CA2086285A1 - Process for the preparation of vicinally-disubstituted bis(diorganophosphino) compounds - Google Patents
Process for the preparation of vicinally-disubstituted bis(diorganophosphino) compoundsInfo
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- CA2086285A1 CA2086285A1 CA 2086285 CA2086285A CA2086285A1 CA 2086285 A1 CA2086285 A1 CA 2086285A1 CA 2086285 CA2086285 CA 2086285 CA 2086285 A CA2086285 A CA 2086285A CA 2086285 A1 CA2086285 A1 CA 2086285A1
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- Prior art keywords
- vicinally
- disubstituted
- alkane
- alkene
- base
- 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.)
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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 System
- 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
- C07F9/5086—Preparation; Separation; Purification; Stabilisation from phosphonium salts as starting materials
-
- 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 System
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
Abstract
TITLE OF THE INVENTION
PROCESS FOR THE PREPARATION OF
VICINALLY-DISUBSTITUTED BIS(DIORGANOPHOSPHINO) COMPOUNDS
ABSTRACT OF THE DISCLOSURE
Vicinally-disubstituted bis(diorganophosphino)-alkanes, -alkenes, or -arenes are prepared by reacting a secondary phosphine with a vicinally disubstituted dihalo-alkane, -alkene or -arene to form a halide salt of the vicinally-disubstituted bis(diorganophosphino)-compound and treating the salt with a base to convert the salt to the free vicinally-disubstituted bis(diorganophosphino)-alkane, -alkene or -arene base.
PROCESS FOR THE PREPARATION OF
VICINALLY-DISUBSTITUTED BIS(DIORGANOPHOSPHINO) COMPOUNDS
ABSTRACT OF THE DISCLOSURE
Vicinally-disubstituted bis(diorganophosphino)-alkanes, -alkenes, or -arenes are prepared by reacting a secondary phosphine with a vicinally disubstituted dihalo-alkane, -alkene or -arene to form a halide salt of the vicinally-disubstituted bis(diorganophosphino)-compound and treating the salt with a base to convert the salt to the free vicinally-disubstituted bis(diorganophosphino)-alkane, -alkene or -arene base.
Description
--' 2~862~
31,814-00 -1- .
PROCESS FOR THE PREPARATION OF
VICINALLY-DISUBSTITUTED BIS(DIORGANOPHOSPHINO) COMPOUNDS
FIELD OF THE INVENTION
The present in~ention relates to a novel, two step method for large scale synthesi~ of vicinally-disubstituted b~s(diorganophosphino)-alkanes, -alkenes and -arenes via the bis phosphonium salt.
BACKGROUND OF THE INVENTION
Bidèntate phosphlne ligand~, especially bidentate ligands with a C2 backbone, are important ligands for reactive catalysts and are replacing the commonly used monodentate tertiary phosphine ligands.
Presently the known chemistry for preparing bidentate ligands uses either the Grignard reagent method or the sodium phosphide method. These methods are meant for small scale preparations. The preparation of bidentate ligands by the Grignard reagent method re~uires anhydrous reaction conditions which are difficult to maintain. The preparation of bidentate ligands by the sodium phosphlde method requires large volumes of sodium metal. The yield of bidentate ligand~ using either of these known methods is often very low and large quantities of byproducts and waste materials are generated.
Alkyl halides, such as allyl bromide, are-not known to combine readily with secondary phosphines to generate phosphonium salts except under the Grignard reagent method or the sodium phosphide meth¢d. However to generate bidentate ligands from dlalkylallyl phosphlnes, a second step under free radical conditions is required and the bidentate ligand~ formed are limited to a C3-backbone and to phosphine alkyl groups with low steric hlnderance.
Dihaloalkanes such as 1,3-dibromopropane and other alpha-omega-dihalogenated hydrocarbons are al~o believed to be relatively unreactive with secondary phosphines for generating phosphonium salts.
~Q~8~
SUMMARY OF THE INVENTION
The present invention provides a direct route to the production of vicinally-disubstituted bis(diorganophosphino)-alkane~, -alkenes or -arenes by reacting vicinally-dihalogenated hydrocarbons with secondary phosphines. The reaction is easily carried out in a single vessel, which is ideal for industrial scale preparations and the waste i8 relatively innocuous salt water. Moreover, any unreacted materials can be distilled from the product and recycled into the next batch.
A further advantage of the present invention over the known methods of bidentate ligand production is that secondary phosphines with bulky substitutents can be produced with reasonably high yields. However, the secondary phosphines with the bulky substituents react ~lightly slower with the vicinally dihalogenated hydrocarbon than the secondary phosphines without bulky substituents.
The method for producing vicinally-disubstituted bis(diorganophosphino)-compounds, according to the prèsent invention, comprises reacting a secondary phosphine with a vicinally disubstituted dihalo-alkane, -alkene or -arene to produce a halide salt of the vicinally-disubstituted bi~(diorganophosphino)-compound. The halide salt of the vicinally-disubstituted bis(diorganophosphino)-compound ia then treated with a base to convert the salt to the free viclnally-disubstituted bis(diorganopho~phino)-alkane, alkene or -arene base. It is preferred that the molar ratio of the secondary phosphine to vicinally disubstituted dihalo-alkane, -alkene or -arene be at least about 2 to 1 of the secondary phosphine to the disubstituted dihalo compound.
