4611 4615.output

* GB785018 (A)

Description: GB785018 (A) ? 1957-10-23

Hydroxyl compounds of the steroid series and the preparation thereof

Description of GB785018 (A)

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CH310411 (A) FR1075376 (A) NL176230 (B) CH310411 (A) FR1075376 (A) NL176230 (B) less Translate this text into Tooltip

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PATENT SPECIFICATION 785,018 Date of Application and filing Complete Specification: Jan 16, 1953. No 1382/53. Application made in Switzerland on Feb 21, 1952. Application made in Switzerland on March II, 1952. Application made in Switzerland on April 8, 1952. Complete Specification Published: Oct 23, 1957. Index at acceptance:-Class 2 ( 3), U 3, U 4 (A 1: A 2: B 2), U 4 C( 1: 2: 3: 4: 5: 9:10), U 4 (D: X). International Classification:-C 07 c. COMPLETE SPECIFICATION Hydroxyl Compounds of the Steroid Series and the preparation thereof We, CIBA LIMITED, a body Corporate c 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 c 9 v described in and by the following statement:This invention relates to 7-oxygenated 9: 11dihydroxy compounds of the steroid series which possess in the rings B and C the OH following structures: O I and to the preparation thereof. The compounds of type II can be converted in excellent yield into A 8:9-7-keto-lilhydroxy-steroids by the action of alkali. The A 8:9-7-keto-ll-hydroxy steroids are important intermediate products for the manufacture of steroids which are unsubstituted in the ring B and contain oxygen in 11-position. To this class of compounds belongs, for example, cortisone, which is A 4-3: 11:20triketo-17 a: 21-dihydroxypregnene. This invention also includes a process by which the compounds of type I can be converted into compounds of type II. The specified 9: 11-dihydroxy compounds of the steroid series are obtained from 7:11dihydroxy-8:9-oxido-steroids possessing in the rings B and C the following structure lPtce 3 f 4 S 6 d when these compounds are treated in a substantially anhydrous medium with an acidic agent of the Lewis type whereby there are formed direct by isomerization 7-keto-9: 11 dihydroxy steroids or with an inorganic acid in a medium containing a substantial amount of water in order to hydrolyze the oxido group, whereby 7 8:9: 11-tetrahydroxy-steroids are formed and, if desired, these compounds are treated with an acidic agent of the Lewis type in an anhydrous medium whereby 7-keto9:'11-dihydroxy-steroids are formed. The direct conversion of the starting materials mentioned to 7-keto-9: 11-dihydroxysteroids is effected by means of acidic agents of the type known as Lewis acids, which includes e g inorganic acids as well as compounds which do not have a hydrogen atom replaceable by a metallic ion, e g boron trifluoride or zinc chloride, preferably used in an anhydrous organic solvent These Lewis acids are preferably used in an anhydrous medium, but if inorganic acids, such as hydrobromic acid of high concentration are used, small amounts of water relative to the amount of acid present do not alter the course of the reaction It is of advantage to use concentrated hydrobromic acid in glacial acetic acid as the acidic agent of the Lewis type. If however a substantial amount of water relative to the amount of acidic agent is present in the reaction mixture a 7:11dihydroxy-8:9-oxido steroid is hydrolyzed to the 7: 8:9: 11 tetrahydroxy compound In this case dilute inorganic acids are especially suitable, e g dilute sulphuric acid in an organic solvent The tetrahydroxy compounds can then be dehydrated by the same acidic agents and under the same reaction conditions used for the direct conversion into 7-keto9: 11-dihydroxy steroids to yield the same

compounds. The 7:11 dihydroxy-8: 9 oxido-steroids used as starting materials in the present case, belong to the cyclopentanopolyhydrophenanthrene series Especial importance is attached to the derivatives of ergostane, cholestane, coprostane, sitostane, stigmastane, spirostane, cholane, allocholane, pregnane, androstane and aetiocholane In addition, the starting materials may be substituted in the nucleus or in the side chain, for example in 3, 5, 6, 17, 20and/or 21-position, by free or functionally converted hydroxyl groups or oxo groups, such as acyloxy groups, for example acetoxy, propionyloxy, benzoyloxy or tosyloxy groups, by alkoxy groups, for example methoxy or ethoxy groups, by acetalized oxo groups, by free or functionally converted carboxyl groups, such as nitrile or esterified carboxyl groups or a lactone group, for example butenolide group The starting materials may have any desired configurations and can also contain double bonds, as for example in 5: 6 or 22:23-position. The starting materials of the present application are easily available by treatment of AS:9-unsaturated steroids, which contain in the positions 7 and 11 free or functionally converted hydroxyl groups, with oxidizing agents, as for example chromium trioxide or organic or inorganic peracids. The products of this invention are intended for therapeutic application or for use as intermediate products for the manufacture of therapeutically useful compounds. The following Examples illustrate the invention, the relation between part by weight and part by volume being the same as that between the gram and the cubic centimetre: EXAMPLE 1. 1.1 parts by weight of A 22:23-3 j 3-acetoxy7:11-dihydroxy-8:9-oxido-ergostene are dissolved in a mixture of 80 parts by volume of glacial acetic acid and 80 parts by volume of dioxane and treated with 0 3 part by volume of 2 N-sulphuric acid The solution is maintained for 16 hours at 20 C and then diluted with a large quantity of ether The ethereal layer is washed four times with water, sodium bicarbonate solution and water, dried and evaporated The residue yields from acetonehexane, followed by recrystallization from methanol-water, pure A 22:23-313-acetoxy-7: 8: 9: '11-tetrahydroxy-ergostene of m p 250252 C (l-lD = + 8 in chloroform); yield 90 per cent. The A 22:23 _ 38 acetoxy-7: 11 dihydroxy8: 9-oxido-ergostene used as starting material, can be prepared as follows: 70 parts by weight of S 8:9; 22:23-3 Jf-acetoxy7: ll 1-dihydroxy-ergostadiene are dissolved in 800 parts by volume of pure dioxane and treated with 67 parts by volume of ethereal monoperphthialic acid containing, per part by 75

volume, 0 051 part by weight of active oxygen, The reaction solution is maintained for 38 hours at 20 C in the dark and then diluted with ether, the ethereal solution washed with water, sodium bicarbonate solution and again 80 with water, dried and evaporated The residue yields from methanol-water 4 1 parts by weight of A 22:23-33-acetoxy-7: ll-dihydroxy8:9-oxido-ergostene in the form of fine needles which melt at 147-148 C (loil,= 85 + 15 5 in chloroform). /A 22:23-3,3-acetoxy _ 7: 11 dihydroxy-8: 9oxido-ergostene can also be prepared by treating _A 8:9; 22:2 _ 3-3-acetoxy _ 7: 11 dihydroxyergostadiene in glacial acetic acid solution 90 carefully with the quantity of chromium trioxide corresponding to one equivalent. EXAMPLE 2. 3 parts by weight of -A 22:23-3 -acetoxy7:11-dihydroxy-8:9-oxido-ergostene are dis 95 solved in 300 parts by volume of absolute benzene, treated with 10 parts by volume of boron trifluoride-ether complex and the whole maintained for two hours at 20 C After standing for a short time, well formed leaflets 100 separate from the solution For working up, the solution is diluted with ether, washed with water, sodium bicarbonate solution and water, dried and evaporated The residue yields from methanol-water 2 5 parts by weight of 105 A 22:23-313-acetoxy 7 keto-9: ll-dihydroxyergostene of m p 269 C (lal,=-62 in chloroform). The semicarbazone of this compound melts at 247-249 C with decomposition 110 The A 22:23-3 '3:11 diacetoxy 7 keto-9hydroxy-ergostene, obtained by acetylation with acetic anhydride in pyridine, melts at 191 C; lcl,=-45 (in chloroform). EXAMPLE 3 115 3 parts by weight of A 22:23-38-acetoxy7: 1-dihydroxy-8: 9-oxido-ergostene are dissolved in 800 parts by volume of glacial acetic acid and maintained together with 100 parts by volume of 2 N-sulphuric acid for 16 hours 120 at 20 C, then for one hour at 40 C The customary working up of the reaction mixture yields 2 parts by weight of the A 22:2333 acetoxy-7-keto 9:11 dihydroxyergostene, described in Example 2, of m p 269 C 125 This substance can be converted into the A 8:9; 22:23 _ 38: 11 dihydroxy 7-keto-ergostadiene, advantageously in the following manner: 0.5 part by weight of -a 2:23-3:-acetoxy 130 785,018 7: 11-dihydroxy-8: 9-oxido-androstane is dissolved in 40 parts by volume of absolute benzene, treated with 0 1 part by volume of boron trifluoride-ether complex and the whole allowed to stand for 4 hours at room tempera 70 ture The yellow solution is diluted with 50 parts by volume of chloroform and washed with water, sodium bicarbonate solution and water, dried and evaporated The solid residue ( 0 58 part

