DE1193942B - Process for the production of tertiary phosphines - Google Patents
Process for the production of tertiary phosphinesInfo
- Publication number
- DE1193942B DE1193942B DES80694A DES0080694A DE1193942B DE 1193942 B DE1193942 B DE 1193942B DE S80694 A DES80694 A DE S80694A DE S0080694 A DES0080694 A DE S0080694A DE 1193942 B DE1193942 B DE 1193942B
- Authority
- DE
- Germany
- Prior art keywords
- hydrogen polysiloxane
- oxide
- general formula
- tertiary phosphines
- hours
- 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 8
- 150000003003 phosphines Chemical group 0.000 title claims description 5
- 238000004519 manufacturing process Methods 0.000 title description 4
- -1 o-anisyl Chemical group 0.000 claims description 34
- 229920001296 polysiloxane Polymers 0.000 claims description 17
- 229910052739 hydrogen Inorganic materials 0.000 claims description 14
- 239000001257 hydrogen Substances 0.000 claims description 14
- MPQXHAGKBWFSNV-UHFFFAOYSA-N oxidophosphanium Chemical class [PH3]=O MPQXHAGKBWFSNV-UHFFFAOYSA-N 0.000 claims description 6
- AUONHKJOIZSQGR-UHFFFAOYSA-N oxophosphane Chemical compound P=O AUONHKJOIZSQGR-UHFFFAOYSA-N 0.000 claims description 5
- 150000003377 silicon compounds Chemical class 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 3
- JHYNEQNPKGIOQF-UHFFFAOYSA-N 3,4-dihydro-2h-phosphole Chemical group C1CC=PC1 JHYNEQNPKGIOQF-UHFFFAOYSA-N 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 125000003342 alkenyl group Chemical group 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 125000000392 cycloalkenyl group Chemical group 0.000 claims description 2
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 125000004437 phosphorous atom Chemical group 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 30
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- 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 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- FIQMHBFVRAXMOP-UHFFFAOYSA-N triphenylphosphane oxide Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)(=O)C1=CC=CC=C1 FIQMHBFVRAXMOP-UHFFFAOYSA-N 0.000 description 7
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 5
- 238000003756 stirring Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 239000000852 hydrogen donor Substances 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- SLESMSCUKLYOGC-UHFFFAOYSA-N 1-[bis[(2-methoxyphenyl)methyl]phosphorylmethyl]-2-methoxybenzene Chemical compound COC1=CC=CC=C1CP(=O)(CC=1C(=CC=CC=1)OC)CC1=CC=CC=C1OC SLESMSCUKLYOGC-UHFFFAOYSA-N 0.000 description 1
- VGSVITFVAXDZAL-UHFFFAOYSA-N 1-bis(2-methylphenyl)phosphoryl-2-methylbenzene Chemical compound CC1=CC=CC=C1P(=O)(C=1C(=CC=CC=1)C)C1=CC=CC=C1C VGSVITFVAXDZAL-UHFFFAOYSA-N 0.000 description 1
- MNZAKDODWSQONA-UHFFFAOYSA-N 1-dibutylphosphorylbutane Chemical compound CCCCP(=O)(CCCC)CCCC MNZAKDODWSQONA-UHFFFAOYSA-N 0.000 description 1
- ZSSWXNPRLJLCDU-UHFFFAOYSA-N 1-diethylphosphorylethane Chemical compound CCP(=O)(CC)CC ZSSWXNPRLJLCDU-UHFFFAOYSA-N 0.000 description 1
- FPIPGXGPPPQFEQ-UHFFFAOYSA-N 13-cis retinol Natural products OCC=C(C)C=CC=C(C)C=CC1=C(C)CCCC1(C)C FPIPGXGPPPQFEQ-UHFFFAOYSA-N 0.000 description 1
- YMKWWHFRGALXLE-UHFFFAOYSA-N 4-methyl-1-phenyl-2,3-dihydro-1$l^{5}-phosphole 1-oxide Chemical compound C1CC(C)=CP1(=O)C1=CC=CC=C1 YMKWWHFRGALXLE-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 241001417495 Serranidae Species 0.000 description 1
- FPIPGXGPPPQFEQ-BOOMUCAASA-N Vitamin A Natural products OC/C=C(/C)\C=C\C=C(\C)/C=C/C1=C(C)CCCC1(C)C FPIPGXGPPPQFEQ-BOOMUCAASA-N 0.000 description 1