The compounds prepared in accordance with the process hereof are useful in the preparation of catalysts by reaction thereof with palladium, which catalysts are used to prepare polyketones from carbon monoxide and `',''':`"`"''"''`",'"''`;'"''.'.`,.'' ' ~'`
-~ 20~$28~
olefins, see EPo Publication No. 0380162 and U.S. Patent No. 5,025,091.
In preferred embodiments of the invention, the secondary phosphine compound is of the following formula: :
the disu~stituted dihalo compound is of the following formula:
X - CH(R3) - CH(R4) - X :
and the vicinally-disubstituted bis(diorganophosphino)-alkane, -alkene, or -alkyne base is of the following formula: I .
R1R2 - P - CH(R3) - CH(R4) - P - R1R2 ~
wherein R1 and R2, independently, are selected from alkyl, ~:
aryl, alkaryl, aralkyl, cycloalkyl, alkylcycloalkyl, 15 alkoxyalkyl, cycloalXylaryl, aminoalkyl, heterocyclyl and ~
heterocyclylalkyl groups, non-terminal alkenyl groups, or ~¦
inertly-substituted such groups; X is a halogen, preferably chlorine, bromine or iodine; and R3 and R4, independently, are selQcted from the ~ame groups a~ defined for R1 and R2, and, ln add~tion hydrogen, and when taken together with the carbon atoms to which they are attached, R1 and R2 form a ~ingle bond, or part of a three to seven membered ring comprising a cycloalkyl, an alkylcycloalkyl, a cycloalkylaryl, a heterocyclyl, a heterocyclylalkyl, an .
aryl, an alkylaryl group, a ring-fu~ed- or an inertly-substituted- such group. Examples of suitable values for R1 and R2 (and R3 and R~) include, but are not limited to methyl; ethyl; n-propyl; isopropyl; n-butyl; isobutyl; sec-butyl; n-pentyl; n-hexyl; n-heptyl; n-octyl; n-nonyl; n-decyl; n-dodecyl; n-tetradecyl; n-hexadecyl; n-eicosyl;
31,814-00 -1- .
PROCESS FOR THE PREPARATION OF
VICINALLY-DISUBSTITUTED BIS(DIORGANOPHOSPHINO) COMPOUNDS
FIELD OF THE INVENTION
The present in~ention relates to a novel, two step method for large scale synthesi~ of vicinally-disubstituted b~s(diorganophosphino)-alkanes, -alkenes and -arenes via the bis phosphonium salt.
BACKGROUND OF THE INVENTION
Bidèntate phosphlne ligand~, especially bidentate ligands with a C2 backbone, are important ligands for reactive catalysts and are replacing the commonly used monodentate tertiary phosphine ligands.
Presently the known chemistry for preparing bidentate ligands uses either the Grignard reagent method or the sodium phosphide method. These methods are meant for small scale preparations. The preparation of bidentate ligands by the Grignard reagent method re~uires anhydrous reaction conditions which are difficult to maintain. The preparation of bidentate ligands by the sodium phosphlde method requires large volumes of sodium metal. The yield of bidentate ligand~ using either of these known methods is often very low and large quantities of byproducts and waste materials are generated.
Alkyl halides, such as allyl bromide, are-not known to combine readily with secondary phosphines to generate phosphonium salts except under the Grignard reagent method or the sodium phosphide meth¢d. However to generate bidentate ligands from dlalkylallyl phosphlnes, a second step under free radical conditions is required and the bidentate ligand~ formed are limited to a C3-backbone and to phosphine alkyl groups with low steric hlnderance.
Dihaloalkanes such as 1,3-dibromopropane and other alpha-omega-dihalogenated hydrocarbons are al~o believed to be relatively unreactive with secondary phosphines for generating phosphonium salts.
~Q~8~
SUMMARY OF THE INVENTION
The present invention provides a direct route to the production of vicinally-disubstituted bis(diorganophosphino)-alkane~, -alkenes or -arenes by reacting vicinally-dihalogenated hydrocarbons with secondary phosphines. The reaction is easily carried out in a single vessel, which is ideal for industrial scale preparations and the waste i8 relatively innocuous salt water. Moreover, any unreacted materials can be distilled from the product and recycled into the next batch.
A further advantage of the present invention over the known methods of bidentate ligand production is that secondary phosphines with bulky substitutents can be produced with reasonably high yields. However, the secondary phosphines with the bulky substituents react ~lightly slower with the vicinally dihalogenated hydrocarbon than the secondary phosphines without bulky substituents.
The method for producing vicinally-disubstituted bis(diorganophosphino)-compounds, according to the prèsent invention, comprises reacting a secondary phosphine with a vicinally disubstituted dihalo-alkane, -alkene or -arene to produce a halide salt of the vicinally-disubstituted bi~(diorganophosphino)-compound. The halide salt of the vicinally-disubstituted bis(diorganophosphino)-compound ia then treated with a base to convert the salt to the free viclnally-disubstituted bis(diorganopho~phino)-alkane, alkene or -arene base. It is preferred that the molar ratio of the secondary phosphine to vicinally disubstituted dihalo-alkane, -alkene or -arene be at least about 2 to 1 of the secondary phosphine to the disubstituted dihalo compound.
