CA2261518A1 - Synthetic method - Google Patents
Synthetic method Download PDFInfo
- Publication number
- CA2261518A1 CA2261518A1 CA 2261518 CA2261518A CA2261518A1 CA 2261518 A1 CA2261518 A1 CA 2261518A1 CA 2261518 CA2261518 CA 2261518 CA 2261518 A CA2261518 A CA 2261518A CA 2261518 A1 CA2261518 A1 CA 2261518A1
- Authority
- CA
- Canada
- Prior art keywords
- reaction
- ammonia
- prepare
- aminophosphonium
- tri
- 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.)
- Abandoned
Links
- 238000010189 synthetic method Methods 0.000 title abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims abstract description 32
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 19
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 33
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 4
- FTAKLPCYEVDAIL-UHFFFAOYSA-N [Cl-].[Cl-].C(C)(C)(C)[PH+](C(C)(C)C)C(C)(C)C.C(C)(C)(C)[PH+](C(C)(C)C)C(C)(C)C Chemical compound [Cl-].[Cl-].C(C)(C)(C)[PH+](C(C)(C)C)C(C)(C)C.C(C)(C)(C)[PH+](C(C)(C)C)C(C)(C)C FTAKLPCYEVDAIL-UHFFFAOYSA-N 0.000 claims description 3
- XESYSKJARUWZEV-UHFFFAOYSA-M amino(tritert-butyl)phosphanium;chloride Chemical compound [Cl-].CC(C)(C)[P+](N)(C(C)(C)C)C(C)(C)C XESYSKJARUWZEV-UHFFFAOYSA-M 0.000 claims description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical group 0.000 claims description 2
- 239000003586 protic polar solvent Substances 0.000 claims 1
- -1 aminophosphonium halide Chemical class 0.000 abstract description 10
- 238000002360 preparation method Methods 0.000 abstract description 9
- 150000001540 azides Chemical class 0.000 abstract description 6
- 150000001336 alkenes Chemical class 0.000 abstract description 2
- 239000003446 ligand Substances 0.000 abstract description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 2
- 239000002685 polymerization catalyst Substances 0.000 abstract description 2
- 239000002243 precursor Substances 0.000 abstract description 2
- 125000002524 organometallic group Chemical group 0.000 abstract 2
- 229910052751 metal Inorganic materials 0.000 abstract 1
- 239000002184 metal Substances 0.000 abstract 1
- 150000002739 metals Chemical class 0.000 abstract 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 18
- 239000007787 solid Substances 0.000 description 17
- 238000005481 NMR spectroscopy Methods 0.000 description 14
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- BWHDROKFUHTORW-UHFFFAOYSA-N tritert-butylphosphane Chemical compound CC(C)(C)P(C(C)(C)C)C(C)(C)C BWHDROKFUHTORW-UHFFFAOYSA-N 0.000 description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 9
- QLNAVQRIWDRPHA-UHFFFAOYSA-N iminophosphane Chemical compound P=N QLNAVQRIWDRPHA-UHFFFAOYSA-N 0.000 description 8
- 239000003039 volatile agent Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 4
- 101150041968 CDC13 gene Proteins 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- XYFCBTPGUUZFHI-UHFFFAOYSA-N phosphine group Chemical group P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 229910001220 stainless steel Inorganic materials 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
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- YMWUJEATGCHHMB-DICFDUPASA-N dichloromethane-d2 Chemical compound [2H]C([2H])(Cl)Cl YMWUJEATGCHHMB-DICFDUPASA-N 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- IXZDIALLLMRYOU-UHFFFAOYSA-N tert-butyl hypochlorite Chemical compound CC(C)(C)OCl IXZDIALLLMRYOU-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- IGNTWNVBGLNYDV-UHFFFAOYSA-N triisopropylphosphine Chemical compound CC(C)P(C(C)C)C(C)C IGNTWNVBGLNYDV-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
- C07F9/54—Quaternary phosphonium compounds
- C07F9/5463—Compounds of the type "quasi-phosphonium", e.g. (C)a-P-(Y)b wherein a+b=4, b>=1 and Y=heteroatom, generally N or O
-
- 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
A process to prepare a bulky trialkyl aminophosphonium halide by the reaction of a precursor dihalide with ammonia. The reaction is facile and may be completed under mild reaction conditions. The bulky trialkyl aminophosphonium halides produced by the process of this invention may be utilized in the preparation of ligands for organometallic complexes (preferably using group 4 metals) which are highly active olefin polymerization catalysts. Prior art methods to prepare such organometallic complexes use an azide as an intermediate. Azides require special expertise to handle on a commercial scale and may explosively decompose. The present synthetic method avoids the use of azides.
