DE941193C - Process for the production of new, bisquaterner phosphonium compounds - Google Patents
Process for the production of new, bisquaterner phosphonium compoundsInfo
- Publication number
- DE941193C DE941193C DET7628A DET0007628A DE941193C DE 941193 C DE941193 C DE 941193C DE T7628 A DET7628 A DE T7628A DE T0007628 A DET0007628 A DE T0007628A DE 941193 C DE941193 C DE 941193C
- Authority
- DE
- Germany
- Prior art keywords
- new
- triphenylphosphine
- production
- compounds
- phosphonium compounds
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 238000000034 method Methods 0.000 title claims description 7
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 150000004714 phosphonium salts Chemical class 0.000 title 1
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 22
- 150000001875 compounds Chemical class 0.000 claims description 11
- 238000002425 crystallisation Methods 0.000 claims description 5
- 230000008025 crystallization Effects 0.000 claims description 5
- 125000005496 phosphonium group Chemical group 0.000 claims description 4
- CIUQDSCDWFSTQR-UHFFFAOYSA-N [C]1=CC=CC=C1 Chemical class [C]1=CC=CC=C1 CIUQDSCDWFSTQR-UHFFFAOYSA-N 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 150000002366 halogen compounds Chemical class 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 125000005842 heteroatom Chemical group 0.000 claims description 2
- 229920006395 saturated elastomer Polymers 0.000 claims description 2
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 21
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 18
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 239000000126 substance Substances 0.000 description 8
- 239000013078 crystal Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- CMSYDJVRTHCWFP-UHFFFAOYSA-N triphenylphosphane;hydrobromide Chemical compound Br.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 CMSYDJVRTHCWFP-UHFFFAOYSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- IBODDUNKEPPBKW-UHFFFAOYSA-N 1,5-dibromopentane Chemical compound BrCCCCCBr IBODDUNKEPPBKW-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- -1 pentamethylene bisphosphonium bromide Chemical compound 0.000 description 2
- 230000001766 physiological effect Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 230000028327 secretion Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- GXFZCDMWGMFGFL-KKXMJGKMSA-N (+)-Tubocurarine chloride hydrochloride Chemical compound [Cl-].[Cl-].C([C@H]1[N+](C)(C)CCC=2C=C(C(=C(OC3=CC=C(C=C3)C[C@H]3C=4C=C(C(=CC=4CC[NH+]3C)OC)O3)C=21)O)OC)C1=CC=C(O)C3=C1 GXFZCDMWGMFGFL-KKXMJGKMSA-N 0.000 description 1
- GTQHJCOHNAFHRE-UHFFFAOYSA-N 1,10-dibromodecane Chemical compound BrCCCCCCCCCCBr GTQHJCOHNAFHRE-UHFFFAOYSA-N 0.000 description 1
- ULTHEAFYOOPTTB-UHFFFAOYSA-N 1,4-dibromobutane Chemical compound BrCCCCBr ULTHEAFYOOPTTB-UHFFFAOYSA-N 0.000 description 1
- FINUUDAOCYEWBV-UHFFFAOYSA-N 1,5-dibromohexane Chemical compound CC(Br)CCCCBr FINUUDAOCYEWBV-UHFFFAOYSA-N 0.000 description 1
- SGRHVVLXEBNBDV-UHFFFAOYSA-N 1,6-dibromohexane Chemical compound BrCCCCCCBr SGRHVVLXEBNBDV-UHFFFAOYSA-N 0.000 description 1
- 241001111317 Chondrodendron tomentosum Species 0.000 description 1
- 239000008709 Curare Substances 0.000 description 1
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical class N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 210000000609 ganglia Anatomy 0.000 description 1
- 229940083122 ganglion-blocking antiandrenergic bisquaternary ammonium compound Drugs 0.000 description 1
- 210000004051 gastric juice Anatomy 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- 230000001734 parasympathetic effect Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-O pyridinium Chemical compound C1=CC=[NH+]C=C1 JUJWROOIHBZHMG-UHFFFAOYSA-O 0.000 description 1
