SE127373C1 - - Google Patents
Info
- Publication number
- SE127373C1 SE127373C1 SE127373DA SE127373C1 SE 127373 C1 SE127373 C1 SE 127373C1 SE 127373D A SE127373D A SE 127373DA SE 127373 C1 SE127373 C1 SE 127373C1
- Authority
- SE
- Sweden
- Prior art keywords
- parts
- weight
- volume
- tetrahydrofluoroantyl
- group
- Prior art date
Links
- 238000000034 method Methods 0.000 claims description 8
- 150000001408 amides Chemical class 0.000 claims description 4
- 239000007858 starting material Substances 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical class C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- XBDQKXXYIPTUBI-UHFFFAOYSA-N Propionic acid Substances CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- -1 acrylic acid nitrile Chemical class 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 150000001350 alkyl halides Chemical class 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- JGDFBJMWFLXCLJ-UHFFFAOYSA-N copper chromite Chemical compound [Cu]=O.[Cu]=O.O=[Cr]O[Cr]=O JGDFBJMWFLXCLJ-UHFFFAOYSA-N 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 241000257303 Hymenoptera Species 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 125000004103 aminoalkyl group Chemical group 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 150000002219 fluoranthenes Chemical class 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 230000002140 halogenating effect Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000012280 lithium aluminium hydride Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 150000003839 salts Chemical group 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 150000003459 sulfonic acid esters Chemical class 0.000 description 1
- 230000001225 therapeutic effect Effects 0.000 description 1
Landscapes
- Hydrogenated Pyridines (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Uppfinnare: K. Hoffmann, H. Ueberwasser och A. Uffer. Inventors: K. Hoffmann, H. Ueberwasser and A. Uffer.
Prioritet begard bin den 28 december 1947 och den 19 november 1948 (Schweiz). Priority was given to bees on 28 December 1947 and 19 November 1948 (Switzerland).
Foremal for foreliggande patent utgor ett nytt forfaringssatt for framstallning av hydro-fluorantener, som i 1-stallning innehalla en fri eller substituerad aminoalkylgrupp. Enligt patentet 122 181 och dess tillaggspatent 125 530 erhallas dessa aminer, om man i narvaro av halogenvateavspaltande medel omsatter hydrerade fluorantener med alkylhalogenider, som innehalla en hasisk grupp eller en i en sadan grupp overfOrbar substituent, och eventuellt overfor de i en basisk grupp overforbara substituenterna i en basisk grupp. Patentet 123 560 avser ett f orfaringssatt, vid vilket man i stallet fiir alkylhalogenider omsatter organiska sulfonsyraestrar av alkanoler. Ett ytterligare forfaringssatt beskrives i patentet 125 181 vilket kannetecknas darav, att man omsatter hydrerade fluorantener med akrylsyranitril, overfor de erhallna foreningarna i NJ/Lo. aminer och eventuellt substituerar aminogruppen. The subject of the present patent is a new process for the preparation of hydrofluorinated antennas, which in the 1-position contain a free or substituted aminoalkyl group. According to patent 122 181 and its additional patent 125 530, these amines are obtained if, in the presence of halogenating agents, hydrogenated fluorantes are reacted with alkyl halides containing a hasic group or a substituent which can be transferred in such a group, and optionally with the substituents which can be transferred in a basic group. in an alkaline group. Patent 123 560 relates to a process in which organic sulfonic acid esters of alkanols are reacted instead of alkyl halides. A further procedure is described in patent 125 181, which is characterized by reacting hydrogenated fluoranthenes with acrylic acid nitrile, to the obtained compounds in NJ / Lo. amines and optionally substitutes the amino group.
Det liar nu visat sig, att dessa aminer aven kunna erhallas, om man behandlar hydrofluoranty1-(1)-alkankarbonsyraamider med reducerande medel. It has now been found that these amines can also be obtained by treating hydrofluoroantyl- (1) -alkanecarboxylic acid amides with reducing agents.
De sasom utgangsamnen anvanda karbonsyraamiderna kunna framstallas av t. ex. de medelst forfaringssatten enligt de ovan angivna paten-ten sasom mellanprodukter erhallan nitrilerna, om man med ammoniak eller aminer overfor dessa Over syrorna eller deras halogenider i amiderna. The carboxylic acid amides used as starting materials can be prepared from e.g. they are obtained by means of the process kit according to the above patents as intermediates as the nitriles, if ammonia or amines are present with these over the acids or their halides in the amides.
Reduktionen kan utforas med t. ex. vate i narvaro av en oadel metallkatalysalor, t. ex. kopparkromit. Man kan emellertid aven anvanda andra reduktionsmedel, som Oro i stand till att reducera en amidogrupp till en aminogrupp. llnligt forfaringssattet erhallna foreningar kunna anvandas for terapeutiska andamal eller shsom mellanprodukter for framstallning av lakemedel. The reduction can be performed with e.g. vate in the presence of an oadel metal catalyst, e.g. copper chromite. However, other reducing agents such as Oro can also be used to reduce an amido group to an amino group. In accordance with the procedure, the compounds obtained can be used for therapeutic purposes or as intermediates for the manufacture of medicaments.
Uppfinningen beskrives narmare i foljande exempel, utan att dess omfattning inskrankes till desamma, varvid mellan viktsdelar och volymdelar fOreligger samma forhallande som Indian gram och kubikcentimeter och temperaturerna angivas i Celsius-grader. The invention is described in more detail in the following examples, without its scope being limited thereto, whereby between parts by weight and parts by volume there is the same ratio as Indian grams and cubic centimeters and the temperatures are given in degrees Celsius.
