* GB784613 (A) Description: GB784613 (A) ? 1957-10-09 New disazo-dyestuffs, copper complexes thereof, and processes for making them Description of GB784613 (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 784,613 Date of Application and filing Complete Specification: Oct 13, 1954. No 29554/54. Application made in Switzerland on Oct 23, 1953. Application made in Switzerland on April 2, 1954. Application made in Switzerland on Aug 18, 1954. Complete Specification Published: Oct 9, 1957. Index at acceptance:-Class 2 ( 4), P 1 A 2 A 2, P 2 G 2 C 1, P 2 H( 3: 5: 6: 9:11:12:15: 21), P 8 (A 1 A: AIB: A 1 C: A 2 A: BI: B 2: DI: D 2), P 9 A( 3 A 1: 3 C 1: 3 F: 4
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* GB784613 (A)
Description: GB784613 (A) ? 1957-10-09
New disazo-dyestuffs, copper complexes thereof, and processes for makingthem
Description of GB784613 (A) Translate this text into Tooltip
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The EPO does not accept any responsibility for the accuracy of data and information originating from other authorities than the EPO; in particular, the EPO does not guarantee that they are complete, up-to-date or fit for specific purposes.
PATENT SPECIFICATION 784,613 Date of Application and filing Complete Specification: Oct 13, 1954. No 29554/54. Application made in Switzerland on Oct 23, 1953. Application made in Switzerland on April 2, 1954. Application made in Switzerland on Aug 18, 1954. Complete Specification Published: Oct 9, 1957. Index at acceptance:-Class 2 ( 4), P 1 A 2 A 2, P 2 G 2 C 1, P 2 H( 3: 5: 6: 9:11:12:15: 21), P 8 (A 1 A: AIB: A 1 C: A 2 A: BI: B 2: DI: D 2), P 9 A( 3 A 1: 3 C 1: 3 F: 4 B). International Classification:-C 09 b. COMPLETE SPECIFICATION New Disazo-Dyestuffs, Copper Complexest thereof, and processes for making them We, CIBA LIMITED, a body corporate organised according to the laws of Switzerland, of Basle, Switzerland, 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 provides new azo-dyestuffs which like, for example, the dyestuff of the formula 0 II CR-Oft go 1 ( 1) /10 W=,,VM/< /1000 /03 S
503 d correspond to the general formula l-o-HV-l/ \ Av ( 2) \ 1 " /-033 in which R, represents the residue of an oxybenzene-ortho-carboxylic acid, R 2 and R, represent benzene residues in which the carbon atoms bound to the azo linkage and the l-CO-NH l-group are separated from one another by at least one carbon atom, R, represents a benzene residue containing:a sulphonic acid group, a carboxylic acid group or a carboxy-methoxy group and UV represents a hydroxyl group, carboxylic acid group or alkoxy group in ortho-position relatively to the azo linkage The invention also provides complex copper compounds of the dyestuffs of the formula ( 2). In one form of the process for making the new dyestuffs a diazo-compound of an aminoazo-dyestuff of the formula ( 3) leo Mvl v in which RI represents the residue of an oxybenzene-ortho-carboxylic acid, Ro and R, represent benzene residues in which the carbon atoms bound to the azo linkage or amino group and the l-CO-HN-l group are separated from one another by at least one carbon atom, and UV represents a hydroxyl group, carboxylic acid group or alkoxy group in orthoposition relatively to the amino group, is coupled with a compound of the formula /10 my' -P 11,035 in which R 4 represents a benzene residue containing a sulphonic acid group, a carboxylic acid group or a carboxy-methoxy group and, if desired, the dyestuff so obtained is treated with an agent yielding copper. As is evident from the foregoing description the dyestuffs of the formula ( 2) can be prepared either from diazo compounds of amino-azodyestuffs of the formula UV ( 4) R-N = N-R,-CO-HN-R,-N Ho or from diazo-compounds of amino-azo-dyestuffs of the formula UV ( 5) R 1-N = N-R 2 NH-OC-R,3-NH_. The amino-azo-dyestuffs of the formula ( 4) are obtainable, for example, by coupling a tetrazo-compound of a diamine of the constitution UV ( 6) HMN-R,-CO-HN-R 3,-NH on one side with an oxybenzene-orthlocarboxylic acid (R,-H) capable of coupling As such coupling components there may be mentioned, for example, 6-chloro or 6-methyl-1oxybenzene-2-carboxylic acid, and especially 1oxybenzene-2-carboxylic acid itself In the diamines of the formula ( 6) the carbon atoms of the benzene residues R and R, which are bound to the amino group and the -CO-HN group are each separated from one another by at least one ring carbon atom, that is to say, the amino groups must not be present in ortho-position relatively to the -CO HN group It is of advantage that these two groups, at least in the case of the residue R 3, should be in para-position relatively to one another, and especially good results are obtained with those diamines in which both amino groups are in para-position relatively to the -CO-HN group.
As diamines of the formula ( 6) there may be used, for example, 1-amino-4-( 4 '-aminobenzoylamino)-benzene-2-carboxylic acids in which both benzene nuclei may contain further substituents, for example, a lower alkyl group or a halogen atom As further suitable diamines there may be mentioned, 1-amino-4( 31 aminobenzoylamino) benzene 2 carboxylic acid, 1-amino-4-( 4 ' or -3 '-aminobenzoylamino)-2-oxybenzene, 1-amino-4-( 4 ' or -3 '-aminobenzoylamino)-2-methoxybenzene, 1ainino-4-( 3 '-methyl or -3 1-chloro-4 '-aminobenzoylamino)-benzene-2-carboxylic acid and 1-amino-4-( 3 '-methyl or -3 '-chloro-4 '-aminobenzoylamino)-2-oxy or -methoxybenzene. The diamines of the formula ( 6) may be tetrazotised by methods in themselves known, for example, by means of hydrochloric acid and sodium nitrite The tetrazo-compounds so obtained are then coupled with the oxybenzene orthocarboxylic acid, advantageously in an allkaline medium. The amino-azo-dyestuffs of the formula ( 5) are obtained by condensing a compound of the formula ( 7) R N = N-R 2-NH. (also an amino-azo-dyestuff) with an acid halide of the formula UV i ( 8) Halogen-OC-R,-NO. in which R 3 represents a benzene residue, and UV represents a hydroxyl group, an alkoxy group or a carboxylic acid group, the group UV being in ortho-position relatively to the nitro group and the acid halide group being in other than ortho-position relatively to the nitro group (advantageously the groups -NO, -UV and Halogen-OC are in 4:3: 1position), and then reducing the nitro group to an amino group As aminoazo-dyestuffs of the formula ( 7) there may be mentioned more especially 4-amino-4 '-oxy-1: 1 '-azobenzene31-carboxylic acids, which may contain in the residue R, or advantageously in the residue R, further substituents As examples, there may be mentioned, in addition to the unsubstituted compound, 2-methyl-4-amino-5-methoxy-4 'oxy-1: l'-azobenzene-3 -carboxylic acid and 2chloro 4 amino-4 '-oxy-1: 1 '-azobenzene-3 'carboxylic acid. As acid halides of the formula ( 8) there are advantageously used 4-nitro-3-alkoxybenzene1-carboxylic acid chlorides containing alkoxy groups having at most 2 carbon atoms. The diazo-compounds of the amino-azodyestuffs of the formula ( 4) or ( 5) are coupled with 2 phenylamino-8-oxynaphthalene-6-sulphonic acids, of which the phenyl residue contains a carboxymethoxy group or advantageously a carboxylic acid or sulphonic acid group As examples there may be mentioned 2-( 2 '-methyl-phenylamino) 8 oxynaphthalene-6: 41-disulphonic acid, 2-( 4 '-methylphenylamino) 8 oxynaphthalene-6: 3 '-disulphonic acid, 2-( 4 '-chlorophenylamino)-8oxynaphthalene-6: 3 '-disulphonic acid, 2-( 4 'carboxymethoxyphenylamino) 8
oxynaphthalene-6-sulphonic acid, 2-phenylamino-8oxynaphthalene-6-sulphonic acid-3 '-carboxylic acid and 2-phenylamino-8-oxynaphthalene6: 3 '-disulphonic acid. Dyestuffs of the formula ( 2) and copper compounds thereof can also be obtained by coupling a diazo-compound of an amino-azodyestuff of the formula ( 9) in which R and R, represent benzene residues in which the carbon atoms bound to the amlno group or the azo linkage and the -CO-HNgroup are separated from one another by at least one carbon atom, UV represents a hydroxyl group, carboxylic acid group or alkoxy 784,613 A / -AI# ? E CO M 1 V 1 \ 11, "O W"-leq C 3-1 vll, 1,10 'S latter treatment is advantageously carried out 50 in such manner that from the ortho-carboxyortho'-oxy-azo grouping ( 13) 9 _ Asv,/ group in ortho-position relatively to the azogroup, and R 4 represents a benzene residue containing a sulphonic acid group, a carboxylic acid or a carboxy-methoxy group or a diazocompound of a complex copper compound obtainable from a dyestuff of this constitution, with an oxybenzene-ortho-carboxylic acid capable of coupling, and if desired, treating the product so obtained with an agent yielding copper. Especially suitable for this method of preparation are the amino-azo-dyestuffs of the formula /40 CO /V W CO Sov /1033 a/2 t Re co -x Jfv t 3 %-,D= N -A/,,Rv,( 10) in which Ro, R 3, R, and UV have the meanings given above, and which can be obtained by coupling a diazo-compound of an amine of the formula UV I X R-NH= in which R, represents a benzene residue, and X represents a substituent convertible into an amino group, for example, a nitro or acetylamino group, and this substituent is in a position other than an ortho-position relatively to the amino group and UV is in ortho-position relatively to the amino group, with a 2-phenylamino-8-oxynaphthalene-6-sulphonic acid containing in the phenyl residue a sulphonic acid group, a carboxylic acid group or a carboxymethoxy group, then converting the substituent X into an amino group, acylating the aminocompound with a meta or advantageously a para-nitrobenzoyl halide, and reducing the nitro group to an amino group. The amino-azo-dyestuffs of the formula ( 10) can also be made by coupling a diazo-compound of a nitro-amine of the formula UV 1 W ( 12) O O N-R_-CO-HN-R,-NHI with a 2-phenylamino-8-oxynaphthalene-6sulphonic acid of the above kind, and then reducing the nitro group to form an amino group. The reactions necessary in order to prepare the dyestuffs of the formula ( 2) and the intetmediate dyestuffs and the other intermediate products mentioned above can all be carried out in known manner The same applies to the treatment of the intermediate products or final products with an agent yielding copper The ( 11) there is formed the