- 150000004023 quaternary phosphonium compounds Chemical class 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 230000001225 therapeutic effect Effects 0.000 description 1
- RIOQSEWOXXDEQQ-UHFFFAOYSA-O triphenylphosphanium Chemical compound C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-O 0.000 description 1
- POXSDSRWVJZWCN-UHFFFAOYSA-N triphenylphosphanium;iodide Chemical compound I.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 POXSDSRWVJZWCN-UHFFFAOYSA-N 0.000 description 1
- WXAZIUYTQHYBFW-UHFFFAOYSA-N tris(4-methylphenyl)phosphane Chemical compound C1=CC(C)=CC=C1P(C=1C=CC(C)=CC=1)C1=CC=C(C)C=C1 WXAZIUYTQHYBFW-UHFFFAOYSA-N 0.000 description 1
- 230000001515 vagal effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/54—Quaternary phosphonium compounds
- C07F9/5449—Polyphosphonium compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
Description
Verfahren zur Herstellung von neuen bisquaternären Phosphoniumverbindüngen Die Erfindung betrifft ein Verfahren zur Herstellung von neuen, bisquaternären Phosphoniumverbindungen.Process for the production of new bisquaternary phosphonium compounds The invention relates to a process for the production of new, bisquaternary phosphonium compounds.
Es ist bekannt, daß die aliphatischen bisquaternären Ammoniumverbindungen, ebenso wie bestimmte Pyridinium- und Chinoliniumverbindungen, curareähnliche Wirkungen zeigen. Auch durch Variation der Liganden werden die Wirkungen dieser quaternären Verbindungen nicht prinzipiell geändert.It is known that the aliphatic bisquaternary ammonium compounds, as well as certain pyridinium and quinolinium compounds, curare-like effects demonstrate. The effects of these are also quaternary by varying the ligands Connections not changed in principle.
Die Erfindung betrifft nun ein Verfahren zur Herstellung von neuen, bisquaternären Phosphoniumverbindungen, die überraschenderweise im Gegensatz zu den obenerwähnten quaternären Verbindungen völlig andersartige physiologische Wirkungen besitzen. Die neuen erfindungsgemäß herstellbaren Verbindungen entsprechen der allgemeinen Formel worin Ar einen gegebenenfalls substituierten Phenylrest, Y eine Kette mit mindestens q. Kohlenstoffatomen, die gesättigt oder ungesättigt, gerade oder verzweigt oder auch durch Heteroatome, .wie z. B. Sauerstoff oder Stickstoff, unterbrochen sein kann, und X ein Halogenatom bedeuten. Diese neuen Verbindungen werden hergestellt, indem man ein Triphenylphosphin Ars P, dessen Phenylreste substituiert sein können, mit einer Dihalogenverbindung X - Y - X, worin Ar, X und Y die oben angegebene Bedeutung besitzen, in einem Verhältnis von mindestens 2 Mol Triphenylphosphin x Mol Halogenverbindung umsetzt und das entstandene Produkt durch Kristallisation isoliert und reinigt.The invention now relates to a process for the production of new, bisquaternary phosphonium compounds which, surprisingly, in contrast to the above-mentioned quaternary compounds, have completely different physiological effects. The new compounds which can be prepared according to the invention correspond to the general formula wherein Ar is an optionally substituted phenyl radical, Y is a chain with at least q. Carbon atoms that are saturated or unsaturated, straight or branched or also by heteroatoms, .wie z. B. oxygen or nitrogen, may be interrupted, and X is a halogen atom. These new compounds are prepared by adding a triphenylphosphine Ars P, the phenyl radicals of which may be substituted, with a dihalogen compound X - Y - X, in which Ar, X and Y have the meaning given above, in a ratio of at least 2 moles of triphenylphosphine x mole Reacts halogen compound and the resulting product is isolated and purified by crystallization.
