DE4134772A1 - Bis-(di-tert.-butyl:phosphino)-methane prepn. - by reaction of alkali metal di-tert. butyl phosphino:formamide with halo-di-tert. butyl phosphine in presence of solvent - Google Patents
Bis-(di-tert.-butyl:phosphino)-methane prepn. - by reaction of alkali metal di-tert. butyl phosphino:formamide with halo-di-tert. butyl phosphine in presence of solventInfo
- Publication number
- DE4134772A1 DE4134772A1 DE19914134772 DE4134772A DE4134772A1 DE 4134772 A1 DE4134772 A1 DE 4134772A1 DE 19914134772 DE19914134772 DE 19914134772 DE 4134772 A DE4134772 A DE 4134772A DE 4134772 A1 DE4134772 A1 DE 4134772A1
- Authority
- DE
- Germany
- Prior art keywords
- tert
- butyl
- phosphino
- methane
- solvent
- 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.)
- Withdrawn
Links
- 229910052783 alkali metal Inorganic materials 0.000 title claims abstract description 5
- 150000001340 alkali metals Chemical class 0.000 title claims abstract description 5
- 239000002904 solvent Substances 0.000 title claims description 9
- 238000006243 chemical reaction Methods 0.000 title description 6
- -1 butyl phosphino Chemical group 0.000 title description 5
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 title 2
- DLIJPAHLBJIQHE-UHFFFAOYSA-N butylphosphane Chemical compound CCCCP DLIJPAHLBJIQHE-UHFFFAOYSA-N 0.000 title 1
- FVZVCSNXTFCBQU-UHFFFAOYSA-N phosphanyl Chemical group [PH2] FVZVCSNXTFCBQU-UHFFFAOYSA-N 0.000 title 1
- 238000000034 method Methods 0.000 claims abstract description 11
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 5
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 4
- 229910052792 caesium Inorganic materials 0.000 claims abstract description 4
- 229910052740 iodine Inorganic materials 0.000 claims abstract description 4
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 4
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 4
- 229910052701 rubidium Inorganic materials 0.000 claims abstract description 4
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 4
- WBMJFMFJCWPAIT-UHFFFAOYSA-N ditert-butyl(ditert-butylphosphanylmethyl)phosphane Chemical compound CC(C)(C)P(C(C)(C)C)CP(C(C)(C)C)C(C)(C)C WBMJFMFJCWPAIT-UHFFFAOYSA-N 0.000 claims description 13
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical compound BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 6
- 239000000460 chlorine Substances 0.000 claims description 4
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 3
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- FFNOZUKFBATOKL-UHFFFAOYSA-N ditert-butyl(methanidyl)phosphane Chemical compound C(C)(C)(C)P(C(C)(C)C)[CH2-] FFNOZUKFBATOKL-UHFFFAOYSA-N 0.000 claims description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 abstract description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract description 4
- 239000003446 ligand Substances 0.000 abstract description 3
- 230000006315 carbonylation Effects 0.000 abstract description 2
- 238000005810 carbonylation reaction Methods 0.000 abstract description 2
- 238000007037 hydroformylation reaction Methods 0.000 abstract description 2
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 2
- 229910052759 nickel Inorganic materials 0.000 abstract description 2
- 229910052763 palladium Inorganic materials 0.000 abstract description 2
- 229910000073 phosphorus hydride Inorganic materials 0.000 abstract description 2
- 229910052697 platinum Inorganic materials 0.000 abstract description 2
- 229910052703 rhodium Inorganic materials 0.000 abstract description 2
- 229910052707 ruthenium Inorganic materials 0.000 abstract description 2
- 229910052723 transition metal Inorganic materials 0.000 abstract description 2
- 150000003624 transition metals Chemical class 0.000 abstract description 2
- 239000003054 catalyst Substances 0.000 abstract 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 12
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-MZWXYZOWSA-N benzene-d6 Chemical compound [2H]C1=C([2H])C([2H])=C([2H])C([2H])=C1[2H] UHOVQNZJYSORNB-MZWXYZOWSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-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
