposed by the invention comprises a sheet metal upsetting or stretching tool having a first part and a second, co-operating part, a support for both parts, and a sheet metal blank clamping device, the support and/or the clamping device being adjustable in position in such manner as to vary the inclination of the parts of the tool relative to the plane of a sheet metal blank

held in the clamping device. An embodiment of the invention will now be described in greater detail by way of example with reference to the accompanying drawings of which:Fig 1 shows a mechanism according to the invention, and Fig 2 shows the different angular positions of the forming tool. The mechanism shown in Fig 1 consists of a clamping device 1 for a sheet metal blank 2, and a power-driven tool assembly, supported in a frame 3. The clamping device for the sheet metal blank 2 can be adjusted for height by means of a spindle 4 The clamping device rests on rollers 5, which can move on rails 51, so that the sheet metal blanks can always be placed in their correct working position, according lPrice 3 s 6 d l to their size The rails 51 are fixed with reference to the frame 3 The clamping device is secured in its desired position by means of bolts 511 These bolts pass through holes 50 5111 in the vertical webs of the rails 51 and through lugs 11 in the pedestal of the clamping device. The power-driven forming tool consists of an upper part 6 and a lower part 7 In order 55 to bend the edge portion of the sheet metal blank 2 to the required angular position, the blank is inserted between these two parts of the tool For this purpose, the two parts of the tool are each provided with one or more 60 pairs of jaws which move in a direction normal to the plane of movement of the parts of the tool when these parts are pressed together The jaws of a pair move, when the parts are pressed together, towards each 65 other to upset or thicken the material or away from each other to stretch the material The thickening or stretching taking place in a direction normal to the edge of the blank 70 The two parts 6 and 7 of the tool, of which the upper part 6 is driven so as to reciprocate at a fast rate, are held in a C-bracket 9. The bracket is supported in the frame 3 such that it can turn about the front edge 10 of 75 the lower part 7 of the forming tool. The sequence of operations during one working cycle is as follows: first the blank is adjusted by means of the clamping device, so that it is in the correct working position 80 For this purpose it is inserted between the parts of the tool to a depth equal to the width of the edge which is to be bent over. At the same time the bracket 9 of the forming tool is set to the first bending stage 85 If now the mechanism of the forming tool is started up by switching on the power supply, the edge will, during a number of working strokes of the upper part of the tool, be gradually bent to the inclination 90 given by the angular position of the forming tool by a gradual upsetting or stretching of the metal normal to the edge of the blank.

The bracket 9 is now moved to a new position and the process repeated In each new position of the bracket 9 the edge 8 will be bent over more as shown by Fig 2, until it finally reaches the desired bent position with the last bending stage The feed of the sheet metal blank between the parts 6 and 7 of the tool can be effected by hand or mechanically. The same applies to the rotation of the forming tool assembly in the bracket 9, the inclination of this part can be varied either by hand, or alternatively by a mechanism, using the graduated circular scale 11 When the bending of one part of the plate is finished, the latter is rotated so that the forming tool can operate on an adjacent part Alternatively, a partial bending of the whole edge can be effected followed by further bending until the desired inclination is reached. Whilst the bending of very thin sheet, of about 0 01 inch to O 1 inch thickness, will in general be carried out with the clamping device in the same position, it might possibly be necessary in the case of sheet of O 1 inch to 0 25 inch thickness to have the necessary tilting movements performed by the clamping device In that case the forming tool may either be rigidly supported, or be given a movable support This version is still within the framework of the invention, which is thus not restricted to the version illustrated by the above example, but includes also thickening and stretching individual sections of the edges of sheet metal blanked to any required curved contour.

* Sitemap * Accessibility * Legal notice * Terms of use * Last updated: 08.04.2015 * Worldwide Database * 5.8.23.4; 93p

* GB785631 (A)

Description: GB785631 (A) ? 1957-10-30

A process for the production of shaped articles from elastomeric polymerscontaining reactive groups

Description of GB785631 (A)

A high quality text as facsimile in your desired language may be available amongst the following family members:

FR1136480 (A) FR1136480 (A) less Translate this text into Tooltip

[78][(1)__Select language] Translate this text into

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.

COMPLETE SPECIFICATION A process for the Production of Shaped Articles from Elastomeric Polymers containing Reactive Groups We, FARBENFABRIKEN BAYER AKTIENGESELLSCHAFT, of Leverkusen - Bayerwerk, Germany, a body corporate organised undler the laws of Germany, do hereby deciare 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 shaped articles from elastomeric polymers containing reactive groups. It has been found that elastomeric shaped articles of high strength, such as for example filaments, films, foils or strips, can be obtained if a solution or emulsion of a synthetic elastomeric polymer containing reactive groups. is introduced into a coagulating bath which contains an agent capable of reacting with the reactive groups to give cross-linking, for example a polyfunctional compound containing at least two groups which are capable of reacting with the reactive groups of the synthetic elastomeric polymer to give crosslinking, and the coagulate formed in the coagulating bath is removed from the bath and dried. Suitable :elastomeric polymers consist essentially of il ear carbon chains to which are linked from 0.005-0.6 molls by weight per 100 parts by weight of elastomeric poly mer of reactive groups such as carbonyl, carboxyl, sulphonic add, amide or basic groups. These polymers can be obtained by copolymerizing monomers which have polymerisable carbon-to-carbon double bonds and have an elastiasing action with organic compounds which contain reactive groups and are

