* GB786124 (A) Description: GB786124 (A) ? 1957-11-13 2:5-dioxopyrrolidine-4-propionic acid derivatives and process for preparing them Description of GB786124 (A) Translate this text into Tooltip [75][(1)__Select language] Translate this text into The EPO does not accept any responsibility for the accuracy of data and information originating from other authorities than the EPO; in particular, the EPO does not guarantee that they are complete, up-to-date or fit for specific purposes. PATENT SPECIFICATION 786324 ^ Date of Application and filing Complete Specification: Oct 19, 1955. No 29858155. Application made in United States of America on Nov 24, 1954. Complete Specification Published: Nov 13, 1957. Index at acceptance:-Class 2 ( 3), C 2 820, C 2 B 37 (C 1: I: L), C 3 A( 8: 14 C 3: 14 C 8 C: 16). International Classification:-CO 7 d. COMPLETE SPECIFICATION 2: 5-Dioxopyrrolidine-4-Propionic Acid Derivatives and process
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* GB786124 (A)
Description: GB786124 (A) ? 1957-11-13
2:5-dioxopyrrolidine-4-propionic acid derivatives and process for preparingthem
Description of GB786124 (A) Translate this text into Tooltip
[75][(1)__Select language] Translate this text into
The EPO does not accept any responsibility for the accuracy of data and information originating from other authorities than the EPO; in particular, the EPO does not guarantee that they are complete, up-to-date or fit for specific purposes.
PATENT SPECIFICATION 786324 ^ Date of Application and filing Complete Specification: Oct 19, 1955. No 29858155. Application made in United States of America on Nov 24, 1954. Complete Specification Published: Nov 13, 1957. Index at acceptance:-Class 2 ( 3), C 2 820, C 2 B 37 (C 1: I: L), C 3 A( 8: 14 C 3: 14 C 8 C: 16). International Classification:-CO 7 d. COMPLETE SPECIFICATION 2: 5-Dioxopyrrolidine-4-Propionic Acid Derivatives and process for preparing them We, MERCK & CO, INC, a corporation duly organised and existing under the laws of the State of New Jersey, United States of America, of Rahway, New Jersey, United States of America, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement: - This invention is concerned with novel pyrrolidine compounds and with processes for preparing them More particularly, it is concerned with 3,3-dimethyl-2,5-dioxo-pyrrolidine-4-propioni'c acids, to their esters, amides and lactones, and to processes for making these
compounds starting with 4-methylpentane1,3,4-tricarboxylic acid compounds These 3,3dimethyl-2,5-pyrrolidine propionic acid compounds and, in particular, the 3,3-dimethyl2,5 dioxo pyrrolidine 4 propionic lactones, esters and amides, have analgesic and antipyretic activity They are also valuable as intermediates in the preparation of the corresponding 3,3-dimethyl-4,5-dialkyl-dehydropyrrolidine-4-propion-amides utilizable as components of fermentation mediums in the mnicro-biological production of vitamin B,,. These novel 3,3-dimethyl-2,5-dioxo-pyrrolidine-4-propionic acid compounds may be chemically represented as follows: CH 3 H 0-01 3 o 7 p 3 =o R 1 where Y is CH 2 CH 2 COR'1 I. or R' is H or OH, and R' is OH, NHS or alkoxy. These 3,3-dimethyl-2,5-dioxo-pyrrolidine propionic acid compounds can be prepared by reacting a 4-methylpentane-1,3,4-tricarboxylic acid compound having free carboxyl groupings attached to the C-3 and C-4 carbon atoms (Compound 1 hereinbelow) with ammonium hydroxide and heating the resulting ammonium salt (Compound 2) to produce the corresponding 3,3 dimethyl 2,5 dioxo pyrrolidine4-propionic acid compound (Compound 3). 3 o 1 1 OOAH CO Compound 1 lPrice 3 s 6 d l cl H 3 Ha H 3 C-C-T Heat 41 coona COONH 4 Compoimd 2 where Y has the significance defined above. CH H 3 C C -y N H Combed 3 0 -1 ' L'n&n 2 o RI When Y stands for -G-HGCH 2 COR O in the above formula, R 1 being H and R being OH, the starting material, which is a known compound, can be represented by the following formula: Oe L H comi ccoia When Y stands for C O;H 20 H 20 CH 3 H 3 C-CH 3 jwr Compound 4 + X-CCCH 2 C Hj O RO C Oonom& 5 6,124 the starting material, 3-hydroxy-4-methylpentane-1,3,4-tricarboxylic acid lactone, can be prepared by reacting an alkyl isobutyrate (Compound 4 hereinbelow) as the alkali-metal enolate with a fl-carbalkoxypropionyl halide (Compound 5) in the presence of a strong enolizing agent to form a dialkyl 7,c -diinethyl1-oxoadipate (Compound 6) The latter compound is reacted with hydrogen cyanide to produce a dialkyl 3-cyano-3-hydroxy-4methylpentane-1,4-dicarboxylate (Compound 7) which is hydrolysed under acidic conditions thereby forming the desired 3-hydroxy-4methylpentane-1,3,4-tricarboxylic acid lactone (Compound 8) These reactions may be chemically represented as follows: OH cl 3 f 13 C C COCH 2 CH 2 COOR O 0 COR com-poud 6 0 CR O COOR c D 1 e 1 H,201 where R and R' represent alkyl groups, which may be the same as or different from each other. In accordance with this invention, the 4methylpentane-1,3,4-tricarboxylic acid compound is dissolved in
aqueous ammonium hydroxide solution containing preferably about one and less than two equivalents of aqueous ammonium hydroxide The solution is heated to remove water and the residual anhydrous ammonium salt is heated under reduced pressure to a temperature above about 150 C. thereby f Qrming the corresponding 3,3-dimethyl 2,5 dioxopyrrolidine 4 propionic acid compound which ordinarily distils at a temperature of about 165 C at a pressure of 1 mm of mercury The resulting oil can be crystallised from water or organic solvents. The 4 methylpentane 1,3,4 tricarboxylic acid starting materials in this procedure include 4-methylpentane-1,3,4-tricarboxylic acid, a 1-carboalkoxy-4 methylpentane-3,4dicarboxylic acid such as 1-carbomethoxy-4methylpentane-3,4-dicarboxylic acid, 1-carboCH-i cb 7 11H 3.C C CCH 2 C O Coon Gund 8 Comipound 8 ethoxy-4-methylpentane-3,4-dicarboxylic acid, 3 hydroxy 4 methylpentane 1,3,4tricarboxylic acid, a 1-carboalkoxy-3-hydroxy4-methylpentane-3,4-dicarboxylic acid such as 1 carbethoxy 3 hydroxy 4 methylpentane-3,4-dicarboxylic acid, 1-carbobutoxy3 hydroxy 4 methylpentane 3,4 dicarboxylic acid, and 3-hydroxy-4-methylpentane-1,3,4-tricarboxylic acid lactone In accordance with the foregoing procedure these starting materials are converted to the corresponding ammonium salts, which upon being heated under reduced pressure form the corresponding 3,3-dimethyl-2,5-dioxopyrrolidine4-propionic acid compounds for example 3,3dimethyl 2,5 dioxopyrrolidine 4 propionic acid, an alkyl 3,3-dimethyl-2,5-dioxopyrrolidine-4-propionate such as methyl 3,3dimethyl 2,5 dioxopyrrolidine 4 propionate, ethyl 3,3-dimethyl-2,5-dioxopyrrolidine-4-propionate, an alkyl 3,3-dimethyl-2,5dioxo 4 hydroxypyrrolidine 4 propionate, such as ethyl 3,3-dimethyl-2,5-dioxo4-hydroxypyrrolidine-4-propionate, butyl 3,3C tion mixture has remained at room temperature for about three hours, additional water is added, the resulting solution is heated under reflux to complete the hydrolysis reaction, and the resulting solution is evaporated substantially to dryness under reduced pressure The resulting crystalline residue is extracted with an organic solvent such as acetone, and the extracted material is crystallized from ether to give 3-hydroxy-4-methylpentane-1,3,4-tricarboxylic acid lactone which is obtained as a substantially pure crystalline material The corresponding acid, acid amide, and ester derivatives may be prepared from the lactone by methods known in the art, and used as starting materials in the process of the invention. The following examples illustrate methods of carrying rout the present invention, but it is to be understood that these examples are given for purpose of illustration and not of limitation.