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- GUVUOGQBMYCBQP-UHFFFAOYSA-N dmpu Chemical compound CN1CCCN(C)C1=O GUVUOGQBMYCBQP-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- UBJFKNSINUCEAL-UHFFFAOYSA-N lithium;2-methylpropane Chemical compound [Li+].C[C-](C)C UBJFKNSINUCEAL-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 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 2
- HTSGKJQDMSTCGS-UHFFFAOYSA-N 1,4-bis(4-chlorophenyl)-2-(4-methylphenyl)sulfonylbutane-1,4-dione Chemical compound C1=CC(C)=CC=C1S(=O)(=O)C(C(=O)C=1C=CC(Cl)=CC=1)CC(=O)C1=CC=C(Cl)C=C1 HTSGKJQDMSTCGS-UHFFFAOYSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- DFXVHMWBGFOKIQ-UHFFFAOYSA-N bromo(ditert-butyl)phosphane Chemical compound CC(C)(C)P(Br)C(C)(C)C DFXVHMWBGFOKIQ-UHFFFAOYSA-N 0.000 description 1
- 235000013877 carbamide Nutrition 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- DMSZORWOGDLWGN-UHFFFAOYSA-N ctk1a3526 Chemical class NP(N)(N)=O DMSZORWOGDLWGN-UHFFFAOYSA-N 0.000 description 1
- 150000004292 cyclic ethers Chemical class 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- MCRSZLVSRGTMIH-UHFFFAOYSA-N ditert-butyl(chloro)phosphane Chemical compound CC(C)(C)P(Cl)C(C)(C)C MCRSZLVSRGTMIH-UHFFFAOYSA-N 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 150000002366 halogen compounds Chemical class 0.000 description 1
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- GKEDFFLJXSCVOI-UHFFFAOYSA-N lithium;ditert-butyl(methanidyl)phosphane Chemical compound [Li+].CC(C)(C)P([CH2-])C(C)(C)C GKEDFFLJXSCVOI-UHFFFAOYSA-N 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- CQRPUKWAZPZXTO-UHFFFAOYSA-M magnesium;2-methylpropane;chloride Chemical compound [Mg+2].[Cl-].C[C-](C)C CQRPUKWAZPZXTO-UHFFFAOYSA-M 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000006263 metalation reaction Methods 0.000 description 1
- 230000011987 methylation Effects 0.000 description 1
- 238000007069 methylation reaction Methods 0.000 description 1
- DVSDBMFJEQPWNO-UHFFFAOYSA-N methyllithium Chemical compound C[Li] DVSDBMFJEQPWNO-UHFFFAOYSA-N 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 238000006384 oligomerization reaction Methods 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000003880 polar aprotic solvent Substances 0.000 description 1
- 239000003586 protic polar solvent Substances 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- WLPUWLXVBWGYMZ-UHFFFAOYSA-N tricyclohexylphosphine Chemical compound C1CCCCC1P(C1CCCCC1)C1CCCCC1 WLPUWLXVBWGYMZ-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- C07F9/5063—Preparation; Separation; Purification; Stabilisation from compounds having the structure P-H or P-Heteroatom, in which one or more of such bonds are converted into P-C bonds
- C07F9/5068—Preparation; Separation; Purification; Stabilisation from compounds having the structure P-H or P-Heteroatom, in which one or more of such bonds are converted into P-C bonds from starting materials having the structure >P-Hal
-
- 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
- C07F9/5027—Polyphosphines
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)
- Crystallography & Structural Chemistry (AREA)
- Catalysts (AREA)
Abstract
Description
Die vorliegende Erfindung betrifft ein Verfahren zur Herstellung von Bis(di-tert.-butylphosphino)methan.The present invention relates to a method for producing Bis (di-tert-butylphosphino) methane.
Wie andere Phosphine, beispielsweise Triphenylphosphin, Tricyclohexyl phosphin oder Trialkylphosphine bildet Bis(di-tert.-butylphosphino)methan, im folgenden als "dtbpm" bezeichnet, als Ligand mit Übergangsmetallen, wie Rhodium, Ruthenium, Palladium, Platin, Kobalt und Nickel, Komplexe, wie sie als Homogenkatalysatoren bei Hydrierungen, Hydroformylierungen, Carbonylierungen sowie bei der Oligomerisation und Cooligomerisation unge sättigter Verbindungen eine breite technische Verwendung finden.Like other phosphines, e.g. triphenylphosphine, tricyclohexyl phosphine or trialkylphosphine forms bis (di-tert-butylphosphino) methane, hereinafter referred to as "dtbpm", as a ligand with transition metals, such as Rhodium, ruthenium, palladium, platinum, cobalt and nickel, complexes such as they as homogeneous catalysts in hydrogenations, hydroformylations, Carbonylations as well as in the oligomerization and cooligomerization saturated compounds find wide technical use.