copolymerisable with said elastidsing monomers. Examples of suitable monomers which have polymerisable carbon-to-carbon double bonds and have ivan elasticising action are acrylic or meithacrylic esters of aliphatic alcohols with at least 4 C-atoms, preferably with 8-14 C-atoms, vinyl alkyl lethers -the alkyl radical of which contains 1-8 C-atoms, and compounds with two' conjugate carbon-to-carbon double bonds, such as for example butadiene or homologues and derivatives of butadiene, such as isoprene, 2: 3-dimethyl butadiene, 2chiorobutadiene and 2-cyanobutadiene. The said monomers which have an .Aasticising action are preferably used in proportions of 15-99 per cent. by weight calculated on the total amount of monomers used. Examples of suitable copolymerisable compounds with reactive groups are those which contain carbonyl, carboxyl, sulphonic acid, amide or basic groups, preferably basic nitrogen groups, which are capable of salt forma- tion wtih organic adds. Examples of polymerdisable compounds containing carbonyl groups are: acrolein: ?-substituted acroleins, such as a-nt'thyl acrolein: vinyl alkyl ketones, such as for example vinyl methyl ketone, vinyl ethyl ketone and isopropenyl methyl ketone. Examples of polymerisable compounds with carboxyl groups are mono- and polycarboxyic a,,0-ethylen!ically unsaturated acids, such as for example acrylic acid, methacrylic acid, sorbic acid, maleic acid, maleic acid anhy dride or fumaric acid. It is also possible to use the mononsters of the polycarboxylic acids, such as mono esters of maleic acid with aliphatic, cycloaliphatic or araliphatic alcohols having 1-14 carbon atoms, as for instance maleic add monomethyl ester, maleic acid monobutyl ester, maleic acid monododecyl ester and maleic acid monocyclohexyl ester. Examples of polymerisable compounds with amide groups are: acrylamide: Q-methacryl- amide: c a-isopropylacrylamide: ? - chioro- acrylamide. Heterocyclic nitrogen bases containing vinyl groups such as 2-vinyl pyridine and 2-vinyl-5-ethyl pyridine are examples of basic unsaturated compounds. Vinyl sulphonic acid can if desired be used as a copolymerisable compound. Said monomers with reactive groups may be used in proportions of 0.550 per cent by weight as calculated on the total amount of monomers. In addition to the said monomers, other organic compounds each containing at least one polymerisable carbon-to-carbon double bond can be used for the production of the copolymers, examples of such compounds being styrene, acrylonlerile, methacrylonitrile, acrylic or methacrylic esters of alcohols with 1-3 C-atoms, vinyl chloride and

l,l-di- chioroethylene. Furthermore, polyfunctional monomers containing at least two active olefine double bonds which act as cross-linking agents can be used: however, these latter compounds should be used in comparatively small proportions, preferably not exceeding 0.001--1 per cent. by weight calculated on the total amount of monomers used. Examples of suitable crosslinking agents are aromatic hydrocarbons containing at least two vinyl groups such as divinylbeozene, esters of polyhydric alcohols or of aromatic compounds containing at least two phenolic hydroxy groups with "ss-etllylenic- ally lmsaturated monocarboxylic acids such as ethylene dimethacrylate, ethylene diacrylate, pentaerythrityl tetramethacrylate, resorcinol dimethacrylate, half-esters of maleic acid or substituted maleic acids such as I-chloro- maleic acid with polyhydric alcohols such as the reaction product of 1 mol of ethylene glyccl or similar dihydric alcohols with 2 mols of maleic anhydride, the reaction product cf trihydric alcohols such as trimethylol propana with two or three mols of maleic anhydride, and also divinyl ether and divinyl suiphone. Other suitable ccpolymerisablg compounds are those which have their reactive groups present in masked form, the said groups being liberated by reaction with a- hydrolysing agent after the polymerisation: examples of such copolymerisable compounds are saponifiable esters, such as acrylic and methacrylic alkyl esters, vinyl sulphonic alkyl esters, (e.g. butyl vinyl sulphonaLe) un saturated nitriles (e.g. acrylonitrile) and the polymerisable amides referred to above. Of the compounds with reactive groups referred to above, those which have proved particularly satisfactory are the polymerisable monomers containing carboxyl groups, since the copolymers obtained with these monomers produce shaped articles such as threads, or filaments of particularly high initial strength after coagulation. For the production of shaped articles, the copolymers are preferably used in the for. of their emulsions. The latter ate obtained by emulsification of the monomers in accordance with lznown processes, preferably in an aqueous medium, and polymerisation in the presence of suitable catalysts. Examples of emulsifiers are the alkali metal salts of paraffin sulphonates obtained by sulphocblorination of long-chained paraffins with 12-18 carbon atoms and subsequent saponifiction (German Patent 750,3304. The polymerisation can be activated with free-radicalforming substances, such as for example azo dinitriles, per-compounds or redox systems. Particularly advantageous activators for the emulsions are aliphatic