Description
FIELD OF THE INVENTION
This invention relates to a novel synthetic method to prepare bulky trialkyl aminophosphonium halides.
BACKGROUND OF THE INVENTION
Olefin polymerization catalysts having phosphinimine ligands ("phosphinimine catalysts") are disclosed in co-pending and commonly to assigned patent applications. See, for example, Canadian patent applications 2,206,944; 2,210,131; 2,243,783; 2,243,775; and 2,243,726, the disclosures of which are incorporated herein by reference.
The prior art preparation of these phosphinimine catalysts uses an azide as an intermediate as disclosed in the above referenced patent applications. As will be appreciated by those skilled in the art, azides may explosively decompose.
It is an object of this invention to mitigate a problem associated with the prior art preparation of phosphinimine catalysts. We have now discovered a synthetic method which enables the production of phosphinimine catalysts without using an azide.
SUMMARY OF THE INVENTION
In one embodiment, there is provided a process to prepare a molecule defined by the formula:
X
G:\Scott\PSCSpec\9183can.doc 2 wherein X is a halogen and each R is an alkyl group, with the proviso that at least one R is selected from isopropyl and cyclohexyl;
wherein said process comprises the reaction of ammonia with a dihalide defined by the formula:
wherein X and each R are as defined above, characterized in that said to reaction is undertaken in a protic medium at a temperature of from -40°C
to 200°C.
In another embodiment, there is provided a process to prepare tri(tertiary-butyl) Aminophosphonium chloride, wherein said process comprises the reaction of ammonia with tri(tertiary-butyl) phosphonium dichloride.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENT
The present process is undertaken under very mild conditions.
Preferred temperatures are from -40°C to 200°C, most preferably from 20 to 100°C. A positive ammonia pressured of from 1 to 13 atmospheres is also preferred.
It is preferred to use a protic reaction medium, especially ethanol or methanol.
3 o The products of the process of the present invention, namely bulky trialkyl aminophosphonium halides, may be reacted with a base (such as sodium hydroxide, sodium methoxide or butyl lithium) to give a trialkyl phosphinimine R3P=NH. The phosphinimine may then be used to prepare the phosphinimine catalysts (described in the above noted patent applications) by reacting it with a metal halide.
G:\Scott\PSCSpec\9183can.doc 3 The term "bulky trialkyl" refers to the steric bulk of the alkyl substituents on the phosphines atom. As used herein, the term "bulky alkyl" means that the steric bulk should be greater than the steric bulk provided by three phenyl substituents. The use of so-called "Tolman cone angles" is conventionally employed to describe the bulk of phosphines.
Triphenyl phosphine is typically described as having a Tolman cone angle to of 145° (see, for example, Chemistry of the Elements, by Greenwood and Earnshaw, published by Pergamon Press). The bulky alkyl substituents preferably provide a cone angle (on the precursor phosphine - i.e. the R3P
fragment) of at least 150°, most preferably at least 160°.
Exemplary bulky alkyl groups include isopropyl, cyclohexyl, and tertiary butyl. It is particularly preferred that each R group be tertiary butyl.
Further details are provided in the following, non-limited examples.