Die Umsetzung kann bei- gewöhnlicher oder bei erhöhter Temperatur erfolgen. Die Reaktion kann sowohl durch direkte Einwirkung der Reaktionskomponenten aufeinander, als auch in Gegenwart von Lösungsmitteln, wie Alkoholen, Estern, Ketonen, insbesondere Butanol,Essigsäureäthylester und Methyläthylketon, vorgenommen werden. Es ist zweckmäßig, mit einem kleinen Überschuß an Triarylphosphin zu arbeiten. Die Isolierung und Reinigung der neuen Verbindungen erfolgt durch Kristallisation aus geeigneten Lösungsmitteln, z. B. $utanol oder Essigsäureäthylester.The reaction can take place at an ordinary temperature or at an elevated temperature take place. The reaction can take place both through direct action of the reaction components on each other, as well as in the presence of solvents such as alcohols, esters, ketones, in particular butanol, ethyl acetate and methyl ethyl ketone are made. It is advisable to work with a small excess of triarylphosphine. the Isolation and purification of the new compounds is carried out by crystallization suitable solvents, e.g. B. $ utanol or ethyl acetate.
Die Herstellung von quaternären Phosphoniumverbindungen aus Triorganophosphinen und Alkylhalogeniden ist zwar bekannt, jedoch wurden Verbindungen der erfindungsgemäßen Art, die eine Kette mit " mindestens 4 Koblenstoffätomen besitzen, bisher nicht beschrieben. Insbesondere war die überraschende therapeutische Wirkung der neuen Verfahrensprodukte nicht vorauszusehen.The production of quaternary phosphonium compounds from triorganophosphines and alkyl halides are known, but compounds of the invention have been Kinds that have a chain with "at least 4 Koblenstoffätomen, not yet described. In particular, the surprising therapeutic effect was the new Process products cannot be foreseen.
Wie schon oben erwähnt, besitzen" die erfindungsgemäß hergestellten Verbindungen völlig andersartige physiologische Wirkungen als die eingangs erwähnten quaternären Verbindungen. Es ist besonders hervorzuheben, daß die Curarewirkung auch bei Verabreichung hoher Dosen dieser Verbindungen zugunsten einer" ausgeprägten Henunung der zentralparasympatisch innervierten Sekretionen ganz zurücktritt. So werden nach Ginzel, Klupp und Werner (Arch. exp. Path. Pharmakol. 22i, 336 [19547) durch die neuen Substanzen unerwarteterweise nur die vagalen Ganglien blockiert; was sich vor allem in einer starken Hemmung der Magensaftsekretion äußert. Beispielsweise hält bei Verabreichung kleiner Dosen von Pentamethylenbisphosphoniumbromid diese Hemmung beim Versuchstier über mehrere Tage an. Diese Wirkungen waren aus den bisher bekannten nicht ableitbar, zumal die entsprechenden stickstoffhaltigen quaternären Bisammoniumverbindungen schon aus rein chemischen Gründen nicht darstellbar sind. " Das erfindungsgemäße Verfahren soll an Hand der folgenden Beispiele näher erläutert werden.As already mentioned above, "have those produced according to the invention Compounds completely different physiological effects than those mentioned at the beginning quaternary compounds. It should be emphasized that the curare effect even when high doses of these compounds are administered in favor of a "pronounced Henunung of the centrally parasympathetic innervated secretions completely recedes. So are according to Ginzel, Klupp and Werner (Arch. exp. Path. Pharmakol. 22i, 336 [19547) unexpectedly only the vagal ganglia blocked by the new substances; which manifests itself mainly in a strong inhibition of gastric juice secretion. For example holds these when given small doses of pentamethylene bisphosphonium bromide Inhibition in the test animal over several days. These effects were from the previously known not derivable, especially since the corresponding nitrogenous quaternary Bisammonium compounds cannot be produced for purely chemical reasons. "The process according to the invention is intended to be explained in more detail using the following examples will.
