DE2114880A1 - Azaphosphole cpds - used as textile auxiliaries - Google Patents
Azaphosphole cpds - used as textile auxiliariesInfo
- Publication number
- DE2114880A1 DE2114880A1 DE19712114880 DE2114880A DE2114880A1 DE 2114880 A1 DE2114880 A1 DE 2114880A1 DE 19712114880 DE19712114880 DE 19712114880 DE 2114880 A DE2114880 A DE 2114880A DE 2114880 A1 DE2114880 A1 DE 2114880A1
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- DE
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- Prior art keywords
- radical
- alkyl
- substituted
- cycloalkyl
- aralkyl
- 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
- VOIAXMKZWHLLBP-UHFFFAOYSA-N 2h-azaphosphole Chemical compound C=1C=NPC=1 VOIAXMKZWHLLBP-UHFFFAOYSA-N 0.000 title claims 2
- 239000004753 textile Substances 0.000 title description 2
- -1 nitro, sulphonyl Chemical group 0.000 claims abstract description 34
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 14
- 125000003710 aryl alkyl group Chemical group 0.000 claims abstract description 9
- 125000000753 cycloalkyl group Chemical group 0.000 claims abstract description 9
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 9
- 150000002367 halogens Chemical class 0.000 claims abstract description 6
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 6
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 3
- 150000001336 alkenes Chemical class 0.000 claims abstract description 3
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 3
- FVZVCSNXTFCBQU-UHFFFAOYSA-N phosphanyl Chemical group [PH2] FVZVCSNXTFCBQU-UHFFFAOYSA-N 0.000 claims abstract description 3
- 125000005328 phosphinyl group Chemical group [PH2](=O)* 0.000 claims abstract description 3
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 claims abstract description 3
- 125000005499 phosphonyl group Chemical group 0.000 claims abstract description 3
- 125000001863 phosphorothioyl group Chemical group *P(*)(*)=S 0.000 claims abstract description 3
- LFGREXWGYUGZLY-UHFFFAOYSA-N phosphoryl Chemical group [P]=O LFGREXWGYUGZLY-UHFFFAOYSA-N 0.000 claims abstract description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 9
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- 150000003254 radicals Chemical class 0.000 claims description 7
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical group [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 150000005840 aryl radicals Chemical group 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 229920006395 saturated elastomer Polymers 0.000 claims description 5
- 150000007859 azaphosphole derivatives Chemical class 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims description 4
- 239000011574 phosphorus Substances 0.000 claims description 4
- 125000004122 cyclic group Chemical group 0.000 claims description 2
- 125000002560 nitrile group Chemical group 0.000 claims description 2
- CFHIDWOYWUOIHU-UHFFFAOYSA-N oxomethyl Chemical compound O=[CH] CFHIDWOYWUOIHU-UHFFFAOYSA-N 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims 2
- 125000005843 halogen group Chemical group 0.000 claims 2
- 239000011593 sulfur Substances 0.000 claims 2
- IVRMZWNICZWHMI-UHFFFAOYSA-N azide group Chemical group [N-]=[N+]=[N-] IVRMZWNICZWHMI-UHFFFAOYSA-N 0.000 claims 1
- 125000003262 carboxylic acid ester group Chemical class [H]C([H])([*:2])OC(=O)C([H])([H])[*:1] 0.000 claims 1
- 239000003085 diluting agent Substances 0.000 claims 1
- 125000004433 nitrogen atom Chemical group N* 0.000 claims 1
- 125000001424 substituent group Chemical group 0.000 claims 1
- 125000003107 substituted aryl group Chemical group 0.000 claims 1
- 125000003118 aryl group Chemical group 0.000 abstract 3
- 125000000623 heterocyclic group Chemical group 0.000 abstract 2
- 150000001408 amides Chemical class 0.000 abstract 1
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 abstract 1
- 150000002825 nitriles Chemical class 0.000 abstract 1