EXAMPLES
Preparation of Tri-isopropyl Aminophosphonium Bromide, iPr3P(NH2)Br To a solution of tri-isopropylphosphine (10g, 62 mmol) in acetonitrile (100 mL) at 0°C was added bromine, Br2 (3.2 mL, 62 mmol). The reaction was stirred for 1-2 hours and ammonia gas was then added to the reaction 3o flask. An exothermic reaction ensued. After the reaction was complete, the volatiles were removed in vacuo to leave a white solid residue. The solid was treated with methylene chloride and then filtered to remove the insoluble NH4Br by-product. The methylene chloride was removed in vacuoto leave the desired product in >95% purity as determined by'H
G:\Scott\PSCSpec\9183can.doc 4 NMR spectroscopy. Yield = 14.6 g, 91%. 'H NMR [200 MHz, CDC13, 8]:
5.34 (br, s, NH2), 2.7 (m, 3H), 1.46 (d, 9H), 1.38 (d, 9H).
Preparation of N-trimethylsilyl Tri-isopropylphosphinimine, iPr3P(=N-SiMe3) from Tri-isopropyl Aminophosphonium Bromide, iPr3P(NH2)Br To a slurry of iPr3P(NH2)Br (14.4 g, 56 mmol) in THF (250 mL) at ~0°C was added a hexane solution of BuLi (45 mL, 2.5 M., 112.5 mmol).
1o During the addition the iPr3P(NH2)Br was observed to dissolve. The reaction was stirred for 60 minutes. It was then added to a solution of trimethylsilyl chloride (10.7 mL, 84 mmol) in THF (200 mL). After 60 minutes the reaction mixture volatiles were removed in vacuo. The resulting oily residue was then treated with hexane and the reaction filtered. Removal of the hexane yielded the desired product in >95% purity as determined by'H NMR spectroscopy. Yield = 13.5g, 98%. 'H NMR
[200 MHz, C~DB]: 1.61 (m, 3H), 0.97 (d, 9H), 0.87 (d, 9H) 0.28 (s, 9H, SiMe3).
Preparation of Tri-tert-butylphosphonium dichloride, tBu3PCl2, in Ether To a solution of tBu3P (5.2 g) in ether (100 ml) at -50°C was slowly added chlorine gas. The reaction was very exothermic and immediately 3o gave a white solid that dissolved as the reaction warmed to 0°C over the one hour chlorine addition period. Once the reaction complete the volatiles were removed in vacuo. The resulting white solid product was then isolated as a pure material in quantitative yield. Yield = 7 g. 'H NMR
[200 MHz, CDC13, 8]: 1.79 (d, J= 17.4 Hz) G:\Scott\PSCSpec\9183can.doc 5 Preparation of Tri-tert=butyl Aminophosphonium Chloride, tBu3P(NH2)CI in Methanol To a solution of tBu3PCl2 (2g) in methanol (30 mL) at 0°C was added ammonia gas at atmospheric pressure. After about 30 minutes it appeared that the solution was saturated with ammonia and the gas addition was terminated. The reaction was then stirred overnight at room to temperature. The reaction volatiles were removed in vacuo to yield a white solid. 'H NMR spectroscopic analysis of this solid demonstrated the formation of the desired product although some starting tBu3PCl2 remained. Consequently, the solid was redissolved in methanol (30 mL) and the solution placed in a stainless steal pressure vessel. The solution was cooled to -40°C and ammonia (10 g) added. The vessel was then sealed and warmed to 50°C for 16 hours.
~H NMR analysis of solution at that time revealed that the reaction had gone to completion with only tBu3P(NH2)CI present. Yield = 1.60 g. 'H
NMR [200 MHz, CDC13, 8]: 5.5 (br, NH2), 1.55 (d, J= 14.1 Hz, tBu) Preparation of Tri-tent butyl Aminophosphonium Chloride, tBu3P(NH2)CI in Methanol To a solution of tBu3P (2.874 g, 14.2 mmol) in methanol (40 ml) at 0°C was added tert-butyl hypochlorite, tBuOCI (1.67 g, 14.2 mmol).
After 30 minutes, the volatiles were removed in vacuo from clear reaction mixture and the resulting solid treated with toluene. The toluene was then removed in vacuo to leave a white solid. (The toluene was added to help ensure removal of all methanol). The white solid was isolated (yield = 2.88 G:\Scott\PSCSpec\9183can.doc g) and characterized by'H NMR spectroscopy. It was found to contain only tBu3PCl2 (~60%) and tBu3P=O (~40%).