by weight) is recrystallized from 75 methanol The 3 P: 17,/-diacetoxy-7-keto-9: 11dihydroxy-androstane is obtained of m p. 267 5-268 C; lal, =-75 in chloroform. The substance exhibits in the ultra-violet spectrum a wide maximum at 285 my, log e = 80 1.52. It can be converted into the A 8:9-3:'1 lla: 17,3-trihydroxy-7-keto-androstene as follows: 0.37 part by weight of 3 P: 17,8-diacetoxy7-keto-9: ll 1-dihydroxy-androstane is dissolved 85 in 30 parts by volume of dioxane, treated with a solution of 0 75 part by weight of potassium hydroxide in 15 parts by volume of water and the whole heated for 6 hours with stirring to C After cooling, acidification is carried 90 out with 1 part by volume of glacial acetic acid and the reaction solution is evaporated under vacuum to dryness The residue is subjected to grinding with 5 parts by volume of water The insoluble material is then filtered off and 95 washed with a little water After recrystallization from a mixture of methanol and water, the filter residue yields A 8:9-3 f:'11 a: 1713trihydroxy-7-keto-androstene of m p 2632670 C; lalD=,-25 in alcohol The sub 100 stance exhibits in the ultra-violet absorption spectrum a maximum at 254 my; log e= 3 99. Acetylation with pyridine and acetic anhydride leads to A 8 s:9-3 p: 11 a: 17,-triacetoxy-7-keto-androstene of m p 143-145 105 C.; absorption maximum at 252 my; log e= 4.02. The 3 P: '17 f-diacetoxy-7: ll 1-dihydroxy8: 9-oxidoandrostane used as starting material can be prepared as follows: 110 0.81 part by weight of A 8:9-3 f 3: 17/fdiacetoxy-7:11-dihydroxy-androstene is dissolved in 40 parts by volume of absolute dioxane and treated with 4 25 parts by volume of an ethereal solution of monoperphthalic acid 115 containing 0 0347 part by weight of active oxygen per part by volume and the whole allowed to stand for 5 days in the dark at + 3 C Dilution is then carried out with 100 parts by volume of chloroform, followed by washing 120 with 0 25-normal sodium bicarbonate solution and water, drying and evaporating under vacuum 0 88 part by weight is obtained of an oily residue which, on grinding with ether, crystallizes It is the crude 313: 17,-diacetoxy 125 7: 11-dihydroxy-8: 9-oxido-androstane which can be recrystallized from ether The pure substance melts at 186-187 C; lcl= + 10 in chloroform.

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* 5.8.23.4; 93p

* GB785019 (A)

Description: GB785019 (A) ? 1957-10-23

Improvements in or relating to smoke observation apparatus


PATENT SPECTIFICATION Inventor: JOHN MARTIN STRANG 785 O 19 Date of filing Complete Specification (under Section 3 ( 3) of the Patents Act, 1949)Jan 28, 1954. Application Date Feb19, 1953 No 4636/53. Application Date Dec21, 1953 No 35436/53. Complete Specification Published Oct 23, 1957. Index at acceptance: -Classes 51 ( 1), B 19 A; and 97 ( 3), Z 3. International Classification: -GO In. COMPLETE SPECIFICATION Improvements in or relating to We, BARR & STROUD LIMITED, a British company, of Caxton Street, Anniesland, Glasgow, W 3, Great Britain, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement: The present invention relates to smoke observation apparatus for use with smokestacks or other smoke-outlet conduits; it is especially suitable for observing the outflow of smoke from furnaces in steam boilers and the like The term "smoke" is intended to embrace visible gases, for example, exhaust gases from internal combustion engines. It is convenient to control combustion, cspecially in furnaces, by observing the quantity and quality of smoke emitted thereby, and the invention is particularly adapted for this purpose. According to the invention we provide smoke observation apparatus comprising a conduit for the smoke, a light source adapted to direct light beam through the smoke flow in said conduit, a screen, and means for intercepting said beam after passage through the smoke to focus an image of the smoke on said screen, said screen being formed of a

lightdispersive material so as to be capable of being viewed over a wide angle. Preferably said screen is spaced laterally from said beam and said intercepting means also includes means for reflecting the beam towards said screen. Preferably also, said intercepting means includes a focussing lens and the reflecting means comprises mirrors, said lens and mirrors being located in a casing formed with upper and lower extensions, the mirrors being at the extensions and the lens between the mirrors, the upper extension is united with the smoke conduit at an aperture formed therein, while the second extension carries the viewing screen. The light beam inlet and outlet to and from the conduit may comprise apertures in the lPnr/cg's 6 d l: Smoke Observation Apparatus conduit wall, said apertures being sealed by optical components of heat-toughened glass. According to the invention we also provide for observing a flow of smoke, apparatus comprising a source of light, means for directing a beam of light from said light source and through said smoke flow, means adapted to be positioned to receive and to deflect said beam after passage through the smoke, a screen, and means for intercepting the deflected beam and focussing an image of the smoke on said screen, said screen being formed of a light-dispersive material so as to be capable of being viewed over a wide angle. Furthermore, the apparatus may include auxiliary illumination means of known or easily determinable value at said screen and which is not substantially affected by the smoke, whereby a standard of illumination is provided for purpose of comparison with the smoke influenced light beam on the screen. Said auxiliary illumination means may comprise an auxiliary light beam directed on to said screen and independent of the light beam affected by the smoke; said auxiliary light beam may be adjustable in intensity Alternatively, a series of light filters of different densities may be provided at said screen and adapted to intercept the smoke-influenced beam. Embodiments of the invention will now be described by way of example, with reference to the drawings accompanying the provisional specifications wherein:- Fig 1 shows a fragmentary view of the smoke observation apparatus according to the invention, the smoke conduit being the uptake of an oil-fired boiler; Figs 2 and 3 are views of sections on the lines II-II and III-III respectively of Fig. 1; and Figs 4 and 5 are views of details of Fig 1 in the directions X and Y respectively; Fig 6 is a front elevation of a modified viewing screen; Fig 7 is a vertical section on the line Vi I-VII of Fig 6; Fig