ortho-carboxy-ortho'-oxymetal complex of the formula C 00 CL O ( 14) -/v =z and from the ortho: ortho'-dioxy-azo-grouping o H so ( 15) 7, Hv Ov and also from the ortho-allkoxy-orthol-oxy-azogrouping there is formed the ortho: ortho' 60 dioxy-azo-metal complex of the formula O-ei o, ( 16) -/> The ortho-oxy-orthol-carboxy and ortho: ortho'-dioxy-azo-dyestuffs may be treated either in a weakly acid medium, for example, with copper sulphate with the addition of sodium acetate or with complex copper ammine compounds from ammonia, pyridine, alkylamines or oxyethylamines In the case of ortho-oxy-orthol-methoxy-azo dyestuffs the last mentioned method which is described and claimed in Specification No 644,883, is the more suitable. The metalliferous dyestuffs so obtained correspond to the formula ( 17) in which R, represents the residue of an oxybenzene-ortho-carboxylic acid, or of an oxybenzene-ortho-carboxylic acid containing a copper atom bound in complex union, R 2 and 80 R, represent benzene residues in which the carbon atoms bound to the azo linkage and the l-CO-IHN-l group are separated from 784,613 one another by at least one carbon atom, R, represents a benzene residue containing a sulphonic acid group, a carboxylic acid group or a carboxy-methoxy group, U represents an -O-bridge or -COO group in orthoposition relatively to the azo linkage. Depending on the stage at which the coppering is carried out, on the reaction conditions and on the quantity of the agent yielding copper, it is possible to obtain complex copper compounds of which the oxybenzene-orthocarboxylic acid residue R, also contains a copper atom bound in complex union or in which the residue R 1 is free from copper in complex union If complex copper compounds of the latter kind are to be made, it is of advantage partially to decopper a dyestuff of the kind first mentioned, which contains 2 atoms of copper in complex union, and this decoppering may be carried out, for example, by treatment with hydrochloric acid at a raised temperature. With regard to the constitution of the cupriferous dyestuffs, the formulae (see, for example, formula ( 17)) undoubtedly represent the correct stoichiometric quantity of copper and the correct position of the copper atom in the complex, but the distribution of the main and secondary valencies in the complex union of the copper has not been established with certainty. The new dyestuffs of the formula ( 2) and the complex copper compounds obtainable therefrom, especially those of the formula ( 17), are suitable for dyeing and printing a very wide variety of materials, especially fibres of natural or regenerated cellulose, such as cotton, linen and artificial silk or staple fibres of regenerated cellulose If the metal-free dyestuffs or only partially coppered dyestuffs (see
above) are used for dyeing, treatment with an agent yielding metal, advantageously an agent yielding copper, may be carried out on the fibre or in the dyebath, and if desired partially on the fibre and partially in the dyebath The dyeings so obtained are distinguished by their very good fastness to light. The following Examples illustrate the invention, the parts and percentages being by weight unless otherwise stated and the relationship of parts by weight to parts by volume being the same as that of the kilogram to the litre: EXAMPLE 1. 27.1 parts of 1-amino-4-( 41-aminobenzoylamino)-benzene-2-carboxylic acid are dissolved in 350 -parts of water with the addition of sodium hydroxide, the mixture is then acidified with 70 parts of hydrochloric acid of 30 per cent strength and tetrazotisation is carried out while cooling with ice in the usual manner with an aqueous solution of 13 8 parts of sodium nitrite The tetrazotisation product is then coupled in the presence of an excess of sodium carbonate first with 16 parts of 2-oxybenzene-l-carboxylic acid and then, after for 65 mation of the intermediate product with 39 5 parts of 2-phenylamino-8-oxynaphthalene6:3 '-disulphonic acid This second coupling may be accelerated by the addition of a small amount of pyridine When the coupling is 70 finished, the dyestuff is separated by the addition of 15 parts of sodium chloride for every parts by volume of reaction mixture For conversion into its copper compound the dyestuff is dissolved at 80-85 ' C in 3000 parts 75 of water, first 15 parts of crystalline sodium acetate are added and 50 parts of acetic acid of 84 per cent strength, and then 25 parts of crystalline copper sulphate dissolved in 100 parts of water, and then the whole is stirred for one 80 hour at 80-85 C The dyestuff, which is completely dissolved, is precipitated by the addition of 350 parts of sodium chloride By filtration and drying, there is obtained a brownblack dyestuff powder, which dissolves in con 85 centrated sulphuric acid with a red coloration and in water or dilute sodium carbonate solution with a brown coloration and dyes cotton brown tints which are fast to light. A dyestuff having approximately the same 90 properties is obtained as follows: 5-Acetylamino-2-aminobenzoic acid is diazotised, and coupled in alkaline solution with 2-phenylamino 8 oxynaphthalene-6: 3 -disulphonic acid The acetylamino group is then split off, 95 the amino-azo-dyestuff is acylated with paranitrobenzoyl chloride, the nitro group is reduced to an amino group, the amino group is diazotised and the diazo-compound is coupled with 2-oxy-benzene-1-carboxylic acid Copper 100 ing is carried out as described above, that is to say with 1 atomic proportion of copper per
molecular proportion of disazo-dyestuff Alternatively, the aminobenzoylamino-dyestuff may first be coppered, and the coupling with the 105 oxybenzene carboxylic acid carried out finally. By using, instead of 39 5 parts of 2-phenylamino 8 oxynaphthalene-6: 3 '-disulphonic acid, 35 9 parts of 2-phenylamino-8-oxynaphthalene-6-sulphonic acid-3 '-carboxylic acid, 110 there is obtained a copper complex which is relatively sparingly soluble, and which is advantageously converted into its sodium salt by suspending it in a small quantity of water and sodium carbonate When dry, the dyestuff as 115 such is a black powder which dissolves in concentrated sulphuric acid with a red coloration and in water with a brown coloration, and dyes cotton brown tints which are fast to light. Further disazo-dyestuffs can be obtained in 120 the manner described above from the tetrazocompounds of the diamines given in Column II of the following Table, from the first components in Column I and from the second components in Column III, and complex copper 125 compounds can be similarly obtained from these disazo-dyestuffs These compounds also dye cellulose-containing fibres brown tints which are fast to light. 784,613 784,613 I II III 1st Coupling 2nd Coupling Component Diamine Component 1 3-chloro-2-oxy 1-amino-4-( 41-amino 2-phenylamino-8benzene-l-carboxylic benzoylamino)-ben oxynaphthaleneacid zene-2-carboxylic 6:31-disulphonic acid acid 2 3-methyl-2-oxy, benzene-l-carboxylic acid 3 1-oxybenzene-2,, 2-( 21-methylphenylcarboxylic acid amino)-8-oxynaphthalene-6:41-disulphonic acid 4,,,, 2-( 41-methylphenylamino)-8-oxynaphthalene-6:31-disulphonic acid 5,, 2-( 41-chlorophenylamino)-8-oxynaphthalene-6:31-disulphonic acid 6,, 1-amino-4-( 31-methyl 2-phenylamino-84 '-aminobenzoyl oxynaphthaleneamino)-benzene-2 6:31-disulphonic carboxylic acid acid 7,, 1-amino-4-( 41-amino 2-( 41-carboxymethbenzoylamino)-benzene oxyphenylamino)-82-carboxylic acid oxynaphthalene-6sulphonic acid l l Finally, there can also be made in the manner described above the copper complex of the disazo-dyestuff from diazotised 4-oxy-4 '( 411 aminobenzoylamino)-1: 11-azobenzene3 33 "-dicarboxylic acid and 2-phenylamino-8oxynaphthalene-6: 3 '-disulphonic acid. EXAMPLE 2. 25.7 parts of 1-amino-2-methoxy-4-( 41aminobenzoylamino)-benzene are tetrazotised and coupled in an alkaline solution first with 13.8 parts of 1-oxybenzene-2-carboxylic acid, and then with 39 5 parts of 2-phenylamino-8oxynaphthalene-6: 3 '-disulphonic acid The dyestuff is isolated, then redissolved in water and stirred for 8 hours at 80-90 C with the addition of an aqueous solution of 55 parts of crystalline copper sulphate in ethanolamine.
The dyestuff is salted out and filtered off In the dry state it is a dark powder which in aqueous solution dyes cotton brown tints which are fast to light. By dissolving the dyestuff, acidifying the solution to a p H value of 2 0 with hydrochloric acid, stirring the mixture for 1 hour while hot, filtering, and then converting the dyestuff into its sodium salt, there is obtained a dyestuff which in aqueous solution likewise dyes cotton brown tints which are fast to light By aftercoppering on the fibre the fastness to light is further increased. EXAMPLE 3. Diazotised 4-nitro-2-methoxy-1-aminobenzene is coupled in alkaline solution with 2phenylamino 8 oxynaphthalene-6: 3 L-disulphonic acid, the product is reduced with sodium sulphide, acylated with 4 nitrobenzoyl chloride, again reduced with sodium sulphide, diazotised, and then coupled with 1-oxybenzene-2-carboxylic acid in alkaline solution The previously isolated dyestuff is then stirred at 80 C as described in the preceding Example with copper sulphate in aqueous solution with the addition of ethanolamine, the dyestuff is separated by filtration, suspended in water, the mixture is acidified to a p H value of 3 0 with hydrochloric acid, stirred for 2 hours at 80 C, filtered, and the dyestuff is converted into its sodium salt This dyestuff dyes cotton from aqueous solution brown tints which are fast to light. EXAMPLE 4. 440 parts of the dyestuff of the formula 6-'//3 1/2 /g I Oo e Ct which is obtained by acylating 2-chloro-4amino-4 '-oxy- 11: 1 '-azobenzene-3 ' carboxylic acid with 3-methoxy-4-nitrobenzoyl chloride followed by reduction with sodium sulphide, are diazotised and then coupled with 395 parts of 2-phenylamino-8-oxynaphthalene-6: 31-disulphonic acid in a solution rendered alkaline with sodium carbonate The dyestuff is precipitated with sodium chloride, filtered off, then suspended in an ammoniacal solution of 525 parts of crystalline copper sulphate, and the mixture is heated under reflux for 8 hours at 80 C The dyestuff is again filtered off, suspended in hydrochloric acid of 5 per cent strength, and the whole is stirred for 2 hours at room temperature The greater part of the hydrochloric acid is then neutralised with sodium carbonate and the mixture is buffered with sodium acetate until a drop of the suspension applied to Congo paper only just still produces a violet coloration Finally the whole is heated for 2 hours at 80 C, filtered, and the filter residue is dried The dyestuff is soluble in sodium carbonate solution with a brown coloration and dyes cotton brown tints from such a solution. The dyeing is remarkably fast to light, and the dyestuff has a good levelling capacity.
EXAMPLE 5. 100 parts of cotton are entered at 40 ' C. into a dyebath which contains in 3000 parts of water 1 part of the cupriferous dyestuff obtainable as described in the first paragraph of Example 1, and dyeing is carried on for 1 hour while increasing the temperature to 90 C 30 parts of crystalline sodium sulphate are then added, and dyeing is continued for a further -2 hour at 90-95 o C The cotton is then rinsed and finished in the usual manner. It is dyed brown, and the dyeing is distinguished by a very good fastness to light.
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* GB784614 (A)
Description: GB784614 (A) ? 1957-10-09
Process for the purification of ethylene glycol by distillation
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PATENT SPECIFICATION Date of filing Complete Specification Nov 2, 1955. Application Date Nov 24, 1954. 784,614 No 34045154.
