DE1176657B - Process for the preparation of quaternary phosphonium compounds - Google Patents
Process for the preparation of quaternary phosphonium compoundsInfo
- Publication number
- DE1176657B DE1176657B DEF32129A DEF0032129A DE1176657B DE 1176657 B DE1176657 B DE 1176657B DE F32129 A DEF32129 A DE F32129A DE F0032129 A DEF0032129 A DE F0032129A DE 1176657 B DE1176657 B DE 1176657B
- Authority
- DE
- Germany
- Prior art keywords
- mol
- quaternary phosphonium
- preparation
- phosphonium compounds
- triphenylphosphine
- 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.)
- Pending
Links
- 238000000034 method Methods 0.000 title claims description 4
- 150000004023 quaternary phosphonium compounds Chemical class 0.000 title claims description 3
- 238000002360 preparation method Methods 0.000 title description 2
- -1 Mannich bases aromatic Chemical class 0.000 claims description 4
- 150000003839 salts Chemical group 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 3
- 150000003003 phosphines Chemical group 0.000 claims description 3
- 150000002391 heterocyclic compounds Chemical class 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 15
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 8
- 238000009835 boiling Methods 0.000 description 6
- 230000008018 melting Effects 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 238000001953 recrystallisation Methods 0.000 description 5
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- RREANTFLPGEWEN-MBLPBCRHSA-N 7-[4-[[(3z)-3-[4-amino-5-[(3,4,5-trimethoxyphenyl)methyl]pyrimidin-2-yl]imino-5-fluoro-2-oxoindol-1-yl]methyl]piperazin-1-yl]-1-cyclopropyl-6-fluoro-4-oxoquinoline-3-carboxylic acid Chemical compound COC1=C(OC)C(OC)=CC(CC=2C(=NC(\N=C/3C4=CC(F)=CC=C4N(CN4CCN(CC4)C=4C(=CC=5C(=O)C(C(O)=O)=CN(C=5C=4)C4CC4)F)C\3=O)=NC=2)N)=C1 RREANTFLPGEWEN-MBLPBCRHSA-N 0.000 description 3
- RLFWWDJHLFCNIJ-UHFFFAOYSA-N Aminoantipyrine Natural products CN1C(C)=C(N)C(=O)N1C1=CC=CC=C1 RLFWWDJHLFCNIJ-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229960005222 phenazone Drugs 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 2
- 230000029936 alkylation Effects 0.000 description 2
- 238000005804 alkylation reaction Methods 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- OCDGBSUVYYVKQZ-UHFFFAOYSA-N gramine Chemical compound C1=CC=C2C(CN(C)C)=CNC2=C1 OCDGBSUVYYVKQZ-UHFFFAOYSA-N 0.000 description 2
- 125000005528 methosulfate group Chemical group 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- RXJKFRMDXUJTEX-UHFFFAOYSA-N triethylphosphine Chemical group CCP(CC)CC RXJKFRMDXUJTEX-UHFFFAOYSA-N 0.000 description 2
- CURCMGVZNYCRNY-UHFFFAOYSA-N trimethylazanium;iodide Chemical compound I.CN(C)C CURCMGVZNYCRNY-UHFFFAOYSA-N 0.000 description 2
- 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 2
- QLAJNZSPVITUCQ-UHFFFAOYSA-N 1,3,2-dioxathietane 2,2-dioxide Chemical compound O=S1(=O)OCO1 QLAJNZSPVITUCQ-UHFFFAOYSA-N 0.000 description 1
- BLRHMMGNCXNXJL-UHFFFAOYSA-N 1-methylindole Chemical compound C1=CC=C2N(C)C=CC2=C1 BLRHMMGNCXNXJL-UHFFFAOYSA-N 0.000 description 1
- GUMOJENFFHZAFP-UHFFFAOYSA-N 2-Ethoxynaphthalene Chemical compound C1=CC=CC2=CC(OCC)=CC=C21 GUMOJENFFHZAFP-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- SQSIMAZFZQFPMH-UHFFFAOYSA-N COS([O-])(=O)=O.C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1 Chemical compound COS([O-])(=O)=O.C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1 SQSIMAZFZQFPMH-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000006957 Michael reaction Methods 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- VEQOALNAAJBPNY-UHFFFAOYSA-N antipyrine Chemical compound CN1C(C)=CC(=O)N1C1=CC=CC=C1 VEQOALNAAJBPNY-UHFFFAOYSA-N 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 125000006222 dimethylaminomethyl group Chemical group [H]C([H])([H])N(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- PSLIMVZEAPALCD-UHFFFAOYSA-N ethanol;ethoxyethane Chemical compound CCO.CCOCC PSLIMVZEAPALCD-UHFFFAOYSA-N 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- MDKXBBPLEGPIRI-UHFFFAOYSA-N ethoxyethane;methanol Chemical compound OC.CCOCC MDKXBBPLEGPIRI-UHFFFAOYSA-N 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 description 1