suiphinic acid salts, preferably n-ith a carbon chain of 12--1S carbon atoms, without the addition of compounds yi-elding oxygen (Makromolekulare Chemie, Volume 3, page 43 (1949)). It is also possible to influence the thermoplastic behaviour of the copolymers by adding regulators. Prior to working up copolymers of butadienes, it is of ccurse advis'able to add stabilisers, such as for example phenyl-P-naphthylamine or suitable phenc!s. The copolymer emulsions can also be prepared by the monomers being polymerised in bulk form or in solution and being subsequently emulsified. The emulsions contain preferably 10-60 per cent by weight of polymers. The polymers can alternatively be used in the dissolved form. Suitable solvents are aromatic hydrocarbons, such as benzene, chlorobenzene, 2,4-dichiorob euzene, ketones, such as methyl ethyl ketone, or mixtures of said solvents. The solution of the polymers in said solvents should contain 8-40, preferably 10--20, per cent. by weight of polymers. The choice of the polyfunctional compounds which are- ro be reacted with the reactive groups of the copolymers is dependent on the nature of the reactive groups of the Co- polymers. Among the numercus combinations which are possible; polyfunctional compounds suitable for reaction with copolymers containing carbonyl groups include polvemines and polyanaides containing at least two NIl groups, such as for example ethylene diamine, butylene diamine, hexamethylene diamine, nonamethylene di amine, diethylene triamine, triethyene tetramine, hexamethylene pentamine, hydrazine, urea, thiourea, oxalic acid diamide, succinic acid diamide, adipic acid diamide, and terephthalic acid diamide. In this case the carbonyl groups of the copolymers react with the amino groups with the formation of > C N linkages. For the copolymers containing carboxyl groups, examples of suitable polyamines are those containing at least two <img class="EMIRef" id="026598855-00030001" /> groups, R1 and R2 may be the same or different and each represents a hydrogen atom, an alkyl radical having 1-18 carbon atoms, an aryl radical such as the phenyl radical, or an aralkyl radical, such as a benzyl radical. Suitable polyamines are those referred to above by way of example: other suitable polyamines are those in which at least one hydrogen atom of one of the amino or imino groups is sub stituted by one of the aforementioned substituents, such as N - methyl-ethylene diamine, N,N1-dimethylethylene diamine and N, N,Nl - NI - tetranisthylethylene diamne. Furthermore, water-soluble salts or hydroxides of polyvalent metals, such as calcium chloride, barium chloride, magnesium chloride, zinc chloride, zinc sulphate, ferrous sulphate, barium hydroxide, calcium

hydroxide, chromium acetate, chrome alum, copper acetate and aluminium salts Isuch as abrainium sulphate can be used. The aforementioned crossslinking agents react with the carboxyl groups of the copolymers with the formation of salts, whereby said agents effect a cross-linkage of the copolymers by way of the salt groups formed The polyamines can also be used in the fonn of their salts with weak organic and inorganic acids such as carbonic acid, acetic acid, benzoic acid, stearic acid and boric acid. If polyamines with primary or secondary amino groups or their salts are used as cross-linking agents the salt groups formed during reaction in the precipitating bath in the first stage are converted into amide or imide groups during the drying process which follows the coagulating step. Other suitable cross-linking agents are organic compounds containing at least two epoxy groups such as: diglycidyl trimethylolpropane, obtained by reaction of 1 mol of trimethylolpropane, with 2 mols of epichiorhydrin; diglycidyl- glycerin, obtained by reaction of 1 mol of glycenin with 2 mols of epichlorhydrin ss,ss - di(glycidyl- cxyphenyl)-propane, obtained by reacting l mol of di-p-hydroxyphenyl - dimethyl-meth- ane with 2 molts of epichiorhydrin; diglycidylaniline. These polyepoxy compounds are preferably used in alcoholic solution. For accelerating the reaction of the epoxy groups with the carboxyl groups of the polymers, whereby polyester formation occurs, the polymer after leaving the coagulation bath can be after treated with alkaline agents such as aqueous solutions of alkali metal hydroxides, alkaline earth metal hydroxides, ammonia, and organic amines such as dibutylamine, trimethylamine and triethylamine. The copolymers containing amide groups can be reacted with aliphatic and/or aromatic aldehydes such as acetalde- hide, propionaldehyde, butyraldehyde, glyoxal, benzaldehyde, preferably fiormaldehyde, its different polymeric modifications or compounds thereof yielding formaldehyde, such as hexamethylene tetramine, the sodium salt of -hydroxy methane sulphinic acid, or compounds containing several reactive methylol groups, such as hexamethylol melamine or dimethylolurea. Polybasic organic acids, such as oxalic acid, itacoric acid, fumaric acid, maleic acid, succinic acid, glutaconic acid, citric acid, adipic acid, tartaric acid, 1,5-naphthalene disulphonic acid and l,3-benzenedisulphonic acid are suitable for reaction with the copolymers containing basic groups. As to the composition of the coagulating baths, preferably water or alcohols such as methanol, ethanol or mixtures of water with alcohols are used as solvents The amount of crosstining agent used can vary within wide limits. Preferably the proportion lof a crosslinking agent should bie sufficient to react with at least 1/10 of the reactive groups. Good results are also obtained if the amount of crosslinking