- FPIPGXGPPPQFEQ-OVSJKPMPSA-N all-trans-retinol Chemical compound OC\C=C(/C)\C=C\C=C(/C)\C=C\C1=C(C)CCCC1(C)C FPIPGXGPPPQFEQ-OVSJKPMPSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- LEFPWWWXFFNJAA-UHFFFAOYSA-N dicyclohexylphosphorylcyclohexane Chemical compound C1CCCCC1P(C1CCCCC1)(=O)C1CCCCC1 LEFPWWWXFFNJAA-UHFFFAOYSA-N 0.000 description 1
- PDDYFPPQDKRJTK-UHFFFAOYSA-N diphenyl(prop-2-enyl)phosphane Chemical compound C=1C=CC=CC=1P(CC=C)C1=CC=CC=C1 PDDYFPPQDKRJTK-UHFFFAOYSA-N 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- YCDHVKWTZBVDKD-UHFFFAOYSA-L disodium 6-hydroxy-5-[(4-sulfonatonaphthalen-1-yl)diazenyl]naphthalene-2-sulfonate Chemical compound [Na+].[Na+].C1=CC=C2C(N=NC3=C4C=CC(=CC4=CC=C3O)S([O-])(=O)=O)=CC=C(S([O-])(=O)=O)C2=C1 YCDHVKWTZBVDKD-UHFFFAOYSA-L 0.000 description 1
- 125000003827 glycol group Chemical group 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- VPYWKXLEQWQLOA-UHFFFAOYSA-N methanedithione;tricyclohexylphosphane Chemical compound S=C=S.C1CCCCC1P(C1CCCCC1)C1CCCCC1 VPYWKXLEQWQLOA-UHFFFAOYSA-N 0.000 description 1
- WCYWZMWISLQXQU-UHFFFAOYSA-N methyl Chemical compound [CH3] WCYWZMWISLQXQU-UHFFFAOYSA-N 0.000 description 1
- SFMJNHNUOVADRW-UHFFFAOYSA-N n-[5-[9-[4-(methanesulfonamido)phenyl]-2-oxobenzo[h][1,6]naphthyridin-1-yl]-2-methylphenyl]prop-2-enamide Chemical compound C1=C(NC(=O)C=C)C(C)=CC=C1N1C(=O)C=CC2=C1C1=CC(C=3C=CC(NS(C)(=O)=O)=CC=3)=CC=C1N=C2 SFMJNHNUOVADRW-UHFFFAOYSA-N 0.000 description 1
- 150000002828 nitro derivatives Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000006772 olefination reaction Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- PARWUHTVGZSQPD-UHFFFAOYSA-N phenylsilane Chemical compound [SiH3]C1=CC=CC=C1 PARWUHTVGZSQPD-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- RLZMYANQLOCZOB-UHFFFAOYSA-M tributyl(methyl)phosphanium;iodide Chemical compound [I-].CCCC[P+](C)(CCCC)CCCC RLZMYANQLOCZOB-UHFFFAOYSA-M 0.000 description 1
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 1
- PPDADIYYMSXQJK-UHFFFAOYSA-N trichlorosilicon Chemical compound Cl[Si](Cl)Cl PPDADIYYMSXQJK-UHFFFAOYSA-N 0.000 description 1
- RXJKFRMDXUJTEX-UHFFFAOYSA-N triethylphosphine Chemical compound CCP(CC)CC RXJKFRMDXUJTEX-UHFFFAOYSA-N 0.000 description 1
- COIOYMYWGDAQPM-UHFFFAOYSA-N tris(2-methylphenyl)phosphane Chemical compound CC1=CC=CC=C1P(C=1C(=CC=CC=1)C)C1=CC=CC=C1C COIOYMYWGDAQPM-UHFFFAOYSA-N 0.000 description 1
- UYUUAUOYLFIRJG-UHFFFAOYSA-N tris(4-methoxyphenyl)phosphane Chemical compound C1=CC(OC)=CC=C1P(C=1C=CC(OC)=CC=1)C1=CC=C(OC)C=C1 UYUUAUOYLFIRJG-UHFFFAOYSA-N 0.000 description 1
- 235000019155 vitamin A Nutrition 0.000 description 1
- 239000011719 vitamin A Substances 0.000 description 1
- 229940045997 vitamin a Drugs 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
- C07F9/50—Organo-phosphines
- C07F9/505—Preparation; Separation; Purification; Stabilisation
- C07F9/509—Preparation; Separation; Purification; Stabilisation by reduction of pentavalent phosphorus derivatives, e.g. -P=X with X = O, S, Se or -P-Hal2
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 tertiären Phosphinen Die Erfindung bezieht sich auf ein Verfahren zur Herstellung von tertiären Phosphinen, durch Reduktion der entsprechenden Phosphinoxyde, welche z. B. als Nebenprodukte bei der Vitamin-A-Herstellung durch Carbonyl-Olefinierung nach Mittig anfallen (vgl.Process for the preparation of tertiary phosphines The invention relates to refer to a process for the production of tertiary phosphines, by reduction the corresponding phosphine oxides, which z. B. as by-products in vitamin A production incurred by carbonyl olefination towards the center (cf.