Exempel 1. 10 viktsdelar p-/tetrahydrofluorantyl-(1)/-propionsyrapiperidid hydreras vid 200 —250° och 200-250 atm. vale i 15 volymdelar dioxan med 5 viktsdelar kopparkromitkatalysator. Efter avslutat vateupptagande avskiljer man frau katalysatorn, avdestillerar losningsmedlet och utvinner ur rabasen genom tillsats av saltsyra hydrokloriden av 1-(y-piperidinopropy1)- 1,2,3,4-tetrahydrofluoranten med for-mein / \ \/ I„CH2 — CH, 1./ CH2 • CH2CH2N:\:CH, \\CH2— CH,' CH, I CH,HC1 vilken smatter vid 2° C. Example 1. 10 parts by weight of p- / tetrahydrofluoroantyl- (1) / -propionic acid piperidide are hydrogenated at 200-250 ° and 200-250 atm. vale in 15 parts by volume of dioxane with 5 parts by weight of copper chromite catalyst. After completion of the hydrogen uptake, the catalyst is separated from the catalyst, the solvent is distilled off and the hydrochloride of the 1- (γ-piperidinopropyl) -1,2,3,4-tetrahydrofluorant with the formene / CH 1. / CH2 • CH2CH2N: \: CH, \\ CH2— CH, 'CH, I CH, HCl which slams at 2 ° C.
Del i detta exempel anvanda utgangsamnet erMlles pa foljande salt: viktsdelar 1-(8-cyanoety1)-1, 2, 3, 4-tetrahydrofluoranten fOrtvalas i 40 volymdelar etylenglykol under aterloppskylning med 15 volymdelar 40%-ig kalilut vid en badtemperatur av 160170°. Sedan ammoniakutvecklingen upphort (35 timmar), avkyler man, utspader reaktionsblandningen med vatten och befriar densamma fran joke sura fOreningar genom utskakning med bensol. Ur den alkaliska losningen utvinner man genom surgoring fi-/tetrahydrofluoranty1-(1)/-propionsyra sasom kristalliniskt pulver (smaltpunkt 174°, ur bensol). Lika viktsdelar av denna karbonsyra och piperidin upphettas i ett destinationskarl till 200-2°, varvid overskottet av piperidin avdestillerar tillsammans med det vid kondensationen bildade vattnet. Genom destillation i hogvakuum erhaller man nastan utan aterstod /3- / tetrahydrofluorantyl- (1)/ - propionsyrapiperidid med kokpunkten (0,04 m/m) 192-194° och formeln — — / /CH,— CH,, I,CH,CH,C01\K'CH, 'CIL— CH,/ CH I112 CH, \/\ sasom nastan farglos, tjockflytande olja. Exempel 2. 5 viktsdelar fi-/tetrahydrofluorantyl-(1)/-propionsyrapiperidid losas i 60 volymdelar absolut eter och idroppas under 10 minuter i en losning av 1 viktsdel litium-aluminiumhydrid i 200 volymdelar absolut eter. Sedan upphettar man Mandl-Ell-Igen under °mewing en timme till kokning. Efter god avkylning med is sOnderdelar man kolvinnehallet med 20 volymdelar vat-ten, sldljer de bagge faserna och extraherar eterskiktet med 10%-ig svavelsyra. Det sura extrak- tet gores nu starkt alkaliskt med 10-normal natronlut, och blandningen extraheras i extraktionsapparat med eter. Man erhaller ph detta satt 4 viktsdelar av den i exempel 1 beskrivna (y-pip eridino-propy1)-1,2,3,4-tetrahydrofluorantenen, vars hydroklorid smaller vid 215°C. Utbyte 80 %. Part of the starting material used in this example is prepared on the following salt: parts by weight of 1- (8-cyanoethyl) -1,2,2,3,4-tetrahydrofluorant are pre-selected in 40 parts by volume of ethylene glycol under reflux with 15 parts by volume of 40% potassium hydroxide at a bath temperature of 160170 ° . After the evolution of ammonia has ceased (35 hours), it is cooled, the reaction mixture is diluted with water and the same is liberated from joke acidic compounds by shaking with benzene. From the alkaline solution, acid / crystalline powder (melting point 174 °, from benzene) is recovered by acidification with fi- / tetrahydrofluoroantyl- (1) / -propionic acid. Equal parts by weight of this carboxylic acid and piperidine are heated in a destination vessel to 200-2 °, the excess piperidine distilling off together with the water formed during the condensation. By distillation in a high vacuum, almost without residue is obtained. , CH, C01 \ K'CH, 'CIL— CH, / CH I112 CH, \ / \ as almost colorless, viscous oil. Example 2. 5 parts by weight of fi- / tetrahydrofluorantyl- (1) / -propionic acid piperidide are dissolved in 60 parts by volume of absolute ether and dropped for 10 minutes in a solution of 1 part by weight of lithium aluminum hydride in 200 parts by volume of absolute ether. Then heat Mandl-Ell-Igen under mewing for one hour until boiling. After good cooling with ice, the flask contents are decomposed with 20 parts by volume of water, the slurry phases are sealed and the ether layer is extracted with 10% sulfuric acid. The acidic extract is now made strongly alkaline with 10-normal sodium hydroxide solution, and the mixture is extracted in an extraction apparatus with ether. This gives 4 parts by weight of the (γ-pip eridinopropyl) -1,2,3,4-tetrahydrofluorantene described in Example 1, the hydrochloride of which is narrower at 215 ° C. Yield 80%.
Claims (3)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| SE127373T |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| SE127373C1 true SE127373C1 (en) | 1949-01-01 |
Family
ID=41925642
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| SE127373D SE127373C1 (en) |
Country Status (1)
| Country | Link |
|---|---|
| SE (1) | SE127373C1 (en) |
-
0
- SE SE127373D patent/SE127373C1/sv unknown
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