The compounds prepared in accordance with the process hereof are useful in the preparation of catalysts by reaction thereof with palladium, which catalysts are used to prepare polyketones from carbon monoxide and `',''':`"`"''"''`",'"''`;'"''.'.`,.'' ' ~'`
-~ 20~$28~
olefins, see EPo Publication No. 0380162 and U.S. Patent No. 5,025,091.
In preferred embodiments of the invention, the secondary phosphine compound is of the following formula: :
the disu~stituted dihalo compound is of the following formula:
X - CH(R3) - CH(R4) - X :
and the vicinally-disubstituted bis(diorganophosphino)-alkane, -alkene, or -alkyne base is of the following formula: I .
R1R2 - P - CH(R3) - CH(R4) - P - R1R2 ~
wherein R1 and R2, independently, are selected from alkyl, ~:
aryl, alkaryl, aralkyl, cycloalkyl, alkylcycloalkyl, 15 alkoxyalkyl, cycloalXylaryl, aminoalkyl, heterocyclyl and ~
heterocyclylalkyl groups, non-terminal alkenyl groups, or ~¦
inertly-substituted such groups; X is a halogen, preferably chlorine, bromine or iodine; and R3 and R4, independently, are selQcted from the ~ame groups a~ defined for R1 and R2, and, ln add~tion hydrogen, and when taken together with the carbon atoms to which they are attached, R1 and R2 form a ~ingle bond, or part of a three to seven membered ring comprising a cycloalkyl, an alkylcycloalkyl, a cycloalkylaryl, a heterocyclyl, a heterocyclylalkyl, an .
aryl, an alkylaryl group, a ring-fu~ed- or an inertly-substituted- such group. Examples of suitable values for R1 and R2 (and R3 and R~) include, but are not limited to methyl; ethyl; n-propyl; isopropyl; n-butyl; isobutyl; sec-butyl; n-pentyl; n-hexyl; n-heptyl; n-octyl; n-nonyl; n-decyl; n-dodecyl; n-tetradecyl; n-hexadecyl; n-eicosyl;
2,4,4-trimethylpentyl; cyclopentyl; cyclohexyl; cyclooctyl;
cyclooctyl ether; 2,4,6-triisopropyl-1,3,5-dioxaphosphorinane; phenyl; p-chlorophenyl; o-tolyl; m-tolyl; p-tolyl; 2,3-dimethylphenyl; 2,4-dimethylphenyl;
2,5-dimethylphenyl; 2,6-dimethylphenyl; 3,4-dimethylphenyl;
cyclooctyl ether; 2,4,6-triisopropyl-1,3,5-dioxaphosphorinane; phenyl; p-chlorophenyl; o-tolyl; m-tolyl; p-tolyl; 2,3-dimethylphenyl; 2,4-dimethylphenyl;
2,5-dimethylphenyl; 2,6-dimethylphenyl; 3,4-dimethylphenyl;
3,5-dlmethylphenyl; p-ethylphenyl; p-octylphenyl; n-butylphenyl; n-octylphenyl; n-hexadecylphenyl; o--' 20~28~
chlorophenyl; m-chlorophenyl; p-chlorophenyl; benzyl;
naphthyl; 1-hydroxycyclohexyl; 2-methyl-1-hydroxypentyl;
alpha-hydroxybenzyl; o-chlorobenzyl, alpha-hydroxy-o-chlorobenzyl; p-chlorobenzyl, alpha-hydroxy-p-chlorobenzyl; alpha-methylbenzyl, 1-hydroxycyclopentyl;
alpha-hydroxy-alphamethylbenzyl; l-methylpentyl; 1-hydroxy-l-methylpentyl; alpha-hydroxybenzyl; (1-hydroxy-1-methylethyl)isopropyl.
In a preferred embodiment of the present invention the secondary phosphine is di-iso-butylphosphine or di-sec-butylphosphine and the vicinally disubstituted dihalo compound is a dibromo-alkane, -alkene or -arene, most prefera~ly a dibromo-alXane such as 1,2-dibromoethane.
In principle, any base can be used to con~ert the pho~phonium salt to the free base. Inorganic bases that can be used include sodium hydroxide, potassium hydroxide, sodium carbonate, pota~sium carbonate, sodium hydrogen carbonate, potas~ium hydrogen carbonate, sodium ethoxide, potassium ethoxide, ammonium carbonate, ammonium hydrogen carbonate, calcium oxide, calclum hydroxide, magnesium oxide and magnesium hydroxide. Organic bases that can be u~ed are amine~, particularly tertiary amines such as tri-ethylamine. Of these base~, sodium hydroxide and sodium hydrogen carbonate are preferred in view of their relative cheapness. The sodium cation forms a sod$um halide salt that can be separated in aqueous solution from the organic solvent in which the free phosphine base di~solve~. In contrast, if an organic base is used it may be necessary to carry out a separation step to remove the amine salt formed, depending upon the use to which the free phosphine base is to be put.
The reaction of the secondary phosphine and disubstituted dihalo compound is carried out in an organic ~olvent. It is preferred that the organic solvent have a boiling point about 10C to about 40C, preferably about 20C to about 30C, higher than the boiling point of the required vicinally disubstituted dihalo compound. Some of " :, 2~862~
the pre~erre~ organic sol~ents are tetradecane, hexadecane, octadecane, docosane and eicosane. The percentage by volume of the organic solvent should be kept to a minimum, keeping the concentration of the reactive agents high and thereby allowing the reaction to reach completion in a shorter period of time.