agents is at least chemically equivalent to the reactive groups present in the polymers. For achieving this result the coagulating bath should preferably contain 1-50 per cent by weight of cross-linking agent, although higher concentrations are also possible. Besides the crossilinking agents the coagulating bath can contain coagulating agents, for instance strong electro,lytes such as sodium chloride, potassium chloride, sodium sulphate, calcium chloride, zinc chloride ior magnesium chlor- ide in amounts of 1 30 per cent by weight. The pH value of the coagulating bath depends on the type of reaction by which cross4ink- ing of the polymers takes place. When polymers with carboxylic or sulphonic acid groups are used, thie pH value is preferably kept at 6-10 if polyamines and their salts and/or hydroxides of polyvalent metals are applied as cross-linking agents. The salts af the polyvalent metals call for a pH value of 4-7. With mixtures of polyvalent metal salts and polyamines the pH value can be kept at 610. For the coagulation lof the polymers with carbonyl groups the coagulation bath should contain polyatnines in the aforementioned concentrations, and the pH value of such coagulation baths should be kept at 7-10. When polymers with amide groups are used the coagulation bath contains aldehydes and may hrave a pH value of 6-10. The precipitation baths can also contain thickening agents, such as polyvinyl alcohol, salts iof polyacrylic acid, alginic acid zor carboxymethyl cellulose, which are soluble in water or alcohol, casein, gelatine or agar-agar in a concentration of 115 per cent. by weight. The temperature of the coagulation bath depends on the reactivity of the components applied. Generally speaking the bath is kept at a temperature of 2070 C. After leaving the coagulation bath the coagulated articles can be washed with water or ethanol in order to remove any surplus of coaguating agents adhering ,to the coagulates. The temperature of the washing agents should be kept at 2070 C. Finally the shaped coagulate is dried at a temperature suitably in the range 50150 C., preferably 90120 C. The process is particularly suitable for the production of threads from aqueous emulsions of butadiene copolymers which contain carboxyl groups. There emulsions are introduced through a nozzle into the precipitating bath. By using polyvalent amines such as ethylene diamine, in the precipitating bath, which advantageously also contains 'electrolytes, such as for example calcium chloride or sodium phosphate, a thread which is ready for use is obtained immediately after the emulsion has entered the precipitating bath, it only being necessary for the said thread to he washed, dried and reeled. This thread sl:otvs excellent

tensile strength values with high elongation only a short time after being dried, such as could not be formerly obtained with butadienecontaining polymers, even from solutions. It is obvious that the copolymer emulsions can have added thereto the conventional vulcanisation auxiliaries, such as sulphur and accelera- tors. The threads can also be heated to a temperature higher than that of the actual drying process, whereupon additional crosslinking may'take place. Such after-treatments can also be carried out under tension or with additional shaping. The butadiene-acrylonitrile copolymers which contain free carboxyl groups present an excellent resistance te solvents and have a high tensile strength and a high resistance to ageing and heat The copolymer ~ emulsions or solutions which have been described can of course also have added thereto other natural or synthetic rubber latices or plastic emulsions, fillers, plasticisers, resins, dyestuffs, pigments, solvents or other high polymers capable of being cross-linked in accordance with the same principle. Examples of such high polymers are polyacrylic acids, carboxymethyi cellulose, alginic acid, protein compounds such as cas=-ir; polyesters can also be used. The mode of carrying out the present invention can be varied within very wide limit. Instead of producing 'threads, webs or films, it is for example also possible to produce hoses by the use of annular nozzles. Moreover, the working up and drying of the shaped coagulates which are obtained can be modified in practically any desired manner, it being of course always necessary to bear iin mind the nature of the polymer to be used. Another possibility is for textile filaments of natural or synthetic nature to be impregnated with the above-described polymer emulsions or solutions and introduced into a coagulation bath which contains suitable poly-functional compounds. Furthermore. textile threads canbe extruded through a nozzle into the above-described coagulatic!n bath simultaneously with the emulsion or solution, whereby threads or filaments with a core d textile fibres are obtained. The process can also be carried out by applying the latex or solution as a thin layer on to a firm surface, for example, a mould, metal plate or a rotating roller or introducing the latex or solution in.t(; a rotating mould and then if desired continuously coagulating and thereafter cross-linking it. Furthermore, leather, textile materials and paper fleeces can be impregnated by using an analogous method. As already mentioned, the threads or moulded bodies produced by the present process show a surprisingly high strength shortly after entering the precipilation bath. This ensures that working up can be carried out satisfactorily. In