8 is a section similar to Fig 7 but showing only a modified auxiliary illumination arrangement; Fig 9 is a front elevation of another modified viewing screen; Fig 10 is a fragmentary sectional view through the smoke flue or uptake showing the means for agitating the smoke flow. In the various figures, the same reference numerals indicate similar parts. Referring to Figs 1 to 5 of the drawings, an uptake 6 of an oil-fired boiler includes smoke observation apparatus comprising a horizontal lamp unit 7 which projects a beam of light through an aperture 8 a in the wall of the uptake 6 through the smoke rising through the uptake, to a diametrally-opposed aperture 8 b and thence to an upper reflecting unit 9 The light beam thus forms an image of the smoke ascending the uptake 6 The light beam is reflected by the unit 9 down an intermediate upright tubular part 10 to a base reflector unit 11 which in turn transmits the image-forming beam outwardly to an upright viewing screen 12. A projector lens 13 is provided in the reflector unit 9, at the end adjacent the upright part 10, to focus the image on to the screen 12. The screen 12 is of light-dispersive or light scattering material, for example, of frosted glass or of a frosted plastic material, whereby a shadow-like image is formed on the screen, which image has a wide angular field of viewing That is to say the image on the screen 12 may be viewed by an observer from practically any position, in front of or on either side of or above or below the screen 12, at which he is able to see the viewing surface thereof In contradistinction, the image of an object reflected from an ordinary mirror can be seen only when the observer is in the relatively narrow path or channel in which the rays from the object are reflected by the mnrror. It is not always possible to position the controls for adjusting the combustion process, for example, the fuel jet controls, control valves and the like, so that they are readily accessible to the observer while standing direcdtly in line with the screen 12 Thus this wide angular field of viewing is very advantageous, since it enables said controls to be adjusted by an observer, while watching the screen 12, even if the controls are located on either side of the screen, for example, up to 6 feet on either side thereof. Thus the controls may be conveniently adjusted until the density of the smoke is gauged to be such that the optimum heating effect is being obtained from the fuel. The lamp unit 7 is in the form of a cylindrical casing whose longitudinal axis is perpendicular to that of the uptake. This casing comprises three main parts, a first part 14 a which is a sliding fit within the aperture Sa and is welded in place therein, a

second part 14 b extending outwardly from said first part 14 a and connected thereto by a bayonet connection 15 and fixable in position by a thumb screw 16, and a third part 14 c which closes the casing and carries a lamp socket 17 connected to a source of electrical supply by a cable 18 The closure part 14 c is clamped to the part 14 b by bolts at 19. A lamp 20 is located in the socket 17 and extends inwardly within the part 14 b Ventilation holes 21 are provided within the part 14 b to allow dissipation of the heat from the lamp 20 A hood 22 is provided, covering said ventilation holes 21 but spaced outwardly therefrom, to reduce access of dirt to the interior of the part 14 b A condenser lens 23, of heat-toughened glass, for example of "Pyrex" (Registered Trade Mark), is clamped to the inner end of the part 14 b by means of a sealing ring 23 a and bolts 24, thus sealing off the uptake 6 The lens 23 is of toughened glass to resist the high temperature of the combustion gases ascending the uptake The lens 23 projects the light from the lamp 20, in the form of a beam, through the aperture 8 a. A one way inlet 25 is provided in the part 14 a by means of which compressed air may be directed onto the uptake side of the lens 23 for cleaning purposes when necessary. Access may of course be made to said lens 23 by undoing the bayonet connection 15 and removing the interconnected parts 14 b and 14 c. A horizontal tubular light-receiving part 26 100 is welded within the aperture 8 b with its axis in alignment with that of the lamp unit 7. The upper reflecting unit 9 is connected at one end to said part 26 by means of internal and external mating screw threads 27, respec 105 tively, and a lock nut 28. The reflecting unit 9 is also connected to the upright part 10 by means of internal and external mating screw threads 29, respectively, and a lock nut 30 110 A reflecting mirror 31 is mounted in said unit 9 at 45 to the axes of the parts 10 and 26, to reflect light passing along one part down the other part. The mirror 31 is carried by a frame 32 and 115 is clampezd therein by bolts at 33 The frame 32 has a central spherical portion 32 a, and is carried by a cover plate 34 hinged at 35, and may be clamped in place by a clasp 36 and a locking thumb screw 37 120 The spherical part 32 a of the frame 32 engages in a complementary socket portion 34 a in the cover plate 34, and is held therein by a three-point adjustable suspension comprising a stud 38 connected to the spherical 125 part 32 a, passing through an enlarged port 39 in the socket portion 34 a, and terminating in a circular platform 40 carrying three peripherally-spaced thumb screws 41 which are normal to the surface of said platform 40 and 130 785,019 785,019 j are screwable downwardly onto the outer surface of the cover plate 34, whereby the plane of the

frame 32 and mirror 31 carried thereby may be adjusted relative to that of the cover plate 34. A sealing window 42 of heat-toughened glass, for example " Pyrex ", is provided at the reflector unit end of the part 26 and is supported by means of a holder 42 a which is hinged to the unit 9 at 43 and is clamped in position by means of a lever 44 and a cam 44 a, the latter being engageable in a groove 44 b in the holder 42 a. Again a one way inlet 45 may be provided on the uptake side of the window 42 for entry of compressed air for cleaning purposes. The projector lens 13 is carried by a holder 46 which is clamped to the lower end of the M O part 9 by bolts at 46 a. The base reflector unit 11 is screw connected to the upright part 10 in a similar manner to that of the upper unit 9, and carries a mirror 47 which is hinged and clamned thereto in an identical manner to that of the mirror 31 Thus the similar parts are denoted by the same reference numerals. The mirror 47 is at 450 to both the longitudinal axis of the upright part 10 and to the normal axis of the screen 12, while the screen 12 is supported by a holder 48 held vertically in place in an extension of the base unit 11 by brackets 49 and bolts 49 a. The reflecting surfaces of the mirrors 31 and 47 face towards one another and are parallel, thus forming intercepting and reflecting means of which the parts 9, 10 and 11 form the casing. The screen 12, may, if desired, be located at a position forward of that shown, the projector-lens 13 being designed accordingly. In use, the lamp 20 is switched on, and the observer views the smoke image on the screen 12; thus one can make the necessary adjustments to the combustion controls until the density and flow of the smoke is gauged to be of the desired order. During alignment of the apparatus, the parallel mirrors 31 and 47 are adjusted by means of the thumb screws 41 until the smoke image is positioned centrally of the viewing surface of the screen 12. The mirrors may be unclamped and hinged outwardly for cleaning purposes without disturbing the aforesaid adjustment. If the point of observation is in the same horizontal plane as the opposed apertures 8 a, 8 b in the uptake 6, the lens 13 and screen 12 may be positioned in alignment with the apertures 8 a, 8 b, the mirror system being in this case omitted. Referring to Figs 6 and 7, the arrangement is similar to that shown in Figs 1 and 5, the smoke-influenced light beam from the flue being reflected by a base reflector unit 11 having a mirror 47, and then forming the smoke-image on viewing screen 12. An auxiliary light source 50 has its beam directed by a casing 51 through a small auxiliary window 52 behind the screen, and 70 this

window thus illuminates the small part of the screen in front of it, independently or separately from the main screen 12 Light source 50 is energised through a manually adjustable rheostat 53 having an indicating 75 dial 54 In this way the light patch from the auxiliary window 52 can be varied until it balances the illumination of the smoke-influenced beam on the main screen, and the reading on the indicator 54 gives a quantitative 80 indication of the smoke intensity. In the modification shown in Fig 8 the arrangement is similar except that a filter disc is interposed in the beam from lamp 50 and is turnable about a pivot at its mid point 85 The filter is graded circurnferentially so that by turning it the illumination of the auxiliary window may be balanced with that of the main screen, and thus the position of the filter disc gives an indication of the smoke intensity 90 In Fig 9 a series of light filters arranged to form a ring on the main screen is indicated generally at 56, and comprises a series of sectors 1 8 forming light filters of graded densities adapted to intercept the 95 smoke-influenced light beam The density of the smoke can thus quickly be estimated by observing which sector or sectors is or are completely dark, and that of lowest density is a measure of the smoke density The lower ioo the density of the completely dark filter, the greater the density of the smoke. Referring to Fig 10, the flue 6 up which the smoke passes has the horizontal tubular part 26 welded into an aperture therein, and 105 the light beam-enters in the direction of arrow A, leaving in the direction of arrow B towards the screen 12 A jet of compressed air or gas is injected through pipe 57 from a pressure source, and this agitates the smoke flow in the 110 flue at the end of part 26, causing a swirling or turbulent motion thereof which thus makes it more easily visible on the screen.