Angew. Chemie, 72 [1960], S. 811).Angew. Chemie, 72 [1960], p. 811).
Wie von J.N.Collic und F. Reynolds (J. Chem. Soc., 107 [1915], S. 367) beschrieben wurde, ist Triäthylphosphinoxyd äußerst widerstandsfähig gegen eine Reihe von Reduktionsmitteln. Dennoch gelang es diesen Autoren das Phosphinoxyd in umständlicher Weise in Triäthylphosphin umzusetzen. As described by J.N. Collic and F. Reynolds (J. Chem. Soc., 107 [1915], p. 367), triethylphosphine oxide is extremely resistant to a range of reducing agents. Nevertheless, these authors succeeded in the phosphine oxide to implement in a complicated manner in triethylphosphine.
Neuerdings sind z. B. von L. H o rn er und Mitarbeitern (Chem. Ber., 91 [1958], S. 1583) und von G. Hamprecht und M. Schwarzmann (deutsche Auslegeschrift 1122 952) Verfahren bekanntgegeben worden, nach denen Phosphinoxyde mit Hilfe von Alanaten reduziert wurden. Ein Nachteil dieser Verfahren ist unter anderem, daß verhältnismäßig kostspielige Reduktionsmittel zur Anwendung gebracht werden sollen.Recently z. B. by L. H o rn er and co-workers (Chem. Ber., 91 [1958], p. 1583) and by G. Hamprecht and M. Schwarzmann (German interpretation 1122 952) procedure has been announced, after which phosphine oxides with the help of Alanates were reduced. A disadvantage of this method is, among other things, that relatively expensive reducing agents are to be used.
Die vorliegende Erfindung ermöglicht nunmehr die Herstellung von tertiären Phosphinen durch Reduktion der entsprechenden Phosphinoxyde mittels wohlfeiler Reduktionsmittel, welche außerdem völlig beständig und lagerfähig sind. Das erfindungsgemäße Verfahren wird dadurch gekennzeichnet, daß man ein Phosphinoxyd der allgemeinen Formel R(R') (R")P = O 0 in der R, R' und R" gleiche oder verschiedene Alkyl-, Alkenyl-, Cycloalkyl-, Cycloalkenyl-, Aryl-, o-Anisyl-, Aralkyl- oder Alkarylreste bedeuten, wobei R und R' zusammen mit dem Phosphoratom den gegebenenfalls durch die Methylgruppe substituierten Phospholinring der allgemeinen Formel bilden können, init einer organischen Siliciumverbindung, welche eine oder mehrere Si-H-Bindungen enthält, bei erhöhter Temperatur umsetzt.The present invention now enables the production of tertiary phosphines by reducing the corresponding phosphine oxides by means of cheaper reducing agents, which are also completely stable and storable. The process according to the invention is characterized in that a phosphine oxide of the general formula R (R ') (R ") P = O 0 in which R, R' and R" are identical or different alkyl, alkenyl, cycloalkyl, cycloalkenyl , Aryl, o-anisyl, aralkyl or alkaryl radicals, where R and R 'together with the phosphorus atom denote the phospholine ring of the general formula which is optionally substituted by the methyl group can form, with an organic silicon compound which contains one or more Si-H bonds, reacted at elevated temperature.