Beispiel i Tetramethylen-I, 4-bis-(triphenylphosphöniumbromid) 9 g (0,o416 Mol) 1,4-Dibrombutan und 21 g (0,0832 Mol) Triphenylphosphin werden in einem offenen Kolben 3 Stunden auf ' 15o° erhitzt. Das Reaktionsgemisch wird nach dem Erkalten -mit absolutem Äther durchgerieben, die erhaltenen Kristalle- abfiltriert und aus einem Gemisch von absolutem Alkohol und Essigsäüreäthylester umkristallisiert. Die in einer Ausbeute von 18,6 g (annähernd 62% der Theorie) erhaltene Substanz zeigt einen Schmelzpunkt von z25 bis 2,300 und ist schwer löslich in Wasser.Example i Tetramethylene 1,4-bis (triphenylphosphonium bromide) 9 g (0.0416 mol) 1,4-dibromobutane and 21 g (0.0832 mol) triphenylphosphine are heated to 150 ° in an open flask for 3 hours. After cooling, the reaction mixture is rubbed through with absolute ether, the crystals obtained are filtered off and recrystallized from a mixture of absolute alcohol and ethyl acetate. The substance obtained in a yield of 18.6 g (approximately 62% of theory) shows a melting point of z25 to 2,300 and is sparingly soluble in water.
Br ber.: 21,7°/o, gef.: 21,3°/o. Beispiel 2 Pentamethylen-i, 5-bis-(triphenylphosphoniumbromid) 1I,5 g (0,05 Mol) I, 5-Dibrompentan werden mit 28,8 g (o,iz Mol) Triphenylphosphin vermischt und 6 Stunden auf 13o° erwärmt. Das Reaktionsgemisch wird dann in 8o ccm siedendem Butanol gelöst und die Lösung mit absolutem Essigsäure. äthylester versetzt. Nach dem Erkalten erhält man ineiner Ausbeute von 23 g (annähernd 6z0/, der Theorie) eine in Wasser schwer lösliche, kristallisierte Substanz vom F. = 262°.Br cal .: 21.7%, found: 21.3%. Example 2 Pentamethylene-1,5-bis (triphenylphosphonium bromide) 1.5 g (0.05 mol) of 1,5-dibromopentane are mixed with 28.8 g (o, iz mol) of triphenylphosphine mixed and heated to 130 ° for 6 hours. The reaction mixture is then in 8o ccm dissolved in boiling butanol and the solution with absolute acetic acid. ethyl ester added. After cooling, you get a yield of 23 g (approximately 6z0 /, the theory) a crystallized substance which is sparingly soluble in water and has a temperature of 262 °.
Br ber.: 21,250/i, gef.: 20,9%.Br calc .: 21.250 / i, found: 20.9%.
Man kann auch so arbeiten, daß man 11,5 g (0,05 M01) I., 5-Dibrompentan und 28,8 g (o,ii Mol) Triphenylphosphin in ioo ccm absolutem Butanol löst und die Lösung 2o Stunden zum Sieden erhitzt. Danach wird mit absolutem Essigsäureäthylester versetzt und nach der Kristallisation filtriert.- Nach dem Umkristallisieren aus Wasser erhält man 21,o g (annähernd 56% der Theorie) eines rein weißen Salzes mit den vorbeschriebenen Eigenschaften. Beispiel 3 Hexamethylen-i, 6-bis-(triphenylphosphonium-" bromid).One can also work in such a way that 11.5 g (0.05 M01) of I., 5-dibromopentane and 28.8 g (o, ii mol) of triphenylphosphine are dissolved in 100 cc of absolute butanol and the solution is heated to the boil for 20 hours . Absolute ethyl acetate is then added and, after crystallization, it is filtered. After recrystallization from water, 21, og (approximately 56% of theory) of a pure white salt with the properties described above is obtained. Example 3 Hexamethylene-1,6-bis (triphenylphosphonium "bromide).