In a preferred embodiment of the invention, water is added to the reaction mixture after the àddition of the vicinally disubstituted dihalo compound but before the addition of the base. ~he addition of the water dissolve~
the intermediate phosphonium salt.
Acetonitrile may also be added to the reaction mixture. It is preferred that the acetonitrile be added at the initial stages of the reaction. One of the benefits of the presence of the acetonitrile in the mixture is that after the base is added to the mixture and the pH of the mixture is greater than 8, the mixture will separate into three phasee, a nonpolar phase, a polar phase and an aqueou~ phase. The nonpolar phase contain~ the unreacted secondary pho~phine, the nonpolar organic solvent, and the vicinally-disubstituted bis(diorganopho~phino) compound.
The polar phase contains the acetonitrile, any secondary phosphine oxides, vicinally disubstituted bis(diorganophosphino) compound oxides and any colour which was generated during the initial reaction. The aqueous phase contains any remaining salts.
If the vicinally disubstituted dihalo compound i8 a prochirally-sub~tituted compound, the product of the present invention will be a racemic mixture comprising a chiral bidentate ligand adapted to be combined with a metal. The result1ng chiral bidentate ligand metal can be used to prepare a catalyst for use in hydroformylation, decarbonylation and hydrogenation reactions. Special mention is made of processes wherein the dihalo compound is of the formula X - CH(R3) - CH(R4) - X
2~2~
wherein at least one of R3 and R4 is other than hydrogen or both R3 and R~ are not the same, one or both of groups -CH(R3) - and - CH(R4) - being chiral groups, whereby the product of the process comprises a racemic mixture of the corresponding chiral bidentate ligand.
DE~AILED DESCRIPTION OF TH~ INVENTION
The invention is further illustrated in the following examples.
A one litre reactor is charged with di-iYo-butylphosphine [DIBP] (304.3 g), 1,2-dibromoethane (196.0 g), tetradecane (79.5 g) and acetonitrile (103.3 g). The two phase mixture is heated to 68-69C. After 3.5 hours the temperature is increased to 73-74C. The upper organic layer gradually decreases as the lower layer increases with the formation of salt. At the end of the reaction period, the mixture is a thick crystalline slurry of salts. Water (19S.0 g) i~ added. NaHCO3 (123 g of a 168 g charge) ls added slowly over five hours to the mixture at 49C. 75~
of the expected base charge is added before the CO2 evolution cease~. The final mixture is separated into three layers. The upper layer (406 g) containing the unreacted di-~so-butylphosphine, tetradecane, di-iso-butyl(2-bromoethyl)phosphine and 1,2-bls(di-iso-butylphosphino)ethane. The middle layer (80 g) isacetonitrile and oxides. The bottom layer (g40 g) consists of water, NaBr and unreacted phosphonium salts.
A one litre reactor is charged with di-~ec-butylphosphine [DSBP3 (320.0 g), acetonitrile (105.8 g) andtetradecane (106.2 g). The two pha~e mixture i8 heated to 78-79C. 1,2-dibromoethane (320 g~ is charged over four hour~ to the reactor mixture. The volume of the phase~
gradually changes and the mixture becomes cloudy. Water (230.0 g) is added. NaHCO3 (113 g of a 148 g charge) is added slowly over three hours. 75% of the expected base is added before the CO2 evolution ceases. The upper layer (432 2 ~
g) contains unreacted di-sec-butylphosphine, tetradecane, di-sec-butyl(2-bromoethyl)phosphino and 1,2-bis(di sec-butylphosphino)ethane.
A reactor is charged with di-iso-butylphosphine, -~
tetradecane, acetonitrile, and 1,2-dibromoethane. ~3he parameters of the reactions are listed in Table 1.
3* 4*~ 5~ 6**
Acetonitrile 103.3g 105.0g 112.6g Tetradecane 79.5g 314.0g 323.0g 108.5g DIBP 304.3g 283.0g 296.8g 394.5g 1,2-dibromoethane 196.0g 149g 149g 190.8g Charge Time - 2.5 hr. 2 hr.
Reaction ~emp. 68-75C 77-81C 82-86C 84-87C
Reaction Time 24 hr. 5 hr. 23 hr. 23 hr.
B3ase ~aHCO3 NaOHt NaOHt NaOHt Ma~s Base 125g 89.9g 208g 100g Base Reaction Temp. 48-49C 35-40C 45-50C 25-26C
~ase Charge Time 5 hr. 20 min. 1.1 hr. 30 min.
* the reaction wa~ conducted in a one litre reactor *~ the reaction was conducted in a two litre round bottom flask heated with a mantle t the base was a 25~ NaON aqueous solution A larger volume of tetradecane is used in Examples 4 and 5 so that the solution can reach the thermometer.
The 1,2-dibromoethane of Example 4 is charged into the reaction flask over 2.5 hours. The mixture i8 30 heated for a further 2.5 hours before it i~ cooled from 80C to 40C. The 25S NaOH aqueous solution is quickly added to the reaction mixture over twenty (20) minutes3.
Only 36S of the expected stoichiometric amount of base is added before the pH increas3es to greater than 8 and the 35 mixture goes3 from two to three phases.