Zwar haben S.Nitsche und M.Wick schon beschrieben (Ang. Chem., 69 [1957], S. 96), daß solche Siliciumverbindungen in Anwesenheit eines Katalysators (eine organische Zinnverbindung) zur Reduktion organischer Verbindungen, wie z. B. Carbonyl- oder Nitroverbindungen, geeignet sind, wobei die Reduktion vorzugsweise in Anwesenheit eines Wasserstoffdonators wie z. B. Alkohol, vorgenommen wird. Es war jedoch nicht vorauszusehen, daß diese Silicium-Wasserstoff-Verbindungen auch zur Reduktion von den bekannterweise schwer reduzierbaren Phosphinoxyden brauchbar sein würden. Tatsächlich hat der Erfinder gefunden, daß unter den von N i ts c h e und Wick beschriebenen Bedingungen, d. h. in Anwesenheit des Katalysators und Wasserstoffdonators, keine Reduktion des Phosphinoxyds stattfindet. Offensichtlich liegt ein anderer Reaktionsmechanismus vor, wie auch aus der von dem Erfinder gefundenen Tatsache hervorgeht, daß z. B. Ketone sich mit Hilfe von Methylwasserstoffpolysiloxanen allein, d. h. in Abwesenheit des Katalysators und Wasserstoffdonators, nicht reduzieren lassen. Although S. Nitsche and M. Wick have already described (Ang. Chem., 69 [1957], p. 96) that such silicon compounds in the presence of a catalyst (an organic tin compound) for reduction organic compounds, such as. B. Carbonyl or nitro compounds are suitable, with the reduction being preferred in the presence of a hydrogen donor such as. B. alcohol is made. It However, it was not foreseeable that these silicon-hydrogen compounds would also useful for the reduction of the phosphine oxides which are known to be difficult to reduce would be. In fact, the inventor has found that among the N i ts c h e and Wick described conditions, d. H. in the presence of the catalyst and Hydrogen donor, no reduction of the phosphine oxide takes place. Apparently there is a different reaction mechanism, as well as that found by the inventor The fact that z. B. ketones with the help of methyl hydrogen polysiloxanes alone, d. H. in the absence of the catalyst and hydrogen donor, do not reduce permit.
Die Erfindung ist insbesondere von Bedeutung für die Reduktion von Triarylphosphinoxyden, wie z. B. The invention is particularly important for the reduction of Triarylphosphine oxides, e.g. B.
Triphenylphosphinoxyd. Die Reduktion der Phosphinoxyde wird vorgenommen
mit organischen Siliciumverbindungen, welche eine oder mehrere Si-H-Bindungen enthalten.
Vorzugsweise verwendet man Wasserstoffpolysiloxane, insbesondere Methylwasserstoffpolysiloxan.
Diese
Polysiloxane enthalten eine Mehrzahl von
Beispiel 1 14 g Triphenylphosphinoxyd (0,05 Mol) und 10 g Methylwasserstoffpolysiloxan werden 2 Stunden auf 280 bis 3000 C gehalten, wobei ständig mit einem Vibromischer durchmischt wird. Das Reaktionsgemisch wird mit Hilfe eines Soxhlet 1 Stunde mit Benzol extrahiert, das Benzol wird abdestilliert und der Rückstand aus Methanol umkristallisiert. Ausbeute 11,4 g, entspricht 860/o der Theorie. F.79"C. Example 1 14 g triphenylphosphine oxide (0.05 mole) and 10 g methyl hydrogen polysiloxane are held for 2 hours at 280 to 3000 C, with a vibromixer constantly is mixed. The reaction mixture is with the help of a Soxhlet for 1 hour Benzene extracted, the benzene is distilled off and the residue from methanol recrystallized. Yield 11.4 g, corresponds to 860% of theory. F.79 "C.
Beispiel 2 28 g Triphenylphosphinoxyd (0,1 Mol) werden zusammen mit 24g Methylwasserstoffpolysiloxan und 50 g Naphthalin 2 Stunden am Rückfluß gehalten. Example 2 28 g of triphenylphosphine oxide (0.1 mol) are together with Refluxed 24 g of methyl hydrogen polysiloxane and 50 g of naphthalene for 2 hours.
Die Hauptmenge des Naphthalins wird an der Ölpumpe abdestilliert und der Rückstand aus Äthanol umkristallisiert. Ausbeute 17 g Triphenylphosphin, entspricht 6501o der Theorie.Most of the naphthalene is distilled off at the oil pump and the residue recrystallized from ethanol. Yield 17 g triphenylphosphine, corresponds 6501o of theory.