- 125000002577 pseudohalo group Chemical group 0.000 abstract 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 38
- 238000003756 stirring Methods 0.000 description 8
- UMQRQWDBOYTCHP-UHFFFAOYSA-N n-phosphanylmethanimine Chemical compound PN=C UMQRQWDBOYTCHP-UHFFFAOYSA-N 0.000 description 7
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 7
- 239000002244 precipitate Substances 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 208000003383 pontocerebellar hypoplasia type 3 Diseases 0.000 description 5
- BBHJTCADCKZYSO-UHFFFAOYSA-N 4-(4-ethylcyclohexyl)benzonitrile Chemical compound C1CC(CC)CCC1C1=CC=C(C#N)C=C1 BBHJTCADCKZYSO-UHFFFAOYSA-N 0.000 description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- FUSUHKVFWTUUBE-UHFFFAOYSA-N buten-2-one Chemical compound CC(=O)C=C FUSUHKVFWTUUBE-UHFFFAOYSA-N 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- VHWPQSRFVAOBEG-UHFFFAOYSA-N 2-phenylethyl methanimidate Chemical compound C(OCCC1=CC=CC=C1)=N VHWPQSRFVAOBEG-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- CIUQDSCDWFSTQR-UHFFFAOYSA-N [C]1=CC=CC=C1 Chemical compound [C]1=CC=CC=C1 CIUQDSCDWFSTQR-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 150000003857 carboxamides Chemical group 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- USJRLGNYCQWLPF-UHFFFAOYSA-N chlorophosphane Chemical compound ClP USJRLGNYCQWLPF-UHFFFAOYSA-N 0.000 description 1
- WMKGGPCROCCUDY-PHEQNACWSA-N dibenzylideneacetone Chemical compound C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1 WMKGGPCROCCUDY-PHEQNACWSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000012454 non-polar solvent Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003573 thiols Chemical class 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
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6581—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and nitrogen atoms with or without oxygen or sulfur atoms, as ring hetero atoms
- C07F9/6584—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and nitrogen atoms with or without oxygen or sulfur atoms, as ring hetero atoms having one phosphorus atom as ring hetero atom
-
- 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
- C07F9/46—Phosphinous acids [R2POH], [R2P(= O)H]: Thiophosphinous acids including[R2PSH]; [R2P(=S)H]; Aminophosphines [R2PNH2]; Derivatives thereof
-
- 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
- C07F9/535—Organo-phosphoranes
- C07F9/5355—Phosphoranes containing the structure P=N-
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)
Abstract
Description
Azaphosphole und Verfahren zu ihrer Herstellung Gegenstand der vorliegenden Erfindung sind neue Azaphosphole einschließlich deren mögliche Tautomere sowie ein Verfahren zur Herstellung dieser Verbindungen. Die neuen Verbindungen besitzen die allgemeine Formel In der Formel I bedeuten R1 und R2 gleiche oder verschiedene, verzweigte oder unverzweigte, gesättigte oder ungesättigte Alkylreste mit 1 - 6 C-Atomen, Cycloalkylreste mit 5 oder 6 C-Atomen im Ring, einen Rest der vorstehenden Bedeutung, der Halogen oder Pseudohalogen-Substituenten, bevorzv.gt Pluor oder Chlor, aufweist, nicht substituierte oder substituierte Aralkyl-oder Arylreste, die als Substituenten Halogen, bevorzugt Fluor, Chlor Brom oder Alkylreste mit 1 - 4 C-Atomen, die auch über Stickstoff- oder Säuerstoffatome an einen Phenylrest gebunden sein können, vorstehend genannte Alkyl-, Cycloalkyl -, Aralkyl- und Arylreste, die über N, 0 oder S an den Phosphor gebunden sind oder einen über N gebundenen Rest eines Stickstoffhetercyclus. Ferner können R1 und R2 zusammen mit dem Phosphor einen 5- oder 6-gliedrigen, gesättigten oder ungesättigten Ring bilden, der als weitere Heteroatome 0, S und/oder N enthalten kann. Beispiele für derartige Ringsysteme können z.B. die folgenden Gruppierungen darstellen: R3 bedeutet Wasserstoff, einen unverzweigten oder verzweigten