Complete Specification Published Oct 9, 1957. Index at acceptance: -Classes 2 ( 3), C 3 A 13 Al (Al: D); and 32, B 5 B. International Classification: -B Old CO 7 c. COMPLETE SPECIFICATION Process for the Purification of Ethylene Glycol by Distillation We, HORACE SPIVEY, of Hexagon House, Blackley, Lancashire, a British Subject, and IMPERIAL CHEMICAL INDUSTRIES LIMITED, of Imperial Chemical House, Millbank, London, S W 1, a British Company, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement:This invention relates to a process for the purification of ethylene glycol. It is known from the prior art to prepare aromatic linear polyesters by reacting a glycol with terephthalic acid or a low aliphatic ester derivative thereof Such polyesters are of great commercial value as fibres and films as they have a high melting point and low degree of solubility even in strong solvents One of these polyesters, the preferred one, is polyethylene terephthalate. It is necessary for the production of polyester fibres and films to have the reacting substances in a high state of purity in order to produce polyesters of good colour We have now found that glycols can be purified by distilling with sodium hypochlorite and that aromatic linear polyesters obtained from glycols distilled with sodium hypochlorite show an improved colour over those obtained from commercial grades of glycol The glycols distilled with sodium hypochlorite appear much brighter in colour than the commercial grades of glycol. Therefore, according to our present invention we provide a process for the purification of ethylene glycol, characterised by the fact that the glycol is distilled in the presence of sodium hypochlorite, preferably alkaline sodium hypochlorite. In our preferred method, we distil the glycol under reduced pressure. The invention is illustrated but not limited by the following example in which parts and percentages are by weight. EXAMPLE. parts of commercial ethylene glycol are lPrti charged to a still and 0 25 parts of caustic soda liquor, having a specific gravity of 700 T', together with 0 175 parts of an 8 % solution of sodium hypochlorite are added. The still is put under a vacuum corresponding to an absolute pressure of 40 mm mercury and heated by steam at a gauge pressure of 80 lb. per square inch The valves on the distillate line of the still are set for total reflux and the contents of the still refluxed for half an
hour in order to obtain steady operating conditions. Distillation is commenced at a reflux ratio of 4: 1 and at regular intervals a sample of the distillate is tested for its boiling range When the boiling range of a 100 ml sample which passes over between 5-95 mls varies by less than 1 50 C, the reflux ratio is reduced to 1:1 and distillation continued until the boiling range exceeds 1 50 C At this point the reflux ratio is increased to 4:1 and when the range again exceeds 1 50 C, distillation is terminated and the residues of the still are discarded. The colour of the distilled glycol is much brighter than that of the original commercial glycol.
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* GB784615 (A)
Description: GB784615 (A) ? 1957-10-09
Diuretics comprising acylated aminotriazines
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COMPLETE SPECIFICATION Diuretics Comprising Acylated Aminotriazines We, IMPERLAL CHEMICAL INDUSTRIES
LIMITED of Imperial Chemical House, Millbank, London, S.W.1, England, a British Company, 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 diuretics and more particularly it relates to diuretics which are triazine derivatives. According to the invention we provide new triazine derivatives which are mono-acyl and di-acyl derivatives of compounds of the formula: - <img class="EMIRef" id="026448770-00010001" /> wherein Ar stands for an aryl radical which bears one or more halogen substituents and, of R and R1, one stands for hydrogen or for a lower alkyl radical and the other stands for hydrogen, wherein the acyl groups are of the form AlkCO- wherein Alk stands for an alkyl radical of the form Alk.OCH2CO- wherein Alk stands for an alkyl radical or of the form ArlCO- or Arl.CHOCO- wherein Ari stands for an aryl radical which may optionally be substituted for example by halogen atoms. We have found that the new triazine derivatives of the above stated formula possess a high degree of diuretic activity and also a relatively low toxicity land that consequently they are of value in the treatment of disease conditions demanding the application of diuretics and are much superior in this respect to many compounds which possess a high degree of diuretic activity in conjunction with an unfortunately high toxicity. As particularly useful compounds there may be mentioned for example, a monoxpropionyl derivative of 2-amino-4-(2:4- di-chloroanilino)-1 : 3 : 5-triazine, m.p. 160-162 C., a monow2-butyryl derivative of 2-amino-4-(2: 4dichloroanilino)-1 :3: 5-triazine, m.p. 160161 C. and a molecular extinction coefficient of 6,200 at a wavelength of 270 m,a in methanol solution (as disclosed in Example 18), a mono-ethoxyacetyl derivative of 2-iso- prcp, no - 4 - p - chloroanilino-1:3: 5-triazine, mp. 118120 C. and a monopropionyl derivative of 2-isopropylamino-4 - (2: 4- dichioroanilino) 1:3:5-triazine, m.p. 128130 C. According to a further feature of the invention we provide a process for the manufacture of the said new triazine derivatives which comprises acylation of a compound of the formula <img class="EMIRef" id="026448770-00010002" /> wherein Ar, R and R1 have the meaning stated above In some cases where it is desired W introduce but one acyl group in the process of manufacture, a suitable acylating agent has been found to be a mixture of the appropriate acid, for example acetic acid, and the acid anhydride, for example acetic anhydride. In certain cases
where it is desired to introduce two acyl groups in the process of manufacture, a suitable acylating agent has been found to be an excess of the anhydride of the appropriate acid for example acetic anhydride and propionic anhydride, but in some cases it is desirable to use additionally a dehydrating agent, for example sulphuric acid. It is to be understood however that in particular cases where it is desired to introduce but one acyl group in the process of manufacture, a suitable acylating agent may be an excess of the anhydride of the appropriate acid in the presence of a dehydrating agent, for example sulphuric acid. Another suitable acylating agent has been found to be a mixture of the appropriate acid chloride and a tertiary base optionally in the presence of an inert solvent or diluent Suitable acid chlorides may be for example palmityl-, n-butyryl-, isobutyryl-, propionyl-, ethoxyacetyl-, -vizleryl-, azKaproyl-, n-caprylyl, n-capryl-, benzoyl-, p-chlorobenzyl- and phenylacetyichloride. As suitable tertiary bases there may be mentioned for example pyridine and diethylaniline and as suitable inert solvents or diluents there may be mentioned for example dioxan and acetone. The said acylation process may be accelerated or completed by the application of heat but it is to be understood that when the process is carried out at a relatively high temperature, for example under reflux conditions, the products obtained may be isomeric with those products which are obtained when the process is carried out at a relatively low temperature for example at ordinary temperatures for example between about 15 C. and about 25 C. According to a further feature of the invention we provide a process for the manufacture of those of the said new triazine derivatives which are mono-acyl derivatives which com- prise acylation of an alkali metal derivative, for example a sodic:-d-rivative, cf a compound of the formula: <img class="EMIRef" id="026448770-00020001" /> wherein Ar, R and R1 have the meaning stated above, with the appropriate acid chloride in an inert solvent or diluent for example dioxan. According to a further feature of the invention we provide a process for the manufacture of the said new triazine derivatives which comprises halogenation of the corresponding phenyl triazine derivatives or of those triazine derivatives wherein the radical Ar is capable of further halogenation. According to still a further feature of the invention we provide diuretic pharmaceutical compositions comprising, as active ingredient, one or more of the said new triazine derivatives. The said diuretic pharmaceutical compositions may be in the form of
tablets or pills in which the active ingredient or ingredients is or are mixed with pharmaceutical excipients suitable for the provision of the said tablets or pills. Suitable excipients may be for example one or more diluents for example calcium carbonate or lactose, o.ne or more disintegrating agents, for example maize starch, one or more lubricating agents, for example stearic acid or magnesium stearate, and lone or more granulating agents or binding agents, for example starch paste, gelatin solution or gum acacia. The tablets or pills may furthermore be coated. The proportion of active ingredient or ingredients in such tablets or pills is preferably not less than 5% by weight and not more than 900, by weight of the composition. The said diuretic pharmaceutical compositions may furthermore be in the form of aqueous dispersions in which the active ingredient or ingredients is or are mixed in aqueous media with pharmaceutical excipients suitable for the provision of stable aqueous dispersions. Suitable excipients may be for example one or more suspending or dispersing agents, for example neutral hydrophilic colloids, for example sodium carboxymethylcellulose, and one or more wetting agents, for example a polyethyleneoxycetanol, and preferably also one or more preservatives, for example an ester of p-hydroxybenzoic acid, for example methyl p-hydroxybenzoate. The pharmaceutical compositions may also contain one or more colouring agents and/or one or more flavouring agents. The proportion of active ingredient or ingredients in such aqueous dispersions is preferably not less than 0.5 O/O by weight and not more than 50 , by weight of the composition. Those aqueous dispersions which contain a proportion of active ingredient less than 0.5 Cc by weight of the composition lead to excessive doses of the cc;nFcsitioa, to be administered and those aqueous dispersions which contain a proportion of active ingredient more than 50% by weight of the composition may be too viscous for convenient administration. The invention is illustrated but not limited by the following Examples in which the parts are by weight: EXAMPLE 1. A mixture of 1.85 parts of 2-amino-4-pchioroanilino - 1: 3 5 - triazine, of 0.9 part of acetic anhydride and 10 parts of acetic acid is heated under reflux for 18 hours and then cooled and filtered. The residue is washed with ethanol, dried, and crystallised from aqueous acetic acid to give a monozacetyl derivative of 2-amino-4-p-chloroanilino-1: 3: 5-triazine, of m.p. 267268 C. EXAMPLE 2. 1 Part of 2-amino-4-p-chloroanilino-1: 3: 5- triazine is dissolved in 6 parts of warm acetic anhydride. 0.1 part of concentrated sulphuric acid is added and the mixture is heated under reflux for 4 hours. It