EXAMPLE 1. 218 mg of 4-methylpentane-1,3,4-tricarboxylic acid is partially neutralized with one equivalent of aqueous ammonium hydroxide. The solution is evaporated to dryness and the residual ammonium salt is heated under reduced pressure An oil distils at about WC /1 mm This is dissolved in acetone, the solvent is evaporated, and the residual material is extracted with ether The ether is concentrated by distillation until crystals are obtained, m p 130-135 C Recrystallization from ether gives 3,3-dimethyl-2,5-dioxopyrrolidine-4-propionic acid melting at 140142 'C. dimethyl 2,5 dioxo 4 hydroxypyrrolidine-4-propionate, and 3,3-dimethyl-2,5dioxo-4-hydroxypyrrolidine-4-propionic acid lactone. The procedure for preparing the 3-hydroxy4-methylpentane-1,3,4-tricarboxylic acid starting materials is conducted as follows: -the alkyl isobutyrate such as methyl isobutyrate, ethyl isobutyrate, or butyl isobutyrate, in the form of its alkali-metal enolate is brought into intimate contact with a f 3-carboalkoxypropionyl halide such as 8-carbomethoxypropionyl chloride, ft-carbethoxypropionyl chloride, or fi-carbobutoxypropionyl bromide, is in solution in an organic solvent, preferably a dialkyl ether such as diethyl ether, in the presence of a strong enolizing agent, such as triphenylmethylsodium, preferably at a temperature within the range of about 20-30 C Under these conditions the reaction is ordinarily complete in about ten minutes, and the product is conveniently recovered from the reaction mixture by acidification, washing the mixture with a weakly alkaline solution and water to remove the by-product metal halide, and distillation under reduced pressure to recover the corresponding dialkyl aa-dimethylI?-oxoadipate such as dimethyl av,-dimethyl13-oxoadipate, methyl ethyl oi,a-dimethyl-/3oxoadipate, diethyl o,,-dimethyl-/,-oxoadipate, and ethyl propyl cz-dimethyl-B-oxoadipate. The reaction between the dialkyl ac,-dimethyl-,6-oxoadipate and the hydrogen cyanide is conveniently conducted by dissolving the adipic acid ester in anhydrous liquid hydrogen cyanide, cooling the resulting solution to a temperature of about 0 to 50 C and adding to the resulting solution a small quantity, e g. about 0 2 %, of a tertiary amine catalyst such as triethylaamine The resulting solution is maintained at a temperature of about 0 to 50 C. for a period of about two hours, at which time the reaction is substantially complete. The resulting solution is allowed to warm to a temperature of about 20 to 250 C; upon evaporation of the hydrogen cyanide there is obtained the corresponding dialkyl 3-cyano-3hydroxy 4 methylpentane 1,4
dicarboxylate such as dimethyl 3-cyano-3-hydroxy-4methylpentane-1,4-dicarboxylate, diethyl 3cyano 3 hydroxy 4 methylpentane 1,4dicarboxylate, methyl ethyl 3-cyano-3-hydroxy4-methylpentane-1,4-dicarboxylate, and dibutyl 3-cyano-3-hydroxy-4-methylpentane-1,4dicarboxylate. The dialkyl 3-cyano-3-hydroxy-4-methylpentane-1,4-dicarboxylate is not ordinarily isolated but, instead, the solution of this compound in liquid hydrogen cyanide is mixed with an excess of an aqueous mineral acid solution and the mixture allowed to warm to room temperature The hydrolysis reaction which occurs is exothermic and some cooling is necessary to maintain the temperature of the mixture below about 30 C After the reacEXAMPLE 2. 0.5 g of 3-hydroxy-4-methylpentane-1,3,4tricarboxylic acid lactone is dissolved in one 105 to two equivalents of aqueous ammonium hydroxide The solution is heated to remove the water The residual ammonium salt is then heated under reduced pressure A distillate is obtained at about 165 C /1 mm Crystalliza 110 tion from water gives 0 27 g of 3,3-dimethyl2,5 dioxo 4 hydroxypyrrolidine 4 propionic acid lactone melting at 152-153 C. Anal Calcd for CH,,0,N: C, 54 81; H, 5.62; N, 7 10; Found C, 54 60; H, 5 50; N, 115 7.21. The 3-hydroxy-4-methylpentane-1,3,4-tricarboxylic acid lactone used as starting material in this example can be prepared as follows: 120 (a) 2500 ml of an ethereal solution containing 170 g of triphenylmethylsodium is added to 77 g of ethyl isobutyrate After 30 minutes, the solution, which has become much lighter in colour, is added to 103 g of A 125 carbethoxypropionyl chloride in 1 5 1 of anhydrous ether The mixture is stirred in an atmosphere of nitrogen The rate of addition is regulated so that the ether does not reflux. After the addition has been completed the 130 786,124 mixture is stirred for an additional ten minutes The mixture is then concentrated by distillation to about 1 1 The residue is washed twice with 5 % acetic acid, twice with 10 % sodium bicarbonate solution and finally with water The ether solution is dried over magnesium sulphate The solution is then concentrated and cooled The triphenylmethane that separates is removed by filtration and washed with a small amount of cold ether. The filtrate is then concentrated and distilled under reduced pressure The portion distilling at 105-1380 C /3 5 mm is redistilled using a six-inch Vigreaux Column giving 41 g of diethyl aoc-dimethyl-8-oxoadipate, nj 3 '1 4353, which distils at 1160 C /2 mm. (b) 10 g of diethyl a,7-dimethyl-fl oxoadipate is added to 35 ml of anhydrous liquid hydrogen cyanide The solution is cooled in 201 an
ice-bath and 0 1 ml of triethylamine is added The solution is kept in an ice-bath for two hours and then allowed to warm to 20250 C for ten minutes The diethyl 3-cyano-3hydroxy 4 methylpentane 1,4 dicarboxylate can be recovered by evaporation of the hydrogen cyanide Instead of isolating the nitrile, however, the solution is hydrolyzed directly by the addition of 150 ml of hydrochloric acid (sp gr 1 19) and allowing it to warm to room temperature The reaction is exothermic and some cooling is necessary A precipitate separates After standing at room temperature for three hours, 150 ml of water is added and the solution heated under reflux overnight The solution is concentrated under reduced pressure Two portions of water are added and evaporated to remove most of the hydrochloric acid The crystalline residue is then extracted with three 200 ml portions of refiuxing acetone The filtrates are combined and evaporated leaving 9 0 g of an oil which solidifies This is extracted with three 500 ml. portions of refiuxing ether The ether extracts are combined, filtered, and concentrated by distillation to about 50 ml After cooling overnight at 00 C, the crystalline material is collected and purified by recrystallization to give substantially pure 3-hydroxy-4-imet hylpentane1,3,4-tricarboxylic acid lactone; m p 1661670 C. The corresponding amides can be made as in Example 1 or 2 by using the appropriate amide as starting material.
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* GB786125 (A)
Description: GB786125 (A) ? 1957-11-13
Improvements in and relating to guiding and control means for a lawn moweror other ground traversing machine
Description of GB786125 (A)
COMPLETE SPECIFICATION Improvements in and relating to Guiding and Control Mens for a Lawn Mower or other Ground Traversing Machine We, TORO MANUFACTURING CORPORATION a Corporation organised according to. the laws of the State of Minnesota, United States of lAmerica, of 3042 Snelling Avenue, Minneapolisolis, Minnesota, United States of America, do hereby declare the invention for which we pray that a patent may be granted to us, and the method by which it is to be performed/to be particularly described in and by the follow- ing statement: This invention relates to hand guided ground traversing machines. More particularly it relates to machines such as lawn mowers having guiding handles pivotally mounted thereon to permit adjustment of the angu- larity between the handle and the ground or machine and. the means for'adjusting the angulation of such handles. Even. more particu- larly, it relates to a guiding and driving assembly.adaptedto.besecuredtoand.readily removed from a ground traversing machine adlapted to be povwer driven. In. the manufacture of power-driven ground traversing machines such as lawn mowers it has been found desirable to provide a single unitary assemblv for guiding and power driving such machines, this assembly. to be adapted to be remoivably secured to a number of machines of different types and functions. In this manner a single engine which is a very substantialpartofthe cost of any such machines can suffice for a large number of different machines and thus a substantial savings may be effected. Use of such an assem- bly in. this manner, however, necessitates the transfer of the assembly, which is quite heavy because of the weight of the engine, and so it is important to facilitate the manual handling in. any way possible. It is also imperative that the assembly be capable of storage in. small compass and hence. the handle must swing-to substantially vertical storing position. The invention is directed toward overcoming these problems. According to the present invention a guid- ing and driving assembly adaptez tu be mounted upon a ground trqversing machine, said assembly comprises an adapter plate adapted to be secured to such a machine, an engine mounted on said adapter plate and adapted to be (connected in driving relation in the machine when said plate is so secured, guiding handle structure pivotallycon- nected with siad plate and extending upwardly therefrom and being adapted. to be Mded from an operative or guiding position into an inoperative or storing position, an arm having a forward portion disposed ahead of said guiding handle structure. and being con- nected to said engine and extending rearwardly therefrom, said arm having an arcuately formed rearward
portion extending through said guiding handle structure and so arranged that the latter can be connected to said curved portion at varying positions spaced lengthwise thereof to permit adjustment of said guiding handle to various guiding positions, said first mentioned portion of said arm being horizonifally disposed when said gmding handle structure is in sitoring posi- tion. to provide elective handle means. to facilitate manual carrying of the entire assembly. The invention also includes a ground traversing machine comprising a machine sup- porting frame having ground traversing supporting elements mounted thereon, an engine mounted on said frame and connected to the machine in driving relation, guiding handle structure pivotally connected wiith said frame and and extending upwardly therefrom and being adapted to be folded from an operative or guiding position into an, inoperative or stor- ing position, an arm having a forward portion disposed ahead of said guiding handle struciture and connected. to said engine and extendsing rearwardly therefrom, said arm having an arcuately curved portion extending irearwardly from said forward portion and through said guiding handle structure,. the latter being engageable with the said curved potion at posi tions spaced along the length of said curved portion to permit adjus. tment of said guiding handle structure to various angularly disposed positions relarve to said frame, said first men tioned portion of said arm being substantially horizontally disposed when said tguiding handle structure is in storing position to pro vide effective handle means to facilitate manual carrying of the entire machine. To enable the invention to be fully under stood it will now be described with reference to the accompanying drawings, in which :- Fig. 1 is a side elevation view of a wheel- type lawn mower with one embodiment of the invention being used thereon; Fig. 2 is a sideelevadonal view of the guid- ing and driving assembly removed from the lawn mower shown in Fig. 1 and with the guiding handle in folded storing position ; Fig. 3 is a rear elevational view of the guid ing handle structure of the assembly with the combined handle and adjusting axm extending therethrough ; Fig. 4 is a vertical sectional view taken along line 4-4 of Fig. I ;