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* GB785020 (A)

Description: GB785020 (A) ? 1957-10-23

Improvements in or relating to floor covering

Description of GB785020 (A) Translate this text into Tooltip



1 N 2 ' ab & PATENT SPECIFICATION 785020 Date of filing Complete Specification: Aug 12, 1954. Application Date: Aug 19, 1953. No 22841/53. Complete Specification Published: Oct 23, 1957. Index at acceptance:-Class 140, A( 2 M 5: 2 N 2: 2 N 3: 5 X: 7: 10 B 2: 10 B 3). International Classification:-B 29 d. COMPLETE SPECIFICATION Improvements in or relating to Floor Covering We, JOHN LEWIS, a British subject, of 28/30, Hythe Road, Willesden, London, N.W 10, and RUBBER IMPROVEMENT Li MITED a Company registered under the laws of Great Britain, of Rilex Works, London Road, Wellingborough, in the County of Northants, 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 floor covering. The invention consists of a floor covering of plastic or rubber having a cement applied to the base thereof the cement being protected by means of a readily removable sheet of polyvinyl chloride or its co-polymers applied over the cement layer. By cement is meant a substance of a tacky and adhesive nature such as used for sticking flooring sheeting or tiles to the sub-floor on which flooring is laid. The removable sheet of polyvinyl chloride or its co-polymers applied

over the cement layer will keep the cement applied on the covering material fresh and tacky, until such time as it is removed from the cement layer. In use the sub-floor on which the covering is to be laid is prepared and cement is applied thereto The removable sheet on the floor covering is then removed and the covering is laid in place. In actual manufacture the floor covering may be buffed so as to give a good anchor to the cement applied thereto The removable sheet can be applied to the floor covering on large surfaces and after its application the floor covering may then be cut up e g into tiles of smaller dimensions. Various modifications may be made within the scope of the invention.


* GB785021 (A)

Description: GB785021 (A) ? 1957-10-23

Improvements in or relating to electronic counting and selectingarrangements


PATENT SPECIFICATION 785021 Date of filing Complete Specification: Nov 29, 1954. Application Date: Sept 3, 1953. No 24351/53. Complete Specification Published: Oct 23, 1957. Indexatacceptance:-Classes 39 ( 1), D( 8:12 B 4:12 86:12 C: 38); 40 ( 4), A 7 J, t 1 U 3; and 103 ( 1), A( 1 C: 9 B: 9 X: 10 B: 10 F). International Classification:-GO 6 f H 01 j H 04 m. COMPLETE SPECIFICATION

Improvements in or relating to Electronic Counting and Selecting Arrangements W'e, ERICSSON TELEPHONES LIMITED, a British Company, of 22 Lincoln's Inn Fields, London, W C 2, and JOHN REGINALD ACTON, a British Subject, of Eriesson Telephone Works, Beeston, Nottingham, 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: Our invention relates to electronic counting and selecting;arrangements, and particularly to such arrangements which include a gaseous discharge tube of a type which contains a plurality of electrodes of one lkind and an electrode of another kind common thereto. In our United Kingdom Patent Specifications numbered 712,171 and 712,215 we described discharge tubes in which a plurality of cathode electrodes arranged a uniform distance iapart in la circular row are disposed equidistantly from a common anode electrode. It is a feature of such discharge tubes that a discharge between the anode and:a cathode electrode in a tube is caused to move from the,invested cathode to another cathode by way of two intervening oathodes when an electrical impulse of,suitable characteristics is applied to a circuit network in which the discharge tube is contained It is a charaoterisitic of such disclharge tubes and circuit networks that a pulse of electrical potential may be derived from a cathode when it is invested by the discharge Arrangements including such discharge tubes and circuit networks may be used to count 'a plurality of electrical impulses, or to select a pre-determined line or station in response to one or more applied impulses. It is one object of our invention to provide improved counting 'and computing arrangements, It is another object of our invention,to provide improved selecting and switching arrangements. Our present invention is in the nature of an improvement on the discharge tubes and counting and selecting arrangemaents described and depicted in the aforesaid United Kingdom Patent Specifications and provides means whereby the production of a discharge in a predetermined position in a discharge,tube mnay be adapted so provide a,conductive path between a selected pair of cathode electrodes, and thereby extend an electrical condition from one cathode electrode to another such electrode. According to our invention there is provided a cold-cathode gaseous discharge device comprising a gas-filled envelope, a common electrode mounted therein and presenting,a discharge surface, three sets of other electrodes mounted within said envelope and spaced from said discharge surface in succession along a closed path to present a

plurality ou discharge gaps between them and the said common electrode at spaced intervals along said path, the said three sets of electrodes being so arranged hat between adjacent electrodes of one set there are interposed in regular succession two electrodes -,one from each of the remaining two sets, commoning connections for separartely,connecting tthe electrodes of each of two said three sets, and 'connectons extending through the envelope whereby the said common electrode and the said three sets of electrodes may be connected respectively to sources of electrical potential, and in which the electrodes of a fourth set of other electrodes mounted within,the envelope concentrically with the three sets of other electrodes are adjacent to the electrodes ou one of the said three sets so that a discharge gap between an electrode in the s:aid fourth set of electrodes and the 'common electrode includes an electrode in the said one of the said three sets. Again according to our invention there is provided,an electronic counting or selecting arrangement including a gaseous discharge device, and comprising mneans for applying potentials derived from a direct-current source J to the electrodes in said device to cause a discharge to be produced between an electrode in a first set of electrodes and the common electrode and to cause a discharge glow of said discharge to invest concurrently an electrode in a second set of electrodes, means for applying pulses of potential in sequence to a third set and a fourth set of electrodes to cause said discharge glow to move to another electrade in the first set of electrodes by way of an electrode in the sa:id third and fourth sets of electrodes and to invest concurrently another electrode in the said second set of electrodes, and means for applying a potential to one of the glow invested electrodes to cause a change of potential thereat, in which a change of potential at one glow invested electrode is communicated automatically to the other concurrently invested electrode. Our invention will now be more fully described with reference to the accompanying drawings in which:Fig la shows in perspective a gaseous discharge tube with tvo concentric rings of electrodes around a common circular electrode. Fig lb shows a cross-section of tthe tube depicted in Fig la. Fig 2 a shows in perspective a gaseous discharge tube with one circular row of electrodes around a concentric common electrode. Fig 2 b shows a cross-section of the tube depicted in Fig 2 a. Fig 3 shows one form of selecting arrangement. Fig 4 shows another form of selecting arrangement. Fig 5 shows a form of counting arrangement. Fig 6 shows a switching arrangement. In the discharge tube depicted in Figs la and lb a central anode