is then cooled, diluted with water and filtered. The residue is washed with water, dried, and crystallised from ethanol to give a di-acetyl derivative of 2amino-4-t-chloroanilino - 1: 3 : 5 - triazine, of m.p. 181" C. EXAMPLE 3. 2.14 parts of 2-amino - 4 - (2:4 - dichloroanilino) - 1: 3 : 5 - triazine, 0.9 part of acetic anhydride and 10 parts of acetic acid are heated together under reflux for 18 hours. The mixture is then cooled and filtered. The residue is washed with acetic acid and then with water. It is crystallised from 2-ethoxyethanol to. give a monoacetyl derivative of 2-amino-4 (2: 4-dichioroanilino) - 1: 3: 5-triazine of m.p. 198 C. EXAMPLE 4. A mixture of 2.14 parts of 2-lamino-4-(2: 4- dichloroanilino)-1: 3: 5-triazine and 10 parts of acetic anhydride is heated under reflux for 5 hours and then cooled, and diluted with water. The suspension is filtered and the residue is washed with water and crystallised from ethanol. There is thus obtained - a di-acetyl derivative of 2-amino-4-(2: 4-dichioroanilino)- 1: 3: 5-triazine, of m.p. 1500 C. EXAMPLE 5. 0.1 part of concentrated sulphuric acid is added to a mixture of 10.7 parts of 2-amino4-(2: 4-dichioroanilino) - 1: 3 : 5-triazine and 30 parts of propionic anhydride. The solution is then heated under reflux for 4 hours, cooled, and filtered. The residue is washed with ethanol, dried, and crystallised from. aqueous 2-ethoxyethanol. There is thus obtained a dipropionyl derivative of 2-amino - 4 - (2: 4-dichloroanllino)-1 : 3 : 5-triazine, of m.p. 173174 C. EXAMPLE 6. 6.06 parts of palmityl chloride are added to a solution of 2.56 parts of 2-amino-4-(2:4- dichloroanilino)-1: 3: 5-triazine in 35 parts of pyridine. The mixture is kept at room tern- perature for 18 hours and then filtered. The filtrate is diluted with dilute aqueous ammonia and the resultant mixture is filtered. The solid residue is washed with water, dried and crystallised from petroleum ether (b.p. 1001200 C.) to give a di-palmityl derivative of 2amino - 4 - (2: 4-dichloroanilino)-l : 3 : 5 - tri- azine. of m.p. 100-103 C. EXAMPLE 7. A mixture of 3 parts of 2-nmino-4-p-chloro- anilino-1 : 3: 5-triazine, 9 parts of propionic anhydride and 0.3 part of concentrated sulphuric acid 'is heated under reflux for 3 hours. The reaction mixture is then cooled and filtered and the residue is washed with propionic anhydride and then with petroleumether (b.p. 100-120 C.) and dried. It is
crystallised from butyl acetate land there is thus obtained a monopropionyl derivative of 2-amino-4:p-chloroanilino-1: 3 : 5-triazine, of m.p. 241242 C. EXAMPLE 8. A mixture of 4.48 parts of 2-amino-4-mchloroanilino-l : 3 : 5-triazine, 25 parts of propionic anhydride and 0.3 part of concentrated sulphuric acid is treated according to the process as described in Example 7. The dried product is crystallised from 2-ethoxyethanol to give a monoprop'ionyl derivative of 2-amino4-m - chloroanilino - 1: 3: 5-triazine, of m.p. 242-243 C. EXAMPLE 9. 3.1 parts of n-butyryl chloride are added to a solution of 2.56 part, of 2-amino-4-(2:4-di- chloroanilino) - 1: 3 : 5-triazine in 35 parts of pyridine. The mixture is kept at 20 C. for 30 minutes and is then boiled under reflux for 5 hours. It is then cooled, diluted with 150 parts of water and filtered. The solid residue is washed with water, dried, and crystallised from ethyl acetate to give a monown-butyryl derivative of 2-amino-4-(2: 4-dichloroanilino)1:3:5-triazine of m.p. 160161 C. In ultra violet light, the product of this Example has a molecular extinction coefficient of 20,400 at a wavelength of 270 m,a in meth- anol solution. The m.p. of 160161 C. is depressed to a m.p. of 140142 C. on admixture of the product of this Example with the isomeric product of Example 15. EXAMPLE 10. When the 3.1 parts of n-butyryl.chloride used as starting material are replaced by 2.3 parts of isobutyryl chloride in the process as described in Example 9 there is obtained a mono-isobutyryl derivative of 2-amino-4-(2: 4-dichloroanilino)-l : 3 : 5-triazine which when crystallised from butyl acetate has m.p. 180181 C. EXAMPLE 11. A mixture of 2.56 parts of 2-amino-4-(2: 5dichloroanilino)-1: 3 : 5 - triazine, 15 parts of propionic anhydride and 0.1 part of concentrated sulphuric acid is heated under reflux for 4 hours. The reaction mixture is then cooled and filtered and the solid residue is washed with petroleum ether (b.p. 60-80" C.) land dried. It is then crystallised from butyl acetate to give a mono-propionyl derivative of 2-amino-4-(2: 5-dichloroanilino)-1: 3: 5-triazine, of m.p. 212-213 C. EXAMPLE 12. A mixture of 4 parts of 2-amino-4-(3:5-di- chloroanilino) - 1:3:5 - triazine, 25 parts of prop ionic anhydride and 0.1 part of
concentrated sulphuric acid is heated under reflux for 4 hours. The reaction mixture is then cooled and filtered, and the solid residue is washed first with propionic anhydride and then with petroleum ether (b.p. 40-60 C.) and dried. It is then stirred with 20 parts of acetone at about 40" C. and the suspension is cooled and then filtered. The solid residue is dried and crystallised first from dioxan and then from 2-ethoxyethanol to give a mono-propionyl derivative of 2Jamino-4-(3: 5 - dichloroanilino)-1:3:5-triazine, of m.p. 258 C. EXAMPILE 13. A mixture of 2.56 parts of 2-amino-4(2: 4 - dichioroanilino) - 1 : 3: 5 - triazine, 1.4 parts of propionyl chloride, 3.7 parts of diethylaniline and 50 parts of dioxan is heated under reflux for 10 minutes and is then kept at room temperature for 48 hours. It is then filtered, the filtrate is poured into water and the mixture is diluted with petroleum ether (b.p. 80-100 C.) The mixture so obtained is filtered and the solid residue is washed with petroleum ether (b.p. 8010D C.) and dried. It is crystallised from a mixture of benzene and cyclohexane to give a monc-propionyl derivative of 2-amino-4-(2: 4 - dichloroanilino)- 1: 3: 5-triazine, of m.p. 160-162 C. EXAMPLE 14. A mixture of 2.56 parts of 2-amino-4-(2: 4dichloroanilino) - 1:3:5-triazine, 2.7 parts of ethoxyacetyl chloride and 40 parts of pyridine is kept at room temperature for 18 hours. The reaction mixture is then poured into water and the resultant mixture cooled to 0 C. and filtered. The solid residue is dried and then crystallised from a mixture of benzene and cyclohexane to give a mono-ethoxyacetyl derivative of 2-amino-4-(2:4-dichloroanilino)- 1: 3: 5-triazine, of m.p. 139-141 C. EXAMPLE 15. A mixture of 2.56 parts of 2-amino-4 (2: 4 - dichlorc'anilino)-1: 3 : 5 - trisazine, 2.6 parts of ez-butyryl chloride and 35 parts of pyridine is treated according to the process as described in Example 17. The dried product is crystallised from ethyl acetate to give a mono-l-butyryl derivative of 2-amino-4-(2:4- dlichloreanilino) - 1: 3: 5-triazine, of m.p. 160 161 C. In ultra-violet light, the product of this Example has a molecular extinction coefficient of 6,200 at a wavelength of 270 mp. in methanol solution. The m.p. of 160161 C. is depressed to a m.p. of 140-142 C. on admixture of the product of this example with the isomeric product of Example 9. EXAMPLE 16.
A mixture of 2.56 parts of 2-amino-4- (2: 4-dichloroanilino)-1: 3 : 5-triazine, 2.6 parts of n-butyryl chloride, 4 pants of diethylaniline and 50 parts of dioxan is treated according to the process as described in Example 13. The dried product is crystallised from butyl acetate and there is thus obtained a mono-n- butyryl derivative of 2-amino-4-(2:4-di- chloroanilino)-1:3:5-triazine of m.p. 160'- 161 C. which is identical with the product obtained by the process as described. in Example 15. EXAMPLE 17. A mixture of 2.56 parts of 2-amino-4-(2: 4-dichloroaniline-1:3:5-triazine, 2.6 parts cf n-valeryl chloride ,and 35 parts of pyridine is treated according to the process as described in Example 14. The dried product is crystallised from butyl acetate, to give a mono-nvaleryl derivative of 2-amino-4-(2: 4-dichioro- anilino)-1 : 3 : 5riazine of m.p. 179 C. EXAMPLE 18. A mixture of 4.05 parts of 2-amino-4-(2: 4dichloro-anilino)1 : 3 : 5-triazine, 2.6 parts of t-caproyl chloride and 60 parts ;of pyridine is treated according to the process as described in Example 14. The dried product is crystal lised from butyl acetate to give a mono-n caproyl derivative of 2-amino-4-(2: 4-dichioro- anilino)-1 : 3 : 5-triazine of m.p. 159-160 C. EXAMPLE 19. A mixture of 2.56 parts of 2-amino-4 (2: 4-dichloroanilino) - 1: 3 : 5 - triazine, 3.58 parts of n.-caprylyl chloride and 35 parts of pyridine is treated according to the process as described in Example 14. The reaction pro duct is washed with dilute aqueous ammonia and dried. It is crystallised from petroleum ether (b.p. 100-120 C.) to give a mono n-caprylyl derivative of 2-amino - 4 - (2: 4-di chloroanilino)-1:3:5-triazine, of m.p. 130 132 C. EXAMPLE 20. When the 3.58 parts of 7t-caprylyl chloride used as starting material are replaced by 4.2 parts of n-capryl chloride in the process as described in Example 19 there is obtained a mono-n-capryl derivative of 2-amino-4-(2:4- dichloroanilino)-1: 3 : 5 - triazine which when crystallised from petroleum ether (b.p. 100
1200 C.) has m.p. 133-134" C. EXAMPLE 21. When. the 2.7 parts of ethoxyacetyl chloride used as starting material are replaced by 3.1 parts of benzoyl chloride in the process as des cribed in Example 14, there is obtained a mono-benzoyl derivative of 2-amino-4-(2:4- dichloroanilino)-1:3:5 - triazine which when crystallised from a mixture of water. and 2 ethoxyethanol has m.p. 19C-197" C. EXAMPLE 22. A mixture of 2.56 parts of 2-amino-4-(2: 4 dichloroanilino)-1 :3: 5-triazine, 4.73 parts of p-chlorobenzoyl chloride, 15 parts of pyridine, and 24 parts of acetone is heated under reflux for 1 hour. The reaction mixture is then cooled and filtered and the filtrate is poured into dilute aqueous acetic acid. The precipi tated oil is separated from the aqueous phase and is crystallised first from ethanol and then from aqueous 2-ethoxyethanol to give a mono p-chlorobenzoyl derivative of 2-amino-4-(2: 4-dichloroanilino) - 1:3:5 - triazine of m.p. 183184 C. EXAMPLE 23. When the 1.4 parts of propionyl chloride used as starting material are replaced by 2.46 parts of phenylacetyl chloride in the process as described in Example 13, except that the time at room temperature is 20 hours instead of 48 hours there is obtained a n:!ono-rhenyl- acetyl derivative of 2-am-.Ino-4-(2: 4-dichloro anilino)-1 : 3 : 5-triazine which when crystal lised from a mixture of benzene and cyclohex ane has m.p. 153 C. EXAMPLE 24. A mixture of 2.64 parts of 4-p-chloro anilinvo-2-isopropyl-amino-1 : 3 : 5: - triazine, 1.6 parts of propioeyl chloride, 3 parts of di ethylaniline and 50 parts of dioxan is heated under reflux for 11 hours. A further 1.06 parts of propionyl chloride are then added and the reaction mixture is then kept at room temperature for 64 hours. It is then filtered, the filtrate is diluted with water land the resultant mixture is filtered.