Fig. 5 is a sectional view taken along line 5-5 of Fig. ; Fig. 6 is a side elevational view taken along line 6-6 of Fig. 2 with parts thereof broken away ; and Fig. 7 is a diagrammatic view showing the operative connections between the combined clutch and throttle control with the dutch and throt2le. One embodiment of the inventicn may include, as shown in Figs. 1-7, a lawn mowe indicated generally as M having a mounting plate 10 extending across the upper surface thereof adapted to engage an adapter plate 11 so as. to fixedly connect @ the two together in conventional manner. As shown, the adapter plate has an upwardly and forwardly extending lip lLa which coKperates with an overhanging lip at the front of the mower M as best shown in Fig. 1 to secure the forward end of the adapter plate. to the connecting plate 10. Suitable fastening means (not shown) is provided at the rear of. the connecting plate fto engage. the rear of the adapter plate 11 and removably secure. the same thereto. As shown, the mower M has ground wheels 12 which enable the mower M to traverse the ground. A gasoline motor or engine 13 is fixedly secured to the upper surface of the adapter plate 11 so that the mo, tor may be moved from machine ito machine for connection in power-driving relation therewith so long as each machine is provided with a connecting plate which will co-operate with the adapter plate 11 for se curingtheentire assembly shown in Fig. 2 and designated by the letter A. The guiding and driving assembly A, as shown, is provided with guiding handle struc- ture indicated generally by the letter H. This guiding handle structure has a lower part 14 and an upper part 15. The lover part 14 has laterally spaced side members 16 and 16a which are pivotally connected. to opposite sides of the adapter plate by pivot bolts 17. These pivot bolts enable the guiding structure H to be swung around the axis of these bolts so as . to extend at various angles. to the. adapter plate 11. Reference to Fig. 3 will show that the side members 16 and 1, converge upwardly and are connected by a connecting panel or plate 18. This plate 18 has a centrally disposed opening 19 formed therethrough and a latching dog 20 is secured to the plate immediately above the opening and extending downwardly a short distance to a point behind the opening. An M-shaped spring 21 is secured by its end portions to the laterally spaced side members 16 and 16a as best shown in Fig. 3 and
this spring, because of its shape and positioning, is constantly urged upwardly tocard a position above the opening 20. A vertically movable locking elemen, t 22 is mounted on the upper portions of the plate member 18 and extends downwardly a short distance therebehind. This locking element 22 is constantly urged downwardly in. to locking position by a spring member (not shown) and can be drawn upwardly by the user pulling on the knob 23. The upper ends of the converging side members 16. and 16c are connected by a pivot bolt 24 which carries a spacer sleeve 25 extending between the lower ends of converging side members 26 and 27 of the upper part 15 of the guiding handle structure. These converging side members 26 and 27 diverge at their medial portions and then turn upwardly and then converge again to form grip members 28 and 29. They are connected by connecting plate 30 at the area where they diverge and this connecting plate serves as a mounting for the combined throttle and cIutch control element to be hereinafter described. A metal plate 31 extends around the lower end portions of the side members 26 and 27 and connects the two. This plate has a recess 32 formed therein which is positioned so that the locking element 22 will snap into position thereinto behind the plate 31 and lock d e upper part 15 in position relative to the lower part 14 of the guiding handle structure H so. that the ane is substantially a continua! tion of the other. Of course, when the locking element 22 is released by pulling on the knob 23,. the upper part 15 of. the guiding handle structure may be folded downwardly to collapsed position as shown in Fig. 2. Mounted on the motor 13 is a bracket 33 and pivotally connected to this bracket by a pivot pin 34 is a combined carrying handle and adjusting arm indicated generally as C. This combined carrying handle and adjusting arm has a horizontally extending portion 35 which is encircled by a rubber sleeve 36 con toured ta Rt the band of the user. As best shown in Fig. 2 this horizontal portion is dis posed ahead of the guiding handle structure when the latter is in stored position. The re mainder of. the combined carrying handle and adjusting arm C is curved as best shown in Figs. 1 and 2, the radius of curvature being equal to the distance from. the pivot bolt 17. to the opening 19 in the plate or panel 1'8 which connects the side members 15 and 16. The rear portion 3, 7ofthiscombinedcarrying handle and adjusting arm C which is so curved extends through the opening 19 and in. co
operation with the spring member 21 and the larching dog 20 engages the same. The rear pordon 37 has a plurality of recesses 318 formed therein at various points along its upper surface so that the guiding handle struc- ture H may be moved. to any position beneath the sleeve 36 and the free end of the arm of the rear portion 3 : 7. It will be noted that the bracket 33 is positioned adjacent the rear of the mo. tor 13 so tlh t the carrying handle 36 is so positioned as to balance the entire assem- bly when it is lifted by. the carrying handle 36. Reference to. Fig. 3 will show that the M-shaped spring 21 engages the underside of the rear ponion 37 of the combined carrying handle and adjusting arm C No as. to urge. the arm upwardly sothat the latching dog 20 will engage the same in one of the recesses 38. Downward pressure upon the spring M will release. the combined carrying handle and ad justing ami C and permit it to move longi tudinally through the opening 20, to other ad justed positions. Mounted on the carrying handle structure and operatively connected to. the. hrrle and clutch of the motor 13 is a combined clutch and throttle control indicated generally as T. This combined clutch and throttle control in cludes, as shown, a jointed control rod having a lower portion 39 and an upper portion 40 pivotally connected as at 41. The upper portion 40 extends through the connect- ing plate 30 at the upper end of the guiding handle structure and a control knob 42 is secured thereto. The jointed control, rod is movable longitudinally and is Notable about its longitudinal axis. IA universal joint 43 is secured to the lower end of the lower portion 39 of. the jointed control arm and this universal joint is connected to a control shaft 44. Reference to Fig. 7 will dis close diagrammatically the manner of connec tion between. the control shaft 44 and the throttle 45 and clutch 46 of the motor.
Longitudinal movement of. the jointed control rod by pushing or pulling upon the control knob 42 win cause. the control shaft 44 to move longitudinally and thereby cause the con trol bracket 47 to pivot upon its pivot 4ES and move the movable portion 46a of the clutch member toward or away from the fixed portion 46b as the case may be, depending upon the direction of movement of the shaft 44. Rotation of the jo ! inted control rod. about its longitudinal axis. will cause the control shaft 44 to rotate about its longitudinal axis and. this will cause the controll bracker 49 to rotate therewith and move the throttle 45 between open and dosed position. s described xbriefly hereinbefore, it is a simple matter to adjust the guiding handle structure H by depressing the M-shaped spring 21. By so doing, the guiding handle H may. be swung to any desired angulation relative to the adapter plate 11 or. the mower It will be noted that the guiding handle s ! tructure H is collapsible and that when the knob 23 is pulled upwardly, the upper por- tion thereof may swing downwardly over the free end portion of the combined carrying handle and adjusting arm C, to stored position as shown in Fig. 2. When in this position, the entire assembly A is well balance and the user may carry the entire assembly from machine to machine by gripping the horizontal handle portion 36. It will be noted thalt the handle portion 36 remains horizontal regardless of the angulation of the guiding handle H so that the user always has a ready and convenient means for gripping the assembly A and moving it from machine to machine. If desired the combined carrying handle and adjusting arm C may be completely removed from the opening 19 and swung upwardly and rest upon the upper end of. the panel 18 to thereby place the assembly in smaller compass taken horizontally. It should also be noted that when the upper portion 15'oftheguidinghandleStructure H is swung downwardly @o collapsed positon, the combined clutch and throttle control also folds at a point adjacent the folding point of the carrying handle H'andtherefore'storage of the entire assembly in small compass is facilitated. Thus it can be seen that there is provided a simple and nexpensive guidling land driving assembly having a combined carrying handle land adjusting arm which makes it always convenient for manual movement of the assembly from machine to mchine. It will be appreciated, of course, that the combined carrying thandle and adjusting arm will aslo facilitate manual movement of entire units nhere the machine remains
attached tot eh adapter plate in the event such is desired.
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* GB786126 (A)
Description: GB786126 (A) ? 1957-11-13
Improvements in and relating to electric transformers provided withcylinder-windings
Description of GB786126 (A)
PATENT SPECIFICATION Date of Application and filing Complete Specification: Oct 28, 1955 J Application made in Netherlands on Nov 29, 1954. Complete Specification Published: Nov 13, 1957. Index at acceptance:-Class 38 ( 2), T( 1 F:7 C 1 A). International Classification:-H 021. COMPLETE SPECIFICATION Improvements in and relating to Electric Transformers provided with Cylinder-windings We, WILLEM SMIT & Co's TRANSFORMATORENFABRIEK N V, of 336, Groenestraat, Niimegen, The Netherlands, a Company organized under the Laws of The Netherlands, 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 invention relates to an electric transformer comprising two separate concentric windings (A and B), of which at least one (A) is a cylinder-winding consisting of a number (p) of branches connected in parallel, the layers of said cylinder-winding (A) firstly having equal numbers of turns, secondly consisting of conductors of equal thickness, thirdly being arranged in a number (n) of groups of p