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- QAJUUSZYZIUHQI-UHFFFAOYSA-N n,n-dimethyl-1-(1-methylindol-3-yl)methanamine Chemical compound C1=CC=C2C(CN(C)C)=CN(C)C2=C1 QAJUUSZYZIUHQI-UHFFFAOYSA-N 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- 150000004714 phosphonium salts Chemical group 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- XKJCHHZQLQNZHY-UHFFFAOYSA-N phthalimide Chemical compound C1=CC=C2C(=O)NC(=O)C2=C1 XKJCHHZQLQNZHY-UHFFFAOYSA-N 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 238000010626 work up procedure Methods 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
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)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Verfahren zur Herstellung von quartären Phosphoniumverbindungen Alkylierungen an Kohlenstoff- und Heteroatomen mit Hilfe von quartären Ammoniumsalzen sind in großer Zahl bekannt. Sie verlaufen erfahrungsgemäß glatt unter relativ milden Bedingungen, wenn entweder die Übertragung eines Liganden des Ammoniumions auf das zu alkylierende Zentrum durch eine Mesomeriestabilisierung dieses Restes als Carbeniumion begünstigt wird oder wenn das Ammoniumsalz nach Eliminierung von tertiärem Amin ein ungesättigtes System zu bilden vermag, welches den Kondensationspartner durch Michael-Reaktion addiert (vgl. Angewandte Chemie, Brd. 65 [1953], S.473 bis 485).Process for the preparation of quaternary phosphonium compounds Alkylations of carbon and heteroatoms with the help of quaternary ammonium salts are in known in large numbers. Experience has shown that they run smoothly under relatively mild conditions, if either the transfer of a ligand of the ammonium ion to the one to be alkylated Center favored by a mesomerism stabilization of this residue as a carbenium ion or if the ammonium salt after elimination of tertiary amine is an unsaturated System capable of forming which the condensation partner through Michael reaction added (cf. Angewandte Chemie, Brd. 65 [1953], pp.473 to 485).
Über Phosphoralkylierungen mit quartären Ammoniumsalzen ist dagegen erst wenig bekannt. Lediglich Kondensationen von Di- und Trialkylphosphiten mit den Methojodiden bzw. Methosulfaten von Gramin (vgl. Journal of organic Chemistry, Bd. 22 [1957], S.972 bis 975; Recueil des Travaux chimiques des Pays-Bas, Brd. 77 [1958], S.1096 bis 1106) und von den Mannichbasen des Acetons, Acetophenons (vgl. Journal of the American chemical Society, Brd. 77 [1955], S.3101 bis 3103) und ß-Acetylindols (vgl. Journal of the American chemicai Society, Brd. 80 [1958], S.3782 bis 3787; USA.-Patentschrift 2 849 454) wurden beschrieben. On the other hand, there is an opposition to phosphorus alkylation with quaternary ammonium salts little known. Only condensations of di- and trialkyl phosphites with the methoiodides or methosulfates from Gramin (see Journal of organic Chemistry, Vol. 22 [1957], pp. 972 to 975; Recueil des Travaux chimiques des Pays-Bas, Brd. 77 [1958], p.1096 to 1106) and from the Mannich bases of acetone, acetophenone (cf. Journal of the American chemical Society, Brd. 77 [1955], pp.3101 to 3103) and ß-acetylindols (cf. Journal of the American Chemicai Society, Brd. 80 [1958], pp. 3782 to 3787; U.S. Patent 2,849,454) have been described.