The solid residue is dried and is then crystallised from petroleum ether (b.p. 100-120 C.) to give a mono-propionyl derivative of 4-p-chlorcanilino- 2 -isopropylamino-1:3:5-triazine, of m.p. 113116 C. EXAMPLE 25. A mixture of 2.64 parts of 4-p-chloroanilino-2-isopropylamino-1:3:5-triazine, 1.85 parts of ethoxyacetyl chloride, 4 parts of diethylaniline and 5 parts of dioxan is heated under reflux for 30 minutes and is then kept at room temperature for 20 hours. The reaction mixture is then filtered and the filtrate is diluted witch water 'and with petroleum ether (b.p. 60--80 C.). The precipitated oil is allowed to crystallise and is then collected and washed with. petroleum ether (b.p. 1001200 C.). It is crystallised from petroleum ether (b.p. 100-120 C.) to give la monoethoxyacetyl derivative of 4-p-chioroaniline-2 isopropyl-amino-1:3:5-triazine, of m.p. 118 -120 C. EXAMPLE 26. A mixture of 3.59 parts of 4-(2 : 4-dichioro- anilino)-2-sopropylamino - 1:3:5 - triazine, 2.65 parts of propionylchloride, 3 parts of diethylaniline and 50 parts of dioxan is heated under reflux for 30 minutes and is then kept at room temperature for 114 hours. The reaction mixture is then filtered and the filtrate is evaporated under reduced pressure. The residual foil crystallises and is then stirred with water and filtered. The solid residue is dried to give a mono-propionyl derivative of 4 (2: 4-dichloroanilino)- 2 -isopropylamino-1: 3: 5-triazine when crystallised from petroleum ether (b.p. 100-120 C.) has m.p. 128130 C. EXAMPLE 27. A mixture of 3.59 parts of 4-(2: 4-dichloroani,lino)- 2 -isopropylamino - 1: 3: 5-triazine, 1.85 parts of ethoxyacetylchloride, 3 parts of diethylaniline and 50 parts of dioxan is heated under reflux for 30 minutes and is then kept at room temperature for 18 hours. The reaction mixture is then filtered and the filtrate is poured into a mixture of water and petroleum. ether (b.p. 60-80 C.) The resultant mixture is filtered and the filtrate is poured into a mixture of water and petroleum ether (b.p. 60800 C.). The resultant mixture is filtered and the solid residue is washed with water and petroleum ether (b.p;. 60-80 C.). It is then crystallised from petroleum ether (b.p. 100-120 C.) to give a mono-ethoxyacetyl derivative of 4-(2: 4-dichloroanilino3-2-isopro- pylamino-1:3:5-triazine, of m.p. l41-142 C. EXAMPLE 28. A mixture of 2.64 parts of 4-p-chloroanilino- 2-isopropylamino-1:3:5 -
triazine, 1 part of sodium ethoxide and 30 parts of dioxan is heated under reflux for 5 minutes. The mixture is then subjected to distillation until 10 parts of distillate have been recovered. 2.11 parts of benzoyl chloride are then adde.d and the reaction mixture is heated under reflux for a furthest 2 hours. Bt is then cooled, diluted with water and filtered. The solid residue is washed with ethanol and dried. It is dissolved in hot xylene and the solution is 'cooled. The first crop of crystals thereby obtained are collected and set aside. The filtrate is kept at room temperature and gives a second crop of crystals which are collected and recrystallised from a mixture of ethyl acetate and petro- leum ether (b.p. 6080 C.) to give la monobenzoyl derivative of 4-p-cbloroaniline-24so- propylamino-l : 3. 5 - triazine, of m.p. 180181 C. Further amounts of the same product may be obtained from the first crop of crystals by retreatment with xylene. EXAMPLE 29. 50 parts of a powdered mono-propionyl derivative of 2-amino-4-(2: 4-dichioroanilino)- 1:3:5-triazine, m.p. 160-162 C., are mixed with 20 parts of maize starch land 25 parts of calcium carbonate and 40 parts of a 10% maize starch paste are then added, The mixture is dried and is then passed through a 16 mesh screen. 1 part of magnesium stearate is then added and the granules are compressed to give tablets suitable for administration. EXAMPLE 30. A mixture of 100 parts of icing sugar, 8 parts of sodium carboxymethylcellulose, 1.25 parts of a 10% aqueous solution of. heptadeca- ethyleneoxycetanol, 0.75 part of methyl p hydroxy-beuzoate, 1.8 parts of a raspberry flavouring agent and 3 parts of a 0.1% aqueous solution of the edible dyestuff of the Colour Index Number 179, is stirred in 400 parts of water. The pharmaceutical base thus obtained is ball-milled and then 25 parts of a mDnc-X-b..ltyryl derivative cf 2-aminc-4-(2 :4< EXAMPLE 32. By working the process as described in Example 30 except that the 25 parts of a mono-n-butyryl derivative of 2-amino-4-(2: 4dichloroanilino)-1 :3: 5 - triazine, m.p. 160161 C., are replaced by 25 parts of a monopropionyl derivative of 2-iso.prepyl- 4 -(2:4dichloroanilino)-l 3 : 5-triazine, m.p. 128- 130 C. there is obtained a stable suspension which may be diluted by the addition of further quantities of the pharmaceutical base as required for administration. What we claim is: - 1. New triazine derivatives which are mono-acyl and di-acyl derivatives of com- pounds of the formula
<img class="EMIRef" id="026448770-00060001" /> wherein Ar stands for an aryl radical which bears one or more halogen substituents and, of R and R1, one stands for hydrogen or for a lower alkyl radical and the other stands for hydrogen, wherein the acyl groups are of the form AlkCO- wherein Alk stands for an alkyl radical, of the form Alk.OCIl2CO- wherein Alk stands for an alkyl radical or of the forms Ar' CO- zor Ar'CH2COwherein Arl stands for an aryl radical which may optionally be substituted for example by halogen atoms. 2. A mono-propionyl derivative, m.p. 160-162" C., of 2-amino- 4 -(2: 4-dichloroanilino)-I : 3 : 5qtriazine. 3. A mono-n-butyryl derivative, m.p. 160161 C., of 2-amino-4-(2: 4-dichloroanilino) - 1: 3: 5 - triazine as disclosed in Example 18. 4. A mono-ethoxyacetyl derivative, m.p. 118120 C. of 2-isopropylamino - 4 - pchloroanilino-1 :3: 5-triazine. 5. A mono-propionyl derivative, m.p. 128 130 C. of 2-isopropylamino- 4 -(2:4-dichloroanilino)-1 : 3 : 5-triazine.
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* GB784616 (A)
Description: GB784616 (A) ? 1957-10-09
Process for the coking of coal
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The EPO does not accept any responsibility for the accuracy of data and information originating from other authorities than the EPO; in particular, the EPO does not guarantee that they are complete, up-to-date or fit for specific purposes.
PATENT SPECIFICATION 7 X 4, B Date of Application and filing Complete Specification: Jan 24, 1955. r No 2095/55. Application made in Germany on June 5, 1951. Complete Specification Published: Ocr 9, 1957. Index at acceptance:-Class 55 ( 2), D 2 H, Dl 11 (Cl: D: E 2: K: W). International Classification:-Cl Ob. COMPLETE SPECIFICATION Process for the Coking of Coal 84,616 We, BERGWERKSGESELLSCHAFT HIBERNIA AKTIENGESELLSCHAFT, of Herne, Germany, a body corporate organised under the laws of Germany, do hereby declare the invention, for S 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 coking of coal. It is known to utilise the heat of freshlymade hot coke to crack oils. It has now been found that if this coke is quenched with oil the oil penetrates so deeply into the capillaries of the coke that the oil coke so produced contains approximately 20 % of its weight of oil We have further found that this oil coke then has the coking properties cf a good quality coking coal A mixture of a coal unsuitable for use in a coking process, brown coal or peat with the oil coke mentioned above when submitted to a coking process results in a coke of a quality which satisfies the demands made on a marketable coke. It has further been found that the coke oven gas produced in the above mentioned coking process contains a greater amount of olefines than the gaseous products produced in a normal coking process. It has been found advantageous to use as the quenching oil the distillation residues from petroleum oil, the high boiling point residue from the hydrogenation of petroleum oil or other paraffin or hydroaromatic products, selective extracts or mixtures of one or more of these substances. Accordingly the present invention provides a process for the production of coke which comprises cokling a mixture of an oil-containing-coke with a coal which is by itself unsuitable for use in a coking process. EXAMPLE 1. 3 Kilograms of a coking coal are coked in a coking chamber at a
temperature of 1100 C After completion of the coking process the hot coke is transferred to a screen situated beneath the coking chamber and is then immersed in a bath charged with commercial fuel oil at a temperature of 120 C The cracking gas produced in this manner has the following composition expressed as percentage by volume: 1.4 25.2 0.8 3.0 30.8 37.0 1.8 % C O O, % Cn H 2 n % 02 %CO % Ha % CH, % N 2 After completing the quenching 2639 grams of a colke remain which contain 28 8 % by weight of oil This oil containing coke is then coked at a temperature of 1100 C with a coal which is known to have properties which 65 render it unsuitable for use in a normal coking process The following results are obtained expressed as percentage by volume: 784,616 1 2 3 4 250 g Coal 500 g Coal 750 g Coal 1000 g Coal 750 g Oil 500 g Oil 250 g Oil coke coke coke % CO 1 4 1 0 1 6 2 0 % Cn H 2 10 2 9 6 6 0 2 1 0 O 0 4 0 6 0 4 0 8 % CO 5 4 1 4 7 4 13 6 o% H 2 49 0 53 0 58 2 49 4 % CH, 32 8 33 8 24 8 25 0 % N 0 8 0 6 1 6 7 1 It will be seen from the values in the above table that there is a considerable increase in the yield of unsaturated hydrocarbons, principally ethylene, and also small quantities as propylene, as the quantity of the added oil coke increases. The coke remaining is of a normal quality and in particular is of the normal breaking size It is only the coke produced from the mixture shown in column 3 of the above table which is somewhat brittle The coke produced as shown in column 4 of the above table crumbled completely The coke produced in experiments 1 and 2 showed a particularly good strength value, for Experiment 1, 104 8 kg/cm 2 and for Experiment 2, 103 6 kg/cm 2; the porosity was in Experiment 1, 51.7 and in Experiment 2, 50 1 per cent by weight The coke conforms in quality to a good oven coke and has the same characteristic dark silver colouring and metallic surface. The strength of an oven coke produced from coking coal without the addition of oil coke is 107 1 kg/cm 2 and the porosity 45 1 %.