successive layers each and fourthly being arranged in each group with the same pattern of radial distances between their conductors, each group of layers forming part of all parallel branches and the turns of each of said branches being positioned in said winding (A) in such a manner that the currents circulating through the branches of said winding only and generated therein as a result of the difference in spatial location thereof are reduced to nil. Such a cylinder-winding is obtained, when a stack of similar conductors, the number of which is equal to the number of parallel branches, is wound simultaneously to form a plurality of concentrically wound multiple layers of laterally adjacent composite turns. In that case each multiple layer of such a winding consists of a group of elementary windings, each of which will form part of an individual branch of the winding, when the conductors thereof are interconnected at their ends. Now, should the composite cylinder-winding be wound with respect to the stack of parallel conductors in the same way as a winding wound of a single conductor, in oplPrice 3/6 l 786,126 No 30954/55. eration the reactances of the parallel branches would differ from one another due to the fact that the branches of the winding would not be spatially located similarly in said winding Owing to these differences in 50 spatial location disturbing circulating currents would be produced in the composite cylinder-winding. In order to avoid these circulating currents it has already been proposed to group the 55 elementary turns of the branches of the composite winding in a special way therein. Examples of these known methods of grouping the turns are illustrated in Fig 1 and Fig 2 of the accompanying drawing 60 showing very diagrammatically an axial sectional view of one half only of two concentric transformer windings A and B In both examples there are interconnected within each group of elementary layers a predetermined 65 number of turns of a layer and an equal number of turns of each other layer The winding A illustrated in Fig 1 is a cylinder-winding and provided with three parallel branches accommodated in four groups of three layers 70 Therein one uninterrupted third part of a layer is connected to one third part of another layer and the latter part is connected to one third part of the remaining layer. Thus each branch of the winding is contained 75 through one continuous third part of the height of the winding in each of the three layers of a group In Fig 2 the cylinderwinding A consists of three groups of three layers and it is constructed in such a man 80 ner that in each group each branch is first contained through one sixth part of the height of the winding in one layer, then through one third part of
said height in another layer, thereupon through one third 85 part thereof in the remaining layer and finally again through one sixth part of said height in the first mentioned layer. It will be apparent that in the composite cylinder-winding A shown in Figs 1 and 2 90 Price 26 p 1 a G r 786,126 each branch thereof is linked with the same flux, so that the mentioned reactances will be equal The disadvantage of said known windings is that they consist of axially spaced portions and between said portions special connections are required Said windings require additional room in the axial direction and the special interconnections of the portions thereof interfere with the winding process and require more work. The invention has for its object to avoid the disadvantages of the known solutions of the problem in question and to provide cylin. der-windings of which, as in the known windings the parallel branches all add to the reactance to an equal extent, so that the circulating currents are reduced to nil, but in which the interconnections of the elementary layers are only situated at the ends of the winding This facilitates the provision of said interconnections and makes it possible to wind the layers without interruption. It has been found that in all transformercylinder-windings of the composite type referred to the conditions that the interconnections between the layers of turns are only situated at the ends of said layers and each of the parallel branches of the cylinder-winding in question adds to the total reactance of the transformer to the same extent are only fulfilled if, in accordance with the invention, in said winding firstly each branch consists of N complete layers connected in series, secondly the number N of groups is a 3 S whole multiple of the number p of branches and thirdly, when the layers are given consecutive reference numbers from 1 to np, inclusive, from the layer farthest from to the layer closest to the other winding (B), in each branch the sum of the reference numbets of all its first, second, last but one layers of n n the groups is equal to + -(n-I), p 2 n p_ + p N N n -(n-i) (p-i) + -(n-1), respec1 p 2 tively. An example of a cylinder-winding for a transformer and constructed in accordance with the invention is illustrated in Fig 3 of the accompanying drawing, in which the cylinder-winding A consists of two parallel branches, which lie in four groups of two layers each In this case n= 4 and pz= 2 A simplified diagram of the composite winding A and the interconnections of its layers is shown in Fig 4, in which the groups are illustrated one next to the other with their first layers uppermost and their second layers lowermost The reference numbers of the layers are 1, 2 8 Tile sum of the reference numbers of the first layers of a branch is 1 + 7 = 8 or 3 + 5 = 8, which comn N 65 plies with the condition -±(n-l) = 4 4 p 1 2 + 6 8 In this case the 1 _
first layer of a group is also the last but one 70 layer thereof. Due to its symmetric and cyclic nature the composite transformer-winding also complies with the conditions that therein firstly the number N of groups of layers is selected 75 with respect to the number p of parallel branches, in such a manner that the value n -(n-i) is a whole number, secondly the 2 80 layers of each branch are arranged in said winding in such a manner that each branch n n contains first layers second layers p p 85 n -last layers of groups and thirdly each p branch the sum of the reference numbers of n 90 all last layers of groups is equal to -(n 1). 2 Consequently, in the winding according to Figs 3 and 4 in each branch the sum of the reference numbers of the second or last 95 layers of groups contained therein is 2 + 8 = or 4 + 6 = 10 corresponding with the conn 4 dition -(n+l) =-( 4 + 1) 10 More1 (X n over the term n-1) = -(n-1) = 3 is a 2 p 4 whole number and both first layers and last n 4 ones of groups are = = 2 times conp: tained in each branch. The conditions as pointed out in accordance with the invention give the designer a 110 means for finding in a very simple way a solution of the problem of which number of layers the composite transformer-winding will have to consist and in which manner these layers will have to be distributed 115 among the parallel branches of said winding. Other cylinder-windings having a symmetric and cyclic nature and corresponding to all above mentioned conditions are, by way of example and in the diagrammatical 120 manner shown in Fig 4 illustrated in Figs. 6, 7, 8, 9, 10, 11, 12, 13. The cylinder-windings shown in Firs 5 6 and 7 have all eight groups and two parallel branches, so that N = 8 and p 2 The 125 same rules may be applied thereto. The windings according to Figs 8 and 9 are as far as their connections are concerned, reflected images of each other Therein n= 786,126 6 and p= 3. The windings illustrated in Figs 10 and 11 are provided with nine groups of layers and three parallel branches Consequently, 5therein n= 9 and p= 3 Also variations, e.g, the reflected image variations, of these windings are possible. Figs 12 and 13 show examples of windings, in which n= 8 and p= 4 Also in this case other ways of interconnecting the layers, e g, reflected image variations and cyclic variations of the connections, are possible. It will be apparent that still other values of N and p may be used The higher the value of N and p the more different interconnections of the
layers complying with the given conditions will be possible. Finally there exist asymmetric or acylic cylinder-windings having two parallel branches (p= 2), which correspond with the main conditions of the invention but in which the number (n) of the groups is 6, 10, 14, 18, etc, that means in which the conditions of n symmetry, according to which -(n-1) or 2 p n -(n-i) must be a whole number and each 4 of both branches contains as many first layers as second layers of groups are not complied with Examples of this type of winding are diagrammatically illustrated in Figs 14, 15, 16, 17, 18, 19, 20, 21, 22, 23. The cylinder-winding shown in Fig 14 has six groups (n = 6) and two branches (p= 2) Therein the sum of the reference numbers of all first or last but one layers (the uppermost series in Fig 14) of groups in a branch is equal to 1 + 3 + 5 + 9 = 18 or 7 + 11 = 18, which corresponds with the conn N N n ditions -±(n-l) or (p-l)-±(n-1) = p 2 p 2 n 2 = 36 = 18 However, this winding does 2 not fulfil the symmetry-condition, according to which the sum of the reference numbers of all second or last layers (the lowermost series in Fig 14) of groups in a branch must n N n be equal to 2-±(n-l) or -(n+ 1) This p 2 2 should have given a total amount of 21, whereas the sum of the reference numbers of the second layers of groups in one branch is 2 + 4 + 6 + 10 = 22 and that of the second layers of groups in the other branch is 8 + 12 = 20. The windings illustrated in Figs 15-23 are all variants of each other Therein n= 10 and p= 2, so that the sum of all first layers of groups in each branch must be equal to n 2 = = 50. It will be evident that all 2 2 diagrams shown in these figures comply with 70 this condition It appears from Figs 15-23 that when the value of N increases the number of possible variants increases considerably.
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* GB786127 (A)
Description: GB786127 (A) ? 1957-11-13
Removal of alkali metal catalyst residues from hydrocarbon polymers
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COMPLETE SPECIFICATION Removal of Alkali Metal Catalyst Residues from Hydrocarbon Polymers We, Esso RESEARCH AND ENGINEERING COMPANY, la Corporation duly organised and existing under the laws of the State of Delaware, United States of America, of Elizabeth, New Jersey, United States of America, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particulIarly described in and by the following statement: This invention relates to a method for the removal of catalyst residues from viscous hydrocarbon liquid polymers. The invention relaItels more particularly to the removal of a finely dispersed alkali metal catalyst residues from the reaction product obtained by the polymerization of an unsaturated hydro-carhon, particularly a conjugated diolelin such as 1,3-butadiene with or without other copolt- merizable monomers, e.g. vinyl aromatic hydrocarbons such as styrene or itis homo- logues. It is known to polymerize various unsaturated hydrocarbons such as olefins or diolefins in the presence of alkali metals or organic compounds thereof such as their alkyl derivatives 'to produce polymers of high molecular weight such as resins, rubbery materials, drying oils and the like. The products obtained by the above polymerization reactions contain the alkali metal or soluble forms thereof dispersed or dissolved therein and these must be removed prior to use in order to avoid the normal hazards due to the presence of free metal and to avoid the effects of alkalinity if the product comes into contact with water. Furthermore, the curing rates of rubber-like compounds are increased
by the presence of sodium or other alkali metal, and liquid polymeric drying oils are rendered cloudy and their use in coating compositions is hindered. The Specification of our Patent No. 704,607 describes a means for destroying sodium residues in drying oil copolymers of diolefins and ethylenically unsaturated monomers prepared using la sodium catalyst The destruction of the catalyst at the end of the polymerization is effected by the following sequence of processes : - addition of excess alcohol, cooling, neutralization with an anhydrous acid, and filtration width a filter acid such as silica gel, clay or charcoal. The specification of our Patent No 718,577 describes a means for destroying sodium residues in a synthetic drying oil which has been obtained by copolymerizing butadiene and styrene in the presence of a sodium catalyst. The destruction of the catalyst at the end of the polymerization is effected by the following sequence of processes : - the addition of excess acetic acid, neutralization of excess acetic acid with anhydrous ammonia, and filtration with a filter aid such as silica gel, clay, or charcoal. It has now been found that liquid poty- m;erization products obtained from unsaturated organic compounds by the use of alkali metal catalysts may be treated to remove the alkali metal catalyst by treating the liquid product with clays having l-25'% bound water content such as attapulgus clay, Super Filtrol, or used cracking catalysts, e.g. silica and/or alumina gels. The clays may be used alone or in combination with conventional filter aids. Filtrol is a registered trade mark. The present invention comprises a process for removing catalyst residues from an alkali metal catalyzed polymer or copolymer of a conjugated diolefin which comprises contacting said polymer or copolymer with clay containing 125 % by weight of bound water. The invention is particularly applicable to the purification of drying oils prepared by the polymerization ob butadiene or the copolymerization of butadiene-styrene mixtures. In accordance with this process 60 to 100 parts by weight of butadiene-1,3 are copolymerized with 0 to 40 parts by weigilt of a vinyl aromatic hydrocarbon, such las styrene, in the presence of 0.5 to 10 parts by weight (based on monomers) of an alkali metal catalyst, such as sc;lium; other alkali metals such as potassium, lithium, caesium or rubidium may be used. The polymerization is carried out in a reaction diluent at a temperature ranging from 25 to 105 C., preferably between 40 and 85"C., either batchwise or in a continuous process. Materials used as