To a solution of the tBu3PCl2/tBu3P=O mixture (2 g) in methanol (30 ml) at -40°C in a stainless steal pressure vessel was added ammonia (5 g).
The vessel was sealed and then warmed to 50°C for 64 hours. The reaction was depressurized and the reaction solution transferred to a glass to Schlenk vessel. The volatile components were then removed in vacuo to leave a white solid. This was treated with methylene chloride and the solution filtered. The methylene chloride was removed in vacuo and the resulting solid washed with toluene to remove residual tBu3P0. The product was then dried in vacuo. Yield = 684 mg. ' H NMR [200 MHz, CD2C12, 8]: 5.9 (br, NH2), 1.57 (d, J= 14.1 Hz). The NMR spectrum revealed ~10% residual tBu3P0 remained in the product.
Preparation of N-trimethylsilyl Tri-tert-butylphosphinimine, tBu3P(=N-SiMe3) from Tri-tert-butyl Aminophosphonium Chloride A sample of tBu3P(NH2)CI (400 mg, 1.6 mmol) contaminated with a small amount of tBu3PCl2 was slurried in tetrahydrofuran (30 mL) at -78°C
and a solution of BuLi in hexane (1.6 M, 2.2 ml, 3.5 mmol) was added.
After 45 minutes, trimethylsilyl chloride (0.4 mL) was added and then the 3o reaction was allowed to warm to room temperature. The reaction mixture volatiles were removed in vacuo to yield a sticky solid. Hexane was added and the reaction filtered. Removal of the hexane gave the desired product as a white solid in >95% purity as determined by'H NMR spectroscopy.
Yield = 443 mg, 97%. 'H NMR [200 MHz, C~D8, 8]: 1.16 (d, J= 12.7 Hz), 0.33 (s, SiMe3).
G:\Scott\PSCSpec\9183can.doc 7 COMPARATIVE EXAMPLES
Reaction of tBu3PBr2 with Ammonia in Methanol To a solution of tBu3PBr2 (1 g) in methanol (25 ml) at 0°C was added ammonia gas at atmospheric pressure. After about 30 minutes, it appeared that the solution was saturated with ammonia and the gas addition was terminated. The reaction was then stirred overnight at room to temperature. The reaction volatiles were removed in vacuo to yield a white solid. 'H NMR spectroscopic analysis of this solid demonstrated that it consisted primarily of starting material with a large number of other materials. None of these other materials had NMR spectra consistent with tBu3P(NH2)Br.
Reaction of tBu3PBr2 with Ammonia in Acetonitrile To a solution of tBu3PBr2 (2g) in acetonitrile (50 ml) at 25°C was added ammonia gas at atmospheric pressure. Gas addition was continued for 2 hours. The reaction volatiles were removed in vacuo to yield a white solid. 'H NMR spectroscopic analysis of this solid demonstrated that it was starting tBu3PBr2.
G:\Scott\PSCSpec\9183can.doc
This invention relates to a novel synthetic method to prepare bulky trialkyl aminophosphonium halides.
BACKGROUND OF THE INVENTION
Olefin polymerization catalysts having phosphinimine ligands ("phosphinimine catalysts") are disclosed in co-pending and commonly to assigned patent applications. See, for example, Canadian patent applications 2,206,944; 2,210,131; 2,243,783; 2,243,775; and 2,243,726, the disclosures of which are incorporated herein by reference.
The prior art preparation of these phosphinimine catalysts uses an azide as an intermediate as disclosed in the above referenced patent applications. As will be appreciated by those skilled in the art, azides may explosively decompose.
It is an object of this invention to mitigate a problem associated with the prior art preparation of phosphinimine catalysts. We have now discovered a synthetic method which enables the production of phosphinimine catalysts without using an azide.