addition, owing to the high strength of Ithe threads which are obtained, a very high withdrawal speed is possible. Whereas according to processes hither- to lmoxvn, withdrawal speeds of 1 metre per minute were adueved, the present process allows of using a withdrawal speed of 50 60 metres per minute. It is surprising that emulsions of comparatively low concentrat.on containing 10--40 per cent. by weight of polymer can also be used for carrying out this process. It is of course also possible for the viscosity of the emulsions to be increased by suitable additives prior to preparation. The high strength also permits 'the production of very thin threads having diameters of 0.05-- 0.2 mm, the preparation of which from emulsons formerly presented difficulties. It is further to be emphasised that the vulcanisation which was formerly necessary can be dispensed with in connection with the polymers containing butadiene. In connection with the dime-free polymers, an increase in strength is produced by the process which is employed, the said increase being such as could otherwise only be obtained by complicated known after-treatment processes, for example with peroxides. The following Examples, in which parts are by weight, further illustrate the invention. EXAMPLE 1. 2200 Parts of butadiene, 1400 parts of acrylonitrile and 400 parts of the monobutyl ester of maleic acid are emulsified in SAEC parts of a solution of 160 parts of the sodium salt of a paraffin sulphon* acid containing 1218 carbon atoms in 5,360 parts of water and 120 parts of N-sulphuric acid and polymer ised while stirring at 25 C. after adding 6.5 parts of diisopropyl xanthogen disulphide and 20 parts of the sodium salt of a paraffin sultunic acid with 12-18 carbon atoms. 19.5 Parts of diisopropyl xanthogen disulphide are addiiionally added in three batches, each of 6.5 parts, when 25, 40 and 55 % of the monomers have polymerised. After 26 hours, 80% of the monomers have polymerised. The reaction is stopped by adding 40 g. of sodium hydrosulphite, 3% (calculated on the monomers introduced) of the conventional stabilisers, such as phenyi-P-naphthylamine, are added and the mixture is degasified by steam distillation of the residual monomers. The emulsion obtained in this manner is extruded at a constant hydro static pressure in an upward direction through a nozzle into a solution of 350 parts of calcium chloride and 210 parts of ethylene diamine in 3500 parts of water at a temperatu;re of 50 C. The thread which is formed is withdrawn over rollers, washed with water at a temperature of 50 C. and dried at 120 C. It is thereafter ready for use, shows a tensile strength of 1700 kg/cm2 with a brealiing elongation lof 720% diameter of the thread

(diameter 0.11 mm) and has an excellent resistance to solvents, to heat and ageing. EXAMPLE 2. 1050 Parts of butadiene, 300 parts of styrene and 150 parts d maleic monobutyl ester are emulsified in 1895 parts of a solution of 60 parts of the sodium salt of a paraffin suphonic acid containing 12-18 carbon atoms in 1850 parts of water and 45 parts of sulphuric acid and polymerised with the addition of 4 parts of diisopropyl xanthogen disulphide, as described in Example 1. With a polymerisation temperature of 35 C. a yield of 60% is obtained after 29 hours. The pre duct is worked up as described in Example 1. When the emulsion is extruded through a nozzle into a solution of 350 parts of calcium chloride and 140 parts of triethylene tetramine in 3,500 parts of water at 65" C. a nontacky thread which can be worked up satisfactorily and which has a high tensile strength after drying is immediately obtained. (Diameter of the thread 0.14 mm, tensile strength 1080 kg/cm2, breaking elongation 700%). EXAMPLE 3. 1950 Parts of butyl acrylate, 950 parts of 1,1-dichioroethylene and 150 palrts lof methacrylic acid are emulsified in 3260 parts of a solution of 105 parts of the sodium salt of a paraffin tsullphonic acid containing 12-18 carbon atoms in 3200 parts of water and 60 parts of suphuric acid, and polyineriset while stirring with the addition of 22.5 parts of the sodium salt of a paraffin sulphinic acid with 12-18 carbon atoms at 25 C. A yield of substantially 100%' is obtained after 4 hours. As described in Example 1, the emulsion thus obtained is extruded through a nozzle sion have a tensile strength of 1270 kg/cm2 and an elongation at a break of 660'% at a diameter of 0.14 mm. EXAMPLE 8. 6500 Parts of butadiene, 2500 parts of methyl methacrylate and 1000 parts of maleic acid monocyclohexyl ester are en:ulsified and polymerised as described in Example 7. At a temperature of 35 C. a yield of 72% is obtained after 32 hours. The threads produced from this emulsion have a tensile strength of 570 kg/cm2 and an elongation at break of 720'% at a diameter of 0.22 mm. EXAMPLE 9. 3000 Parts of butadiene, 2500 parts of acrylonitrile, 3500 parts of methyl methacrylate and 1000 parts of maleic acid monobutyl ester are emulsified and polymerised as described in Example 7. At a polymerisation temperature of 45 C. a yield of 75% is obtained after 35 hours. The thread produced from this emulsion is extraordinarily resistant to heat and ageing and, after heating to 140 C. for 30 hours, has a tensile strength of 446 kg/cm2 and an