diluents in the polymerizatioa are inert hydrocarbons which remain liquid under the reaction conditions employed. Diluents boiling between about - 15 and 2000Q are therefore suitable. The diluents are employed in amounts ranging from 50 to 500, preferably 200 to 300, parts per 100 parts of monomers. It is also desirable to employ about 1040 parts of an ether promoter per 100 parts of monomers. It is also possible to employ the ether as the sole diluent in the process in which case the larger quantities as described above are used. The use of the ethers are highly desirable since they improve the reproducibility of the process, shorten the initial induction period and are particularly effective in producing a substantially colorless product. Particularly suitable ethers are dioxane when a batch process is used and diethyl ether when a continuous process is used. However, the ethers may be used interchangeably in either of these methods. It is also desirable to include 1 to 35 parts by weight of an alcohol in the recipe ;to activate the catalyst Suitable alcohols include methanol, isopropanol, normal pentanol and the like. According to one embodiment of the invention, liquid products obtained by the above polymerization processes are passed Ithrough a filter or column containing clay such as atta- pulgus clay. According to another embodiment, the product is mixed with the clay by agitation, allowing sufficient time for neutralization of the catalyst, and the oil-clay mixture is filtered, e.g. -through a rotary-type filter. In still another embodiment the product is first filtered, settled or centrifuged to remove the bulk of the alkali metal catalyst, followed by percolation of the filtrate through a column packed with the clay. It is therefore one object of this invention to remove finely dispersed alkali metal catalyst residues from a hydrocarbon liquid polymer. It is another object of this invention to remove alkali metal alkyls and other similar highly reactive and soluble compounds of alkali metals from inert liquids. It is an important feature of this invention that a final product free from alkali metals can be obtained only by contacting the polymer oil with clay containing carefully constrolled amounts of water. The water content of the clay should be between 1 and 25 wt. P/o, preferably between 10 and 2o1 ,o, land should be firmly bound therein. If desired, the clay may be acid-treated but care must be taken during the subsequent drying step to avoid the loss of too much moisture, In general conventional oven drying for 16 hours at 1900F. is too drastic while air drying, even for as much as 100 hours, is satisfaotory. When acidtreated clay is used, the moisture content of the clay is
preferably not over 1.5 to 2%, otherwise 'the treated oil will have a yellow color. When low-moisture content clays are acid -treated and used in accordance with this invention, water-lvhite products large obtained. If desired, a two-stage process can be used wherein a clay having a moisture content of 10-25% can ba used in the first stage and the effluent from this stage can be percolated through an acid-treated clay of 1.5 to 2% water content. 1-25 wt. O of clay, based on polymer oil, is sufficient to completely neutralize ithe polymer oil. The present invention can be used to remove an alkali metal from any liquid which is inert with respect to the clay un;der the conditions of treatment. It has particular application to hydrocarbon solutions of polymers produced by the catalytic action of an alkali metal upon unsaturated hydrocarbons as discussed above. It applies particularly to treating hydrocarbon solutions of polymers made by polymerization in solution of conjugated diolefins, such as butadiene-1,3, isoprene, or 2,3-dimethyl-butadiene-1,3, either alone or in admixture with each other and/or with minor amounts of other monomers copolymerizable therewith such as myrcene, styrene, methyl styrene, vinyl naphthalene or the like EXAMPLE I A butadiene-styrene drying oil was prepared from the following charge: Pants Butadiene-1,3 80 Styrene 20 Varsol (b.p.150-200 C.) 200 Dioxane 40 Isopropanol 0.2 Sodium (10--15 microns) 1.5 (based on monomers) Temperature 50"C, A portion of the crude reaction product was centrifuged and filtered through fluted paper to give a water-white product free of any suspended material. A drop of phenolphthalein solution added to the filtered product gave an intense red color indicating residual alkalinity. Another portion of the crude product was filtered on a Buchner filter using attapulgus clay as a filter aid. The residue gave no reaction with water indicating neutralization of the catalyst The filtrate was water-white and gave no basic reaction when 'tested with phenolphthalein. EXAMPLE II One hundred grams of a 15t% sodium dispersion were added to 1000 grams of the crude polymer oil of Example I. After stirring the product was
filtered through a Buchner funnel using attapulgus clay. The filtrate was water-white and showed no alkalinity when treated with phenolphthalein. The filter cake gave no reaotion when treated with water. When the sodium dispersion in the polymer oil was added to the clay a temperature rise of about 25"F. was noted and gas was evolved. EXAMPLE III Twenty grams of a 15,% sodium dispersion were added to 300 grams of the crude polymer oil of Example I followed by the addition of 5 wt. % of attapulgus clay having a water content of about 20%. The mixture was stirred for about 10 minutes and a temperature rise of 22 F. was noted. The filtrate was water-white but basic to phenolphthalein. The filter cake gave no evidence of reaction with water. EXAMPLE IV Twenty grams of a 15,% sodium dispersion were added to 300 grams of the crude polymer oil of Example I followed by the addition of 3 wt. % of an acid-treated attapulgus clay which had been oven-dried for 16 hours at 190 C. A 3-4 F. temperature rise was noted on stirring The filtrate was water-white and basic to phenolphthalein. The filter cake reacted with water giving off la gas thus indictating the presence of unreacted sodium. Examples II to IV inclusive are comparative examples and are included to demonstrate the way in which various amounts of sodium catalyst may be removed from the polymers by 'the process of the present invention. The 15 % sodium dispersion used in these comparative examples approximates to the alkali metal catalyst residues remaining from the prepara Itive polymerization. The 15% sodium dispersion referred to in the comparative examples II to IV was pre- pare!d by heating Varsol and 15,% by weight of sodium above the melting point of sodium and rapidly stirring the heated mixture while cooling ,to a temperature below the Eolidifica- tion temperature of sodium so as to obtain sodium in a highly dispersed form i.e. particle sizes of the order of 10 to 50 microns. EXAMPLE V Various amounts of attapulgus clay and Filtrol D were added to samples of the polymer oil of Example I. The lattapulgus clay was used with and without acid treatment. The acid-treated clay was both lair-dried and ovendried. The suspension was stirred for 10-15 minutes and filtered 'through a Buchner funnel in the presence of a charcoal filter aid. The following results were obtained: Run Wt. % Filtrate No. Clay Wt. % 8160- Clay Added Treatment of Clay Volatile* Color Phenolphthalein 105 Attapulgus 1 No treatment 11-12 Water White Basic
105 Attapulgus 3 No treatment 11-12 Water White Basic 105 Attapulgus 5 No treatment 11-12 Water White Basic 105 Attapulgus 10 No treatment 11-12 Water White Basic 105 Attapulgus 20 No treatment 11-12 Water White Acid 106 Filtrol D 3 No treatment 19-20 Water White Basic 106 Filtrol D 5 No treatment 19-20 Water White Basic 106 Filtrol D 10 No treatment 19-20 Water White Basic 106 Filtrol D 20 No treatment 19-20 Water White Acid 107 Attapulgus 2 Oven dried 16 Hrs. @ 190 F. 1.5-2.0 Water White Basic 107 Clay Acid 5 Oven dried 16 Hrs. @ 190 F. 1.5-2.0 Water White Acid 107A Treated** 5 Air dried 16 Hrs. 49-50 Yellow Basic 107B 5 Air dried 40 Hrs. 35-36 Yellow Basic 107 5 Air dried 100 Hrs. 22-23 Yellow Basic * Wt. % loss on ignition 3 hours at 190 F. ** Aqueous solution of 10% H2SO4 acid added to the clay. Filtrol is a registered trade mark. Runs 107A and 107B are included for comparative purposes. The above results show that the acidity or basic of the filtered product can be varied by the amount of clay used and by the use of acid-treated clay. However, when acid-treated clay was used, the air-dried clay gave a yellow product. However, as shown, in Example IV, the acid-treated oven dried Iclay did not neutralize all of the sodium ,as indicated by the reaction of the residue with water or acetic acid. The data in Example III also show that 2-3 wt. % of clay is sufficient to neutralize each 1% sodium used in the synthesis step. For complete neutralization of all residual alkalinity, as much as 20% clay may be required; acidtreated clays are generally more efficient in this respect. What we claim is: - 1 A process for removing catalyst residues from an alkali metal catalysed polymer or copolymer of a conjugated diolefin which comprises contacting said polymer or copolymer with clay containing 1-25% by weight of bound water. 2. A process according to claim 1 in which the polymer or copolymer is filtered through the clay. 3. A process according to claims 1 and 2 in which the polymer or copolymer is first treated to remove at least a major proportion of the alkali metal and then percolated through the clay. 4. A process according to any of claims 1 to 3 in which the polymer or copolymer is first mixed with the clay and then filtered. 5. A process according to any of claims 1 to 4 in which the clay is acid-treated. 6. A process according to claim 5 in which The acid treated clay has. a moisture content of 1 to 2%. 7. A process according to any of claims 1 to 6 in which the conjugated olefin is butadiene.
8. A process according to any of claims 1 to 7 in which the alkali metal is sodium. 9. A process according to any of claims 1 to 8 in which the copolymer is a copolymer of butadiene and a vinyl aromatic hydrocarbon. 10. A process according to claim 9 in which the copolymer is obtained by the polymerization lof 60 to 100 parts by weight of butadiene and 0 to 40 parts by weight of styrene in the presence of 0.5 to 10 parts by weight of sodium. 11. A process according to any of claims 1 to 10 in which the copolymer is percolated in a first stage through a column of clay containing 10-25;% water and then passing the effluent from the said first stage through a column of acid-treated clay containing 1.52l% water. 12. A polymer or copolymer purified by the process according to any of claims 1 to 11. 13. A process for removing catalyst residues from an alkali metal catalysed polymer or copolymer of a conjugated diolefin and the polymer or copolymer so purified substantially as hereinbefore described with particular ref er- pence to examples I and V.