electrode 1 is surrounded by forty cathode electrodes arranged in two circular rows each concentric with the disc shaped anode 1 To facilitate an understanding of the circuit arrangements and for the convenience of description we will term ten of the cathodes in such an electrode assembly the First guides, another ten will be termed Second guides, a further ten will be termed First cathodes, the remaining ten will be termed Second cathodes, and we will designate the said cathode electrodes FG 1 to FG 10, SG 1 to SG 10, F O to F 9 and SO to 59 respectively The First guides FG, Second guides SG anl First Cathodes F are arranged in a circular row some 12 0 millimetres in diameter around the anode 1 in the cyclic order First cathode F, First guide FG, Second guide SG, and are spaced a uniform distance apart equidistantly from the periphery of anode 1 in numerical sequence commencing First cathode FO, First guide FG 1, Second guide SG 1. The First cathodes F are spaced some thirty six degrees apart on radii from the centre of anode 1, and the Second cathodes S are arranged on the same or similarly spaced radii in a circular row some 14 0 millimetres in diameter around the row containing the First cathodes F with each Second cathode S adjoining a like numbered First cathode F 70 In the tube depicted in Fig la each First Cathode F O to F 9 is provided with a separate lead-out wire 2 which passes through the wall of a hollow cylindrical pinch 3 into the foot 4 of the cylindrical envelope 5, and thence 75 to a terminal 6 attached to an end ring 7 of insulating material fastened to the lower end of envelope 5 Each Second Cathode SO to 59 is also provided with a separate lead-out wire 8 which passes through the wall of a 80 hollow cylindrical pinch 9 into a foot 10 of envelope 5 and thence to a terminal 6 a fitted to an end ring 11 fastened to the upper end of the envelope 5 The First guides FG 1 to FG 10 are commoned together by means of a 85 ring member 12, formed from nickel sheet, which has ten equally spaced radial arms projecting from a central ring, and is connected by means of lead-out wire 2 to a terminal 6 in a similar mnanner to the First cathodes The 90 Second guides SG 1 to SGI O are commoned to ring member 13 and extended by way of a lead-out wi re 2 to on external terminal 6. The cathode electrodes in such an assembly consist of nickel wire rods some 0 4 milli 95 metres in diameter, and the anode electrode consists of a thin nickel disc some 10 0 millmetres in diameter A nickel rod 14 serves to extend the anode electrode 1 to a leadout wire which projects through the centre of 100 the circular foo t 3 and is cvnnected to one of the terminals 6 The component parts of the described electrode assembly are maintained in position with respect to each other by insulating discs 15, 16 and 17 which are 105 provided witih a central hole for' the anode rod 14 and one or more circular

rows of perforations through which the cathode electrodes pass Discs 15, 16, and 1 7 may be formed from mica or other suitable material 110 Fig lb shows a cross-section of the electrode assembly and illustrates the relationship between the concentric rings of cathode electrodes FO F 9/FG 1 FG 10/SG 1SG 10 and SO-59, and the anode electrode 1, 115 andl also shows the order in which the cathode eletro-des are arranged. The method of constructing the coldcathode discharge tube shown in Fig 2 of the accompanying drawings is similar to that de 120 scribed with reference to Fig 2 of the U K. Patent Specification Number 712,177 In such a tube a cylindrica I glass bulb 31 is attached at its lowver end to a circular glass base 32 and contains three _mica discs 35 spaced apart 125 and facing each other, part of each mica disc has been removed to clarify the illustration. Each disc 35 is pierced at the centre and has thirty six holes pierced 10 0 millinetres therefrom on radii spaced at intervals of ten 130 785,021 Idischarge The discharge with its integral, glow in such a discharge tube is caused to move from an invested cathode to an adjoining cathode when the potential at,the said adjoining cathode becomes some fifteen volts 70 more negative than the potential at the invested cathode. One form of selecting arrangement will now be described with reference to 'Fig 3 of the accompanying drawing, in this circuit a gase 75 ous discharge tube DTA has an electrode assembly comprising an anode, ten First athodes F designated F O to F 9 and ten Second cathodes S deslgnated SO to 59, of these electrodes only First cathodes F 0, Fl, 80 F 8 and F 9 land Second,cathodes SO 0, 51, 58 and 59 are shown and each such First cathode F and Second cathode S has separate means of access from the containing bulb The electrode assembly also contains ten First guide 85 electrodes FG designated FG 11 to F G 10, and ten Second guide electrodes SG designated SIG 1 to SG 10 respectively, one only such First guide FG land Second guide SG is shown as he guide eleotrodes in each group are con 90 nected together within the bulb and provided with a common lead-out wire Such a discharge tube is depicted and described with reference to Figs la and lb The anode of discharge tube DTA is connected by way of 95 a 330 K ohm resistor R 6 to the positive pole of a direct current supply from which a potential of the order of 600 volts may be derived; this direct current source is represented by battery symbol BA Each First cathode FO to 100 F 9 is connected to ia common lead at zero potential by way of a 100 K ohm resistor R 10 to R 19 respectively, and by way of separately operable switching means SW O to S'W 9 respectively to the positive pole of a direct 105 burrent source, represented by battery symbol BC, from

which a potential of the order of 108 volts may be derived The secdid-cathodes SO to 59 iare also connected tor the common lead at zero potential by way of 100 110 K resistors R 20 to R 29 respectively, and to an associated outgoing pulse lead SPO to SP 9 respectively The commoned First guide electrodes FG are connected to an incoming pulse lead Dl P by way of 270 KI ohm resistor 115 R 1, and to the zero common by way,of 330 K ohm resistor R 2. The Commoned Second guide electrodes SG are 'connected to the in'coming-pulse lead DP by way of two 47 K ohm resistors R 3 and 120 R 4, land to the zero potential common by way of 0 001 microfarad,capacitor C 2 The leads from the First guides FG and Second guides SG are biassed by a positive potential,of the order of nine volts, derived from a suitable 125 direct 'current source shown by battery BB, and are extended to a source of negative-going pulses by way of a 0 5 microfarad capacitor C 1 and lead DR. With diseharge tube DTA connected to the 130 degrees The anode 1, in the form of a thin nickel disc some 10 0 millimetres in diameter, is arranged six millimetres tabove the uppermost disc 35 and is attached to;that end of a nickel rod 37 which projects from a glass tube 3.6 The other end of rod 3,7 is welded,to a lead-out wire 33 of base pin 50 The glass tube 36 is fitted firmily within, and passes through, the central hole in each disc 35 and through the centre of ring members 43, 44 and SIC. The cathode electrodes F O ito F 8, SO to 58, F Gl to 'FG 9, and S Gl,to SG 9 consist of thirty six nickel rods each 0 4 millimetres in diameter; each such rod projects some six millimetres through a radially spaced hole in each disc 35 and the cathode discharge points are thus located in a circular row each equidistant from the anode 1. The thirty six cathode electrodes consists of nine First cathodes F O to F 8, nine Second cathodes SO to 58, nine First guides F Gl to FG 9, and nine Second guides SG 1 to SG 9. Each group of cathode electrodes is numbered in sequence in a cloclkwise direction as seen from the top of the tube The Firs t guides FG 1-FG 9 are welded to ring member 44, Second guides SG 1-SG 9 are welded to ring member 43, Second cathodes SO-SO are welded to ring memlber SC Each such ring member is formed from nickel sheet and has nine equally spaced radial arms projecting from a central ring part Each group of cormmoned cathode electrodes is connected ae the lead-out wire of an;associated pin in base 32, for example, ring member 43 and Second guides S Gl-SG 9 are connected to lead-out wire 40 and thence to base pin 38 Each First cathode FO to F 8 is wired directly to the lead-out wire of an associated base pin as shown, for example, by First cathode F 7 which is connercted by way of lead-out wire 49 to base pin 39 Anode 1 is connected by way of lead-out wire 33