SUMMARY OF THE INVENTION
In one embodiment, there is provided a process to prepare a molecule defined by the formula:
X
G:\Scott\PSCSpec\9183can.doc 2 wherein X is a halogen and each R is an alkyl group, with the proviso that at least one R is selected from isopropyl and cyclohexyl;
wherein said process comprises the reaction of ammonia with a dihalide defined by the formula:
wherein X and each R are as defined above, characterized in that said to reaction is undertaken in a protic medium at a temperature of from -40°C
to 200°C.
In another embodiment, there is provided a process to prepare tri(tertiary-butyl) Aminophosphonium chloride, wherein said process comprises the reaction of ammonia with tri(tertiary-butyl) phosphonium dichloride.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENT
The present process is undertaken under very mild conditions.
Preferred temperatures are from -40°C to 200°C, most preferably from 20 to 100°C. A positive ammonia pressured of from 1 to 13 atmospheres is also preferred.
It is preferred to use a protic reaction medium, especially ethanol or methanol.
3 o The products of the process of the present invention, namely bulky trialkyl aminophosphonium halides, may be reacted with a base (such as sodium hydroxide, sodium methoxide or butyl lithium) to give a trialkyl phosphinimine R3P=NH. The phosphinimine may then be used to prepare the phosphinimine catalysts (described in the above noted patent applications) by reacting it with a metal halide.
G:\Scott\PSCSpec\9183can.doc 3 The term "bulky trialkyl" refers to the steric bulk of the alkyl substituents on the phosphines atom. As used herein, the term "bulky alkyl" means that the steric bulk should be greater than the steric bulk provided by three phenyl substituents. The use of so-called "Tolman cone angles" is conventionally employed to describe the bulk of phosphines.
Triphenyl phosphine is typically described as having a Tolman cone angle to of 145° (see, for example, Chemistry of the Elements, by Greenwood and Earnshaw, published by Pergamon Press). The bulky alkyl substituents preferably provide a cone angle (on the precursor phosphine - i.e. the R3P
fragment) of at least 150°, most preferably at least 160°.
Exemplary bulky alkyl groups include isopropyl, cyclohexyl, and tertiary butyl. It is particularly preferred that each R group be tertiary butyl.
Further details are provided in the following, non-limited examples.
EXAMPLES
Preparation of Tri-isopropyl Aminophosphonium Bromide, iPr3P(NH2)Br To a solution of tri-isopropylphosphine (10g, 62 mmol) in acetonitrile (100 mL) at 0°C was added bromine, Br2 (3.2 mL, 62 mmol). The reaction was stirred for 1-2 hours and ammonia gas was then added to the reaction 3o flask. An exothermic reaction ensued. After the reaction was complete, the volatiles were removed in vacuo to leave a white solid residue. The solid was treated with methylene chloride and then filtered to remove the insoluble NH4Br by-product. The methylene chloride was removed in vacuoto leave the desired product in >95% purity as determined by'H
G:\Scott\PSCSpec\9183can.doc 4 NMR spectroscopy. Yield = 14.6 g, 91%. 'H NMR [200 MHz, CDC13, 8]:
5.34 (br, s, NH2), 2.7 (m, 3H), 1.46 (d, 9H), 1.38 (d, 9H).
Preparation of N-trimethylsilyl Tri-isopropylphosphinimine, iPr3P(=N-SiMe3) from Tri-isopropyl Aminophosphonium Bromide, iPr3P(NH2)Br To a slurry of iPr3P(NH2)Br (14.4 g, 56 mmol) in THF (250 mL) at ~0°C was added a hexane solution of BuLi (45 mL, 2.5 M., 112.5 mmol).
1o During the addition the iPr3P(NH2)Br was observed to dissolve. The reaction was stirred for 60 minutes. It was then added to a solution of trimethylsilyl chloride (10.7 mL, 84 mmol) in THF (200 mL). After 60 minutes the reaction mixture volatiles were removed in vacuo. The resulting oily residue was then treated with hexane and the reaction filtered. Removal of the hexane yielded the desired product in >95% purity as determined by'H NMR spectroscopy. Yield = 13.5g, 98%. 'H NMR
[200 MHz, C~DB]: 1.61 (m, 3H), 0.97 (d, 9H), 0.87 (d, 9H) 0.28 (s, 9H, SiMe3).