* GB786128 (A)
Description: GB786128 (A) ? 1957-11-13
New phenylalkylamines and process for their production
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COMPLET SPECIFICATION New Phenylalky ! ammes and process for their production
We, CHEMISCHE FABBIK PROMONTA GESELLSCHAFT MIT BESCHRANKTER HAFTUNG, a German Body Corporate, of Hammer Landstrasse 162-178, Hamburg 26, Germany, do hereby declare this 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 follow- ing statement :- This invention relates to new phenylalkyl- amines and a process for their production. The new phenylalkylamines of the present invention are those of the general formula: <img class="EMIRef" id="026415661-00010001" /> vsherein R represents a saturated or unsaturated aliphatic hydrocarbon group, or an alkoxy- alkyl, cyc70alkyl, aryl (preferably phenyl or naphthyl) cr aralkyl group, the aryl group and the aryl moeity of the aralkyl group being either unsubstituted or substituted by one or more halogen atoms or alky,, alkoxy or nitro groups, R, and R2 either each represent individual alkyl groups containing not more than 6 carbon atoms or together with the nitrogen atom to which they are attached collectively represent a mononuclear saturated heterocyclic group such as morpholina, piperidino or pyrrolidino, and n represents an integer greater than 1, preferably 2 or 3. These compound are therapeutically useful as local anaesthetics. The production of these new substances by methods generally employed for the preparation of ethers of compound containing an amino substituent involves unpleasant working conditions and results in poor yields. According to, a feature of the present invention the new phenylalkylamines of general formula I are prepared by a process which comprises reacting a phenylalkyl dicllloride cf the formula : <img class="EMIRef" id="026415661-00010002" /> (wherein n is as hereinbefore defined) with an alkali metal derivative of a compound containing a hydroxyl group, of the general formula : R O M (wherein R is as hereinbefore defined and M represents an alkali metal atom) and reacting the compound so obtained having the general formula : <img class="EMIRef" id="026415661-00010003" /> with an amine of the formula HNRlR2 (wherein Rl and R2 are as hereinbefore defined). The phenylalkyl dichloride of formula II may be prepared by chloromethyl- ating by loiown methods a phenylalkyl chloride of the general formula C6H5(CH2)nCl (wherein n is as he : reinbefcre defimed). By the expression"lrnown methods"as used herein and in the appended claims is meantg metlmods heretofore employed or described in the
chemical literatre. The alcoholate employed in the aforesaid process may be, for example, the sodium deriz vative of primary, secondary cx tertiary aliphatic, araliphatic or alkoxy substituted aliphatic alcohols, such as ethanol, isopropanol, tert-butyl alcohol, n-hexyl alcohol, n-octyl alcohol, benzyl alcohol and ethoxyethanol. Also unsaturated aliphatic alcools, such as allyl alcohol, and alcohols derived from cyclo- alkyl compound, such as cyclohexanol, may be employed. When the reactant R O M is a phenolate, the scdum derivative is preferably employed and the benzene nucleus may be substituted as aforesaid. By way of illustration, the sodium derivatives of the following phenolic compounds may be used in the process : phenol, p-nitrophenol, 2-chloro-, 4-chlorc-and 2: 4dichlorophenol, 2-bromo- and 4-bromophenol, 3-methyl-4-chlorophenol, 2-methyl-, 3-methyl- and 4-methylphenol, thymol and 3-metl1oxy- phenol; and in addition the sodium derivative of UB-naphthol. The following Examples in which the parts stated are parts by weight illustrate. the inveIl- tion. EXAMPLE I. 2.3 Parts of sodium are dissolved in 50 parts of methanol. After the addition of 9.4 parts of phenol, 23 parts of - (4-chlcrcmethyl- phenyl) ethyl chloride are added and the mixture is agitated under reflux at 60'C. for 24 hours. The methanol is then distilled off and the ss-(4-phenoxymethylphenyl)ethyl chloride formed) is obtained from the residue m a yield 75% of the theoretical. It boils at 159-171 C. under a pressure of 0.5 mm. Hg, and forms f colourless crystals melting at 49-50 C. when crystallised from petroleum-ether. 15 Parts of ?- (4-phaioxymethylphenyl)- ethyl chloride are heated under reflux at 125 C. for 24 hours with 43 parts of morpholine. The excess of morpholine is then distilled off, and the N-[ss-9-(4-phenoxymethylphenyl)ethyl]morpholine formed in a yield 80% of the theoretical is purified by way of its hydrochloride. It forms colourless crystals melting : at 91-92 C. when ciystallised from benzenepetroleum-ether. The ss-(4-chloromethylphenyl)ethyl chloride employed as starting material is prepared as fellows : A mixture of 703 parts rf -phenylethyl chloride, 75 parts of paraformaldehyde and 75 parts of anhydrous zinc chloride is v. moously agitated with heating at 50 C. for about 45 minutes. The reaction mixture is then cooled to 30 C. and rapidly saturated with dry hydrogenchloridewithviolentcentrifuging. The mixture is cool- ta ensure that the reaction temperature does nor
exce-d 45 C. After saturation, the reaction mixture, which is stirred, is allowed to cool hile a weak current of hydrogen chloride de is passed threugh it. The reaction mixture is then thoroughly shaken with petroleum-ether in a separating funnel and the aqueous phase is separated off. The petroleum-ether layer is washed successively with water, sodium bicarbonate solution and again with : water, and then dried over calcium chloride. The petroleum-ether is distilled cif and the residue is fractionated. In the firsr fraction, unchanged ! i-phenylethyl chloride is recevered, and in addition 326 parts of/ ?- (4- chloromethylphenyl) ethyl chloride, b. p. 158- 160 C./25 mm. Hg, are obtained. The yield is 75% of the theoretical calculated on the reacted 13-phenyleth-) rl chloride. EXAMPLE II. 2. 3 Parts of. sodium are dissolved. in 50 parts of absolute ethanol and 24 parts of ?-(4- chloromethylphenyl) propyl chloride are added. The mixture is then agitated under reflux for 8 hours at 809 G The precipitated sodium chloride is then filtered off employing a suction pump from the reacticn mixture, the excess of cthanol is removed and the residue is fractionated. y- (4-Ethexymethylphenyl)- propyl cMorideb. p. 172-173 C./20 mm. Hg, is obtained in a yield 93% ouf the theoretical. 10 Parts of y-(4-ethoxymethylphenyl) propyl chloride and 18 parts of mcxpholine are heated under reflux at 130'C. fcr 24 hours with occasional agitation. The reaction mixtura after cooling is mixed with an excess of hydrochloric acid and shaken once or twice with ether. The hydrochloric acid solution is made alkaline and the morpholine derivative containing portion is extracted and subjected to fractional distillation. N- [?-(4-Ethoxymethyl- phenyl) propyl]-mcrpholine, b. p. 16Z164 C./0. 4 mm. Hg, is obtained in a yield 79""D of the theoretical. The ?-(4-chlomethylphenyl)propyl chloride employed as starting material is prepared in a similar manner to that described in the preceding Example for lire preparation of. - (4- cbloromethylphenyl) eLhyl chloride. Thus, 389 parts of ?-(4-chloromethylphenyl)propyl chloride, b.p. 176-178 C./24 mm. Hg, are obtained by the acticn cf hydrogel, chloride on a mixture of 773 parts of y-phenylpropyi chloride, 75 parts of paraformaldehyde and 75 parts of anhydrous zinc chloride at 40 C. The yield is 80% of the theoretical, calculated on the reacted y-phenylprcpyi chloride. EXAMPLE III. 2. 3 Parts of sodium are dissolved with cooling in 100 parts of isopropanol and after the addition of 13 parts of o-chiorophenol the
reaction mixture is heated to 60 C. 23 Parts of ss-(4-chloromethylphenyl)ethylchloride are added dropwise with stirring over a period of 30 minutes, and the reaction mixture is then agitated under reflux for 24 hours after which it is treated as described in Example I t) give , ss(4-21-chlorophenoxymethylphenyl)ethyl chloride, b. p. 107-108 C./0. 4 mm. Hg. 18 Parts of ss-(4-21-chlorophenoxymethylphenyl) etlyl]-morpholine, being effected by way of ts bitartrate. It forms colourless crystals melting at 99-101 C. when crystallised from benzene-petroleum-edier. EXAMPLE IV. 64 Parts of dry sodium phenolate are dissolved in 300 parts of methylisobutyl ketone by heating at 110 C. 103 Parts of ?-(4- chloromethylphenyl)propyl chloride are added, dropwise with agitation, and the mixture is maintained at 110 C. fcr a period of 4 hours with constant agitation. After cooling, the reaction mixture is washed 2 or 3 times with 100 parts of water and the methylisobutyl betsne is distilled ofF under reduced pressure. The residue is taken up in 200 parts of pctroleum-ether and y- (4-phenoxymethyl- phenyl) propyl chloride is crystallised by addition of ice water. The crystals are filtered off employing a suction pump and dried at 100 C. in vacuo (10 mm. Hg) for 1 to 2 hours. The y- (4-phenoxymethylphenyl) propyl chloride melts at 55-56 C. after recrystallisation from petroleum-ether. 130 Parts of y 4-phenoxymethylphenyl)propyl chloride are heated under reflux at 140 C. for 24 hours with 130 parts of morpholine. The reaction mixture is treated as described in Example I to give N-[?-(4-phenoxymethyl phenyl) propyl]-morpholine, which fcms colourless crystals melting at 52-53 C. when crystallised from n-heptane. EXAMPLE V. 4.6 Parts of sodium are dissolved with cooling in 100 parts of methanol. After the intro duction of 28 parts of 4-nitrcphenol, 41 parts, of-y- (4-chloromethylphenyl) propyl chloride are added dropwise with stirring over a period of 1 hour to the reaction mixture heated to 75 C. and the mixture is agitated for a further 48 hours. After the methanol has been distilled off, th residue is extracted with ether, the ethereal layer is washed a number of times with 4% caustic soda solution and thereafter with water and dried over calcium chloride. The ether is then driven off and the residue fractionally distilled. The ?-(4-41-nitrophen- oxymethylphenyl) propyl chloride thus obtained boils at 238-23S C./0. 6 mm. Hg and melts at 70-71 C. when