10 g (0,°412`M°1) i, 6-Dibromhexan werden mit 30 g (0,1l5 M°1) Triphenylphosphin vermischt und 3 Stunden auf dem siedenden Wasserbad erhitzt, wobei vollständige Kristallisation eintritt. Nach dem Erkalten wird mit absolutem Äther dufchgerieben, die erhaltenen Kristalle werden abfiltriert und aus einem Butanol/Essigsäureäthylester-Gemisch umkristallisiert. Die Ausbeute beträgt 259 (annähernd 8o0%, bezogen auf i, 6-Dibromhexan). Die in kaltem Wasser schwer lösliche Substanz besitzt einen Zersetzungsschmelzpunkt von über 27o°.10 g (0, ° 412`M ° 1) i, 6-dibromohexane are mixed with 30 g (0.1l5 M ° 1) triphenylphosphine and heated for 3 hours on a boiling water bath, during which complete crystallization occurs. After cooling, it is rubbed with absolute ether, the crystals obtained are filtered off and recrystallized from a butanol / ethyl acetate mixture. The yield is 259 (approximately 80%, based on 1,6-dibromohexane). The substance, which is sparingly soluble in cold water, has a decomposition melting point of over 270 °.
Br ber.: 2o,60/0, gef.: 2o,10/0. Beispiel 4 Decamethylen-i, io-bis-(triphenylphosphoniumbromid) -10 g (0,0334 MOl) i, io-Dibromdecan werden mit 30 g (o,115 M°1) Triphenylphosphin unter Rühren während 1,6 Stunden auf 12o bis 13o° erhitzt. Es bildet sich eine zähflüssige Masse, welche beim Stehen über Nacht glasartig erstarrt. Das Reaktionsprodukt wird in einer Reibschale pulverisiert und mit absolutem Äther durchgerieben. Zur Reinigung kristallisiert man aus einem Butanol/Essigsäureäthylester-Gemisch um. Es werden in kaltem Wasser schwer lösliche Kristalle vom F. = 228 bis 2300 in einer Ausbeute von 23 g (annähernd 830/0, bezogen auf das Decamethylenbromid) erhalten.Br ber .: 2o, 60/0, found: 2o, 10/0. Example 4 Decamethylene-i, io-bis (triphenylphosphonium bromide) -10 g (0.0334 MOL) i, io-dibromodecane are mixed with 30 g (0.115 M ° 1) triphenylphosphine while stirring for 1.6 hours to 12o bis 13o ° heated. A viscous mass forms, which solidifies like glass when standing overnight. The reaction product is pulverized in a mortar and rubbed through with absolute ether. For purification, it is recrystallized from a butanol / ethyl acetate mixture. Crystals with a melting point of 228 to 2300, which are sparingly soluble in cold water, are obtained in a yield of 23 g (approximately 830/0, based on the decamethylene bromide).
Br ber.: 19,5%, gef.:19,3%. Beispiel 5 Pentamethylen-1, 5-bis-[tri-(p-tolyl)-phosphoniumbromid] 2,3 g (0,01 M01) 1, 5-Dibrompentan werden mit 6,o8 g (o,o2 Mol) Tri-p-tolyl-phosphin vermischt und 8 Stunden auf 12o bis 130°_ erhitzt. Das Reaktionsprodukt wird in einer Reibschale mit absolutem Äther gut durchgerieben und nach Filtration aus Butanol/Äther umgefällt. Die in einer Ausbeute von 5,1 g (annähernd 610/0 der Theorie) erhaltene Substanz schmilzt bei 8o° und ist in kaltem Wasser löslich. Br ber.: 1g,10/" gef.: 19,5"/o.Br calc .: 19.5%, found: 19.3%. Example 5 Pentamethylene-1, 5-bis- [tri- (p-tolyl) -phosphonium bromide] 2.3 g (0.01 M01) 1,5-dibromopentane mixed with 6, o8 g (o, o2 mol) tri-p-tolyl-phosphine and heated to 12o to 130 ° _ for 8 hours heated. The reaction product is rubbed thoroughly with absolute ether in a mortar and reprecipitated after filtration from butanol / ether. The in a yield of 5.1 g (approximately 610/0 of theory) obtained substance melts at 80 ° and is in cold Water soluble. Br ber .: 1g, 10 / "found: 19.5" / o.