elongation at break of 375%. EXAMPLES 10-17. 7000 Parts of butadiene, 1000 parts of acrylonitrile, 1250 parts of styrene, 500 parts of maleic acid monobutyl ester and 250 parts of methacrylic acid are emulsified and polymerised as described in Example 7. At a polymerisation temperature of 20 C. a yield of 81% is obtained in 17.5 hours. The emulsion thus prepared is coagulated in different coagulating baths. The composition of these baths and th physical data of the threads prepared from this emulsion under the conditions set forth are given in the table blow: Example No. 10 11 12 13 14 15 16 17 water, cc. 3500 3500 3500 3500 3500 - - 3500 ethyl alcohol, cc - - - - - 3500 3500 calcium chloride, g. 350 - - - 300 240 240 barium chloride, g - 250 - - - - - - barium hydroxide, g. - 110 - - - - - - copper acetate, g. - - 250 - - - - - zinc acetate, g. - - - 250 - - - - calcium acetate, g. - - - - - - - 250 ethylene diamine g. 115 - 100 110 - 130 - 120 triethylene tetra amine, g. - - - - 105 - -. - glycerine diepoxide, g. - - - -- - - 210 Tensile strength, kg/cm2 960 210 432 362 782 695 215 562 Elongation at break, per cent 680 820 580 630 620 540 470 710 The glycerine diepoxide was produced by the process disclosed in U.S. Specification No. 2,581,464. It had a chlorine content of 8.7%, a molar weight of 330 and contained per 149 g one mol by weight of epoxide. EXAMPLE 18. 7000 Parts of butadiene, 2500 parts of acrylonitrile and 500 parts of vinyl methyl ketone are emulsified in 10,800 parts of water with the addition of 2000 parts of a 10% solution of the sodium salt of a paraffin sulphonic acid containing 12-18 carbon atoms and 200 parts of N-sulphuric acid. The polymerisation is initiated by the addition of 40 parts of the sodium salt of a paraffin sulphinic acid containing 12 to 18 carbon atoms. 30 Parts of n-dodecyl mercaptan are added in two portions during polymerisation to control the polymerisation process. At a polymerisadon temperature of 25 C. a yield of 82% is obtained in 32 hours. The polymerisation is interrupted by the addition of 3C g of hydroquinone and the latex stabilised with 3t% by weight of phenyl-ss-naphthylamine referred to the monomers used. The emulsion is then freed of its residual monomers by steam distillation and extruded through a nozzle into :a solution of 180 parts of ethylene diamine and 320 parts of calcium chloride in 3500 parts of water at 500 C. The thread thus formed is withdrawn over rollers washed and dried. It has

a tensile strength of 375 kg/cm2 and an elongation at break of 520%. EXAMPLE 19. 7000 Parts of butadiene, 2500 parts of acrylonitrile and 500 parts of methyl acrolein are emulsified and polymerised as described in Example 19. The degasified emul- sion is extruded through a slot-shaped nozzle into a solution of 125 parts of ethylene diamine and 370 parts of calcium chloride in 3500 parts of water, and the coagulation sheer thus formed is withdrawn over rollers, washed at 50 C. and dried at 110 C. The resulting rubber sheet has a tensile strength of 215 kg/cm2 and an elongation at break of 450% ar a thickness of 0.2 mm. EXAMPLE 20. 2100 Parts by weight of butyl acre'late and 900 parts by weight of methyl methacrylate are emulsified in 3700 parts by weight of a solution of 110 parts by weight of the sodium salt lob a paraffin sulphonic acid containing 12 -18 carbon atoms in 3200 parts by weight of water and 60 parts by weight of N - sul- phuric acid and polymerised with the addition of 22.5 parts by weight of the sodium salt of a paraffin sulphinic acid containing 12-18 carbon atoms at 30 C. while stirring. After 6 hours a yield of almost 100% is obtained. 5000 Parts by weight of this emulsion are slowly mixed while stirring with 1400 parts by weight of a 10.?4 aqueous caustic soda solu- tion and stirred at 50 C. for 5 hours. The emulsion is then mixed while stirring with 100 parts by weight of a polyglycol ether of lauryl alcohol and acidified with dilute sulphuric acid to plI 4. By extruding this emulsion through a nozzle into a solution of 150 parts by weight of lethylene diamine and 350 parts by weight of calcium chloride in 3500 parts by weight of water, a thread is obtained which is resistant to ageing. What we claim is: 1. A process for the production of shaped articles, which comprises introducing a solu- tion or emulsion of a synthetic elastomeric polymer containing reactive groups into a coagulating bath which contains an agent capable of reacting with the reactive groups to give Cross-linking, removing the coagulate formed in the coagulating bath from the bath and drying the coagulate. 2. A process as claimed in claim 1, wherein the reactive groups of the synthetic elastomeric polymer are carbonyl, carboxyl, sulphonic acid, amidle or basic nitrogen groups. 3. A process as claimed in claim 1 or 2, wherein the cross-linking agent in, the coagulating bath is a polyamine, a polyepoxy compound, a water-soluble salt of a polyvalent metal, a water-soluble hydroxide of a polyvalent metal, an aldehyde, a polycarboxylic acid loir an organic polysulphonic acid.