NaOH is a preferred solution because it is added as an aqueous solution allowing for a quicker charge time3. s NaHCO3 is le~s preferred because it require3s the addition of 20862~5 water to the reaction mixture before the addition of the powder form of the NaHC~3. Furthermore when NaHC03 is used, it evolves C02 that slows the rate at which the base may be charged and creates foam so that the reaction volume must be lowered to allow for additional head space for volume expansion in the reactor.
Table 2 compares the product distribution in the final organic layers for Examples 3-6 as determined by ga~
chromatography.
Acetonitrile 3.26 2.27 3.19 0 MIBP 0 0.19 0 0.34 1,2-dibromoethane 1.72 3.03 0.98 5.97 DIBP 28.5 35.9 22.0 65.8 DIBPO 1.34 0.21 0.65 0.53 Tetradecane 26.8 56.6 64.1 25.5 R2PCH2CH2Br 2.81 1.22 0.94 1.8 R2PcH2c~2P~2 33.0 0 9.09 0 Product Oxides 0.82 0 0 0 Table 2 shows that no bidentate liqand ls generated in Example 4. The GC analysis of the final product of Example 4 does show a small amount of the 1:1 adduct di-iso-butyl(2-bromoethyl)phosphine formed.
The product yield is expected to increase if the reaction temperature, the reaction time and the relative amount of the secondary phosphine to the 1,2-dibromoethane are ~ncreased. However in Example 5 the temperature could not be increased higher than 86C due to the refluxing temperature of the acetonitrile. ~y allowing the reaction to run overnight, the conversion to the product i~
approximately 70~ based on the amount of base required before the pH increases to qreater than 10.
In order to increase the reaction temperature in Example 6, acetonitrile is not used. A larger excess of DIBP (1.3 equivalents) is used and a smaller amount of tetradecane is used as the solvent. Even with running the 20~628~
:
g - ,~
reaction overnight at a higher temperature, no product ls generated.
The applicants do not wish to be limited to any particular theory but it is believed from the re~ults listed in Table 2 that a polar solvent may be required for generation of the phosphonium salt. It is al~o believed that a large excess of secondary phosphine is required to react completely with the 1,2-dibromoethane. Furthermore, -it is believed that the percentage by volume amount of organic solvent used should be kept to a minimum so that the concentration of the reactive agents i5 increased thereby increasing the conversion.
Similarly increasing the reaction temperature should increase the conversion. Conducting the reaction at higher temperatures will require a vessel that can withstand higher pressure so that the reflux temperature of the acetonitrile can be increased. The reaction probably cannot be performed in an autoclave because the phosphonium salts are too corrosive.
A one litre reactor is charged with di-sec-butylphosphine, tetradecane, acetonitrile, and 1,2-dibromoethane. The parameters of the reactions are llsted in Table 3.
2 ~ ~
Aceton~tr$1e 105.8g lOl.Og Tetradecane 106.2g 104.0g DSBP 320.0g 428.0g 1,2-dibromoethane 165g 240.4g Charge Time 3.9 hr.
Reaction Temperature 78-80C 86-88C
Reaction Time 22.5 hr. 23 hr.
10 Base NaHCO3 NaoHt Mass Base 105g 345g Base Reaction Temperature 48-49C 49-S1C
Base Charge Time 3 hr. 4.5 hr.
t 25% aqueous solution IS Example 7, employs 1.3 equivalents of DSBP to 1,2-dibromoethane. ~he haloalkane is added to the reactor over 3.9 hour~. After 22.5 hours of react$ng, the reactor i9 cooled from 79C to 48C. NaHCO3 is added to the mixture and approximately 75% of the stoichiometric amount of the base is added before the C2 evolution cea~es and three layers are formed.
All of the reagent~ in Example 8 are combined in the reactor and heated to the reaction temperature of 87C.
The reaction is left overnight and 85% of the expected NaOH
aqueous solutlon charge is added before the pH increases above 8. The mixture remsins in two phase~ until the pH
becomes alkaline.
Table 4 compare~ the product distribution in the final nonpolar organic layer for Examples 7 and 8 as determined by gas chromatography.
".
Acetonitrile 2.80 3.04 MSBP 0.11 0.16 1,2-dibromoethane 1.94 0.82 DSBP 37.4 27.7 DS~PO - 3 Isomers 0.80 1.67 Tetradecane 33.0 28.6 R2PCH2CH2Br 1.04 2.08 R2PCH2CH2PR2 18.0 31.7 Product Oxides 1.31 0.68 ~he results listed in ~able 4 indicate that the higher the temperature and reagent concentration the higher the converslon to the desired product.
A one litre resin reactor is charged with di-sec-butylphosphine, tetradecane, acetonitrile, and 1,2-dibromoethane. The parameters of the reactions are listed ln Table 9.
TAB~E S
9* 10 11*
Acetonitrile 110.4g 102.9g 106.lg tetradecane 100.3g 103.39 106.9g DSBP 565.8g 577.4g S71.2g 1,2-dibromoethane 282.4g 282.2g 283.4g Reaction Temperaturet 87-88C 67-68C 91-96C
* the reaction is run for only 5.5 hours and is heated by steam The di~appearance of the reagents in Example~ 9-11 was monitored by gas chromatography to determine the effects of temperature on the reaction kinetics.
The rate of disappearance of 1,2-dibromoethane is a~sumed to be pseudo-first order because an exces~ of secondary phosphine is u~ed in each reaction. The fir~t 3S order rate equations are;
' :,.