Einer breiten technischen Verwendung des Phosphinliganden "dtbpm" stand bislang seine in technischen Mengen präparativ schwierige Zugänglichkeit entgegen. So liefert die einzige bislang bekannte Synthese von "dtbpm" (Z. Naturforsch. 38b, 1027 (1983)) ausgehend von der aus Aluminium und Dichlormethan gebildeten metallorganischen Verbindung über mehrere Synthesestufen das gewünschte Produkt nur in einer völlig unzureichenden Ausbeute, welche deren industrielle Nutzung ausschließt.A wide range of industrial uses for the phosphine ligand "dtbpm" stood So far, its accessibility in technical quantities is difficult opposite. The only known synthesis of "dtbpm" (Z. Naturforsch. 38b, 1027 (1983)) based on that of aluminum and Dichloromethane formed organometallic compound over several Synthesis stages the desired product only in a completely inadequate Yield, which excludes their industrial use.
Der vorliegenden Erfindung lag daher die Aufgabe zugrunde, ein Verfahren zu finden, das die industrielle Herstellung von "dtbpm" wirtschaftlich und in guter Ausbeute ermöglicht.The present invention was therefore based on the object of a method to find that the industrial manufacture of "dtbpm" economically and enabled in good yield.
Dementsprechend wurde ein Verfahren zur Herstellung von Bis(di-tert.- butylphosphino)methan der Formel IAccordingly, a process for the preparation of bis (di-tert.- butylphosphino) methane of the formula I.
tBu₂P-CH₂-P-tBu₂ (I)tBu₂P-CH₂-P-tBu₂ (I)
gefunden, das dadurch gekennzeichnet ist, daß man ein Alkalimetall-di- tert.-butylphosphinomethanid der allgemeinen Formel IIfound, which is characterized in that an alkali metal di tert-butylphosphinomethanide of the general formula II
tBu₂-P-CH₂-Me (II)tBu₂-P-CH₂-Me (II)
in der Me Lithium, Natrium, Kalium, Rubidium oder Cäsium bedeutet, mit einem Halogeno-di-tert.-butylphosphin der allgemeinen Formel IIIwhere Me means lithium, sodium, potassium, rubidium or cesium, with a halogeno-di-tert-butylphosphine of the general formula III
tBu₂-P-Hal (III)tBu₂-P-Hal (III)
in der Hal für ein Chlor-, Brom- oder Jodatom steht, in Gegenwart eines Lösungsmittels umsetzt. in which Hal represents a chlorine, bromine or iodine atom, in the presence of a Implement solvent.
Die erfindungsgemäße Umsetzung kann durch die folgende allgemeine Reaktionsgleichung (1) dargestellt werden:The implementation of the invention can by the following general Reaction equation (1) can be represented:
Zur Herstellung von "dtbpm" I können die Di-tert.-butylphosphino methanide (II) aller Alkalimetalle Me, also die des Lithiums, Natriums, Kaliums, Rubidiums oder Cäsiums, eingesetzt werden. Als bevorzugtes Ausgangsmaterial wird jedoch Lithium-di-tert.-butylphosphinomethanid verwendt. Dieses kann ausgehend von einem Phosphor(III)halogenid, wie Phosphortrichlorid, beispielsweise durch dessen Umsetzung mit einer tert.-Butyl-Grignard-Verbindung, wie tert.-Butylmagnesiumchlorid (s. hierzu: Rec. Trav. Chim. 82, 302 (1963); Chem. Ber. 100, 692 (1966); Inorg. Synth. 14, 4 (1973)), Methylierung des erhaltenen Halogeno-di- tert.-butylphosphins (III) mit zum Beispiel Methyllithium (J. Gen. Chem. USSR 51, 2125 (1981); Chem. Ber. 99, 1134 (1966)) und Metallierung, beispielsweise mit t-Butyllithium (tBuLi) (Z. Naturforsch. 32b, 762 (1977)) in guten Ausbeuten, gemäß Reaktionsschema (2) erhalten werden.To prepare "dtbpm" I, the di-tert-butylphosphino methanides (II) of all alkali metals Me, i.e. those of lithium, sodium, Potassium, rubidium or cesium can be used. As a favorite However, the starting material is lithium di-tert-butylphosphinomethanide used. Starting from a phosphorus (III) halide, such as Phosphorus trichloride, for example by reacting it with a tert-butyl Grignard compound, such as tert-butyl magnesium chloride (s. on this: Rec. Trav. Chim. 82, 302 (1963); Chem. Ber. 100, 692 (1966); Inorg. Synth. 14, 4 (1973)), methylation of the halogeno-di- tert-butylphosphine (III) with, for example, methyl lithium (J. Gen. Chem. USSR 51, 2125 (1981); Chem. Ber. 99, 1134 (1966)) and metalation, for example with t-butyllithium (tBuLi) (Z. Naturforsch. 32b, 762 (1977)) can be obtained in good yields according to reaction scheme (2).