crystallised from benzene- petroleum-ether. 31 Paris of y- (4-4-nitropheno. xymethyl- phenyl)propyl chloride are dissolved in 50 parts of benzene) and heated to 50 C. A solution of 17 parts of morpholine in 50 parts of benzeas is then added dropwise with agitation after which the reaction mixture is heated for 24 hours at 75 C. and forl a further 24 hours at boiling point. After cooling, the morpholine hydrochloride formed is filtered off, the reaction mixture is washed to free it from morpholine by shaking it with water and, thereafter N- ['y- (4-4-nitrophenc'xymethylpheByl)- propyl]-morpholine is extracted with 4% hydrochloric acid. The hydrochloric acid solution is mixed with an excess of ammonia, the morpholine derivative is extracted with ether and the ethereal layer is dried over potassium carbonate. On evaporatiioo of the ether, N- [y- (4-41-nitrophenoxymethylphenyl)propyl]morpholine remains in the form of colourless crystals, which melt at 9091 G after recrystallisation from benzene-petroleum-ether. EXAMPLE VI. 4.6 Parts of sodium are dissolved with cooling in 100 parts of ethanol. After the intro- duction of 26 parts of o-chlorophenol, 48 parts of ?-(4-chloromethylphenyl)propyl chloride are added dropwise to'the reaction mixture heated at 80 C., which is maintained with agitation for 8 hours at this temperature. The reaction mixture is treated as described in Example I to give y- (4-21-chlorophenoxymethylphenyl)- propyl chloride, b. p. 208209 C./0. 8 mm. Hg. 15 Parts of y-(4-21-chlorophenoxymethyl- phenyl) propyl chloride are heated at 140 C. for 24 hours with 17 parts of morpholine in 25 parts of toluene. After separation of the morpholine hydrochloride formed by suctin filtration, the toluene is distilled off in vacuo and the N- [y- (4-21-chlorophenoxymethyl- phenyl) propyl]-morpholine so obtained is puri- fied by way cf its hydrochloride. It boils at 229 -232 C. under a pressure of 0.6 mm. Hg. EXAMPLE VII. In a manner similar to that described in Example VI, 2.3 parts of sodium, 13 pars of 4-chlorophenol and 24 parts of y-(4-chloro- methylphenyl) propyl chloride are reacted in. 100 parts of ethanol to form ?-(4-4l-chloro- phenoxymethylphenyl) propyl. chloride, which melts at 65 C. after recrystallisation from petroleum-ether. Proceeding as described in Example VI, 7 parts ofY-(4-4'-chlorophen.oxymethylphenyl)- propyl chloride are reacted with 17 parts G'i morpholine in 50 parts of toluene to give N [7-
(4-4-chlorophenoxymethylphenyl)- propyl]-morpholine vehich when crystallised from aqueous methanol forms colourless crystals melting at 69-70 C. EXAMPLE VIII. In a manner similar to that described in Example VI, 2. 3 parts of sodium in, 100 parts of methanol are reacted with 16 parts of 2:4dichlorophenol and 24 parts of Y- (4-chloro- methylphenyl) propyl chloride to give-/- (4-21e4l-dichlorophenoxymethylphenyl)- propyi chloride, which boils at 219-220 C. under a pressure of 0.8 mm. Hg. 17 Parts of y- (4-21 : 41-dichlorophenoxy- methylphenyl) propyl chloride dissolved in 30 parts of toluene are reacted with 26 parts of morpholine as, described in the aforementioned Example to'give after analogous treatment N- [-- (4-21 : 41-dichlorophenoxymethylphenyl)- propyl]-morpholine, b. p. 283-288 C./3 mm. Hg. EXAMPLE IX. In a similar manner to that described in Example VI, 2.3 parts of sodium Mi 100 parts. of methanol are reacted with 17 parts of obromophenol and 24 parts of y- (4-chloro- methylphenyl) propyl chloride tc'give y- (4-2- bromophenoxymethylphenyl) propyl chloride, b. p. 188-191 C./0. 2 mm. Hg. 21 Parts of ?-(4-21-bromophenoxymethyl- phenyl) propyl chloride are heated at 125 C. for 24 hours with 43 parts of morpholine in 25 parts of toluene and the reaction mixture is then treated as described in the aforementioned Example. The N- [-y- (4-2-bromophen- oxymethylphenyl) propyl]-morpholine formed is purified by way of its bitarlrate. It hc : ls between 257 and 262 C. under a pressure of 1 mm. Hg. EXAMPLE X. 2.3 Parts of sodium are dissolved in 100 parts of ethanol vvliereafter 17 parts of pbromophenol ; are added. 24 Parts of y- (4- chloromethylphenyl)propyl chloride are then added dropvvise cver a period of 30 minutes to the agitated mixture heated to'70 C. and the reaction mixture is maintained at that tem- perature for 3 hours. On treatment of the reacdon. mixture as described in Example I there is obtained y- (4-41-bromophenoxymethyl- phenyl) propyl chloride, which forms colourless ; crystals melting at Sl C. when crystallised from benzene-petroleum-etler. 8.5 Parts of y-(4-41-bromophenoxymetllyl- phenyl) propyl chloride in 50 parts of toluene are healed at 140 C. for 23 hours with 17 parts of morpholine and the reaction mixture is then treated as described in
Example VI. The N- [y- (4-4-bromophenoxym ethylphenyl)- propyl]-morpholine thus formed is purified by way of its bitartrate and forms on crystallisa- tion from 72-heptane colourless crystals melt- ing at 77-78 C. EXAMPLE XI. Ey reacting as described in Example VI 4.6 parts of sodium in 100 parts of methanol with 29 parts of 4-chloro-m-cresol and 48 parts of -y- propyl chloride there is obtained y-(4-41-chloro-3l-methylphenoxy- methylphenyl) propyl chloride, which forms colourless crystals melting at 42-43 C. when crystallised from petroleum-ether. 15 Parts of ?-(4-41-chloro-31-methylphen- oxymethylphenyl) propyl cI ide in 30 parts of toluene are heated at 140 C. for 24 hours with 17 parts of morpholine. Treatment of the reaction mixture as described in the aforemen- tioned Example gives N- [-/- (4-4-chloro-3- methylphenoxymethylphenyl)-propyl]-mor- pholine, b. p. 252-253 c./1 mm. Hg. EXAMPLE XII. 2. 3 Parts of sodium are dissolved with cooling in 100 parts of methancl. After the intro- duction of 13 parts of o-cresol there are added dropwise to the reaction mixture heated at 75 C. 25 parts of y-(4-chlorometI1ylphenyl)- propyl chloride ; the reaction mixture is agitated for a total of 17 hours. Following the procedure described in Example I there is obtained ?-(4-21-methylphenoxymethyl- phenyl) propyl chic-ride, b.p. 178-181 C./0.4 mm. Hg. 16 Parts of ?-(4-21-methylphenoxymethyl- phenyl) propyl chloride are heated for 24 hours : at 125 C. with 17 parts of morpholine and from the reaction mixture there is obtained following the treatment described in Example I N- [y-(4-2l-methylphenoxymethylphenyl)- propyl]-morpholie, b.p. 220-223 C./0.2 mm. Hg. EXAMPLE XIII. Following closely the procedure described in the preceding Example but starting with mcresol there is obtained y-(4-31-methylphen- oxymethylphenyl) propyl chloride boiling at 183-189 C. under a pressure of 0.5 mm. Hg. Rection of the I ; ast mentioned compound with morpholine gives N-[?-4-31-methylphen- cxymethylph. 2nyl) propyl]-morpholine, b. p. 228 C./0. 4 mm. Ug. EXAMPLE XIV. Following closely the procedure described in Example XII but starting with p-cresol, there is obtained y- (4-4-methylphenoxymethyl- phcnyl) propyl chloride b. p. 175-177 C./0.2 mm. Hg, which forms colouriess crystals melting at 62 C. on crystallisaticn from petroleum-ether. Rection of the last-mentioned
compound with morpholine gives N- [-i- (4-4'- methylphenoxymethylphenyl)-propylj-mor- pholine, colourlesb crystals melting at 54'C. when crystallised from petroleum-ether. EXAMPLE XV. 4.6 Parts of sodium are dissolved with cooling in I00 parts of ethanol. After the addi- tion of 25 parts of resorcLiol monomethyl ether, there are added dropwise with stirring 4H parts of-,'- (4-chloromethylphenyl)-propyl chloride over a period of 30 minutes. The reaction mixture is then slowly heated to 80 C. and maintained for a further 8 hours at this temperature. After cooling the reaction mixture, the sodium chloride formed is removed by suction filtration, the ethanol is distilled off and the residue is taken up in ether and washed free from phenol with dilute 2% caustic soda solution. After drying the ethereal layer over calcium chloride, first the solvent and then the y- (4-ethoxymetlzylphenyl) propyl chloride formed as by-product are distilled off. Crude y.- (4-3-methc < xyphenoxymet3iylphenyl) propyl chloride remains, as residue. 48 Parts of this crude product are dissolved in 50 parts of toluene and heated for 24 hours at 130 G. with 36 parts of pyrrolidine. After cooling, the excess pyrrolidine and toluene are distilled off in a low vacuum, and the residue of N- ['y- (4-3'-methoxyphenoxymethylphenyl)- propyl]-pyrrolidine is purified by way of its hydrochloride. It boils at 232-235'C./0. 7 mm. Hg. EXAMPLE XVI. 2. 3 Parts of sodium are dissolved in 100 parts of methanol and 15 parts of thymol are then added. 24 Parts of ^,/-(4-chloromethyl- phenyl) propyl chloride are added dropwise with agitation to the solution heated to 75 C. and the mixture is stirred for a further 23 hours. Treatment of the reaction mixture as described in Example I gives ^S-(4-61-iso- propyl-31-methylphenoxymethyphenyl)propyl chloride, which boils at 186-187 C./0. 7 mm. Hg. 16 Parts of the last-mentioned compound are heated at 125 C. for 24 hours with 17.4 parts o, morphcline after which the reaction mixture is treated in accordancewithExample I to give N- [y- (4-61-isopiopy1-1-methylphenoxy- methylphenyl) propyl]-morpholine, b. p. 221- 223 C./0. 2 mm. Hg. EXAMPLE XVII. 22 Parts of y-(4-phenoxymethylphen. yl)- propyl chloride, prepared as described in Example IV, are mixed with 37 parts of anhydrous diethylamine and heated for 24 hours at 140 C. in a closed vessel. After cooling and distilling cN the excess diethylamine, the residue of N-[?-(4-phenoxymethylphenyl)- propyl]-diethylamine is purified by way of its hydrochloride. It boils at 182-184 C./0. 4 mm. Hg. EXEMPLE XVIII.