, .
~8~2~
-d r BrCH~CHzBrl = k[BrCH2CH2Br~ or ln([lBBrcCN2cC~B ~ ~ kt By plotting ln(~BrCH2CH2Br]) vs. time, the rate constant k can be determined. The plot for Example 10 was linear. The plot for Example 9 and 11 were slightly curved and the slopes were greater than the slope of the plot for Example 10. Because the reaction for Example 11 was only run for 5.5 hours, the plot is curved and not a true indication of the rate constant, but by extending the plot of Example 11 using the last few points the slope of Sxample 11 ~s greater than the slope of'Example 9. The rate constants (k) for Examples 9 to 11 are reported in Table 6.
lS ExamPle k 9 1.7E-4 minl ~
3.5E-3 min ;
11 3.4E-l min~
This data indicates that the reaction rate i~
very temperature sensitive. It is believed that by running the reaction under slight pressure, the reaction temperature can be increased allowing the reaction to be completed within eight ~8) hourg.
The procedure of Example 1 is repeated, substituting 1,2-dibromopropane for 1,2-dibromoethane. The corresponding product is obtained. The product i~ a racemate of two optically-active enantiomers by virtue of the prochiral - CH(CH3J - group in the starting material.
The product can be resolved into its respective optical lsomers in Xnown ways, e.g., by formlng a complex salt with an optically active acid and fractlonal crystallization, or by chromatography on an optically-active adsorbent or by other procedures.
The procedure of Example 1 is repeated, substituting 2,3-dlbromopentane for 1,2-dibromoethane. The corre~ponding product iCi obtained. The pro~uct i~ a S racemate of four optically-active enantiomers by virtue of the prochiral - CH(CH3) - and - CH(C2~s) - groups in the starting material. The product can be resolved into its respective optical isomers in known ways, e.g., by forming a complex salt with an optically active acid and fractional cry~tallization, or by chromatography on an optically-active adsorbent or by other procedures.
The procedure of Example 1 is repeated, su~stituting 1,2-di~romoethene for 1,2-dibromoethane The corresponding 1,2 bis(dialkylphosphino) alkene product 1 obtained.
The procedure of Example 1 is repeated, substituting 1,2-dibromopropene-1 for 1,2-dibromoethane.
The corresponding 1,2 bis(dialkylphosphino) alkene prodùct is obtained.
The procedure of Example 1 is repeated, substituting 1,2-dibromobenzene for 1,2-dibromoethane. The corresponding 1,2 bi~(dialkylphosphino) arene product i~
obtained.
~ he procedure of Example 1 ic repeated, substituting 1,2-dichloroethane for 1,2-dibromoethane. ~he same 1,2 bis(dialkylphosphino) alkane product is obtained.
The procedure of Example 1 is repeated, substituting 1,2-diiodoethane for 1,2-dibromoethane. The same 1,2 bis(dialkylphosphino) alkane product is obtained.
The above mentioned patent(s), any publication(~) and any test method(s) are incorporated herein by reference.
~' 20~2~
Many variations in the present invention w$11 suggest themselves to those skilled in this art in light of the above detailed descript$on. All such obvious modifications are within the full intended scope of the appended claims.
~'" ,,, ' ' :''
chlorophenyl; m-chlorophenyl; p-chlorophenyl; benzyl;
naphthyl; 1-hydroxycyclohexyl; 2-methyl-1-hydroxypentyl;
alpha-hydroxybenzyl; o-chlorobenzyl, alpha-hydroxy-o-chlorobenzyl; p-chlorobenzyl, alpha-hydroxy-p-chlorobenzyl; alpha-methylbenzyl, 1-hydroxycyclopentyl;
alpha-hydroxy-alphamethylbenzyl; l-methylpentyl; 1-hydroxy-l-methylpentyl; alpha-hydroxybenzyl; (1-hydroxy-1-methylethyl)isopropyl.
In a preferred embodiment of the present invention the secondary phosphine is di-iso-butylphosphine or di-sec-butylphosphine and the vicinally disubstituted dihalo compound is a dibromo-alkane, -alkene or -arene, most prefera~ly a dibromo-alXane such as 1,2-dibromoethane.
In principle, any base can be used to con~ert the pho~phonium salt to the free base. Inorganic bases that can be used include sodium hydroxide, potassium hydroxide, sodium carbonate, pota~sium carbonate, sodium hydrogen carbonate, potas~ium hydrogen carbonate, sodium ethoxide, potassium ethoxide, ammonium carbonate, ammonium hydrogen carbonate, calcium oxide, calclum hydroxide, magnesium oxide and magnesium hydroxide. Organic bases that can be u~ed are amine~, particularly tertiary amines such as tri-ethylamine. Of these base~, sodium hydroxide and sodium hydrogen carbonate are preferred in view of their relative cheapness. The sodium cation forms a sod$um halide salt that can be separated in aqueous solution from the organic solvent in which the free phosphine base di~solve~. In contrast, if an organic base is used it may be necessary to carry out a separation step to remove the amine salt formed, depending upon the use to which the free phosphine base is to be put.