Das zur erfindungsgemäßen Umsetzung benötigte Halogeno-di-tert.-butyl- phosphin (III), in dem Hal für ein Chlor-, Brom- oder Jodatom steht, kann beispielsweise nach dem Verfahren gemäß Schema (2), Gleichung (a), ge wonnen werden. Bevorzugt wird im erfindungsgemäßen Verfahren das Chlor- oder Brom-di-tert.-butylphosphin III umgesetzt.The halogeno-di-tert.-butyl- phosphine (III) in which Hal represents a chlorine, bromine or iodine atom for example according to the method according to scheme (2), equation (a), ge be won. This is preferred in the process according to the invention Chlorine or bromo-di-tert-butylphosphine III implemented.
Zur Herstellung von "dtbpm" I setzt man zweckmäßigerweise stöchiometrische Mengen der Ausgangsstoffe II und III im allgemeinen in Gegenwart eines Lösungsmittels um. Ein Überschuß des einen oder anderen Reaktionspartners wirkt sich auf das Ergebnis der Umsetzung in der Regel nicht negativ aus. Üblicherweise wird bei der Herstellung von I vorteilhaft so verfahren, daß man die Halogenverbindung III oder eine Lösung von III zur Suspension der metallierten Verbindung II in einem Lösungsmittel dosiert. Die umgekehrte Zugabereihenfolge dieser Verbindungen kann beim erfindungsgemäßen Ver fahren ebenfalls angewandt werden.To produce "dtbpm" I, it is expedient to use stoichiometric Amounts of the starting materials II and III in general in the presence of a Solvent around. An excess of one or the other reactant generally has no negative impact on the result of the implementation. Usually the procedure for the preparation of I is advantageously such that the halogen compound III or a solution of III to suspend the metalated compound II metered in a solvent. The reverse The order in which these compounds are added can be used in the inventive Ver driving can also be applied.
Als Lösungsmittel werden zweckmäßigerweise unter den Reaktionsbedingungen inerte, polare-aprotische Lösungsmittel, wie cyclische Ether, beispiels weise Tetrahydrofuran (THF), cyclische Harnstoffe, beispielsweise Dimethylethylenharnstoff (DMEU) oder Dimethylpropylenharnstoff (DMPU) oder Phosphorsäuretriamide, beispielsweise Hexamethylphosphorsäuretriamid, verwendet. Vorzugsweise wird THF als Lösungsmittel benutzt.Appropriately as a solvent under the reaction conditions inert, polar aprotic solvents, such as cyclic ethers, for example as tetrahydrofuran (THF), cyclic ureas, for example Dimethylethylene urea (DMEU) or dimethyl propylene urea (DMPU) or Phosphoric acid triamides, for example hexamethylphosphoric acid triamide, used. THF is preferably used as the solvent.
Die Umsetzung wird im allgemeinen bei Temperaturen oberhalb des Gefrier punktes des verwendeten Lösungsmittels, in der Regel bei Temperaturen zwischen -100°C und Raumtemperatur vorgenommen. Zweckmäßigerweise werden die beiden in flüssiger Form, in der Regel in Lösung, Suspension oder als Flüssigkeit vorliegenden Reaktanten, bei tiefer Temperatur miteinander vermischt und die erhaltene Reaktionsmischung bis auf Raumtemperatur aufgewärmt. Zur Vervollständigung der Umsetzung kann es u.U. auch förder lich sein, die Reaktionsmischung auf Temperaturen oberhalb Raumtemperatur, beispielsweise bis zum Siedepunkt des Lösungsmittels Tetrahydrofuran zu erwärmen. Im allgemeinen ist dies aber nicht notwendig.The reaction is generally carried out at temperatures above freezing point of the solvent used, usually at temperatures between -100 ° C and room temperature. Expediently the two in liquid form, usually in solution, suspension or as Liquid reactants present at low temperature with each other mixed and the reaction mixture obtained up to room temperature warmed up. It may be possible to complete the implementation. also funding the reaction mixture to temperatures above room temperature, for example up to the boiling point of the solvent tetrahydrofuran heat. In general, however, this is not necessary.