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* GB784617 (A)
Description: GB784617 (A) ? 1957-10-09
Improvements in or relating to processes and apparatus for drawing fusedbodies
Description of GB784617 (A)
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CH330205 (A) DE1044768 (B) US2783168 (A) DE1134967 (B) CH330205 (A) DE1044768 (B) US2783168 (A) DE1134967 (B) less Translate this text into Tooltip
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PATENT SPECIFICATION 7849617 Date of Application and filing Complete Specification: Feb 23, 1955. No 5504/55. Application made in Germany on Feb 23, 1954. Application made in Germany on March 2 1954. Complete Specification Published: Oct 9, 1957. Index at acceptance:-Classes 32, C; and 37, K( 1 CX: 1 D 1: 2: 3 E 2: 3 H: 3 J). International Classification:-B Old H Ol L COMPLETE SPECIFICATION Improvements in or relating to Processes and Apparatus for Drawing Fused Bodies We, SIEMENS-SCHUCKERTWERKE Ai KTIENGESELLSCHAFT, a German Company, of Berlin and Erlangen, 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 a process and an apparatus for drawing a fused rod-shaped crystalline body. It is known to produce a rod-shaped crystalline body, such as a
semi-conductor body, by drawing the material from a heated container (crucible) that is to say, by withdrawing it continuously but slowly in the molten state, (a nucleus of the same material as the melt first having been dipped into the molten material by means of a holder movable perpendicularly and relatively to the liquid surface of the material) in the upward direction together with the liquid by which it is wetted A bead of the molten material thus remains suspended from the solidified lower end and solidifies at a short distance from the point of withdrawal, so that a rod-shaped fused body is gradually formed Thus, for example, mono-crystals of germanium or silicon or of semi-conducting compounds of elements of the 3rd and 5th or 2nd and 6th groups of the Periodic System, such as indium antimonide, are produced which, after having been divided into small sections are treated to form directional conductors, transistors and the like In order that the rod drawn from the melt may have a regular cross-section, the temperature of the supply melt must be maintained constant with very great accuracy This is achieved, for example, in accordance with one known process by maintaining a constant quantity of liquid in the crucible by continuously feeding a fresh supply of material to the melt during the withdrawal of the fused rod In this process, the crystalline fused rod is withdrawn upwardly from the surface of the liquid and the fresh material is supplied to the liquid surface from above In this known process, the volume of the melt is relatively large, and is preferably not substantially smaller than the volume of the with 50 drawn rod. According to one aspect of the present invention there is provided a process for drawing a fused rod-shaped crystalline body of predetermined quantity from a melt in a 55 crucible, wherein fresh material is supplied to the melt in the crucible during the withdrawal of the fused body in such a way that the quantity of the melt is kept considerably smaller than said predetermined quantity of 60 said body. In accordance with another aspect of the present invention there is provided an apparatus for drawing a fused rod-shaped crystalline body of predetermined quantity from a 65 melt, comprising a crucible for containing said melt and being dimensioned to hold at most one tenth of said predetermined quantity, said crucible having an outlet aperture located to be below the liquid surface of said melt, a 70 heating device for heating said crucible, a holder situated opposite said aperture for withdrawing said body from said melt, said holder and said crucible being movable felatively to one another in the direction in which 75 said body is to leave said aperture, and means for supplying fresh material to said melt in said crucible in such a way that the quantity of said melt is kept smaller than said predetermined quantity 80 It is advantageous to carry out the drawing
process with a small quantity of liquid material, not only because of the saving of expenditure in heating power and the simplicity of temperature regulation, but also 85 because the incorporation of any required additives and the change in the type of additives incorporated are thereby facilitated. The quantity of liquid material may be kept particularly small, down to 1 cm' or less, if 90 the fused body, which may be referred to as a rod, is withdrawn in a direction differing from the direction in which the fresh material is supplied It is then possible, to employ a very small crucible having an internal diameter which need only be slightly larger than the diameter of the fused rod or of a rod produced from the supply material, so that the melting crucible holds at a maximum, for example, one-tenth of the quantity of material required for the fused rod finally formed. Thus, for example, if the fused rod is 20 cm. long, and has a cross-section of 0 8 cm 2, a crucible having a capacity of 1 5 cmn or less would be sufficient The quantity of liquid material actually contained therein will be maintained at 1/30th of the whole quantity of material required for the fused rod finally formed An improvement can be effected when the drawing process is carried out by means of an apparatus in which the point of withdrawal from the melting crucible is situated below the liquid surface of the melt in the form of an outlet aperture, opposite which a holder for the fused rod is so arranged as to be movable in the direction of withdrawal in relation to the container, so that the already solidified end of the fused rod lies at a short distance in front of the outlet aperture Thus only a small quantity of the liquid emerges, more especially by reason of the low liquid level and the low pressure of the supply of molten material in the crucible, the quantity of which is small, as mentioned, the small quantity of liquid solidifying as the rod is gradually withdrawn and being constantly replenished by the flow of further liquid molten material in proportion as the rod grows The speed of withdrawal may be so adjusted in accordance with the flow of fresh material that a fused rod of uniform crosssection is formed. In a known drawing process in which the fused rod is drawn upwardly from the surface of the liquid, the size of the cross-section of the fused rod formed is rather narrowly limited by the surface tension of the suspended bead of liquid, so that the cross-section of the crystalline fused rod must be subdivided or reduced by additional working operations (sawing or cutting) after the drawing operation in order to form very small finished elements such as are required for directional conductors, transistors and the like In contrast thereto, in the present process the size of the cross-section of the rod is
determined by the size of the outlet aperture, by the height of the liquid level of the melt above the outlet aperture, which in turn depends upon the heat supply, and by the speed of withdrawal With an outlet aperture of given size, the speed of withdrawal may vary within a range determined by the surface tension of the melt By appropriate adaptation of the aforesaid quantities to one another, a fused rod having a cross-section of any desired size may be produced Thus, for example, it is possible to draw the bar so thin that finished semi-conductor elements of the size required for directional conductors, transistors or the like are formed by simply severing discs therefrom without further subdivision or reduction 74 By reason of the possibility of additionally influencing the cross-section of the fused rod by the size of the outlet aperture of the crucible and by the pressure of the liquid melt at the point of discharge, the present process 71 has advantages compared to the known vertical zone melting process in which no crucible is employed As compared with the earlier known zone melting in a horizontally disposed elongated crucible, the present process affords 81 the same advantage as zone melting without a crucible, namely that the melt is not in contact with the crucible at the instant of solidification and thus cannot cake thereon and cannot absorb any foreign materials from the crucible 8 ' For a better understanding of the invention and to show how the same may be carried into effect, reference will now be made to the accompanying drawings in which:Fig 1 shows a side view, partly in section 9 ( along a line I-I of Fig 2, of an apparatus for forming crystalline bodies, Fig 2 shows a plane view of a section along the line II-II of Fig 1, Fig 3 shows an enlarged view of details 9 ' shown in Figs 1 and 2, Figs 4 and 5 show an enlarged side and plane view respectively of parts shown in Fig 1, Fig 6 shows a front view, partly in section, 10 of an apparatus for forming crystalline bodies, Fig 7 shows a fragmentary side view of a part shown in Fig 6, Figs 8, 9 and 10 show details, on an enlarged scale, of parts shown in Fig 6, 10 Figs 11, 12, 14 and 15 show sections of parts of apparatus, Fig 13 shows a plane view of part of an apparatus, and, Fig 16 shows a side view, partly in section, 11 l of an apparatus for forming crystalline bodies. Referring now to the drawings, in Figures 1 to 3, a crucible 11 is provided which may consist, for example, of graphite or magnesium oxide or aluminium oxide These materials 11 are distinguished by their very high temperature resistance of up to 30000, 25000 and 2000 C respectively Graphite is especially suitable for the treatment of germanium, indium antimonide and like semi-conductor 12 compounds with which graphite does not react Graphite reacts with various other semi-conductor materials, such for example as silicon and aluminium
antimonide, but the carbides thus formed are stable, so that the 12 crucible is not further attacked after a corresponding lining has been formed, and the melt also remains unaffected Situated in the bottom on the crucible, which contains in the liquid state, for example, one-thirtieth of the 13 784,617 from the part 24 and connected to a heating transformer by leads By contact-making between the clamping plates 21 and the clamping plates 19, the preheating device 20 may be connected in parallel with the main heating 70 member 17 to a common heating transformer. The support 18 is slidably guided by means of two vertical steel guide pins 22 and is moved upwards or downwards by a spindle 23 The guide pins 22 are connected together 75 at their two ends by cross beams 31, 32 and mounted on a steel base plate 30 They are preferably internally hollow and cooling water may be passed therethrough, such cooling water being fed to one of the two pins 22 80 from below by way of the base plate 30, flowing from its upper end through the hollow transverse beam 32 to the other guide pin 22 and leaving this guide pin at the bottom through the base plate 30 85 The upper part 24 also slides on the guide pins 22, but is not in engagement with the spindle 23, so that when the upper part 24 has been secured in position the support 18 can be separately moved upwards and down 90 wards below the upper part It is thus possible for the fused rod 12 to be melted zonewise again by the arrangement described after it has been completed should this be necessary for the further purification or for the pro 95 duction of a mono crystal. For this purpose, not only is the preheating device 20 placed out of operation but the heating device 17 is also temporarily rendered inoperative before the commencement of the 100 further drawing operation, so that the crucible 11 cools due to solidification of the melt at the upper end of the fused rod 12 The crucible 11 is then made fast and serves in the subsequent zone drawing as a holder for 105 the upper end of the fused rod 12. The entire apparatus is enclosed by a metal hood 33, which is mounted in vacuum-tight fashion on the base plate 30 and provided with an observation window 35 The base 110 plate 30 has a branch tube 34 for the connection of a vacuum pump or a storage container for protective gas, so that the drawing process may be carried out under a high vacuum or in a protective gas atmosphere, of 115 for example, argon or nitrogen Leading-in conductors 37 are also let into the base plate for the connection of the heating current conductors 36 The lower end of the spindle 23 in the form of a stub shaft is also passed 120 in vacuum-tight fashion through the base plate and is coupled through gearing 38 with an adjustable driving motor 39 Provided on the base plate 30 is an adjusting sleeve 40, by which the entire apparatus is