Preparation of Tri-tert-butylphosphonium dichloride, tBu3PCl2, in Ether To a solution of tBu3P (5.2 g) in ether (100 ml) at -50°C was slowly added chlorine gas. The reaction was very exothermic and immediately 3o gave a white solid that dissolved as the reaction warmed to 0°C over the one hour chlorine addition period. Once the reaction complete the volatiles were removed in vacuo. The resulting white solid product was then isolated as a pure material in quantitative yield. Yield = 7 g. 'H NMR
[200 MHz, CDC13, 8]: 1.79 (d, J= 17.4 Hz) G:\Scott\PSCSpec\9183can.doc 5 Preparation of Tri-tert=butyl Aminophosphonium Chloride, tBu3P(NH2)CI in Methanol To a solution of tBu3PCl2 (2g) in methanol (30 mL) at 0°C was added ammonia gas at atmospheric pressure. After about 30 minutes it appeared that the solution was saturated with ammonia and the gas addition was terminated. The reaction was then stirred overnight at room to temperature. The reaction volatiles were removed in vacuo to yield a white solid. 'H NMR spectroscopic analysis of this solid demonstrated the formation of the desired product although some starting tBu3PCl2 remained. Consequently, the solid was redissolved in methanol (30 mL) and the solution placed in a stainless steal pressure vessel. The solution was cooled to -40°C and ammonia (10 g) added. The vessel was then sealed and warmed to 50°C for 16 hours.
~H NMR analysis of solution at that time revealed that the reaction had gone to completion with only tBu3P(NH2)CI present. Yield = 1.60 g. 'H
NMR [200 MHz, CDC13, 8]: 5.5 (br, NH2), 1.55 (d, J= 14.1 Hz, tBu) Preparation of Tri-tent butyl Aminophosphonium Chloride, tBu3P(NH2)CI in Methanol To a solution of tBu3P (2.874 g, 14.2 mmol) in methanol (40 ml) at 0°C was added tert-butyl hypochlorite, tBuOCI (1.67 g, 14.2 mmol).
After 30 minutes, the volatiles were removed in vacuo from clear reaction mixture and the resulting solid treated with toluene. The toluene was then removed in vacuo to leave a white solid. (The toluene was added to help ensure removal of all methanol). The white solid was isolated (yield = 2.88 G:\Scott\PSCSpec\9183can.doc g) and characterized by'H NMR spectroscopy. It was found to contain only tBu3PCl2 (~60%) and tBu3P=O (~40%).
To a solution of the tBu3PCl2/tBu3P=O mixture (2 g) in methanol (30 ml) at -40°C in a stainless steal pressure vessel was added ammonia (5 g).
The vessel was sealed and then warmed to 50°C for 64 hours. The reaction was depressurized and the reaction solution transferred to a glass to Schlenk vessel. The volatile components were then removed in vacuo to leave a white solid. This was treated with methylene chloride and the solution filtered. The methylene chloride was removed in vacuo and the resulting solid washed with toluene to remove residual tBu3P0. The product was then dried in vacuo. Yield = 684 mg. ' H NMR [200 MHz, CD2C12, 8]: 5.9 (br, NH2), 1.57 (d, J= 14.1 Hz). The NMR spectrum revealed ~10% residual tBu3P0 remained in the product.
Preparation of N-trimethylsilyl Tri-tert-butylphosphinimine, tBu3P(=N-SiMe3) from Tri-tert-butyl Aminophosphonium Chloride A sample of tBu3P(NH2)CI (400 mg, 1.6 mmol) contaminated with a small amount of tBu3PCl2 was slurried in tetrahydrofuran (30 mL) at -78°C
and a solution of BuLi in hexane (1.6 M, 2.2 ml, 3.5 mmol) was added.
After 45 minutes, trimethylsilyl chloride (0.4 mL) was added and then the 3o reaction was allowed to warm to room temperature. The reaction mixture volatiles were removed in vacuo to yield a sticky solid. Hexane was added and the reaction filtered. Removal of the hexane gave the desired product as a white solid in >95% purity as determined by'H NMR spectroscopy.