Beispiel 6 1- Methylpentamethylen -1, 5 - bis - (triphenylphosphoniumbromid) 2,44 g (o,o1 Mol) 1-Methyl-1, 5-dibrompentan werden mit 5,24 g (o,o2 Mol) Triphenylphosphin mehrere Stunden auf 16o° erhitzt. Danach reibt man das Reaktionsprodukt mit Äther durch und fällt die erhaltenen Kristalle nach Abfiltriereri aus Butanol/Äther um. Man erhält 5,3 g (annähernd 70% der Theorie) einer in Wasser löslichen Substanz vom F. = 7o bis 75°.Example 6 1- methylpentamethylene -1, 5 - bis - (triphenylphosphonium bromide) 2.44 g (0.1 mol) of 1-methyl-1,5-dibromopentane are mixed with 5.24 g (0.02 mol) of triphenylphosphine heated to 16o ° for several hours. The reaction product is then rubbed with ether through and the crystals obtained precipitate after filtering off from butanol / ether. 5.3 g (approximately 70% of theory) of a substance soluble in water are obtained from F. = 7o to 75 °.
Br ber.: 2o,8o0/" gef.: 20,450/0. Beispiel 7 Dibutyläther-4, 4'-bis-(triphenylphosphoniumjodid) 19 g (0,05 Mol) 4, 4'-Dijoddibutyläther werden mit 27 g (0,103 Mol) Triphenylphosphin 8 Stunden auf 15o° erwärmt. Die entstehende zähflüssige Masse wird mit Äther verrieben und die auf diese Weise erhaltenen Kristalle aus Butanol/Essigsäureäthylester umkristallisiert. Man erhält 319 (annähernd 68% der Theorie) einer in Wasser schwer löslichen Substanz, welche bei 211 bis 21q.° schmilzt.Br calc .: 2o, 8o0 / "found: 20.450 / 0. Example 7 Dibutyl ether-4, 4'-bis (triphenylphosphonium iodide) 19 g (0.05 mol) of 4,4'-diiododibutyl ether are mixed with 27 g (0.103 mol) of triphenylphosphine Heated to 150 ° for 8 hours. The resulting viscous mass is rubbed with ether and the crystals obtained in this way are recrystallized from butanol / ethyl acetate. 319 (approximately 68% of theory) of a substance that is sparingly soluble in water are obtained, which melts at 211 to 21q. °.