displaceably 125 secured to a pillar 41 The lower end of the pillar 41 is let into a pedestal 42. The free end of the fused rod 12, especially if the latter is very thin, is preferably held centrally in relation to the crucible outlet 130 total quantity of material to be treated, is an outlet aperture from which the liquid material can escape downwardly Below the aperture is shown a finished length 12 of the fused rod, which is secured at its lower end in a holder 13 Situated between the upper end and the crucible 11 is a bead 10 of the melt, which progressively cools and solidifies from the bottom upwards, so that fused rod 12 grows upwardly The holder 13 is movable in the axial direction of the fused rod, so the fused rod can be gradually withdrawn in the downward direction with the aid thereof during its growth Fresh material is supplied, for example in solid form, from the top, a rod 14 of the supply material, which may be produced by pressing and if desired sintering or by melting, for example in a boat, or by casting in a mould, being lowered into the crucible 11 by means of a holder 15 The actual outlet aperture in the bottom of the crucible 11 is formed, for example, by means of a nozzle-like insert 16, which may consist of the same material as the crucible 11 or of another suitable material and projects both inwardly and outwardly The inwardly extending edge thus formed within the outlet aperture has the advantage-for example in the treatment of aluminium antimonide-that a coating of reaction product situated on the freshly fed material cannot escape, but is retained within the crucible The outwardly projecting edge of the outlet aperture prevents the discharged melt from wetting the bottom of the crucible The melt thus cannot spread out outside the crucible, and it is thus possible to draw the fused rod with any desired small cross-section. The crucible is surrounded at its lower end by an annular heating device known per se in such a way that the outlet aperture of the crucible is situated substantially in the middle of an annular heating member 17 as seen in the axial direction The heating member is shown as a resistance heating member heating by radiation, but it may alternately be an inductively acting heating coil The heating member shown is made of, for example, a strip of sheet molybdenum or sheet tungsten, the ends of which are clamped to a support 18 made of copper or the like or to a brass plate 19 secured in insulated fashion to the support 18, and are connected to movable leading-in conductors 36, which lead to a variable heating transformer of known-type. The crucible 11 is engaged at its upper edge in a holder 20 which is secured by means of clamping plates 21 to a separate upper supporting member 24 in order that the holder of the crucible may be separated from the heating device during operation The holder may also consist
of a sheet-metal resistance element similar to the heating device 17, which element serves at the same time for preheating the crucible 11, it being insulated 784,617 4 784,617 aperture at a short distance below the melting zone by means of a movable guide device 25 secured to the support 18 The guide device contains a number of guide members 26, 27 which are disposed opposite one another and come into contact with the periphery of the fused rod 12, at least one of the said guide members being adapted to yield, for which purpose it is, for example, loaded by a spring 28 In addition, a heat shield 29, for example in the form of an annular disc of sheet nickel may be disposed between the outlet aperture of the crucible 11, on the one hand, and the solidifying end of the fused rod 12, on the other hand, and may be secured to the support 18 by an extension A further similar heat shield may be disposed around the rod 14 above the melting crucible 11 and secured to the upper part 24 of the support. The holders 13 and 15 may also be moved in the axial direction of the fused rod in the same manner as the support 18 Various possible combinations of a number of movements will be briefly mentioned in the following: In a first series of movements, the crucible 11 remains stationary, the fused rod 12 is withdrawn in the downward direction and a supply rod 14 is fed from above In another possible series, the upper rod 14 remains stationary, the crucible 11 is moved upwards and the fused rod 12 is withdrawn in the downward direction In a third series, the fused rod is not moved in the axial direction, while the crucible 11 and-at a lower speed -the supply rod 14 are moved upwards in the direction in which the fused rod grows. In addition, in a further series, the fused rod 12 may be withdrawn in the downward direction, more especially if it is to be as thin as possible In addition to the movement in the axial direction, a rotational movement may also be imparted to the rods 12 and 14 By rotation of the supply rod 14, the melt in the crucible 11 is stirred A rotation of the fused rod 12 serves not only to produce a uniform circular cross-section, but also-when relatively high speeds are used to convey undissolved foreign bodies in the melt by centrifugal force to the outer surface of the fused rod, whence they can subsequently be removed by chemical and/or mechanical means. For carrying out the various aforesaid movements, each of the two holders 13 and is disposed on the free end of a shaft 43, 45, which is passed in vacuum-tight fashion through the base plate 30 and the top wall of the hood 33 respectively, and coupled with gearing 44, each gearing being arranged to transmit a movement in the axial direction and independently thereof a rotational movement from two driving motors 46, of which only one is shown in the drawing in each instance,
to the shafts 43 and 45 respectively. The driving motors 46 may also be secured to the pillar 41 by adjusting sleeves 47. With the described arrangement, the following procedure is adopted With the hood 33 open, a mono-crystalline nucleus 12 in the form of a short section of a previously produced mono-crystal rod is clamped in the lower holder 13 A sintered rod 14 produced from the supply material is clamped in the upper holder 15, and when the hood 33 has been closed the support 18 together with the heating device 17 and with the upper part 24 and the crucible 11 secured thereto is raised until the lower end of the rod 14 is in the crucible 11 The lower holder 13 is also raised until the nucleus almost or precisely touches the crucible 11 When the necessary high vacuum has been established, the heating current is switched on, so that the lower end of the supply rod 14 melts The upper end of the nucleus 12 also becomes liquid The melting bead descending from the opening in the bottom of the crucible 11 combines with the nucleus The part 12 is then slowly withdrawn downwardly, for example at a speed in the order of magnitude of from 0 5 to 5 mm per minute, while constantly rotating about its axis, for example at 400 r p m The rod 14 is fed from above in proportion as molten liquid is thus used The melt in the crucible 11 is well stirred by constant rotation of this rod, for example at 300 r p m or less. In order to incorporate additives in the melt, for example for the purpose of producing p-n or n-p-junctions or a succession of such junctions, an incorporating arrangement is provided in accordance with Figure 1, the details of which are more clearly shown in Figures 4 and 5 The incorporating arrangement consists of a plate 48, which is secured to a rod 49 and can follow the upward and downward movements of the crucible 11 with the said rod, which extends in vacuum-tight fashion through the end wall of the hood 33. Rotatably mounted on the shaft 49 above the plate 48 is a flat hollow cylinder 50, the interior of which is subdivided into a number of individual chambers by radial plates 51. With the hood 33 open, the additives to be incorporated may be introduced into the said chambers in predetermined quantities, for example in the form of one or more compressed pellets of pulverous material, in accordance with any desired programme of incorporation The top of the hollow cylinder may thereafter be closed by a cover 52 The hollow cylinder 50 is provided with a toothed annulus on its outer periphery, with which toothed annulus there engages a pinion 56, which may be rotated by means of a rod 53 extending in vacuum-tight fashion through the hood 33 During the rotation, the pellets to be introduced are carried along by the partitions 51 and finally reach a recess 54
in the plate 48, through which they fall, so that they slide through a descending tube 55 provided at this point and fall into the crucible 11. 784,617 784,617 5 The pinion 56 may be rotated to the extent of one chamber at a time in the intervals determined by the programme of incorporation, either by hand or automatically by means of a suitable coupling gear or an automatically regulated electric drive in dependence upon the drawing operation. In the apparatus illustrated in Figures 6 to 10, the drawing apparatus is disposed within a transparent quartz tube 60, which is closed in vacuum-tight fashion at both ends by ground-in metal end seals 57 and 58 The seals are pressed together by end plates 59 and clamping bolts 61 These parts form a frame resting on legs 62 A nipple 63 is provided on the end seal 58 for the connection of a high-vacuum pump or a storage container for protective gas For the heating, an induction coil 64 is here provided, which also serves to support the melting crucible 11. The crucible is for this purpose provided with an external annular bead 66, which is situated slightly above its outlet aperture. The heating coil 64 may also be disposed outside the quartz tube 60 and the crucible 11 may be secured within the quartz tube by other means, for example as hereinafter described The induction coil 64 and its connecting conductors 67 consist of a single length of copper tube, the ends of which extend in vacuum-tight fashion through the upper closure cover 57 Terminals 68 are provided on the outer ends of the tube sections 67 to connect a high-frequency generator, which operates, for example, at a frequency of a few magacycles per second In addition, flexible rubber tubes are connected to the tube ends to pass cooling water through the tube and thus through the induction coil 64 For preheating the crucible 11 and the melt situated therein, a closed heating ring 65 consisting of tungsten-molybdenum or nickel sheet is employed, which rests on the bead 66. The crude material is here fed to the crucible 11 in the form of powder For this purpose, a storage container 70, for example of glass, is detachably secured to the upper end seal 57, for example by means of a bayonet joint. The glass container 70 has at its lower end a narrowed outlet aperture, for example in the form of the neck of an hour glass, so that the finely crushed semi-conductor powder situated in the storage container trickles down in a thin stream and enters the melting crucible 11 In contrast to the illustration, the melting crucible 11 may be secured to the container 70, and preferably suspended thereon The outlet aperture of the container 70 may be closed by means of a plug 69 situated on the lower end of a rod 71 The rod is passed in
vacuum-tight fashion through the end seal 57 and is pivotally connected to a hand lever 72, so that the plug 69 may be raised and lowered by actuation of the lever. Situated below the outlet aperture of the crucible 11 is the bead 10 of molten material, below which is situated the already solidified end 12 of the fused rod, which may be clamped fast in the holder 13 and withdrawn 70 downwardly by means of a device 44 secured to the lower end seal 58 and may be rotated independently thereof, as described, for example, with reference to Figure 1 The driving motors have been omitted from the 75 drawing in the case of the present constructional example. An incorporating arrangement is provided at the lower end of the storage container 70 as shown in Figures 6 and 7 Details of this 80 incorporating arrangement are shown in Figures 8 to 10 Figures 8 and 9 are fragmentary sections along the lines VIII and IX. Figure 10 is a view from below The stationary part of the incorporating arrange 85 ment in this case consists of two halves 73 and 74, which are separately disposed around the neck of the storage container 70 and are then held together by clamping members 75. The clamping members 75 themselves are 90 secured in wedge-shaped dovetail guides at the parts 73 and 74 The part 73 has an aperture 77, below which a descending tube 76 is secured The rotatable upper part of the incorporating arrangement consists of a 95 flat hollow cylinder 78 closed on one side and having partitions 79 and an outer toothed annulus with which a pinion 56 engages, the shaft 53 of which pinion extends in vacuumtight fashion through the upper end seal 57 100 The incorporating arrangement is not charged and mounted on the storage container as illustrated, but in the inverse position. The pellets to be incorporated are first introduced into the individual compartments of 105 the upper part 78, whereafter the upper part 78 is mounted-on the neck of the storage container 70 and the two lower halves 73 and 74 are then introduced and connected together by clamping members 75 The storage con 110 tainer may be rotated with the incorporating arrangement attached thereto and thus brought into the operative position, secured to the end seal 57 and introduced into the quartz tube together with the heating coil 64 and the 115 crucible 11 mounted thereon and the annular heating member 65 In securing the filled storage container 70 to the end seal 57, the plug 69 is pressed into the outlet aperture, which is thereby sealed In addition, the 120 pinion 56 is brought into the position of engagement. A mono-crystalline nucleus firmly clamped in the holder 13 is then withdrawn upwardly by means of the driving device 44 as far as 125 the outlet aperture of the crucible 11, which is thereby sealed The crucible 11 can consequently be charged partly with powder from the