Yield = 443 mg, 97%. 'H NMR [200 MHz, C~D8, 8]: 1.16 (d, J= 12.7 Hz), 0.33 (s, SiMe3).
G:\Scott\PSCSpec\9183can.doc 7 COMPARATIVE EXAMPLES
Reaction of tBu3PBr2 with Ammonia in Methanol To a solution of tBu3PBr2 (1 g) in methanol (25 ml) at 0°C was added ammonia gas at atmospheric pressure. After about 30 minutes, it appeared that the solution was saturated with ammonia and the gas addition was terminated. The reaction was then stirred overnight at room to temperature. The reaction volatiles were removed in vacuo to yield a white solid. 'H NMR spectroscopic analysis of this solid demonstrated that it consisted primarily of starting material with a large number of other materials. None of these other materials had NMR spectra consistent with tBu3P(NH2)Br.
Reaction of tBu3PBr2 with Ammonia in Acetonitrile To a solution of tBu3PBr2 (2g) in acetonitrile (50 ml) at 25°C was added ammonia gas at atmospheric pressure. Gas addition was continued for 2 hours. The reaction volatiles were removed in vacuo to yield a white solid. 'H NMR spectroscopic analysis of this solid demonstrated that it was starting tBu3PBr2.
G:\Scott\PSCSpec\9183can.doc
Claims (7)
1. A process to prepare a molecule defined by the formula:
wherein X is a halogen and each R is an alkyl group, with the proviso that at least one R is selected from isopropyl and cyclohexyl;
wherein said process comprises the reaction of ammonia with a dihalide defined by the formula:
wherein X and each R are as defined above;
characterized in that said reaction is undertaken in a protic medium at a temperature of from -40°C to 200°C.
wherein X is a halogen and each R is an alkyl group, with the proviso that at least one R is selected from isopropyl and cyclohexyl;
wherein said process comprises the reaction of ammonia with a dihalide defined by the formula:
wherein X and each R are as defined above;
characterized in that said reaction is undertaken in a protic medium at a temperature of from -40°C to 200°C.
2. The process of claim 1 wherein each R group is independently selected from isopropyl and cyclohexyl.
3. The process of claim 1 wherein said protic medium is selected from the group consisting of methanol and ethanol and further characterized in that said reaction is undertaken at a pressure of from 1 to 13 atmospheres.
4. The process of claim 1 wherein X is selected form bromine and chlorine.
5. A process to prepare a molecule defined by the formula:
wherein each R is an alkyl group, with the proviso that at least one R is a tertiary butyl group, and wherein said process comprises the reaction of ammonia with a dichloride defined by the formula:
R3PCl2 wherein each R is as defined above.
wherein each R is an alkyl group, with the proviso that at least one R is a tertiary butyl group, and wherein said process comprises the reaction of ammonia with a dichloride defined by the formula:
R3PCl2 wherein each R is as defined above.
6. A process to prepare tri(tertiary-butyl) Aminophosphonium chloride, wherein said process comprises the reaction of ammonia with tri(tertiary-butyl) phosphonium dichloride at a pressure of from 1 to 13 atmospheres and a temperature of from -40°C to 200°C.