The reaction of the secondary phosphine and disubstituted dihalo compound is carried out in an organic ~olvent. It is preferred that the organic solvent have a boiling point about 10C to about 40C, preferably about 20C to about 30C, higher than the boiling point of the required vicinally disubstituted dihalo compound. Some of " :, 2~862~
the pre~erre~ organic sol~ents are tetradecane, hexadecane, octadecane, docosane and eicosane. The percentage by volume of the organic solvent should be kept to a minimum, keeping the concentration of the reactive agents high and thereby allowing the reaction to reach completion in a shorter period of time.
In a preferred embodiment of the invention, water is added to the reaction mixture after the àddition of the vicinally disubstituted dihalo compound but before the addition of the base. ~he addition of the water dissolve~
the intermediate phosphonium salt.
Acetonitrile may also be added to the reaction mixture. It is preferred that the acetonitrile be added at the initial stages of the reaction. One of the benefits of the presence of the acetonitrile in the mixture is that after the base is added to the mixture and the pH of the mixture is greater than 8, the mixture will separate into three phasee, a nonpolar phase, a polar phase and an aqueou~ phase. The nonpolar phase contain~ the unreacted secondary pho~phine, the nonpolar organic solvent, and the vicinally-disubstituted bis(diorganopho~phino) compound.
The polar phase contains the acetonitrile, any secondary phosphine oxides, vicinally disubstituted bis(diorganophosphino) compound oxides and any colour which was generated during the initial reaction. The aqueous phase contains any remaining salts.
If the vicinally disubstituted dihalo compound i8 a prochirally-sub~tituted compound, the product of the present invention will be a racemic mixture comprising a chiral bidentate ligand adapted to be combined with a metal. The result1ng chiral bidentate ligand metal can be used to prepare a catalyst for use in hydroformylation, decarbonylation and hydrogenation reactions. Special mention is made of processes wherein the dihalo compound is of the formula X - CH(R3) - CH(R4) - X
2~2~
wherein at least one of R3 and R4 is other than hydrogen or both R3 and R~ are not the same, one or both of groups -CH(R3) - and - CH(R4) - being chiral groups, whereby the product of the process comprises a racemic mixture of the corresponding chiral bidentate ligand.
DE~AILED DESCRIPTION OF TH~ INVENTION
The invention is further illustrated in the following examples.
A one litre reactor is charged with di-iYo-butylphosphine [DIBP] (304.3 g), 1,2-dibromoethane (196.0 g), tetradecane (79.5 g) and acetonitrile (103.3 g). The two phase mixture is heated to 68-69C. After 3.5 hours the temperature is increased to 73-74C. The upper organic layer gradually decreases as the lower layer increases with the formation of salt. At the end of the reaction period, the mixture is a thick crystalline slurry of salts. Water (19S.0 g) i~ added. NaHCO3 (123 g of a 168 g charge) ls added slowly over five hours to the mixture at 49C. 75~
of the expected base charge is added before the CO2 evolution cease~. The final mixture is separated into three layers. The upper layer (406 g) containing the unreacted di-~so-butylphosphine, tetradecane, di-iso-butyl(2-bromoethyl)phosphine and 1,2-bls(di-iso-butylphosphino)ethane. The middle layer (80 g) isacetonitrile and oxides. The bottom layer (g40 g) consists of water, NaBr and unreacted phosphonium salts.
A one litre reactor is charged with di-~ec-butylphosphine [DSBP3 (320.0 g), acetonitrile (105.8 g) andtetradecane (106.2 g). The two pha~e mixture i8 heated to 78-79C. 1,2-dibromoethane (320 g~ is charged over four hour~ to the reactor mixture. The volume of the phase~
gradually changes and the mixture becomes cloudy. Water (230.0 g) is added. NaHCO3 (113 g of a 148 g charge) is added slowly over three hours. 75% of the expected base is added before the CO2 evolution ceases. The upper layer (432 2 ~
g) contains unreacted di-sec-butylphosphine, tetradecane, di-sec-butyl(2-bromoethyl)phosphino and 1,2-bis(di sec-butylphosphino)ethane.
A reactor is charged with di-iso-butylphosphine, -~
tetradecane, acetonitrile, and 1,2-dibromoethane. ~3he parameters of the reactions are listed in Table 1.
3* 4*~ 5~ 6**
Acetonitrile 103.3g 105.0g 112.6g Tetradecane 79.5g 314.0g 323.0g 108.5g DIBP 304.3g 283.0g 296.8g 394.5g 1,2-dibromoethane 196.0g 149g 149g 190.8g Charge Time - 2.5 hr. 2 hr.
Reaction ~emp. 68-75C 77-81C 82-86C 84-87C
Reaction Time 24 hr. 5 hr. 23 hr. 23 hr.
B3ase ~aHCO3 NaOHt NaOHt NaOHt Ma~s Base 125g 89.9g 208g 100g Base Reaction Temp. 48-49C 35-40C 45-50C 25-26C
~ase Charge Time 5 hr. 20 min. 1.1 hr. 30 min.
* the reaction wa~ conducted in a one litre reactor *~ the reaction was conducted in a two litre round bottom flask heated with a mantle t the base was a 25~ NaON aqueous solution A larger volume of tetradecane is used in Examples 4 and 5 so that the solution can reach the thermometer.
The 1,2-dibromoethane of Example 4 is charged into the reaction flask over 2.5 hours. The mixture i8 30 heated for a further 2.5 hours before it i~ cooled from 80C to 40C. The 25S NaOH aqueous solution is quickly added to the reaction mixture over twenty (20) minutes3.