Es wurde nun gefunden, daß man quartäre Phosphoniumsalze dadurch erhalten kann, daß man quartäre Salze von Mannichbasen aromatischer oder heterocyclischer Verbindungen in einem organischen Lösungsmittel mit tertiären Phosphinen unter Rückfluß erhitzt. It has now been found that quaternary phosphonium salts can thereby be obtained can be obtained by quaternary salts of Mannich bases of aromatic or heterocyclic Compounds in an organic solvent with tertiary phosphines under reflux heated.
Die Reaktion wird durch das folgende Formelschema veranschaulicht: Als organische Lösungsmittel eignen sich z. B.The reaction is illustrated by the following equation: Suitable organic solvents are, for. B.
Methanol oder Dimethylformamid. Die Umsetzung wird vorzugsweise unter Durchleiten von Stickstoff durchgeführt.Methanol or dimethylformamide. The implementation is preferably under Passing through nitrogen carried out.
Von den als Ausgangsstoffe geeigneten quartären Salzen von Mannichbasen seien vor allem die Methojodide und Methosulfate der Dimethylaminomethylderivate von Antipyrin, Indol, N-Methylindol, Nerolin, Phthalimid und Acetophenon, von den geeigneten tertiären Phosphinen vor allem Triäthyl- und Triphenylphosphin genannt. Of the quaternary salts of Mannich bases suitable as starting materials are especially the methoiodides and methosulfates of the dimethylaminomethyl derivatives of antipyrine, indole, N-methylindole, neroline, phthalimide and acetophenone, of the suitable tertiary phosphines especially called triethyl and triphenylphosphine.
Die Erzeugnisse des erfindungsgemäßen Verfahrens sind wertvolle Zwischenprodukte für die verschiedensten Synthesen. Einige von ihnen eignen sich auch zur Verwendung als Pharmazeutica. The products of the process according to the invention are valuable intermediate products for a wide variety of syntheses. Some of them are also suitable for use as pharmaceuticals.
Beispiel 1 3,87 g (0,01 Mol) Dimethylaminomethyl-antipyrinmethojodid und 3,93 g (0,15 Mol) Triphenylphosphin werden in 25 ccm Dimethylformamid 3 Stunden unter Durchleiten von Stickstoff am Rückfluß gekocht, wonach die Menge des entwickelten Trimethylamins (identifiziert durch Misch-Schmelzpunkt seines Pikrats und kontrolliert durch Auffangen in vorgelegter l/lo n-Salzsäure) 950/0 der Theorie erreicht hat. Nach dem Verdampfen des Lösungsmittels im Vakuum und dem Entfernen des überschüssigen Triphenylphosphins durch Auskochen des pulverisierten glasklaren hellgelben festen Rückstandes werden 5,6 g (96 0/o) eines gelben Produktes vom Schmelzbereich 180 bis 190"C erhalten. Das Umkristallisieren aus Wasser ergibt 3,9 g Antipyrylmethyl-triphenyl-phosphoniumjodid (67 0/o) vom Schmp. 193 bis 194"C. Example 1 3.87 g (0.01 mol) of dimethylaminomethyl antipyrine methoiodide and 3.93 g (0.15 mol) of triphenylphosphine are in 25 cc of dimethylformamide for 3 hours refluxed while bubbling with nitrogen, after which the amount of evolved Trimethylamine (identified by its mixed melting point Picrats and controlled by collecting in 1 / lo n hydrochloric acid) has reached 950/0 of theory. After evaporating the solvent in vacuo and removing the excess Triphenylphosphine by boiling the powdered, crystal clear, light yellow solid 5.6 g (96%) of a yellow product with a melting range of 180 are left behind up to 190 "C. Recrystallization from water gives 3.9 g of antipyrylmethyl-triphenyl-phosphonium iodide (67%) from m.p. 193 to 194 "C.