to base pin 50 A suitable mounting for the described tube is provided by clip 51 part of which has been removed to clarify the illustration of the electrode assembly. Fig 2 b shows the cyclic order in which the groups of oathode electrodes are disposed arounad the common anode electrode. The characteristics of a cold cathode discharge tube with an electrode assembly of the type described wlth reference to Figs. la and lb, or to Figs 2 a and 2 b, are such that when the containing bulb, is filled with a gaseous mixture ef the order of 92 1 % neon, 7.0 %' hydrogen, and 0 9 % argon to 'a pressure equivalent to some fifty millimetres of mercury, and the tube is connected to a suitable direct-current source which produces a potential difference of the order of 200 volts between the anode and a cathode, a discharge is maintained between the said cathode and anode and the cathode is invested by a glow of the 785,021 described resistor/capacitor network and sources of potential a discharge will be produced between the anode and a First cathode F and,a discharge glow will invest the current carrying First cathode F It is a characteristic of such discharge,tubes that when connected to suitable direct current sources a discharge will be produced between the anode and the most negative cathode electrode, thus in the arrangement shown in Fig 3 a discharge glow may be caused to invest any selected First cathode F by operating ithe switching means SW of the remaining First cathodes F and so causing a potential derived from the positive pole of the direct-current source BC to be applied to the said First cathodes In these circumstances, with the First guides FG and Second guides SG connected to the positive pole of direct-current source BB the discharge glow will invest the selected First cathode F which is at the most negative potential. When a discharge has been produced on a selected First cathode F, for example First cathode F 0, the switching means SW 1 to SW 9 are returned to their unoperated condition but the glow continues to invest First cathode F 0. A discharge glow investing a cathode electrode in such a tube however is moved,to and invests an adjoining cathode when the potential at the said adjoining cathode is made some fifteen volts more negative than the potential at the invested cathode. When the incoming pulse lead DP is connected to a source of suitable 150 volt negative-going pulses of some 80 micro-seconds duration, the receipt of the initial pulse causes the potential at First guide FG 1 to become rapidly more negative than the potentials at the,adjoining First cathode F O and Second guide SG 10, and the discharge moves to and invests First guide FG 1 The second guides SG 1 SG 10 acquire 'a negative potential from the initial pulse more slowly, and after the

pulse of the First guides G-FG 1 FGO h 3 s passed its most negative value the potential at the Second guides becomes some 15 volts more negative than the potentials at the First guide FG 1 land First cathode F O In these circumstances conditions for the transfer of the discharge again prevail, and ithe discharge moves to and invests Second guide S Gl After the negative voltage pulse to the Second guides SG 1 to SG 10 passes its most negative value the potential thereat returns to a positive value in consequence of the positive potentfial derived from the biassing source of potential EB by way of resistor R 5, and the discharge moves to and invests the adjoining more negative First cathode Fl. Each subsequent pulse on lead DP passes by way of capacitor C 1, rand resisters R 1, R 2, R 3 and,R 4 to the commoned First guides FG and commoned Second guides SG{ and causes the discharge in the tube DTA to move from the First cathode F on which it is halted to the adjoining First guide FG, Second guide SG and First cathode F in that order, and to halt on the First cathode to which it has moved until a further pulse is received Such a tube will respond satisfactorily when the fre 70 quency at which the described negative-going pulses are applied does not exceed 1500 per second. With such an arrangement when the spacing between each pair of First and Second 75 cathodes, and the value of the resistors between the said cathodes and the common at zero potential are both suitable the discharge glow which is caused to invest a First cathode F tends to " divide," and in so doing to invest 80 both the First and Second cathode of a pair. This simultaneous investment of a pair of separate electrodes causes the discharge current through tube DTA to divide, and current flows both through resistor particular to the 85 First cathode F and through the resistor particular to the Second cathode S The proportion of ithe discharge current which flows through each electrode of an invested pair of First and Second cathodes and through their 90 associated resistors may be adjusted by modifying the value of the said resistors, or by biassing either electrode from a suitable source of potential Such current adjusting means affect the potential at each of the cathodes of a 95 pair when invested by a discharge glow. When ithe switching means associated with a First cathode F is unoperated, and when both the First cathode F and its associated Second cathode S are connected 'to zero poten 100 tial by resistors of substantially equal value as in the arrangement depicted in Fig 3, a substantially equal amount of current flows through each of the said resistors when a discharge gl'ow is caused 'to invest both of the 105 said cathodes simultaneously Such a flow of current through the resistor associated with the Second cathode S raises the positive

potential at both the First and Second Cathodes to substantially the same value, and develops a 110 positive potential at the associated outgoing pulse lead SP When the switching means SW associated with an invested First cathode F is operated the positive potential derived from source BC raises the value of the positive 115 potential at the invested First cathode F This has the effect of reducing the potential difference between the anode electrode and the First cathode F invested by the discharge, and in consequence reduces the value of the current 120 through the invested First cathode F and its associated resistor The increased positive potential at the First cathode F also tends to increase the proportion of the discharge current which flows through the invested Second 125 cathode S, and has the effect of raising the positive potential at both the Second cathode and the associated output lead SP This increase in the positive potential at the output lead SP is superimposed on the potential de 130 7 85,021 ' discharge to move to and invest each First cathode F O,to F 9 in turn and firnally to return to and halt on First 'cathode F 0, when in this position the associated switching means SW O are,operated following the previously described 70 praotice, and cause the device indicative of the number ten to be displayed. In another application of the arrangement shown in Fig 3 the:signli,' g devices associated with leads SP 0, S Pl to SP 8 and SP 9 75 are arranged to operate to a brief pulse of,the voltage derived from the operation of a switching device SW, and to remain operated in a display position until a release signal is given. With such an arrangement one or more switch 80 ing devices SW O so SW 9 are operated prior to the application of a train,of impulses to lead DP The movement of the discharge to each Fjirst cathode F O to F 9 in turn in response to 'a train 'of ten impulses will cause a signal 85 to be applied in ordered sequence to a selected number of output leads SPO to SFP 9 The transmission of such signals to a selected number of signalling devices may be;adapted to select,and signal a number in code form 90 For example, if the "lit" and "unlit" conditions of a visual signalling device be arranged to simulate the two digits 'of a binary code then upwards of a thousand different signals may be selected and sent by way of 95 the described tube with ten First cathodes and tea Second cathodes. In, the selecting arrangements shown in Fig. 4 a gaseous discharge tube DTC, of the type described with reference to Figs 2 a and 2 b, 100 has 'an electrode assembly consisting of an anode, nine First cathodes designated F O to F 8, each with sep:arate means of access from the containiing bulb, and nine Second cathodes designated SO to S,8 which are connected to 105 gether within the bulb and provided with a common lead-out;wire designated SC In addition the

electrode iassembly contains nine First guides designated FG 1 to FG 9, and nine Second guides designated SG 1 to SG 9; the 110 electrodes of each group of guides are connetared together within the bulb and are provided with,common lead-out wires FG and SG For convenience of drafting the symbols for First cathodes F 2 to F 6 and Second cath 115 odes 52 to 56 have not been shown, and each group FG and SG of guide electrodes is represented by a single symbol. The First 'cathodes F O to F 8 are connected to zero potential by way of resistors R 30 to 120 R 38 similarly to those in Fig 3,;and in addition are extended to outgoing pulse leads PPO to 'PP 8 respectively The commoned Second cathodes SO to,58 are oonneicted to, zero potential by a 100 l K ohm resistor R 7, and to the 125 moving contaat of switching means SW 10. The fixed contact of switching means:SW 10 is connected to a 108 volt direct-current source BC. The First guides FG and Second guides 130 rived from the investment of the associated Second cathode by the discharge. When 'a discharge glow invests a First cathode F and adjoining Second,cathode S the restoration of the associated switching means SW to an unoperated position reduces the positive potential at 'the First cathode F and tends to increase the current through it, this causes the positive potential at ithe Second cathode S to fall and terminates the described superimposed positive voltage pulse at the output lead SP The positive potential at ithe output lead S'P ceases when the discharge in the tube DTA is moved from the associated Second cathode S and adjoining First cathode F The application of a positive potential to a First cathode F which is not invested by a discharge glow has no effect on the potential at the associated Second cathode S. The basic selecting arrangement shown ain Fig 3 may be used in a variety of different ways in one of which, for example, each output lead SP is 'connected to a separate device adapted to respond,to positive potential of a particular vallue,,and not to respond to;a lower value of such potential Each such device is arranged on operation to provide 'a visual signal indicative of a particular number With output lead SPO' connected to a device indicative of the number ten, each,output lead S Pl to SP 9 connected to a device indicative of a digit one to, nine respectively, and the discharge glow in the tube DTA caused to invest First cathode FO land Second cathode 'SO 0, the receipt of a number of impulses indicative of the number it is 'desired to select will cause the discharge in tube DTA to move to a like numbered First cathode F O land also to invest the associated Second cathode SO Thus if it is desired to extend a signal to the device associated with Second 'cathode 58 and lead SP 8, a