Beispiel 3 14 g Triphenylphosphinoxyd und 10 g Methylwasserstoffpolysiloxan wurden mit 50 ml Diäthylenglykoldimethyläther 3 Stunden unter Rückfluß gekocht. Example 3 14 g of triphenylphosphine oxide and 10 g of methyl hydrogen polysiloxane were refluxed with 50 ml of diethylene glycol dimethyl ether for 3 hours.
Anschließend wurde mit 30 ml 300/, Natronlauge versetzt und mit 500 mol Wasser verdünnt. Die ausgefallenen Kristalle wurden abgesaugt und aus Methanol umkristallisiert. Ausbeute 7,5 g, entspricht 57% o/<> der Theorie an Triphenylphosphin.Then 30 ml 300% sodium hydroxide solution were added and 500 ml mol of water diluted. The precipitated crystals were suctioned off and off Methanol recrystallized. Yield 7.5 g, corresponds to 57% o / <> theory of triphenylphosphine.
Beispiel 4 14 g Triphenylphosphinoxyd und 10 g Methylwasserstoffpolysiloxan werden mit 25 ml Diphenyloxyd 3 Stunden am Rückfluß gehalten. Anschließend wird mit 50 ml 300/o Natronlauge versetzt, die organische Phase mit Wasser gewaschen, mit MgSO4 getrocknet, das Lösungsmittel abdestilliert und der Rückstand aus Methanol umkristallisiert. Ausbeute 10,1 g, entspricht 76,5 °/o der Theorie an Triphenylphosphin. Example 4 14 g of triphenylphosphine oxide and 10 g of methyl hydrogen polysiloxane are refluxed with 25 ml of diphenyl oxide for 3 hours. Then will 50 ml of 300 / o sodium hydroxide solution are added, the organic phase is washed with water, dried with MgSO4, the solvent was distilled off and the residue from methanol recrystallized. Yield 10.1 g, corresponds to 76.5% of the theory of triphenylphosphine.
Beispiel 5 6,4 g Tri-o-tolylphosphinoxyd (0,02 Mol) und 6 g Methylwasserstoffpolysiloxan werden 2 Stunden unter Rühren mit einem Vibromischer auf 300"C gehalten. Example 5 6.4 g tri-o-tolylphosphine oxide (0.02 mole) and 6 g methyl hydrogen polysiloxane are kept at 300 ° C. for 2 hours while stirring with a vibromixer.
Das Reaktionsprodukt wird mit Benzol extrahiert, das Benzol abdestilliert und der Rückstand aus Methanol umkristallisiert. Ausbeute an Tri-o-tolylphosphin 6,1 g, entspricht 990/o der Theorie.The reaction product is extracted with benzene and the benzene is distilled off and the residue is recrystallized from methanol. Yield of tri-o-tolylphosphine 6.1 g, corresponds to 990 / o of theory.
Beispiel 6 19,2 g 1-Oxo-l-phenyl-3-methylphospholin (0,1 Mol) und 20 g Methylwasserstoffpolysiloxanwerden2 Stunden unter Rühren mit einem Vibromischer auf 2400 C erhitzt. Anschließend wird mit Benzol extrahiert und fraktioniert destilliert. Ausbeute an l-Phenyl-3-methylphospholin: 15,5 g entspricht 880/o der Theorie, Kp.,,,,, 79 bis 80"C. Example 6 19.2 g of 1-oxo-1-phenyl-3-methylphospholine (0.1 mol) and 20 g of methyl hydrogen polysiloxane are added for 2 hours while stirring with a vibromixer heated to 2400 C. Then it is extracted with benzene and fractionally distilled. Yield of l-phenyl-3-methylphospholine: 15.5 g corresponds to 880 / o of theory, bp ,,,,, 79 to 80 "C.
Analyse: Berechnet... C 75,9, H 7,39, P 17,6; gefunden ... C 74,7, H 7,1, P 17,5.Analysis: Calculated ... C 75.9, H 7.39, P 17.6; found ... C 74.7, H 7.1, P 17.5.
Zur Identifizierung wurde diese Verbindung mit CH3J umgesetzt und ergibt l-Phenyl-l-methylphospholiniumjodid der Formel Analyse: Berechnet ... C 45,3, H 5,07, P 9,76; gefunden ... C45,1, H5,1, P9,9.For identification, this compound was reacted with CH3J to give l-phenyl-l-methylphospholinium iodide of the formula Analysis: Calculated ... C 45.3, H 5.07, P 9.76; found ... C45.1, H5.1, P9.9.