unsubstituierten oder z.B. mit F oder C1 substituierten Alkylrest mit bis zu 17 Kohlenstoffatomen oder Cycloalkylrest mit 5 oder 6 Kohlenstoffatomen im Ring, weiterhin einen Aralkyl-oder Arylrest, der durch Halogene, Alkyl- und/oder Alkoxygruppen substituiert sein kann, oder einen über Sauerstoff gebundenen Alkyl-, Cycloalkyl- oder Aralkylrest der vorstehenden Art.Azaphospholes and Process for Their Production The present invention relates to new azaphospholes including their possible tautomers and a process for the production of these compounds. The new compounds have the general formula In formula I, R1 and R2 denote identical or different, branched or unbranched, saturated or unsaturated alkyl radicals with 1 - 6 carbon atoms, cycloalkyl radicals with 5 or 6 carbon atoms in the ring, a radical of the above meaning which is halogen or pseudohalogen Substituents, preferably fluorine or chlorine, unsubstituted or substituted aralkyl or aryl radicals, the substituents halogen, preferably fluorine, chlorine, bromine or alkyl radicals with 1-4 carbon atoms, which are also attached to a phenyl radical via nitrogen or oxygen atoms The above-mentioned alkyl, cycloalkyl, aralkyl and aryl radicals which are bonded to the phosphorus via N, O or S or a radical of a nitrogen heterocycle bonded via N can be bonded. Furthermore, R1 and R2, together with the phosphorus, can form a 5- or 6-membered, saturated or unsaturated ring which can contain 0, S and / or N as further heteroatoms. Examples of such ring systems can be, for example, the following groupings: R3 denotes hydrogen, an unbranched or branched unsubstituted or, for example, F or C1-substituted alkyl radical with up to 17 carbon atoms or a cycloalkyl radical with 5 or 6 carbon atoms in the ring, furthermore an aralkyl or aryl radical which is substituted by halogens, alkyl and / or alkoxy groups can be, or an alkyl, cycloalkyl or aralkyl radical of the above type bonded via oxygen.
R4 kann einen aliphatischen oder aromatischen Acylrest oder Formylrest, einen Carbonsäureester - oder Carbonsäureamidrest, eine Nitrilgruppe, eine Phosphonyl-, Phosphoryl-, Phosphinyl-, Phosphonium-, Phosphino-, Nitro-, Sulfonyl-, Thiophosphonyl-, Thiophosphoryl-, Thiophosphinylgruppe oder den Rest eines Azomethinderivats bedeuten.R4 can be an aliphatic or aromatic acyl radical or formyl radical, a carboxylic acid ester or carboxamide residue, a nitrile group, a phosphonyl, Phosphoryl, phosphinyl, phosphonium, phosphino, nitro, sulfonyl, thiophosphonyl, Mean thiophosphoryl, thiophosphinyl group or the remainder of an azomethine derivative.
R5 kann Wasserstoff, einen Alkylrest, bevorzugt Methyl, oder einen unsubstituierten oder z.B. mit F, C1, N02, oder CN substituierten Phenylrest bedeuten oder die Bedeutung von R4 annehmen.R5 can be hydrogen, an alkyl radical, preferably methyl, or a denote phenyl radicals which are unsubstituted or substituted, for example, by F, C1, N02, or CN or take on the meaning of R4.
Beispie].e für <iie erfindungsgemäßen Substanzen sind: 2,2-Dimethyl-4-cyano-5-phenyl-1,2-azaphosphol, 2,2-Dimethyl-4-methoxyearbonyl-5-phenyl-1,2-azaphoßphol, 2,2-Dimethyl-4-cyano-5-äthoxy-1,2-azaphosphol, 2,2-Diphenyl-4-cyano-5-äthoxy-1,2-azaphosphol, 2,2-Dimethyl-4-methoxycarbonyl-5-äthoxy-1,2-azaphosphol, 2,2-Dimethyl-4-acetyl-5-äthoxy-1,2-azaphosphol, 2,2-Dimethyl-5-phenyl-4-benzalacetyl-5-Xthoxy-1,2-azaphophol, I)ie Erfindung betrifft weiterhin ein Verfahren zur Herstellung der Azaphosphole I, das dadurch gekennzeichnet ist, daß aquimolare Mengen eines Alkoxymethylenamino-phosphins TI bei dem R1, R2 und R3 dle vorstehenden Bedeutungen besitzen können und R6 einen Alkyl-, Cycloalkyl- oder Aralkylrest, bevorzugt Methyl- oder Äthyl- bedeutet, und eines aktivierten Olefins III bei dem R4 und R5 die vorstehenden Bedeutungen besitzen können, ohne Lösungsmittel oder in einem gegenüber den Reaktan--ten inerten