GB784613 (A) patent summary

* GB784613 (A)
Description: GB784613 (A) ? 1957-10-09
New disazo-dyestuffs, copper complexes thereof, and processes for making
them
Description of GB784613 (A)
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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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* 5.8.23.4; 93p
* GB784614 (A)
Description: GB784614 (A) ? 1957-10-09
Process for the purification of ethylene glycol by distillation
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.
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
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
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.
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:
wherein Ar, R and R1 have the meaning stated above, with the
appropriate acid chloride in an inert solvent or diluent for example
dioxan.
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 - triazine. of m.p. 100-103 C.
EXAMPLE 7.
A mixture of 3 parts of 2-nmino-4-p-chloroanilino-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-dichloroanilino) - 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 methanol 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-dichloroanilino) - 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-dichloroanilino)-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
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
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-dichioroanilino)-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-isopropylamino-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 petroleum 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 compounds of the formula

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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Description: GB784616 (A) ? 1957-10-09
Process for the coking of coal

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.
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 fused
bodies
A high quality text as facsimile in your desired language may be available
amongst the following family members:
CH330205 (A) DE1044768 (B) US2783168 (A) DE1134967 (B)
CH330205 (A) DE1044768 (B) US2783168 (A) DE1134967 (B) less
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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GB784613 (A) patent summary

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GB784613 (A) patent summary