4. A process as claimed in any of Claims 1-3, wherein the synthetic elastomeric polymer consists essentially of a linear carbon chain to which are linked from 0.005-0.6 mols by weight of reactive groups per 100 parts by weight of polymer. 5. A process as claimed in any of claims 2-4, wherein the synthetic elastomeric poiy mer is obtained by copolymerising in aqueous emulsion a monomer which has at least one polymerisable carbon-to-carbon double bond and has an olasticising faction with a copolymerisabie ethylenically unsaturated organic compound containing as reactive groups carbonyl, carboxyl, sulphonic acid, amide or basic nitrogen groups. 6. A process as claimed in any of Claims 1-5, wherein the coagulating bath contains an electrolyte having a coagulating action in addition to the component which causes crosslinking. 7. A process as claimed in any of Claims 1-6, wherein the polymer is extruded through a nozzle into the coagulating bath. 8. A process as claimed in any of Claims 1 d, wherein the polymer is introduced into the coagulating bath while in contact with a firm support. 9. A process for the production of shaped articles substantially as described with reference to any of the Examples. 10. Shaped articles whenever produced by the process claimed in any of the preceding

* Sitemap * Accessibility * Legal notice * Terms of use * Last updated: 08.04.2015 * Worldwide Database * 5.8.23.4; 93p

* GB785632 (A)

Description: GB785632 (A) ? 1957-10-30

Delay line circuitry for colour television receivers

Description of GB785632 (A)

A high quality text as facsimile in your desired language may be available amongst the following family members:

BE543181 (A) US3042873 (A) BE543181 (A) US3042873 (A) less Translate this text into Tooltip

[81][(1)__Select language] Translate this text into

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 785,632 i) Date of Application and filing Complete Specification Oct 28, 1955. @ No 30891/55. Application made in United States of America on Nov 29, 1954. Complete Specification Published Oct 30,1957. Index at acceptance: -Class 40 ( 3), F 3 B. International Classification: -H 04 n. COMPLETE SPECIFICATION Delay Line Circuitry for Colour Television Receivers We, STANDARD TELEPHONES AND CABLES LIMITED, a British Company, of Connaught House, 63, Aldwych, London, W C 2, England, 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:- The present invention relates to delay line circuitry for colour television receivers, and more particularly to delay line circuitry for delaying the usual luminance signals to coinside in time with the usual chrominance signals upon arrival at the picture tube. In conventional colour television receivers, at some point in the circuitry the luminance and chrominance signals are separated into two channels The luminance signals, which correspond to the conventional monochrome signals, are amplified and thereafter coupled to suitable elements such as the control grids of a tri-gun picture tube The chrominance signal is handled in such a manner as to derive therefrom three suitable colour signals which are coupled to the picture tube The combination of the luminance and the colour signals in the picture tube thereby serve in the reproduction of an image in substantially natural colour.

The circuitry for handling the chrominance signals introduces a time delay which normally causes the luminance signals to arrive at the picture tube ahead of the colour signal, whereupon it is necessary in conventional receivers to delay the arrival of the luminance signals so they will arrive in time coincidence with the colour signals The use of delay lines or delay circuitry in the luminance channel is conventional This invention constitutes a decided improvement over the conventional arrangements in that the circuitry of the luminance channel is materially simplified and reduced in cost As will be explained in the' following, this invention leads to the elimination of one amplifying stage in the luminance channel. lPio 3 s 6 d l A full explanation of the conventional colour television standard and of symbols and terms are found in "Proceedings of the I.R E " January, 1954 50 In the known arrangements a separate resistor was used for terminating the input circuit of the delay line and the second detector was coupled thereto by an amplifying stage The principal object of the present invention is 55 to eliminate the terminating resistor and the amplifying stage. The object is achieved according to the invention by providing a colour television receiver comprising a detector circuit for 60 recovering the luminance and chrominance signals from the intermediate frequency carrier wave, and a delay line for delaying the luminance signals having its input circuit connected directly to the output of the detector 65 circuit and its output circuit connected to a terminating impedance substantially equal to the characteristic impedance of the delay line, the detector circuit being without any amplifying means, and having an output impedance 70 substantially equal to the characteristic impedance of the delay line. Fig 1 is a block diagram of a conventional colour television receiver showing the luminance and chrominance signal channels; 75 Fig 2 is a detailed block diagram of a portion of the arrangement of Fig 1; Fig 3 is an illustration of wave forms used in explaining the operation of this invention; Fig 4 is an illustration of prior art delay 80 line circuitry; and Fig 5 is a circuit diagram of this invention. Referring to the drawings, and more particularly to Figs 1, 2 and 3, the luminance 85 and chrominance channels, indicated generally by the reference numerals 1 and 2, respectively, are shown to divide at a point 3, which may be located either before or after they second detector of the luminance channel In 90 Fig 5, this point of separation is shown as following the second detector The luminance 785,632 or monochrome signals pass through a delay line 4 and are amplified by the usual amplifier 5 for application to the electron guns of the picture tube 6. The chrominance signals are separated into individual chroma signal