Lösungsmittel w.e z.B. Diäthyläther, Methylenchlorid oder Acetonitril bei -30 bis +100 ºC, bevorzugt bei 20 bis 600C, umgesetzt werden. Dabei läuftEeine Reaktion im Sinne der folgenden Gliederung ab: Die Reaktion läuft üblicherweise bei Normaldruck ab. Die Anwendung von erhöhtem bzw. vermindertem Druck ist jedoch ebenfalls möglich.Examples of the substances according to the invention are: 2,2-dimethyl-4-cyano-5-phenyl-1,2-azaphosphole, 2,2-dimethyl-4-methoxy-carbonyl-5-phenyl-1,2-azaphosphol , 2,2-dimethyl-4-cyano-5-ethoxy-1,2-azaphosphole, 2,2-diphenyl-4-cyano-5-ethoxy-1,2-azaphosphole, 2,2-dimethyl-4-methoxycarbonyl -5-ethoxy-1,2-azaphosphole, 2,2-dimethyl-4-acetyl-5-ethoxy-1,2-azaphosphole, 2,2-dimethyl-5-phenyl-4-benzalacetyl-5-xthoxy-1 , 2-azaphophol, I) The invention further relates to a process for the preparation of the azaphospholes I, which is characterized in that equimolar amounts of an alkoxymethyleneamino-phosphine TI in which R1, R2 and R3 can have the above meanings and R6 denotes an alkyl, cycloalkyl or aralkyl radical, preferably methyl or ethyl, and an activated olefin III in which R4 and R5 can have the above meanings, can be reacted without a solvent or in a solvent which is inert towards the reactants, such as diethyl ether, methylene chloride or acetonitrile at -30 to +100 ° C, preferably at 20 to 60 ° C. A reaction takes place in the sense of the following structure: The reaction usually takes place at normal pressure. However, it is also possible to use increased or reduced pressure.
Die Verbindungen I fallen dabei aus der Reaktionslösung kristallin und in reiner Porm aus oder kristallisieren nach Abziehen des Lösungsmittels. Sie sind bis zu ihrem Schmelzpunkt thermostabil, verändern sich aber beim Zutritt von Feuchtigkeit.The compounds I fall out of the reaction solution in crystalline form and in pure form or crystallize after removal of the solvent. she are thermally stable up to their melting point, but change when exposed to Humidity.
Die Reaktionskomponenten II können aus einem Chlorphosphin, (oder dessen Hydrochlorid) wie z.B. RlR2PCl (worin R1 und R2 wieder-die bereits erwähnten Bedeutungen haben) und einem Imin, wie z.B. HN = CR3 - OR6 (R3 bzw. R6 wie oben) unter Zusatz von einem (bzw. zwei) Moläquivalent einer Hilfsbase, z.B. Triäthylamin, in einem unpolaren Lösungsmittel, z.B.The reaction components II can consist of a chlorophosphine, (or its hydrochloride) such as RlR2PCl (in which R1 and R2 again - those already mentioned Have meanings) and an imine, such as HN = CR3 - OR6 (R3 or R6 as above) with the addition of one (or two) molar equivalents of an auxiliary base, e.g. triethylamine, in a non-polar solvent, e.g.
Diäthyläther hergestellt werden. Feuchtigkeit und zum Teil auch der Luftsauerstoff sind hierbei auszuschließen.Diethyl ether can be produced. Moisture and partly also the Atmospheric oxygen is to be excluded here.
Das bei der Umsetzung ausfallende Hydrochlorid der Hilfsbase wird abgetrennt und das Filtrat als solches oder nach Abziehen des Lösungsmittels mit III wie vorstehend beschrieben umgesetzt.The hydrochloride which precipitates during the implementation of the auxiliary base is separated and the filtrate as such or after removal of the solvent with III implemented as described above.
Verbindungen II, in denen R1 und/oder R2 über N, 0, S gebundene Reste bedeuten, können auch aus II(in denen R1 und/oder R2 C1 bedeutet),durch Umsetzen mit Aminen bzw. Alkoholen oder Thiolen und einer Hilfsbase hergestellt werden.Compounds II in which R1 and / or R2 radicals bonded via N, O, S mean, can also from II (in which R1 and / or R2 means C1), by reaction be prepared with amines or alcohols or thiols and an auxiliary base.
Die erfindungsgemäßen Verbindungen sind sehr gut für den Einsatz als Textilhilfsmittel geeignet.The compounds of the invention are very good for use as a Textile auxiliaries suitable.