13 Parts of y- (4-phenoxymethylphenyl)- propyl chloride, prepared as described in Example IV, are heated at 125 C. for 48 hours with 17 parts of N-meliyl-n-butylamine. The reaction mixture is. treated as described in Example I to give N-[y-phenoxymethyl- phenyl) prcpyl]-methylbutylamine, which boils at 192-193 C. under a pressure of 0. mm. H9. EXAMPLE XIX. 2.3 Parts of sodium are dissolved in 100 parts of ethanol and 14 parts of ss-naphthol are added. 24 Part, s of y-(4-chloromethyl- phenyl) propyl chloride are added dropwisa over a period of 30 minutes with stirring to the solution heated to 70 C. The reaction ; mixture is stirred for a further 14 hours and then treated as described in Example XV. Crude y-(4-l8-naphthoxymethylphenyl) propyl chloride is obtained as a brownish oil. 27 Parts of the crude product are dissolved in 50 parts of toluene and heated at 140 C. for 14 hours with 26 parts of morpholine. Treatment of the reaction mixture as described in Example VI gives N- [y-(4 Rnapl1thoxymethylphenyl)- propyl]-morpholine, b. p. 276-279 C./0. 8 mm. Hg. EXAMPLE XX. 12 Parts of sodium phenclate are dissolved in 70 parts, of methylisobutyl ketone by heating at 110 C. 22 Parts of -(4-chloromethyl- phenyl) butyl chloride are added dropwise with agitation over a period of 30 minutes, the reaction mixture is centrifuged for 4 more hcqlrs at 110 C. and then allowed to cool. The methylisobutyl ketone is distilled off under reduced pressure and the residue is : with ether. The ethereal layer is washed a number of times with water and dried over calcium chloride. After evaporation of the ether, the residue is distilled under a pressure of 0.7 mm. Hg and #-(4-phenoxymethyl- phenyl) butyl chloride distilling between 199 and 203 C. is obtained. 7 Parts of 8- (4-phenoxymethylphenyl) butyl chloride are dissolved in 30 parts of xylene' and heated under reflux for 24 hours with 9 parts of morpholine. The excess morpholine and xylene are removed by distillation and the N- [- (ph~ac'xymethylphenyl) butyl]-morpho line thus obtained is purified by way of its hydrochloride. It melts at 49-50 C. after xecrystallisation from petroleum-ether. The S- (4-chloromethylphenyl) butyl chloride employed as starting material is prepared as follows : A mixture of 68 parts of #-phenylbutyl chloride, 6 parts of parafcTmaldehyd, and 4 parts of anhydrous zinc chloride is vigorously agitated with heating at 50 C. for about 30 minutes. The reaction
mixture is then rapidly saturated with dry hydrogen chloride with vigorous centrifuging and is cooled to prevent the temperature frcm rising above 60 C. After saturation, the reaction mixture is agitated and allowed to ccol while a weak current of hydrogen chloride is passed throughout. Treatment of the reaction mixture as described in Example I gives - (4-chloromethylphenyl)-' butyl chloride, b.p. 169-171 C./11 mm. Hg, in a yield 79% of the theoTetical calculated on reacted -phenylbuLyl chloride. EXAU4PLE XXI. 2.3 Parts of sodium are dissolved with heating in 100 parts of absolute isopropanol ; 24 parts of 1- (4-chloromerhylphenyl) propyl chloride are added and the mixture is agitated ! and heated under reflux at 80 C. for 14 hours. Treatment of the reaction mixture as described in Example II gives /-(4-isopropoxymethyl- phenyl) propyl chloride as a colourless oil, b. p. 172-175 C./20 mm. Hg. 11 Parts of the last-mentioned compound are dissolved in 50 parts of toluene and heated under reflux at 130 C. for 24 hours with 17 parts of piperidine. The piperidine hydro chloride is separated by suction filtration, the excess piperidine and solvent are removed under a low vacuum and the procedure described in Example II is then followed. The N- [y- (4-isopropoxymethylphenyl) propyl]- piperidine thus obtained bosls ! at 162 164 C./0. 6 mm. Hg. EXAMPLE XXII. 15 Parts of tertbutanol are dissolved in 50 parts of toluene ; 2. 3 parts of finely divided sodium are then introduced and the mixture' is heated at boiling point until the sodium dissolves. 20 Parts of-y- (4-chlcTomethyl- phenyl) propyl chloride dissolved in 20 parts of toluene are thereafter added dropwise over a period of 60 minutes with agitation to the reaction, mixture heated to, 90 C. and agitation is continued for a further 48 hours at 90 C. After cooling, the solvent and excess butanol are distilled off in a low vacuum from the reaction mixture and the y-(4-ertbutoxymethyl- phenyl) propyl chloride formed is extracted from the residue with ether. It boils at 226 - 230 C./13 mm. Hg. and is a yellowish oil. 7 Parts of y- (4-tertbutoxymethylphenyl)- propyl chloride are dissolved in 20 parts of toluene and heated under reflux with 9 parts of morpholine for 24 hours at 125'C. Treat ment of the reaction mixture as described in Example II gives N-[y < 4-tei-tbutoxymethyl- phenyl) propyll-morpholine, a yellowish oil boiling at 198201 G./0. 6 mm. Hg.
EXAMPLE XXIII. 4.6 Parts of sodium are dissolved with heat- ing in 108 parts of benzyl alcohol and 48 parts of y- (4-chloromethylplienyl) propyl chloride are added dropwise tri the solution heated to. and agitated at 75 C. after which the reaction mixture is centrifuged for 6 hours at the same temperature. The reaction mixture is then cooled and taken up in ether, the ethereal layer is washed with water and dried over calcium chloride. After evaporating the ether, the excess benzyl alcohol is distilled off under a vacuum created by a water pump and the residue is fractionally distilled under a pressure of 1.5 mm. Hg. y- (4-Benzyloxymethylphenyl)- propyl chloride distils at 198 C. 200 C. 14 Parts of the last-mentioned compound are heated. with 14 parts of pyrrolidine in 25 parts of toluene for 24 hours at 130 C. after which the toluene and excess pyrrolidine are distilled off under a low vacuum, the residue is mixed with an excess of 4% hydrochloric acid and the hydrochloric acid solution is washed with ether until it becomes clear, and is then made alkaline. The precipitated amine is taken up in ether and the ethereal layer is dried over potassium carbonate. The ether is evaporated off and the residue fractionally distilled to, give N- [?-(4-benzyloxymethyl- phenyl) propyl]-pyrrolidine, b. p. 199-201 C. 10. 6 mm. Hg. EXEMPLE XXIV. 2.3 Parts of sodium are dissolved with cooling in 90 parts of ethoxyethyl alcohol and after the addition of 24 parts of ?-(4-chloromethyl- phenyl) propyl chloride the reaction mixture is agitated for 8 hours at 80 C. Treatment of the reaction mixture as described in Example ! I I gives y- (4-ethoxyethyloxymethylpkenyl)- propyl chloride, b. p. 165168 C./0. 6 mm. Hg. 13 Parts of y- (4-ethoxyethyloxymethyl- phenyl) propyl chloride are heated for 24 hours at 130 C. with 17 parts of morpholine in 50 parts of toluene. Following the procedure : described in the aforementioned Example there is obtained N- [y- (4-ethoxyethyloxymethyl- phenyl) propyl]-morpholine, b. p. 225-226 C./1. 5 mm. Hg. EXEMPLE XXV. 2. 3 Parts of sodium are dissolved with heating in 100 parts of n-hexanol and after the addition of 24 parts of y- (4-chloromethylphenyl) propyl chloride the reaction mixture is heated for 6 hours at 75 C. with agitation. The reaction mixture is then cooled, diluted with 100 parts of ether and shaken a number of times with water. The ethereal layer is then dried over sodium sulphate, the ether is evaporated off and the excess of n-hexanol is
removed by distillation under a vacuum created by a water pump. The residue con- sisting of ?-(4-n-hexoxymethylphenyl) propyl chloride boils at 203 and 204 C./14 mm. Hg. 11 Parts of the last-mentioned compound in 25 parts of toluene are heated under reflux for 24 hours at 130 C. with 17 parts of mor pholine. Treatment of the reaction mixture as described in Example XXI gives N- [y- (4-K- hexoxymethylphenyl) propyl]-morpholine, boil ing at 200201 C./0. 6 mm. Hg. EXAMPLE XXVI. 33 Parts of n-octyl alcohol are dissolved in 50 parts of benzene and 2.3 parts of sodium are dissolved therein by heating. 24 Parts of -/- (4-cblr, Tomethylpheny) propyl chloride are added dropwise over a period of 30 minutes with vigorous agitation and the mixture is then agitated for 8 hours at 80 C. Following treat ment of the reaction mixture as described in Example XXI there is obtained y- (4-n-octoxy- methylphenyl) propyl chloride, b. p. 177-179 C./0. 5 mm. Hg. 15 Parts of the last-mentioned compound in 50 parts of xylene are heated under reflux for 24 hours at 140 C. with 17 parts of mor pholine. Treatment of the reaction mixture in a manner similar to that described in Example XXI gives N- [y- (4-n-octoxymethylphenyl)- propyl]-morpholine, b. p. 211213 C./0. 6 mm. Hg. EXEMPLE XXVII. 4.6 Parts of sodium are dissolved with cool ing in 116 parts of allyl alcohol and after the dropwise addition ; of 48 parts of 7e (4-chloro- methylphenyl) propyl chloride, the reaction mixture is agitated for 7 hours at 80 C. Treatment of the reaction mixture as described in Example II gives y- (4-allyloxymethyl- phenyl) propyl chloride, b. p. 173-175 C./15 mm. Hg. 11 Parts of the last-mentioned compound in 50 parts of toluene are heated for 24 hours
under reflux at 130 C. with 17 parts of mor pholine. Following the procedure described in Example XXI there is obtained N- [y- (4-allyl oxymethylphenyl) propyl]-morpholine, b. p. 191-193 C./2 mm, Hg. EXAMPLEXXVIII. 50 Parts of cyclohexanol are dissolved in 50 parts of benzene and 2. 3 parts of sodium are dissolved therein by heating. 24 Parts of y- (4- chlorcmethylphenyl) propyl chloride are added dropwise over a period of 30 minutes, the re action mixture is agitated for 8 hours at 80 C. and then treated as described in Example XX (4Zyclohexoxymethylphenyl) propyl chloride, b. p. 188-192 C./1 mm. Hg, is thus obtained. 10 Parts of 7- (4-eycMiexoxymethylphenyI)- propyl chic-rid in 25 parts of toluene are heated under reflux for 24 hours at 130 C. with 17 parts of morpholine. Treatment of the reaction mixture as described in Example XXI gives N-- ['/- (4-cyohexoxymethylphtenyl)- propy'l]-morpholin, b. p. 214-215 C./0. 6 mm. Hg. EXAMPLE XXIX. 2. 3 Parts of sodium are dissolved with cooling in 45 parts of ethoxyethyl alcohol and to the resultant solution heated at 75 c. there are added dropwise over a period of 60 minutes and with agitation 23 parts, -(4chlorcmethylphenyl) ethyl chloride. The reaction mixture is then centrifuged for 18 hours at the aforesaid temperature. Treatment of the reaction mixture as described in Example II gives -(4-ethoxyethyloxymethylphenyl)ethyl chloride, b. p. 190-193 C./10 mm. Hg. 7 Parts of - (4-ethoxyethyloxymethyl- ph, enyl) ethyl chloride are heated under reflux for 24 hours at 125 C. with 17 parts of morpholine and from the reaction mixture treated as described in Example II there is obtained ; N- [ -(4-ethoxyethyloxymethylphenyl)ethyl]morpholine, b. p. 221-222 C./0. 6 mm. Hg. What we claim is :- 1. Phenylalkylamines of the formula : <img class="EMIRef" id="026415661-00070001" /> wherein R represents a saturated or unsaturated aliphatic hydrocarbon group, GT an alkoxyalkyl, cycloalkyl, aryl (preferably phenyl or naphthyl) or aralkyl group, the aryl group and the aryl moeity of the aralkyl group being either unsubstituted or substituted by one or more
halogen atcms or alkyl, alkoxy or nitro groups R1 and R2 either each represent individual alkyl groups containing not more than 6 carbon atoms or togeher with the nitrogen atom to which they are attached collectively represent a mononuclear saturated heterocyclic group, and n represents an integer greater than 1.
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