Beispiel 7 7,6 g Tri-o-anisyl-phosphinoxyd (F. 222"C), 5 g Methylwasserstoffpolysiloxan und 50 ml Diphenyläther werden 3 Stunden auf 220 bis 260"C erwärmt. Example 7 7.6 g of tri-o-anisylphosphine oxide (M.p. 222 "C), 5 g of methylhydrogen polysiloxane and 50 ml of diphenyl ether are heated to 220 to 260 ° C. for 3 hours.
Anschließend wird mit Benzol extrahiert, das Benzol abdestilliert. Im Rückstand fielen 2,6 g Trianisylphosphin aus. F. 204° C, entspricht 33,5 0/, der Theorie.It is then extracted with benzene, and the benzene is distilled off. 2.6 g of trianisylphosphine precipitated in the residue. F. 204 ° C, corresponds to 33.5 0 /, the theory.
Beispiel 8 11 g Tri-n-butylphosphinoxyd (0,05 Mol) und 10 g Methylwasserstoffpolysiloxan werden unter Rühren mit einem Vibromischer 1,5 Stunden auf 200"C erhitzt. Example 8 11 g of tri-n-butylphosphine oxide (0.05 mole) and 10 g of methyl hydrogen polysiloxane are heated to 200 ° C. for 1.5 hours while stirring with a vibromixer.
Tri-n-butylphosphin wird bei 113 bis 121°C/14 Torr abdestilliert. Ausbeute 6,6 g 65°/o der Theorie.Tri-n-butylphosphine is distilled off at 113 to 121 ° C / 14 Torr. Yield 6.6 g, 65% of theory.
Zur Identifizierung wurde diese Verbindung mit Methyljodid zum Tri-(n-butyl)-methylphosphonium jodid, F. 135"C, umgesetzt. This compound was identified with methyl iodide to form tri- (n-butyl) methylphosphonium iodide, F. 135 "C.
Beispiel 9 15 g Tricyclohexylphosphinoxyd (0,05 Mol) und 10 g Methylwasserstoffpolysiloxan werden unter Rühren mit einem Vibromischer 1 Stunde auf 270 bis 3000 C erhitzt. Anschließend wird mit heißem Petroläther extrahiert, vom polymeren Siloxan abgesaugt und die Petrolätherlösung mit Schwefelkohlenstoff versetzt. Es fallen rote Kristalle des Tricyclohexylphosphin - Schwefelkohlenstoff- Adduktes aus. Example 9 15 g of tricyclohexylphosphine oxide (0.05 mole) and 10 g of methyl hydrogen polysiloxane are heated to 270 to 3000 C for 1 hour while stirring with a vibromixer. It is then extracted with hot petroleum ether and suctioned off from the polymeric siloxane and carbon disulfide is added to the petroleum ether solution. Red crystals fall of the tricyclohexylphosphine - carbon disulfide adduct.
Diese wurden abgesaugt und mehrmals mit Petroläther gewaschen. Ausbeute 12 g, entspricht 65°/o der Theorie. F. 117"C (aus Methanol).These were filtered off with suction and washed several times with petroleum ether. yield 12 g, corresponds to 65% of theory. M.p. 117 "C (from methanol).
Beispiel 10 20,85 g (0,075 Mol) Triphenylphosphinoxyd und 5,4 g Phenylsilan (0,05 Mol) werden 2 Stunden auf 120"C erhitzt. Anschließend wird aus Methanol umkristallisiert. Ausbeute 16 g Triphenylphosphin, entspricht 82°/o der Theorie. F. 78"C. Example 10 20.85 g (0.075 mole) triphenylphosphine oxide and 5.4 g phenylsilane (0.05 mol) are heated to 120 ° C. for 2 hours. It is then recrystallized from methanol. Yield 16 g triphenylphosphine, corresponds to 82% of theory. F. 78 "C.
Beispiel 11 Zu Triphenoxysilan, welches durch Zutropfen von 13,5 g Silicochloroform zu einer benzolischen Lösung von 28,2 g Phenol und abdestillieren des Benzols erhalten wurde, wurden 14,0 g Triphenylphosphinoxyd gegeben. Nach 2stündigem Erwärmen auf 2500 C wurde die Reaktionsmischung in 400/,ige NaOH gegossen. Das ausgefallene Triphenylphosphin wurde abgesaugt, mit Wasser gewaschen und aus Äthanol umkristallisiert. Ausbeute 11,2 g (840/o). F. 78"C. Example 11 To triphenoxysilane, which by dropwise addition of 13.5 g of silicochloroform to a benzene solution of 28.2 g of phenol and distill off of benzene was obtained, 14.0 g of triphenylphosphine oxide were added. After 2 hours The reaction mixture was heated to 2500 ° C. and poured into 400% strength NaOH. The unusual one Triphenylphosphine was filtered off with suction, washed with water and recrystallized from ethanol. Yield 11.2 g (840 / o). F. 78 "C.