Die Beispiele erläutern die Erfindung: Beispiel 1: 2, 2-Dimethyl-4-cyano-5-phenyl-l , 2-azaphosphol: In eine Lösung von 10 mMol des Methylenaminophosphins aus Dimethylohlorphosphin und Phenyläthoxymethylenamin in etwa 50 ml trockenem Äther werden unter Eiskühlung und Rühren 10 mMol Acrylnitril in 5 ml trockenen Äther zugetropft. Nach weiterem 3 stündigem Rühren bei Raumtemperatur wird der ausgefallene farblose Niederschlag abgefrittet, 2 mal mit je 4 ml Äther gewaschen und getrocknet.The examples explain the invention: Example 1: 2,2-Dimethyl-4-cyano-5-phenyl-1,2-azaphosphole: In a solution of 10 mmol of methylenaminophosphine from dimethylohlorphosphine and phenylethoxymethyleneamine in about 50 ml of dry ether, 10 mmol of acrylonitrile in 5 ml of dry ether are added dropwise while cooling with ice and stirring. After stirring for a further 3 hours at room temperature, the colorless precipitate which has separated out is fritted off, washed twice with 4 ml of ether each time and dried.
Blaßgelbe Kristalle, Fp. 142 - 1440 unter Zers.; Ausbeute 1,2 g = 56 % NMR-Spektren: OH3: 6 1H = -1.70 ppm, JPCH = 14,2 Hz; CH2 # lH = - 3,12 ppm, JPCH = 10,0 Hz; #31P = -68,9 ppm.Pale yellow crystals, m.p. 142-1440 under dec .; Yield 1.2g = 56% NMR spectra: OH3: 6 1H = -1.70 ppm, JPCH = 14.2 Hz; CH2 # lH = - 3.12 ppm, JPCH = 10.0 Hz; # 31P = -68.9 ppm.
Beispiel 2: 2s2-Dimethyl-4-methoxyearbonyl-5-phenyl-1,2-azaphosphol: Die ätherische Lösung von 10 mMol des oben angegebenen Methylenaminophosphins wird bei Raumtemperatur unter Rühren mit 10 mMol Acrylsäuremethylester versetzt. Nach etwa 5 Min. tritt ein erster Niederschlag auf. Nach 2 Tagen Rühren bei Raumtemperatur werden die gelben Kristalle abgefrittet, mit Äther gewaschen und getrocknet. Fp. 103 - 1050 unter Zers.; Ausbeute: 1,2 g = 48 .Example 2: 2s2-Dimethyl-4-methoxyearbonyl-5-phenyl-1,2-azaphosphole: The ethereal solution of 10 mmol of the methylenaminophosphine given above is mixed with 10 mmol of methyl acrylate at room temperature while stirring. A first precipitate appears after about 5 minutes. After stirring for 2 days at room temperature, the yellow crystals are fritted off, washed with ether and dried. M.p. 103-1050 under dec .; Yield: 1.2 g = 48.
NMR-Spektren : PCH3: #1H = - 1,67 ppm, JPCH = 13,5 Hz; CH2 #1H = - 3,19 ppm, JPCH = 9,3 Hz; OCH3 : #1H = - 3,49 ppm; # 31P = -42,4 ppm.NMR spectra: PCH3: # 1H = -1.67 ppm, JPCH = 13.5 Hz; CH2 # 1H = - 3.19 ppm, JPCH = 9.3 Hz; OCH3: # 1H = - 3.49 ppm; # 31P = -42.4 ppm.
Beispiel 3: 2,2-Dimethyl-4-cyano-5-äthoxy-1,2-azaphosphol: Eine Lösung von 10 mMol des Methylenaminophosphins in 50 ml trockenem Äther wird unter Rühren und Kühlen auf 0 ºC mit 10 mMol Acrylnitril in 10 ml Äther tropfenweise versetzt. Nach weiteren 15 Stunden Rühren bei Raumtemperatur wird der Niederschlag abgefrittet, mit Äther gewaschen und getrocknet.Example 3: 2,2-Dimethyl-4-cyano-5-ethoxy-1,2-azaphosphole: 10 mmol of acrylonitrile in 10 ml of ether are added dropwise to a solution of 10 mmol of methylenaminophosphine in 50 ml of dry ether, while stirring and cooling to 0 ° C. After stirring for a further 15 hours at room temperature, the precipitate is fritted off, washed with ether and dried.