train of eight impulses is passed by way of lead DP and the described guide electrode network to discharge tube DTA This impulse train causes the discharge to move to, invest, and halt on First cathode F 8 'and Second cathode S'8 With,the discharge halted on First cathode F 8 ithe 'operation of the associated switching means SW 8 raises the value of the positive potential at First cathode F 8 which increases the value of the positive potential at Second cathode 58 by some thirty volits in the manner described, and raises the value of the positive voltage pulse to the signalling device associated with lead SP 8 The increased value of the voltage applied to the signalling device is such as to cause it to respond and to provide the desired visual signal. After selecting and signalling the desired number the switching means SW 8 is returned to its unoperated condition, and the discharge is returned to its position at rest ion First cathode F O When it is desired to signal the number ten, a train of ten impulses causes the 785,021 SG of tube DTC are connected to an impulse source and resist Lor/capacitor natworlk similar to those depicted and described with reference to tube DTA in Fig 3 Thus when the characteristics of tube DTC in Fig. 4 are similar to those of tube DTA in Fig. 3 the values of the components in the networks associated with tube DTC are similar to those in like positions with respect;to tube DTA in Fig 3. When discharge tube DTC is connected in the manner shown to a suitable source of potential, derived from a 600 volt directcurrent source BA, a discharge is produced in tube DTC between the anode and a First cathode F The cathode glow of the discharge which invests the said First cathode F tends to divide and to invest the Second cathode S associated therewith In so doing the discharge glow invests both First and Second cathodes F;and S concurrently Such an investing discharge glow is moved from the pair of First and Second cathodes F and S on which it is halted to an adjacent pair of First and Second cathodes F/S, by way of an intervening First guide FG and Second guide SG, when a suitable 150 volt negative going impulse is received on incoming pulse lead DP. The concurrent investment of a First cathode F and Second cathode S by a discharge glow causes a positive potential to boe produced on both cathodes, and when the value of theresistors by which they are connected to the zero potential common is substantially equal current of similar value flows through the said First and Second cathodes F and S, and the value of the positive potential at the said cathodes F and S is also equal With such an arrangement the value of the positive potential at an invested First cathode F is raised when the switching

means SW 10 are operated. The operation of these means SW 10 applies a positive potential of the order of 100 volts to the invested Second cathode S, this tends to reduce the current through the said Second cathode S and to increase the current through the invested First cathode F This in turn raises the potential at the said First cathode F by some thirty volts and increases the -value of the voltage pulse at the associated output lead PP The restoration of the switching means SW 10 to an unoperated condition reduces the positive potential at the invested Second cathode S, which causes the values of the potentials at the associated First cathode F and output lead PP to return to their prelvious value The subsequent movement of the discharge from the invested cathod es will cause the pulse of positive potential at the output lead PP to cease. With such an arrangement a discharge in a tube DTC is caused to move to and invest the First and Second cathodes F and S particular to a selected line by means of one or more impulses applied to pulse lead DP, and a pulse of positive potential is applied to the selected line on the operation of switching means SW 10 which cause the positive potential at a selected output lead PP to be raised. By way, of example, when the discharge 70 in the tube DTC is halted on First cathode F 0, output lead PP 7 is selected and a signal pulse is passed thereto by the application of a train of seven suitable negative-going pulses, to lead DP, and the subsequent operation 75 and release of switching means SW 10 Each pulse applied,to lead DP causes the discharge to move from the First and Second cathodes F and S on which it is halted, and to pass by way of the adjacent First guide and Second 80 guide in that order to an adjacent pair of First and Second cathodes A train of seven impulses wili thus cause the discharge to move from First cathode F 0, to halt on and invest First cathode F 7 and Second cathode S 7, and cause 85 a positive potential to be developed at PP 7. Switching means SW 10 are then, operated, and the positive potential derived from source BC raises the positive potential at Second cathode 57, which tends to reduce,the propor 90 tion' of discharge current which flows through the said cathode 57, and to increase the proportion of current which flows through First cathode F 7 This in turn causes the positive potential at First cathode F 7 to rise, and raise 95 the value of the positive potential at output lead PP 7 On restoration of switching means SW 10 to their unoperated condition the values of the potential at the First and Second cathodes F 7 and 57 and that at lead PP 7 return 100 to their previous value, and the superimposed pulse of positive potential at the selected lead PP is terminated This application of such a pulse to the selected lead PP 7

may be repeated if necessary, throughout the invest 105 ment of First and Second cathodes F 7 and 57 by the discharge, by subsequent operations of the switching means On completion of the signal pulses to the selected lead or line the discharge may be moved to select another lead 110 1 In this way a signal sending lead in the form of the discharge in a tube may be extended to a plurality of signal receiving leads in cyclic order, and at least one signal pulse of one order and any number or no signal 115 pulses of another order be passed to each s Ilgnal receiving lead in turn. The counting arrangements shown in Fig. resemble the arrangements shown in Fig 4, and differ in that the commoned Second cath 120 odes SC are connected to an outgoing lead OPC, and each First cathode FO to F 8 is provided with separate switching means SX O to SX 8 connected to a common source of direct current BC In this arrangement the value of 125 resistors R 1 to R 6 and R 40 to R 48, capacitors C 1 and C 2 and the sources of potential BA, BB and BC are similar to those in like positions in 'Figs 3 and 4, and the Second cathode SC resistor R 8 is of the order of 100 K ohms 130 785,021 785,021 Thus a discharge will be produced in discharge tube DTC, when it is connected in the manner shown to the sources of potential descrilbed previously, and the resultant discharge glow will invest a pair of First and Second cathodes F and S The potential at the Second cathode S invested by the discharge glow will produce a positive potential at output lead OPC. When the discharge in tube DTC is "driven" or caused,to move to and invest each pair of First and Second cathodes F and S in turn, by means of suitable 150 volt negative-going pulses applied to lead DP, a series of positive-going pulses of potential of one order is,applied ito lead O 1 P'C as the discharge invests in turn each Second cathode S The operation of any of the plurality of switching means SX O ito SX 8 causes the positive potential derived from direct-cunrent source BC to be applied to an associated First cathode F. The investment by a discharge of a First cathode F connected to operated:switching means SX, tends to reduce the proportion of discharge current carried by the First cathode F, and the positive potential at the associated Second cathode S and output lead OPC is raised This increase in the positive-potential at lead OPC forms a po sitive-going pulse of potential of a higher value than the previously described pulse at lead O'PC Such a pulse which we will term a signal pulse may be applied to suiable counting means of known type adapted not to respond to a potential of one order and to operate in response to a signal pulse of the described higher value. The basic circuit arrangements shown, in Fig 5 provide facilities whereby signals in the form of periodic applications of positivegoing