J ber.: 27,80/0, gef.: 27,70/0.J ber .: 27.80 / 0, found: 27.70 / 0.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DET7628A DE941193C (en) | 1953-03-27 | 1953-03-27 | Process for the production of new, bisquaterner phosphonium compounds |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DET7628A DE941193C (en) | 1953-03-27 | 1953-03-27 | Process for the production of new, bisquaterner phosphonium compounds |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE941193C true DE941193C (en) | 1956-04-05 |
Family
ID=7545643
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DET7628A Expired DE941193C (en) | 1953-03-27 | 1953-03-27 | Process for the production of new, bisquaterner phosphonium compounds |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE941193C (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2867665A (en) * | 1956-07-09 | 1959-01-06 | Searle & Co | Alkylenebis [trialkylphosphonium halides] and processes for the manufacture thereof |
| DE1170404B (en) * | 1958-11-17 | 1964-05-21 | American Cyanamid Co | Process for the production of an organic, tetrasubstituted diphosphine with a bridge between the phosphorus atoms |
| US3364107A (en) * | 1965-08-23 | 1968-01-16 | American Cyanamid Co | Controlling algae, bacteria, and fungi growth with alpha, omega-alkylenebis[triphenyl-phosphonium salt] |
-
1953
- 1953-03-27 DE DET7628A patent/DE941193C/en not_active Expired
Non-Patent Citations (1)
| Title |
|---|
| None * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2867665A (en) * | 1956-07-09 | 1959-01-06 | Searle & Co | Alkylenebis [trialkylphosphonium halides] and processes for the manufacture thereof |
| DE1170404B (en) * | 1958-11-17 | 1964-05-21 | American Cyanamid Co | Process for the production of an organic, tetrasubstituted diphosphine with a bridge between the phosphorus atoms |
| US3364107A (en) * | 1965-08-23 | 1968-01-16 | American Cyanamid Co | Controlling algae, bacteria, and fungi growth with alpha, omega-alkylenebis[triphenyl-phosphonium salt] |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| DE887506C (en) | Process for the production of organic compounds | |
| CH640224A5 (en) | 2-pyrrolidone derivatives, PROCESS FOR PREPARING THEM AND THEIR USE FOR PRODUCING 4-AMINOHEX-5-enoic acid. | |
| DE1906527B2 (en) | Thionine derivatives, processes for their production and pharmaceutical preparations containing them | |
| DE941193C (en) | Process for the production of new, bisquaterner phosphonium compounds | |
| DE2120868C2 (en) | Fluorinated sulfoxylated ampholytes and processes for their preparation | |
| DE814294C (en) | Process for the preparation of insecticidal phosphorus compounds | |
| DE2166270C3 (en) | Nicotinoylaminoethanesulfonyl-2amino-thiazole | |
| DE1274100B (en) | Process for the preparation of 1,6-dibromo-1,6-dideoxydulcite | |
| DE2627985B2 (en) | 4-homoisotwistane-3-carboxylic acid ester and process for their preparation | |
| DE1125922B (en) | Process for the production of new phosphorane compounds | |
| CH533619A (en) | Phenyl-substd pyrrole derivs with anti- - inflammatory activity | |
| DE1670967C3 (en) | 3-Imino-1,2-benzisothiazoline salts and process for their preparation | |
| DE942149C (en) | Process for the preparation of substituted glycine amides | |
| DET0007628MA (en) | ||
| DE2065698A1 (en) | PROCESS FOR THE PREPARATION OF 2ISOPROPYL-6-METHYL-4 (3H) -PYRIMIDONE | |
| DE1445659C (en) | Pyndyl phosphorus compounds and processes for their preparation | |
| DE1795350C3 (en) | Pyrimldinylthiophosphoric acid esters, process for their preparation and compositions containing them | |
| DE1595875C (en) | Phenothiazines and processes for their preparation | |
| AT242688B (en) | Process for the preparation of new dinitro-alkylphenylbutyrates | |
| DE1695580C (en) | Quaternary compounds of benzil acid beta piperidino ethyl ester and a process for their preparation | |
| DE2932951A1 (en) | METHOD FOR PRODUCING HEXAMETHYLENE-BIS-DICYANDIAMID | |
| DE1620054C (en) | Process for the preparation of quinolindenvates and drugs containing these compounds excretion from 1470047 | |
| DE951270C (en) | Process for the purification of bis-quaternary ammonium salts | |
| DE1643890C (en) | alpha- Hy droxy-gamma-methy lmercaptobutyric acid-methylsulfonium halides and process for their preparation | |
| DE1793690C3 (en) | 1 S-Hydroxy-9-oxoprosta-5-cis-10,13-trans-trienoic acid and its salts and processes for their preparation |