7. The process of claim 6 wherein completed in a protic solvent.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CA 2261518 CA2261518A1 (en) | 1999-02-12 | 1999-02-12 | Synthetic method |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CA 2261518 CA2261518A1 (en) | 1999-02-12 | 1999-02-12 | Synthetic method |
Publications (1)
Publication Number | Publication Date |
---|---|
CA2261518A1 true CA2261518A1 (en) | 2000-08-12 |
Family
ID=29555135
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA 2261518 Abandoned CA2261518A1 (en) | 1999-02-12 | 1999-02-12 | Synthetic method |
Country Status (1)
Country | Link |
---|---|
CA (1) | CA2261518A1 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1506974A1 (en) * | 2003-08-04 | 2005-02-16 | DSM IP Assets B.V. | Process for the preparation of a metalloorganic compound comprising at least one imine ligand |
-
1999
- 1999-02-12 CA CA 2261518 patent/CA2261518A1/en not_active Abandoned
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1506974A1 (en) * | 2003-08-04 | 2005-02-16 | DSM IP Assets B.V. | Process for the preparation of a metalloorganic compound comprising at least one imine ligand |
WO2005014663A1 (en) | 2003-08-04 | 2005-02-17 | Dsm Ip Assets B.V. | Process for the preparation of an metalloorganic compound comprising at least one imine ligand |
WO2005014665A1 (en) | 2003-08-04 | 2005-02-17 | Dsm Ip Assets B.V. | Process for the preparation of a metalloorganic compound comprising at least one imine ligand |
WO2005014666A1 (en) * | 2003-08-04 | 2005-02-17 | Dsm Ip Assets B.V. | Process for the preparation of a metal-organic compound comprising at least one imine ligand |
WO2005014664A1 (en) | 2003-08-04 | 2005-02-17 | Dsm Ip Assets B.V. | Process for the preparation of a metal-organic compound comprising at least one imine ligand |
US7524906B2 (en) | 2003-08-04 | 2009-04-28 | Dsm Ip Assets B.V. | Process for the preparation of a metal-organic compound comprising at least one imine ligand |
US7655592B2 (en) | 2003-08-04 | 2010-02-02 | Dsm Ip Assets B.V. | Process for the preparation of a metal-organic compound comprising at least one imine ligand |
US7674867B2 (en) | 2003-08-04 | 2010-03-09 | Dsm Ip Assets B.V. | Process for the preparation of an metal-organic compound comprising at least one imine ligand |
US7737070B2 (en) | 2003-08-04 | 2010-06-15 | Dsm Ip Assets B.V. | Process for the preparation of a metal-organic compound comprising at least one imine ligand |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US2863894A (en) | Production of aluminium alkyls | |
JP5107243B2 (en) | Process for the preparation of monoalkyltin trihalides and dialkyltin dihalides | |
JP3856081B2 (en) | Method for producing halopropyldimethylchlorosilane compound | |
US5068386A (en) | Preparation of tertiary-hydrocarbylsilyl compounds | |
EP0582114B1 (en) | Process for preparing metallocenes | |
JP2938731B2 (en) | Method for producing halopropyldimethylchlorosilane and catalyst for its synthesis | |
CA2261518A1 (en) | Synthetic method | |
US4778908A (en) | Process for preparing disilylmethanes | |
US8148286B2 (en) | Activated alkaline earth metal, in particular magnesium, for the preparation of organoalkaline earth metal compounds | |
PL94075B1 (en) | ||
EP0044558B1 (en) | Method for the preparation of alkyne-1 compounds | |
JP5488786B2 (en) | Process for producing azaboracyclopentene compound and synthetic intermediate thereof | |
JP5463750B2 (en) | Method for producing azaboracyclopentene compound | |
JP3856905B2 (en) | Method for producing trityltetrakis (pentafluorophenyl) borate | |
JP4055212B2 (en) | Method for producing organic transition metal complex | |
JP5488789B2 (en) | Process for producing alkoxyazaboracyclopentene compound | |
JP2907046B2 (en) | Hydrocarbonation of chlorosilanes | |
JPH0925284A (en) | Production of cyclopentadienyltitanium trialkoxy derivative | |
JP5423212B2 (en) | Method for producing aminoazaboracyclopentene compound | |
WO1997014698A1 (en) | Synthesis of perfluoroaryl-substituted compounds | |
JP4174650B2 (en) | Method for producing halopropyldimethylchlorosilane compound | |
RU2135504C1 (en) | METHOD OF PREPARING 1-(n-PROPYL)-2-MAGNESIUM HALOGEN (60) FULLERENES | |
JP2023537859A (en) | Monosubstituted cyclopentadiene and metal cyclopentadienyl complexes, and methods for synthesizing the same | |
Pimanova et al. | Reactions of bis (phenylethynyl) ytterbium with trimethylsilicon, triphenylgermanium, and triphenyltin chlorides | |
JP2799619B2 (en) | Method for producing N, 0-bis (t-butyldimethylsilyl) trifluoroacetamide |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
FZDE | Dead |