Das bei der Umsetzung erhaltene Reaktionsgemisch kann nach gängigen Verfahren, Zugabe eines protischen Lösungsmittels und Extraktion des erhaltenen Produktes, aufgearbeitet werden. Die Isolierung und Reinigung von dtbpm I kann nach den üblichen Methoden, beispielsweise Kristalli sation oder Destillation, durchgeführt werden.The reaction mixture obtained in the reaction can be made according to conventional ones Process, addition of a protic solvent and extraction of the product obtained, worked up. Isolation and cleaning of dtbpm I can by the usual methods, for example crystalli sation or distillation.
Das erfindungsgemäße Verfahren erlaubt die Herstellung von dtbpm I in guter Ausbeute und im industriellen Maßstab.The process according to the invention allows the production of dtbpm I in good yield and on an industrial scale.
Zu einer Suspension von 30,87 g Lithium-di-tert.-butyl-phosphinomethanid (0,186 mol) in einem Liter Tetrahydrofuran wurden bei -78°C 33,67 g Di-tert.-butyl-chlorphosphin (0,186 mol) dosiert und die erhaltene Re aktionsmischung innerhalb von 15 Stunden unter ständigem Rühren auf Raum temperatur erwärmt. Anschließend wurde das Tetrahydrofuran abdestilliert, die zurückbleibende graue Suspension mit 80 ml einer 4 gew.-%igen Lösung von Ammoniumchlorid in Wasser versetzt und die erhaltene Mischung mit 100 ml Pentan extrahiert. Die erhaltenen Phasen wurden getrennt und die wäßrige Phase zweimal mit je 100 ml Pentan nachgewaschen. Die vereinigten organischen Phasen wurden mit Magnesiumsulfat getrocknet, filtriert und das Pentan bei Atmosphärendruck destilliert. Der ölige Rückstand wurde bei Raumtemperatur solange mit Methanol versetzt, bis eine völlig klare Lösung entstand. Innerhalb 15 Stunden kristallisierte bei einer Temperatur von -10°C ein großer Teil des entstandenen dtbpm aus. Die Kristalle wurden abfiltriert und die Mutterlauge eingeengt. Bei -10°C kristallisierte der größte Teil des verbliebenen Produktes aus. Es wurden insgesamt 45,18 g dtbpm, entsprechend einer Ausbeute von 79,9%, in Form farbloser, nadeliger Kristalle isoliert. To a suspension of 30.87 g of lithium di-tert-butyl-phosphinomethanide (0.186 mol) in one liter of tetrahydrofuran was 33.67 g at -78 ° C Di-tert-butyl-chlorophosphine (0.186 mol) metered in and the Re Action mixture within 15 hours with constant stirring in the room temperature warmed. The tetrahydrofuran was then distilled off, the remaining gray suspension with 80 ml of a 4 wt .-% solution of ammonium chloride in water and the mixture obtained with Extracted 100 ml of pentane. The phases obtained were separated and the aqueous phase washed twice with 100 ml of pentane. The United organic phases were dried with magnesium sulfate, filtered and the pentane distilled at atmospheric pressure. The oily residue became Add methanol at room temperature until a completely clear solution originated. Crystallized within 15 hours at a temperature of -10 ° C a large part of the resulting dtbpm. The crystals were filtered off and the mother liquor concentrated. The crystallized at -10 ° C most of the remaining product. A total of 45.18 g dtbpm, corresponding to a yield of 79.9%, in the form of colorless, needle crystals isolated.