Beispiel 2 2,9 g (0,0075 Mol) Dimethylaminomethyl-antipyrin-methojodid und 1,8 g (0,015 Mol) Triäthylphosphin entwickeln beim Kochen in 25 ccm Dimethylformamid unter Stickstoff bereits innerhalb von 40 Minuten 900/o der berechneten Menge an Trimethylamin. Nach 3l/2stündigem Kochen wird das Lösungsmittel im Vakuum verdampft, der schmierige gelbe Rückstand aus einem Äthanol-Äther-Gemisch zur Kristallisation gebracht. Man erhält 3 g Antipyrylmethyl-triäthyl-phosphoniumjodid (88°/o) vom Schmp. 179 bis 1800C. Example 2 2.9 g (0.0075 mol) of dimethylaminomethyl antipyrine methoiodide and 1.8 g (0.015 mol) of triethylphosphine develop on boiling in 25 cc of dimethylformamide under nitrogen within 40 minutes 900 / o of the calculated amount of Trimethylamine. After 3l / 2h boiling the solvent is evaporated in vacuo, the greasy yellow residue from an ethanol-ether mixture for crystallization brought. Man receives 3 g of antipyrylmethyl-triethyl-phosphonium iodide (88 ° / o) from m.p. 179 to 1800C.
Beispiel 3 3,0 g (0,01 Mol) Gramin-methosulfat werden mit 0,393 g (0,015 Mol) Triphenylphosphin 1 l/2 Stunden in 30 ccm Methanol unter Stickstoff gekocht. Die Aufarbeitung gemäß der im Beispiel 6 beschriebenen Weise führt nach dem Umkristallisieren aus Wasser zu 3,5 g Skatyl-triphenyl-phosphonium-methylsulfat (70 0/o), eines schwach rosa gefärbten Salzes vom Schmp. 185 bisl86°C. Example 3 3.0 g (0.01 mol) of gramin methosulfate are added with 0.393 g (0.015 mol) triphenylphosphine 1 1/2 hours in 30 cc of methanol under nitrogen cooked. Working up in the manner described in Example 6 follows recrystallization from water to give 3.5 g of skatyl triphenyl phosphonium methyl sulfate (70%), a pale pink colored salt with a melting point of 185 to 186 ° C.
Beim Erwärmen mit Natronlauge tritt Skatolgeruch auf. When heated with caustic soda, the scent odor occurs.
Beispiel 4 N-Methylskatyl-triphenyl-phosphoniumjodid erhält man nach lstündigem Kochen von 3,3 g (0,01 Mol) N-Methylgramin-methojodid mit 0,393 g (0,015 Mol) Triphenylphosphin in 25 ccm Dimethylformamid unter Stickstoff und Aufarbeitung wie im Beispiel 1. Das Umkristallisieren aus Wasser-Äthanol (2:1) ergibt 3,7 g (700/o). Schmp. 218 bis 219"C. Example 4 N-methylskatyl-triphenyl-phosphonium iodide is obtained after Boiling 3.3 g (0.01 mol) of N-methylgramine methoiodide with 0.393 g (0.015 Mol) triphenylphosphine in 25 ccm dimethylformamide under nitrogen and work-up as in Example 1. Recrystallization from water-ethanol (2: 1) gives 3.7 g (700 / o). M.p. 218 to 219 "C.
Beispiel 5 3,6 g (0,01 Mol) x-Dimethylaminomethyl-nerolinmethojodid vom Schmp. 148 bis 149"C und 3,4 g (0,013 Mol) Triphenylphosphin entwickeln beim Kochen in 30 ccm Dimethylformamid unter Stickstoff innerhalb von 90 Minuten 950/0 des zu erwartenden gasförmigen Amins. Nach 2stündiger Reaktionsdauer wird das Lösungsmittel im Vakuum entfernt und der hellgelbe Rückstand mit Methanol-Äther zur Kristallisation gebracht. Example 5 3.6 g (0.01 mol) of x-dimethylaminomethyl-neroline methoiodide of m.p. 148 to 149 "C and 3.4 g (0.013 mol) of triphenylphosphine develop at Boiling in 30 cc of dimethylformamide under nitrogen for 90 minutes 950/0 of the expected gaseous amine. After a reaction time of 2 hours, the solvent becomes removed in vacuo and the pale yellow residue with methanol-ether for crystallization brought.