components by the usual circuits 7 and applied over three separate coupling lines 8, 9 and 10 to the electron guns of the picture tube 6 In the illustrated embodiment, the separated chroma signals are indicated as being the components (R-Y), (B-Y) and (G-Y) These chroma signals are mixed with the monochrome signal in the picture tube for deriving the true colours. In Fig 2 is shown in more detail the point at which the luminance and chrominance channels separate This point of separation or pick-off is located in the stage of the second detector 11 of the luminance channel The signal leaving the second detector 11 and coupled to the delay line 4 is seen in graph A of Fig 3 One of the chrominance signals generated by the chrominance circuits 7 is shown in graph B It occurs later than the signal A, due to slower rise time in the chrominance circuits The delay line 4 serves to delay the signal A as illustrated by graph C to occur in substantial time coincidence with the chroma signal B These two signals B and C as shown arrive at the picture tube in time coincidence and are there combined in the form of graph D to provide the composite colour signal which is utilized by the picture tube 6 for producing a colour image By use of the delay line, it is nov understood thatthe chroma and monochrome signals are applied in proper phase or time relationship to the picture tube. In Fig 4 is shown prior art delay line circuitry wherein the output circuit 13 of the intermediate frequency amplifiers is coupled to a diode detector 11, 14 of which in turn is connected to the grid 15 of a conventional amplifier 16 The anode 17 of this ampliifier is connected to a delay line 18 which is properly terminated at its input by a resistor 19, The output end of the delay line 18 is also properly terminated by resistor 20 The output line 21 is coupled directly to tue luminance or monochrome amplifier in the usual manner. The two resistors 19 and 20 are requiredto terminate the delay line 18 The iuped ance presented to the plate circuit or the amplifier 16 is therefore one-half the vaiue oi one of these terminating resistors This being true, fifty per cent of the power applied to the delay line is lost in matching, and this loss in power is overcome by the use of an extra amplifier stage 16 The stage 16 and resistor 19 can be eliminated according to the invention by the arrangement shown in Fig 5 In this figure, the second detector circuit 11 shown in Fig. 2 comprises a rectifier 14 which may, for example, be a crystal rectifier, followed by a low-pass filter 30 which includes a series inductance formed by the two chokes 22 and 23, and the shunt condenser 27 'The lower terminal of the condenser 27 is connected to ground through a relatively large condenser 70 28, and to a positive direct current source which has its negative terminal connected to ground and which supplies a bias potential of 4 volts, for example, for biassing

the rectifier 14 into the high resistance condition 75 The output of the filter 30 (which is also the output of the detector circuit 11), is connected to the input circuit of the delay line 18, the output circuit of which is terminated by a resistor 24 and a choke 26 connected in go series to ground as shown A direct current ieturn circuit is thereby obtained, and the dhoke 26 is provided to assist the filter 30 in keeping the intermediate frequency waves out of the delay line 18 85 The luminance signals are obtained from the output of the delay line 18 through an amplifying valve 25, and the chrominance signals are supplied from the junction point of the chokes 22 and 23 through a blocking 90 capacitor 29 connected to the control grid of a valve 12 representing the chrominance circuits 7 of Fig 2 This control grid is connected to ground through a leak resistor 31 of sufficiently large value to ensure that the con 95 nection to the valve 12 does not appreciably load the filter 30. The detector circuit 11 should be designed so that the impeiance presented by the output of the filtew 30 is substantially equal to the 100 characteristic impedance of tile delay line 18. The value of the resistor 24 is likewise chosen so that together with the resistance oi the choke 26 -te total resistance terminating the delay line 18 is substantially equat to its 105 characteristic impedance. The arrangement shown in Fig 5 provides the most efficient connection _ossibie between the detector circuit 11 and the delay line 18, so that the impedance discontinuity between 110 tue valve 16 and the delayl ine arrangement in Fig 4 is avoided This allows both the valve 16 and the resistor 19 to be dispensed with. The delay line 18 is of conventional design, and may, for example, have a characteristic 115 impedance of 2800 ohms, and may introduce a delay of 08 microsecond over a frequency band of 0 to 4 megacycles per second. As an example, the following values of the circuit components of Fig 5 are given: 120 Choke 22 93 microhenries Choke 23 50 microhenries Choke 26 75 microhenries Resistor 24 2700 ohms Condenser 27 5 6 micromicrofarads 125 Condenser 28 0 0047 microfarad Condenser 29 180 micromicrofarads

* Sitemap * Accessibility * Legal notice * Terms of use * Last updated: 08.04.2015 * Worldwide Database * 5.8.23.4; 93p