Farolose Kristalle, Fp 145 - 1500 unter Zers.; Ausbeute 1,25 g = 65 %.Farolose crystals, m.p. 145-1500 under dec .; Yield 1.25g = 65 %.
NMR-Spektrum: PCH3 : #1H = - 1,75 ppm, JPCH = 14,0 Hz; PCH2 : A 1H = -3s05 ppm, JpCEI = 11,2 Hz; C2H5 : # 1H = -4,26 ppm, -1,28 ppm, JHCCH - 7,1 Hz.Nuclear Magnetic Resonance Spectrum: PCH3: # 1H = -1.75 ppm, JPCH = 14.0 Hz; PCH2: A 1H = -3s05 ppm, JpCEI = 11.2 Hz; C2H5: # 1H = -4.26 ppm, -1.28 ppm, JHCCH - 7.1 Hz.
Beispiel 4: 2,2-Diphenyl-4-cyano-5äthoxy-1,2-azaphosphol : Die ätherische Lösung von 10 mMol des Methylenaminophosphins in 50 ml Äther wird bei 200 mit 10 mMol Acrylnitril versetzt.Example 4: 2,2-Diphenyl-4-cyano-5ethoxy-1,2-azaphosphole: The ethereal solution of 10 mmol of methylenaminophosphine in 50 ml of ether is mixed with 10 mmol of acrylonitrile at 200.
Dann wird noch 15 Stunden gerührt, der Niederschlag abgefrittet, mit Äther gewaschen und getrocknet.The mixture is then stirred for a further 15 hours, and the precipitate is fritted off with Ether washed and dried.
Blaßgelbe Kristalle, Fp.107 - 1100 unter Zers.; Ausbeute 1,35 g = 42 r.Pale yellow crystals, m.p. 107-1100 under dec .; Yield 1.35g = 42 r.
NMR-Spektrum: PCH2 : 6 1H = 13,51 ppm, JPCH = 1C,9 Hz; C2H5 : #1H = - 4,47 ppm, - 1,32 ppm, JHCCH = 7,2 Hz.Nuclear Magnetic Resonance Spectrum: PCH2: 6 1H = 13.51 ppm, JPCH = 1C, 9 Hz; C2H5: # 1H = - 4.47 ppm, - 1.32 ppm, JHCCH = 7.2 Hz.
C C H N Mol.Gewicht Ber. 70,1 5,6 9,1 308,3 gef. 69,7 5,6 9,2 307 Beispiel 5: 2,2-Dimethyl-4-methoxycarbonyl-5-äthoxy-1,2-azaphosphol : Die ätherische Lösung von 10 mMol des Methylenaminophosphins wird mit 10 mMol Acrylsäuremethylester in 10 ml Äther unter Rühren bei 0 ºC tropfenweise versetzt. Dann wird noch 15 Stunden bei Raumtemperatur gerührt. Die farblösen Kristalle werden abgefrittet und mit Äther gewaschen. Weitere Kristalle wurden durch Abziehen des Äthers und Alkohols, erneutes Versetzen mit Äther und 10 Min. Rühren gewonnen.CCHN Mol. Weight Calc. 70.1 5.6 9.1 308.3 found. 69.7 5.6 9.2 307 Example 5: 2,2-Dimethyl-4-methoxycarbonyl-5-ethoxy-1,2-azaphosphole: 10 mmol of methyl acrylate in 10 ml of ether are added dropwise to the ethereal solution of 10 mmol of methylenaminophosphine while stirring at 0.degree. The mixture is then stirred for a further 15 hours at room temperature. The colorless crystals are fritted off and washed with ether. Further crystals were obtained by stripping off the ether and alcohol, adding ether again and stirring for 10 minutes.
Ausbeute 1,3 g = 60 %; Fp. 126 - 1300 unter Zers.Yield 1.3 g = 60%; Mp. 126-1300 under decomp.