Schmelzpunkt = 45-46°C,
Siedepunkt = 75-80°C/10-3 mm,
¹H-NMR (C₆D₆) = 1,10 ppm, "t" (C(CH₃), |³JPH+⁵JPH|=10.3 Hz),
1,61 ppm, t(PCH₂P, ²JPH=1,8 Hz),
³¹P-NMR (C₆D₆) = 21,3 ppm, s,
¹³C-NMR (CDCl₃) = 32,6 ppm, dd (C(CH₃), ¹JPC=10,8 Hz, ³JPC=9,8 Hz),
30,1 ppm, "t" (C(CH₃), |²JPC+⁴JPC|=15,7 Hz),
12,7 ppm, t (PCH₂P, ¹JPC = 36,2 Hz),
IR (KBr) = 425 cm-1 m, 461 m, 588 m, 672 s, 714 s, 785 s, 808 vs,
930 m, 982 w, 1017 s, 1130 m, 1174 b, vs, 1362 vs,
1385 s, 1459 b, vs, 2900 b, vs.Melting point = 45-46 ° C,
Boiling point = 75-80 ° C / 10 -3 mm,
1 H-NMR (C₆D₆) = 1.10 ppm, "t" (C (CH₃), | ³J PH + ⁵J PH | = 10.3 Hz), 1.61 ppm, t (PCH₂P, ²J PH = 1.8 Hz) ,
31 P NMR (C₆D₆) = 21.3 ppm, s,
13 C-NMR (CDCl 3) = 32.6 ppm, dd ( C (CH 3), 1 J PC = 10.8 Hz, 3 J PC = 9.8 Hz), 30.1 ppm, "t" (C ( C H 3) , | ²J PC + ⁴J PC | = 15.7 Hz), 12.7 ppm, t (PCH₂P, ¹J PC = 36.2 Hz),
IR (KBr) = 425 cm -1 m, 461 m, 588 m, 672 s, 714 s, 785 s, 808 vs, 930 m, 982 w, 1017 s, 1130 m, 1174 b, vs, 1362 vs, 1385 s, 1459 b, vs, 2900 b, vs.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19914134772 DE4134772A1 (en) | 1990-10-31 | 1991-10-22 | Bis-(di-tert.-butyl:phosphino)-methane prepn. - by reaction of alkali metal di-tert. butyl phosphino:formamide with halo-di-tert. butyl phosphine in presence of solvent |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4034604 | 1990-10-31 | ||
| DE19914134772 DE4134772A1 (en) | 1990-10-31 | 1991-10-22 | Bis-(di-tert.-butyl:phosphino)-methane prepn. - by reaction of alkali metal di-tert. butyl phosphino:formamide with halo-di-tert. butyl phosphine in presence of solvent |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE4134772A1 true DE4134772A1 (en) | 1992-05-07 |
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| Application Number | Title | Priority Date | Filing Date |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0778281A1 (en) | 1995-11-29 | 1997-06-11 | Basf Aktiengesellschaft | Process for the preparation of methylen-bridged hetero compounds and novel bis (diorganylphosphino) methanes |
| US5876467A (en) * | 1994-02-15 | 1999-03-02 | Basf Aktiengesellschaft | Use of carboxylic esters as fuel additives or lubricant additives and their preparation |
| WO1999047528A1 (en) * | 1998-03-16 | 1999-09-23 | Ineos Acrylics Uk Limited | Process for the preparation of bisphosphines |
| US6812306B2 (en) | 2000-07-06 | 2004-11-02 | Basf Aktiengesellschaft | Metallic compounds and the use thereof in the polymerization of olefins |
-
1991
- 1991-10-22 DE DE19914134772 patent/DE4134772A1/en not_active Withdrawn
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5876467A (en) * | 1994-02-15 | 1999-03-02 | Basf Aktiengesellschaft | Use of carboxylic esters as fuel additives or lubricant additives and their preparation |
| EP0778281A1 (en) | 1995-11-29 | 1997-06-11 | Basf Aktiengesellschaft | Process for the preparation of methylen-bridged hetero compounds and novel bis (diorganylphosphino) methanes |
| US5698743A (en) * | 1995-11-29 | 1997-12-16 | Basf Aktiengesellschaft | Preparation of methylene-bridged hetero compounds and novel bis (diorganophosphino) methanes |
| WO1999047528A1 (en) * | 1998-03-16 | 1999-09-23 | Ineos Acrylics Uk Limited | Process for the preparation of bisphosphines |
| US6376715B1 (en) | 1998-03-16 | 2002-04-23 | Ineos Acrylics U.K. Limited | Process for the preparation of bisphosphines |
| US6812306B2 (en) | 2000-07-06 | 2004-11-02 | Basf Aktiengesellschaft | Metallic compounds and the use thereof in the polymerization of olefins |
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