potential, applied to a discharge tube at random over a plurality of leads are transferred in a pre-determined sequence to an outgoing lead when a plurality of negative-going pulses of potential are applied to the said discharge tube By way of example, each switching means,SX O,to SX 8 may be formed by the contact of a relay or the like in a selecting switch or similar piece of app aratus in a telephone switching centre, and be operated throughout the period the apparatus is in use. Thus when the discharge in the tube DTC is caused to move periodically to each First cathode F O O-F 8 in cyclic order, and to invest concurrently each associated Second cathode SO58, the number of signal pulses applied to the outgoing pulse lead Og PC at each cyclic movement is indicative of the number of switches min use at each such time This arrangement may also be used in other counting arrangements in which the random operation of a switching means SX extends a pulse of potential to a First cathode F which is conveyed periodically to an output lead OP'C on the cyclic movement of the discharge. The arrangement shown in 'Fig 6 employs the type of discharge tube,described with reference to Figs la and lb and is similar to, that used in the arrangemient described with reference,to Fig 3 Each First cathlode F O to F 9, and each Second cathode SO to 59 is con 70 nected to the zero common by way of a resistor of the order of 100 K ohms and designated R 50 to R 59, and R 60 to R 69 respectively. Each First cathode F O to F 9 and Second cathode SO to 59 is also connected ito an output 75 lead APO to AP 9 and B'PO to B P 9 respectively. This basic,circuit arrangement may be used in a variety of different counting, selecting, and computing arrangements and the concur 80 rent investment of a pair of First and Second cathodes be used to produce a pulse of potential at one cathode of a pair when a suitable positive potential is applied to the other catrhode Such an arrangement may be used for 85 extending a pulse signal in one direction from a First cathode F to a Second cathode S and subsequently sending a pulse signal in the reverse direction during a signal period in which the discharge is halted on the said cath 90 odes By connecting one cathode of a First and Second caithode pair to the positive pole of a source of direct-current from which a potential of the order of 100 volts may be derived, a positive-going pulse of potential of 95 the order of 30 volts may ibe produced at the associated cathode. When used in switching arrangement the movement of the discharge to successive pairs of,cathodes, in response to a train of suitable 100 negative-going pulses, may be used to link each First cathode lead AP to,the associated Second cathode lead DP, and to extend a positive going pulse of potential to either lead As a selecting arrangement the

discharge 105 is caused to move to a predetermined pair of First and Second cathodes in response to one or more suitable impulses applied to line DP and thereby to link the selected pair of cathodes in such a manner 110 that a positive going pulse of potential may be passed between the cathodes in either direction In oneform of counting arrangement two or more cathodes of 'a like kind may be connected together to form one or mere groups 115 of cathodes of one kind, and each cyclic movement of the discharge in,the counting tube DTA be arranged to extend positive-going pulses of potential derived from ungrouped cathodes of another kind to one or more out 120 put leads each common to a group of cathodes. Thus when the potential at one of a pair of First and Second cathodes is made suitably more positive, and the said cathodes are invested by a discharge glow,,the potential 125 at the other cathode is also, caused to become more positve; in this way a change of potential at one cathode is communicated to the other cathode of a pair. Although our invention has been described 130 with reference to discharge tubes with nine and ten pairs of First and Second cathodes we do not confine it to discharge tubes with such pluralities of pairs of cathodes and may in other embodiments of our invention employ discharge tubes with either smaller or larger electrode assemblies. Other arrangements embodying our invention will become obvious after the basic circuit arrangements herein described are understood, and may be used to form electronic switches and selectors, electronic counters, aggregators and computers, and other such devices.


* GB785022 (A)

Description: GB785022 (A) ? 1957-10-23

Manufacture of cyclo-alkanone-oximes

Description of GB785022 (A) Translate this text into Tooltip



PATENT SPECIFICATION 785,022 Date of Application and filing Complete Specification Oct 23, 1953. No 29400/53. Application made in Germany on Oct 23, 1952. Complete Specification Published Oct 23, 1957. Index at Acceptance: -Class 2 ( 3), C 2 B 36. International Classification: -C 07 c. COMPLETE SPECIFICATION Manufacture of Cyclo-Alkanone-Oximes We, FARBWERKE HOECHST AKTIENGESELLSCHAFT vormals Meister Lucius & Bri Uning, a body corporate recognised under German law, of Frankfurt(M)-Hachst, 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: Various processes are already known for reducing secondary cycloaliphatic nitro-hydrocarbons, for example with stannous chloride or with hydroxylamine, or with hydrogen and a catalyst, so as to obtain cycloalkanone-oximes. The present invention is based on the observation that oximes are manufactured when salts, preferably the water-soluble salts, of secondary nitro-compounds of the cycloaliphatic series and salts of hydroxymethane sulphinic acid, for instance Na HSO 2 CHO 2 H O O, are brought together in an aqueous medium. It has furthermore been observed that reaction occurs in neutral to acid solution, but does not occur in an alkaline solution Since, on adding an acid to an aqueous solution of a salt of a nitro-cycloalkane in the presence of a salt of hydroxymethane sulphinic acid, the reaction make take place in different directions, exactly defined reaction conditions have to be observed The acid should preferably be introduced rapidly, and the temperature may be as high as 80 C, but it is advantageous to operate at a temperature between + 10 C and 300 C. The acid should preferably be added rapidly for the following reasons

The acid causes the liberation of the hydroxymethanesulphinic acid from its salt Rapid addition of the acid is advantageous in that it causes the freed acid to exert its reducing action immediately after its formation, spontaneous decomposition with formation of elementary sulphur being thus avoided In view of these statements those skilled in the art can easily determine the period, in each individual case, during which the acidification must take place. The reduction takes place only after addition of such a quantity of acid to the aqueous lPrice 3 s 6 d l alkaline mixture of solutions of the secondary nitro-cycloalkane salt and the salt of hydroxy 50 methane sulphinic acid that the solution shows a neutral to acid reaction This occurs as soon as the alkali of the alkaline nitro-cycloalkane solution has been neutralised and the pt-value has been adjusted to between 2 and 7 55 The ratio of the quantity of hydroxymethane sulphinic acid to nitro-cycloalkane suitably amounts to about to about 1 3 mol of reducing compound to 1 mol of the nitro compound 60 The reaction occurs very rapidly and is complete when stirring has been continued for to 60 minutes In worlding up, it should be noted, in order to avoid loss that the cycloalkanone-oximes have a better solubility in the 65 presence of the sulphur compounds than in pure water The process can be considerably improved by adding, before or after the introduction of the acid, a small quantity of hydroxylamine or of a salt thereof or of a mix 70 ture of compounds yielding hydroxylamine under the reaction conditions For example, a mixture of sodium nitrite and sodium bisulphite in aqueous solution may also be used, which, according to the so-called Raschig pro 75 cess, yields hydroxylamine sulphonates which themselves give rise to hydroxylamines 1/1 o to 1/4, mol of hydroxylamine is sufficient for 1 mol of the nitro-cycloalkane used. As starting materials may be used all the 80 cycloaliphatic secondary nitro-compounds, such as nitrocyclopentane, nitro-cyclohexane or the like All the water-soluble salts of hydroxymethane sulphinic acid, such as the alkali metal and ammonium salts, are suitable as reducing 85 components Among the alkali metal salts the sodium and potassium salts are particularly suitable. As cations of the nitro-cycloalklane salts the radicals named may also be used Finally, it 90 is also possible to use instead of the watersoluble salts of the reaction components the water-insoluble salts in the form of their aqueous suspensions. The oximes obtained by the present process 95 are, in general, useful without any further treat785,022 ment for the great variety of applications of the oximes. The yields attained by the present process amount to about 85 per cent.

As acids which may be used for the acidification of the reaction mixture may be named the strong inorganic adcids, especially hydrochloric and sulphuric acids. It is also possible to mix at a low temperature the hydroxymethane-sulphinic acid salt and the acid to be added to the reaction mixture; the salt solution of nitro-cycloaliphatic hydrocarbon is then caused to run in Here again the object is to ensure that the sulphurcontaining acid set free does not undergo a decomposition with separation of sulphur, before it can exert its reducing action. The following example illustrates the invention, the parts being by weight unless otherwise stated and the relation between part by weight and part by volume being the same as that between the kilogram and the litre:EXAMPLE 1 A saturated aqueous solution of 200 parts of sodium hydroxymethane sulphinate is introduced at room temperature into a solution of parts of nitro-cyclohexane in 605 parts by volume of 2 5 N-sodium hydroxide solution. The mixture is stirred for 1 hour, 650 parts by volume of 2 N-hydrochloric acid are then rapidly added and stirring is continued for 1 hour After an adjustment to a hydrogen ion concentration corresponding to a p H-value of 6-7, the mixture is filtered with suction, the filtrate is extracted with ether, the ether is evaporated and finally the product is distilled under reduced pressure The yield amounts to 70 parts of cyclohexanone-oxime (= 65 per cent).


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