storage container 70 by temporarily lifting the plug 69 When the interior of the quartz 130 784,617: tube 60 has been exhausted, the highfrequency heating is started and, if the semiconductor material has not yet sufficiently high conductivity for the inductive heating, the auxiliary heating ring 65 is first heated. The heat is transmitted from the auxiliary heating ring 65 through the wall of the crucible to the powder contained in the crucible 11 until it cakes together and becomes so highly conductive that the heat necessary for the melting is then generated directly in the semi-conductor material itself by highfrequency induction currents The energy thus transmitted to the auxiliary heating ring 65 is thus automatically reduced, so that it henceforth serves only for the preheating When the contents of the crucible have become liquid and the upper end of the nucleus has also been melted down and the outlet aperture of the crucible thus freed, the withdrawal of the fused rod 12 may be commenced with the aid of the device 44 By raising the plug 69, the necessary supply of fresh material is effected in the form of powder which trickles out. The incorporation is effected as in the case of the apparatus shown in Figure 1 by the upper part 78 of the incorporating arrangement being rotated to the extent of one chamber at a time by means of the pinion 56 and a pellet for incorporation thus being fed through the descending tube 76 into the crucible 11. Figure 11 illustrated a modification of the arrangement shown in Figure 3 In Figure 11,the cross-section of the outlet aperture of the melting crucible 11 is variable by means of a needle 80 adjustable in the axial direction. Provided at the upper end of the needle is a plug 81, by means of which the outlet aperture may be completely closed The needle and the plug are secured to a rod 82, which may be clamped instead of the feed rod 14 in the upper holder 15 of the arrangement illustrated in Figure 1 According to Figure 11, the fresh material for the melt is fed in comminuted form or in powder form from a storage container 70 having a narrowed outlet as in an hour glass, in the manner described with reference to the arrangement illustrated in Figure 6 The storage container 70 may be secured to the upper part 24 of the support in the arrangement according to Figure 1. In a further modified form as shown in Figures 12 and 13, the crucible 11 may be rotated about the axis of its outlet aperture. For this purpose, it is suspended by means of projections 83 in its interior from the lower end, provided with arms 84, of a rod 85 which consists of the same heat-resistant material as the crucible itself or of a material similar thereto The rod 95 may be clamped in the upper
holder 15 of the arrangement according to Figure 1 and may be rotated together with the latter by the driving device 44 The supply rod 14 is held by a further holder 86, the holding rod 87 of which in the arrangement according to Figure 1 may extend in vacuumtight fashion through the end wall of the hood 33 in addition to the shaft 45, and the supply rod is slowly moved downwards by means of 70 a suitable driving device No rotation is necessary The molten material situated in the crucible 11 rotating about its axis is stirred by the supply rod 14, which is stationary in this case 75 Figure 14 shows an arrangement in which the outlet aperture of the crucible 11 is situated in the lateral wall thereof and the holder 13 for the fused rod 12 is situated laterally adjacent the outlet aperture and in axial 80 alignment therewith, so that the fused rod is withdrawn in the horizontal direction The holder for the crucible and the heating devices are with advantage stationarily mounted in this case The fresh material may be supplied 85 either in the form of powder or in solid form, as described. As shown in Figure 15, a crucible 11 has the form of a U-shaped tube, the arms of which are of different lengths The holder 90 13 for the fused rod 12 is situated above the upwardly directed outlet aperture of the shorter of the two arms The supply material is fed, for example, in the form of a rod 14 to the surface of the liquid in the longer of 95 the two arms The fused rod 12 in this arrangement is withdrawn upwardly as in a known drawing process However, the difference resides in that in the known process the fused rod is withdrawn upwardly from the free 100 surface, while in the arrangement shown in Figure 15 a special outlet aperture is provided, which by its width and its difference in level in relation to the liquid surface can additionally influence the cross-section of the fused 105 rod In addition, with this form of crucible, any impurities present on the freshly supplied material in the form of a coating consisting of a reaction product are retained. The modifications to the holding and driving 110 devices in the case of Figures 14 and 15 which result from the different position of the fused rod in relation to the arrangement according to Figure 1 may be derived from the preceding illustrations 115 The process described is especially suitable for the production of rod-shaped fused bodies from high-melting metals such as titanium and zirconium or from corresponding alloys Such fused elements may be employed, for example 120 as shafts or sections thereof, as journals or the like. For electrotechnical purposes, semi-conductor mono-crystals having a series of zones of different types of conduction are required, 125 for example p-n-p or n-p-n crystals, which may be employed for transistors Such crystals consist, as is known, of a uniform basic material such
as germanium, silicon or a semiconducting compound of elements of the 3rd 130 784,617 preceding zone, is thus rendered possible. In this way, therefore, a change in the time of incorporated material can also be effected and repeated as often as desired with low expenditure, so that a semi-conductor having 70 an unlimited series of zones of different types of conduction can thus be produced For the various additives, a number of auxiliary fused rods may be provided, which are employed alternately to empty the crucible in such 75 manner that each takes up only one type of additive. The process may be carried out with particular advantage by withdrawing the main fused element downwardly and supplying the 80 fresh material from above The latter may be fed, for example, in granular and preferably fine-grained form or in the form of a sintered or fused rod In addition, a number of supply rods already containing different types of addi 85 tives may be alternately employed to produce a zone in the main fused element. Figure 16 illustrates an apparatus for carrying out the developed process, which is similar to that shown in Figure 1 Formed in the 90 bottom of the crucible 11, which contains a small quantity of the material in liquid form to be worked up, is an outlet aperture from which the liquid material escapes in the downward direction A finished portion 12 of the 95 fused rod finally formed, which is secured in a holder 13 at its lower end, is shown below the aperture The holder 13 is movable in the axial direction of the fused element, so that the latter can be gradually withdrawn in the 100 downward direction with the aid thereof. Consequently, the bead 10 situated between the upper end of the part 12 and the molten crucible 11 is progressively 'cooled and solidified from the bottom upwards, so that 105 the fused element 12 grows (upwardly) For carrying out the drawing movement, a gearing 44 is provided, which can transmit a movement in the axial direction from two driving motors 46, of which only one is shown in the 110 drawing, to the shaft 43 and can transmit independently thereof a rotational movement serving inter alia to stir the melt The gearing 44 is mounted on a steel base plate 30 through which the shaft 43 extends in vacuum-tight 115 fashion Mounted on the base plate 30 is a frame 18 to which a holder 20 for the crucible 11 is secured An annular heating device 17 surrounds the crucible 11 at its lower end The heating device 17 is also secured to the frame 120 18, and current leads 36 extend therefrom through leading-in insulators 37, which are let into the base plate 30 in vacuum-tight fashion, to a variable heating transformer which is not shown in the drawing 125 The entire apparatus is enclosed in a steel hood 33, which is mounted in vacuum-tight fashion on the base plate 30 and is provided with an observation
window 35 The base plate has a branch 34 for connection to a 130 and 5th or 2nd and 6th groups of the Periodic System The different type of conduction of the individual parts of a crystal is due to the ratio of their content of different types of additives, that is, donors and acceptors which product n or p-conductivity, depending upon which of the two types of additive are present in greater quantity in the basic material. For drawing a p-n-p mono-crystal from the melt, for example of a p-conductive germanium, the additive incorporated in the melt must be changed twice during the drawing process For this purpose, after the production of a p-zone, donor material, for example antimony, may be added in known manner to the liquid p-conductive germanium, in such proportion that the quantity thereof in the solid material is greater than the quantity of acceptors therein, and when an n-zone has thus been drawn, acceptor material, for example gallium, may be added in a correspondingly higher proportion, so that in the further drawing a further p-zone is formed. The content of additive in the melt and consequently its conductivity increase progressively as a result of the repeated change of the type of incorporated material The number of possible changes of additive incorporated is thus limited. In contrast thereto, a further development of the described process permits the drawing of a semi-conductor crystal with a series of zones having a different type of conduction, the conductivity of which does not increase progressively, but may be graduated as desired. This further development is based upon the idea of avoiding an increase in the conductivity of the next zone after the production of one -zone by reducing the content of additives in the liquid melt For this purpose, it is necessary first to reduce as far as possible the quantity of liquid melt remaining from the production of the preceding zone Therefore, after the production in the fused element of a zone permeated by impurity centres by incorporation of additives, a part of the quantity of liquid which has remained in the crucible is removed from the crucible before the supply of fresh material For example, this may be achieved by drawing out an auxiliary fused rod Since this auxiliary fused element need not grow in mono-crystalline form, its drawing speed may be made as high as is permitted by the surface tension of the melt A relatively high distribution coefficient can thus be achieved-especially if the usual rotational movement of the fused element is avoidedand the preponderant quantity of additive may thus be withdrawn from the melt The additive content of the remaining drop of liquid material is reduced by feeding suitable fresh supply material and the drawing of a new zone of the mono-crystalline main fused rod, which may even be of lower conductivity than the 784,617
vacuum pump or a storage container for protective gas Also mounted on the base plate is an adjusting sleeve 40, by which the entire apparatus is displaceably secured to a pillar 41 The lower end of the pillar 41 is let into a pedestal 42 The driving motors 46 may be secured to the pillar 41 by means of adjusting sleeves 47. Supply material is fed to the crucible 11 from above in the form of a rod 14, which is suspended in a holder 15 In addition, an auxiliary fused rod 64 is suspended in a holder above the crucible 11 The holders 15 and are mounted on a turntable 22, the shaft 45 of which extends through the hood 33 in vacuum-tight fashion and is moved in the axial direction by means of gearing 44 and a corresponding auxiliary motor not shown in the drawing, and is so rotated independently thereof that the auxiliary fused rod 64 or the supply rod 14 moves into its position of use exactly vertically above the crucible 11 as required When a number of auxiliary fused rods 64 and/or a number of storage rods are employed, they may also be held to the turntable 22. For incorporating additives in the melt, an incorporating arrangement 50 is provided, which is secured to a rod 49 extending in vacuum-tight manner through the end wall of the hood 33 By means of the arrangement, the additives for incorporation which have previously been introduced therein can be fed in a predetermined quantity, for example in the form of one or more grains, into the crucible in accordance with a predetermined programme of incorporation The rotation through a small angle necessary for this purpose may be effected by means of the rod 53 in the intervals determined by the programme of incorporation or it may be automatically effected by means of a suitable coupling gear or an automatically controlled electric drive in dependence upon the drawing operation. With the described apparatus, the following procedure is adopted: As soon as, for example, a p-zone has been formed at the upper end of the final fused rod 12, the supply rod 14 is withdrawn from the crucible and the auxiliary fused rod 64 is lowered in its place until its lower tip comes into contact with the molten liquid It is then withdrawn upwardly at a relatively high speed and carries up with it the liquid contained in the crucible 11, which liquid adheres thereto and solidifies when it reaches the end of the upward movement. Substantially only the bead 10 remains from the molten material When the supply rod 14, which will be assumed to contain no additives forming impurity centres, is returned into the crucible and about 9 times the quantity of the bead 10 has been melted therefrom, a reduction in concentration occurs, in that the content of additives in the total quantity of liquid now present is lowered to one-tenth Accordingly, the melt also has reduced conductivity.
Donor material from the incorporation arrangement may now be added thereto, for example in such quantity that an n-zone can be drawn, 7 ( the conductivity of which is not higher than the conductivity of the p-zone previously drawn The quantity of liquid containing the incorporated material can then be withdrawn from the crucible by means of the auxiliary 75 fused rod, as already described and an additive of the opposite type can then be incorporated. The alternate change of the type of additive incorporated may be repeated as often as desired A number of zones having the same 80 type of conduction, but different degrees of conductivity may be drawn directly in succession to one another Moreover, zones in which both types of additives are present in substantially equal proportions may be produced 85 between zones having similar or different types of conduction, that is to say, in which either the donors or the acceptors are preponderant. A desired sequence of zones may be determined by charging the incorporating arrangement 50 90 in accordance with a corresponding programme. So-called Hall" rectifiers having the zone sequence ni-n 2-p or pi-p 2-n and transistors of various types may be produced by the described drawing process 95
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