NMR-Spektrum: PCH3 : #1H r -1,72 ppm JPCH = 14,0 Hz; PCH2 : #1H = - 3,08 ppm, JPCH = 10,5 Hz; OCH3 : #1H = -3,52 ppm; O2H5 : # 1H = -4,27 ppm, -1,28 ppm, JHCCH = 7,2 Hz Beispiel 6: 2,2-Dimethyl-4-acetyl-5-äthoxy-1,2-azaphosphol : Die ätherische Lösung von 10 mMol des Methylenaminophosphins wird mit 10 mMol Methylvinylketon versetzt und bei Raumtemperatur 24 Stunden gerührt. Der ausgefallene Niederschlag wird mit trockenem Äther gewaschen, abgefrittet und getrocknet.Nuclear Magnetic Resonance Spectrum: PCH3: # 1H r -1.72 ppm JPCH = 14.0 Hz; PCH2: # 1H = -3.08 ppm, JPCH = 10.5 Hz; OCH3: # 1H = -3.52 ppm; O2H5: # 1H = -4.27 ppm, -1.28 ppm, JHCCH = 7.2 Hz Example 6: 2,2-Dimethyl-4-acetyl-5-ethoxy-1,2-azaphosphole: The ethereal solution of 10 mmol of methylenaminophosphine is mixed with 10 mmol of methyl vinyl ketone and stirred at room temperature for 24 hours. The deposited precipitate is washed with dry ether, fritted and dried.
Ausbeute: 1,3 g = 65 %; Zers. 130 - 1350 (Braunfärbung) NMR-Spektrum: PCH3 : 6 1H = -1,73 ppm, JPCH = 14,1 Hz; PCH2 : #1H = - 3,14 ppm, JPCH = 9,5 Hz; C(O)CH3: #1H = -2,17 ppm; 02H5 : S 1H = -4,32 ppm, -1,34 ppm, JHCCH = 7,2 Hz Beispiel 7t 2,2-Dimethyl-3-phenyl-4-benzalacetyl-5-äthoxy-1,2-azaphoSphor Die Ätherische Lösung von 10 mMol des Methylenaminophosphins wird mit 10 mMol Dibenzalaceton versetzt und bei Raumtemperatur 24 Stunden gerührt. Der ausgefallene intesiv gelbe Niederschlag wird mit trockenem Äther gewaschen, abgefrittet und aus Methylenchlorid / Äther umkristalliert.Yield: 1.3 g = 65%; Decomp. 130-1350 (brown color) NMR spectrum: PCH3: 6 1H = -1.73 ppm, JPCH = 14.1 Hz; PCH2: # 1H = -3.14 ppm, JPCH = 9.5 Hz; C (O) CH3: # 1H = -2.17 ppm; 02H5: S 1H = -4.32 ppm, -1.34 ppm, JHCCH = 7.2 Hz Example 7t 2,2-Dimethyl-3-phenyl-4-benzalacetyl-5-ethoxy-1,2-azaphoSphor The ethereal solution of 10 mmol of methylenaminophosphine is mixed with 10 mmol of dibenzalacetone and stirred at room temperature for 24 hours. The resulting intense yellow precipitate is washed with dry ether, fritted and recrystallized from methylene chloride / ether.
Ausbeute : 2 g = 55 %, Fp. 190 - 195 ºC unter Zers.Yield: 2 g = 55%, m.p. 190-195 ° C with decomp.
NMR~Spektrum : PCH3 : #1H = - 1,22 u. - 1,73 ppm,JPCH = 13,6 u. 13,5 Hz; PCH : #1H = - 4,63 ppm, JPCH = 16,3 Hz; C2H5 : #1H = - 4,47 ppm, - 1,48 ppm, JHCCH = 7,2 Hz.Nuclear Magnetic Resonance Spectrum: PCH3: # 1H = -1.22 and -1.73 ppm, JPCH = 13.6 and 13.5 Hz; PCH: # 1H = -4.63 ppm, JPCH = 16.3 Hz; C2H5: # 1H = - 4.47 ppm, - 1.48 ppm, JHCCH = 7.2 Hz.
Claims (3)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19712114880 DE2114880A1 (en) | 1971-03-27 | 1971-03-27 | Azaphosphole cpds - used as textile auxiliaries |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19712114880 DE2114880A1 (en) | 1971-03-27 | 1971-03-27 | Azaphosphole cpds - used as textile auxiliaries |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE2114880A1 true DE2114880A1 (en) | 1972-10-12 |
Family
ID=5802940
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE19712114880 Pending DE2114880A1 (en) | 1971-03-27 | 1971-03-27 | Azaphosphole cpds - used as textile auxiliaries |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE2114880A1 (en) |
-
1971
- 1971-03-27 DE DE19712114880 patent/DE2114880A1/en active Pending
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