Beispiel 12 12,0 g Allyldiphenylphosphinoxyd (F. 94 bis 95°C, Kp.2 200 bis 202°C) und 11,0 g Methylwasserstoffpolysiloxan wurden gründlich durchmischt und unter Stickstoff 3 Stunden bei 250 bis 2700 C gehalten. Nach dem Abkühlen wurde Allyldiphenylphosphin aus der gelartigen Reaktionsmasse im Wasserstrahlvakuum abdestilliert. Ausbeute 11,0 g, entspricht 98,3 0/o der Theorie. Siedepunkt bei 12 Torr 176"C (Literatur: Siedepunkt bei 15 Torr 194 bis 200°C). Example 12 12.0 g of allyldiphenylphosphine oxide (m.p. 94 to 95 ° C, boiling point 2 200 to 202 ° C) and 11.0 g of methyl hydrogen polysiloxane were mixed thoroughly and held at 250 to 2700 ° C. under nitrogen for 3 hours. After cooling it was Allyldiphenylphosphine from the gel-like reaction mass in a water jet vacuum distilled off. Yield 11.0 g, corresponds to 98.3% of theory. Boiling point at 12 Torr 176 "C (literature: Boiling point at 15 torr 194 to 200 ° C).
Claims (2)
Priority Applications (8)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| BE635518D BE635518A (en) | 1962-07-31 | ||
| GB1054166D GB1054166A (en) | 1962-07-31 | ||
| NL295914D NL295914A (en) | 1962-07-31 | ||
| DES80694A DE1193942B (en) | 1962-07-31 | 1962-07-31 | Process for the production of tertiary phosphines |
| US297952A US3280195A (en) | 1962-07-31 | 1963-07-26 | Reduction of phosphine oxides |
| CH941263A CH441305A (en) | 1962-07-31 | 1963-07-29 | Process for the production of phosphines |
| GB2996163A GB1025570A (en) | 1962-07-31 | 1963-07-29 | Process for the preparation of phosphines |
| FR943027A FR1364938A (en) | 1962-07-31 | 1963-07-29 | Process for the preparation of phosphines |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DES80694A DE1193942B (en) | 1962-07-31 | 1962-07-31 | Process for the production of tertiary phosphines |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE1193942B true DE1193942B (en) | 1965-06-03 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DES80694A Pending DE1193942B (en) | 1962-07-31 | 1962-07-31 | Process for the production of tertiary phosphines |
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| DE (1) | DE1193942B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4835202A (en) * | 1987-11-20 | 1989-05-30 | Ciba-Geigy Corporation | (Hydroxyphenyl) phosphine stabilized compositions |
| US5332846A (en) * | 1993-06-01 | 1994-07-26 | Eastman Kodak Company | Hydroformylation process using novel phosphine-rhodium catalyst system |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2727880A (en) * | 1953-01-22 | 1955-12-20 | Mcgraw Electric Co | Organo-silicon compounds from acetone and trichlorosilane |
| DE1031520B (en) * | 1956-07-13 | 1958-06-04 | Rhone Poulenc Sa | Process for the preparation of alkoxy and aralkoxymethyl polysiloxanes |
-
1962
- 1962-07-31 DE DES80694A patent/DE1193942B/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2727880A (en) * | 1953-01-22 | 1955-12-20 | Mcgraw Electric Co | Organo-silicon compounds from acetone and trichlorosilane |
| DE1031520B (en) * | 1956-07-13 | 1958-06-04 | Rhone Poulenc Sa | Process for the preparation of alkoxy and aralkoxymethyl polysiloxanes |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4835202A (en) * | 1987-11-20 | 1989-05-30 | Ciba-Geigy Corporation | (Hydroxyphenyl) phosphine stabilized compositions |
| US5332846A (en) * | 1993-06-01 | 1994-07-26 | Eastman Kodak Company | Hydroformylation process using novel phosphine-rhodium catalyst system |
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