Man erhält 4,5 g [2-Methoxynaphthyl-(l )-methyl]-triphenyl-phosphoniumjodid (80 0/o). Der Schmelzpunkt ist scharf, schwankt jedoch mit der Erhitzungsgeschwindigkeit zwischen 226 und 245°C. 4.5 g of [2-methoxynaphthyl- (1) -methyl] -triphenylphosphonium iodide are obtained (80 0 / o). The melting point is sharp but fluctuates with the rate of heating between 226 and 245 ° C.
Beispiel 6 3,46 g (0,01 Mol) Phthalimidomethyl-trimethylammoniumjodid und 3,93 g (0,015 Mol) Triphenylphosphin werden in 40 ccm Methanol 4 Stunden unter Durchleiten von Stickstoff (Trimethylaminentwicklung nach 2 Stunden bereits 80°/o) am Rückfluß gekocht. Beim Erkalten fällt ein fast farbloser Niederschlag aus, der abgesaugt und mit Methanol gewaschen wird. Rohausbeute: 5 g (90 0/o) vom Schmelzbereich 255 bis 265"C. Nach dem Umkristallisieren aus Wasser erhält man 3,2 g (58 0/o) Phthalimidomethyl-triphenyl-phosphoniumjodid vom Schmp. 264 bis 267"C (Zersetzung) mit Gelbfärbung ab 255"C. Example 6 3.46 g (0.01 mole) of phthalimidomethyl trimethylammonium iodide and 3.93 g (0.015 mol) of triphenylphosphine are in 40 cc of methanol for 4 hours Passing through nitrogen (trimethylamine development after 2 hours already 80%) refluxed. When cooling down, an almost colorless precipitate separates out, the is suctioned off and washed with methanol. Crude yield: 5 g (90%) from the melting range 255 to 265 ° C. After recrystallization from water, 3.2 g (58%) of phthalimidomethyl triphenylphosphonium iodide are obtained from m.p. 264 to 267 "C (decomposition) with yellow color from 255" C.
Beispiel 7 3,2 g (0,01 Mol) (B-Benzoyläthyl)-trimethyl-ammoniumjodid und 3,93 g (0,015 Mol) Triphenylphosphin werden unter Durchleiten von Stickstoff in 50 ccm Methanol gekocht, bis nach 6 Stunden 950/o der Theorie an Trimethylamin entwickelt worden sind. Example 7 3.2 g (0.01 mol) of (B-benzoylethyl) trimethylammonium iodide and 3.93 g (0.015 mol) of triphenylphosphine are passed through with nitrogen Boiled in 50 cc of methanol until after 6 hours 950 / o of theory of trimethylamine have been developed.
Nach Abdampfen des Lösungsmittels im Vakuum bleibt eine bald erstarrende Schmiere zurück, die nach Zerreiben im Mörser und Auskochen mit Benzol 4 g (ß-Benzoyläthyl)-triphenyl-phosphoniumjodid (77 °/0) vom Schmp. 158 bis l59C liefert.After evaporation of the solvent in vacuo, a soon solidifying remains Smear back, which after grinding in a mortar and boiling with benzene 4 g (ß-benzoylethyl) triphenylphosphonium iodide (77 ° / 0) from m.p. 158 to 159C.
Nach dem Umkristallisieren aus Wasser Schmp. 160 bis 161"C.After recrystallization from water, m.p. 160 to 161 "C.
Claims (1)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
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DEF32129A DE1176657B (en) | 1960-09-15 | 1960-09-15 | Process for the preparation of quaternary phosphonium compounds |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
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DEF32129A DE1176657B (en) | 1960-09-15 | 1960-09-15 | Process for the preparation of quaternary phosphonium compounds |
Publications (1)
Publication Number | Publication Date |
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DE1176657B true DE1176657B (en) | 1964-08-27 |
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DEF32129A Pending DE1176657B (en) | 1960-09-15 | 1960-09-15 | Process for the preparation of quaternary phosphonium compounds |
Country Status (1)
Country | Link |
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DE (1) | DE1176657B (en) |
-
1960
- 1960-09-15 DE DEF32129A patent/DE1176657B/en active Pending
Non-Patent Citations (1)
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