Only 36S of the expected stoichiometric amount of base is added before the pH increas3es to greater than 8 and the 35 mixture goes3 from two to three phases.
NaOH is a preferred solution because it is added as an aqueous solution allowing for a quicker charge time3. s NaHCO3 is le~s preferred because it require3s the addition of 20862~5 water to the reaction mixture before the addition of the powder form of the NaHC~3. Furthermore when NaHC03 is used, it evolves C02 that slows the rate at which the base may be charged and creates foam so that the reaction volume must be lowered to allow for additional head space for volume expansion in the reactor.
Table 2 compares the product distribution in the final organic layers for Examples 3-6 as determined by ga~
chromatography.
Acetonitrile 3.26 2.27 3.19 0 MIBP 0 0.19 0 0.34 1,2-dibromoethane 1.72 3.03 0.98 5.97 DIBP 28.5 35.9 22.0 65.8 DIBPO 1.34 0.21 0.65 0.53 Tetradecane 26.8 56.6 64.1 25.5 R2PCH2CH2Br 2.81 1.22 0.94 1.8 R2PcH2c~2P~2 33.0 0 9.09 0 Product Oxides 0.82 0 0 0 Table 2 shows that no bidentate liqand ls generated in Example 4. The GC analysis of the final product of Example 4 does show a small amount of the 1:1 adduct di-iso-butyl(2-bromoethyl)phosphine formed.
The product yield is expected to increase if the reaction temperature, the reaction time and the relative amount of the secondary phosphine to the 1,2-dibromoethane are ~ncreased. However in Example 5 the temperature could not be increased higher than 86C due to the refluxing temperature of the acetonitrile. ~y allowing the reaction to run overnight, the conversion to the product i~
approximately 70~ based on the amount of base required before the pH increases to qreater than 10.
In order to increase the reaction temperature in Example 6, acetonitrile is not used. A larger excess of DIBP (1.3 equivalents) is used and a smaller amount of tetradecane is used as the solvent. Even with running the 20~628~
:
g - ,~
reaction overnight at a higher temperature, no product ls generated.
The applicants do not wish to be limited to any particular theory but it is believed from the re~ults listed in Table 2 that a polar solvent may be required for generation of the phosphonium salt. It is al~o believed that a large excess of secondary phosphine is required to react completely with the 1,2-dibromoethane. Furthermore, -it is believed that the percentage by volume amount of organic solvent used should be kept to a minimum so that the concentration of the reactive agents i5 increased thereby increasing the conversion.
Similarly increasing the reaction temperature should increase the conversion. Conducting the reaction at higher temperatures will require a vessel that can withstand higher pressure so that the reflux temperature of the acetonitrile can be increased. The reaction probably cannot be performed in an autoclave because the phosphonium salts are too corrosive.
A one litre reactor is charged with di-sec-butylphosphine, tetradecane, acetonitrile, and 1,2-dibromoethane. The parameters of the reactions are llsted in Table 3.
2 ~ ~
Aceton~tr$1e 105.8g lOl.Og Tetradecane 106.2g 104.0g DSBP 320.0g 428.0g 1,2-dibromoethane 165g 240.4g Charge Time 3.9 hr.
Reaction Temperature 78-80C 86-88C
Reaction Time 22.5 hr. 23 hr.
10 Base NaHCO3 NaoHt Mass Base 105g 345g Base Reaction Temperature 48-49C 49-S1C
Base Charge Time 3 hr. 4.5 hr.
t 25% aqueous solution IS Example 7, employs 1.3 equivalents of DSBP to 1,2-dibromoethane. ~he haloalkane is added to the reactor over 3.9 hour~. After 22.5 hours of react$ng, the reactor i9 cooled from 79C to 48C. NaHCO3 is added to the mixture and approximately 75% of the stoichiometric amount of the base is added before the C2 evolution cea~es and three layers are formed.
All of the reagent~ in Example 8 are combined in the reactor and heated to the reaction temperature of 87C.
The reaction is left overnight and 85% of the expected NaOH
aqueous solutlon charge is added before the pH increases above 8. The mixture remsins in two phase~ until the pH
becomes alkaline.
Table 4 compare~ the product distribution in the final nonpolar organic layer for Examples 7 and 8 as determined by gas chromatography.
".
Acetonitrile 2.80 3.04 MSBP 0.11 0.16 1,2-dibromoethane 1.94 0.82 DSBP 37.4 27.7 DS~PO - 3 Isomers 0.80 1.67 Tetradecane 33.0 28.6 R2PCH2CH2Br 1.04 2.08 R2PCH2CH2PR2 18.0 31.7 Product Oxides 1.31 0.68 ~he results listed in ~able 4 indicate that the higher the temperature and reagent concentration the higher the converslon to the desired product.
A one litre resin reactor is charged with di-sec-butylphosphine, tetradecane, acetonitrile, and 1,2-dibromoethane. The parameters of the reactions are listed ln Table 9.
TAB~E S
9* 10 11*
Acetonitrile 110.4g 102.9g 106.lg tetradecane 100.3g 103.39 106.9g DSBP 565.8g 577.4g S71.2g 1,2-dibromoethane 282.4g 282.2g 283.4g Reaction Temperaturet 87-88C 67-68C 91-96C
* the reaction is run for only 5.5 hours and is heated by steam The di~appearance of the reagents in Example~ 9-11 was monitored by gas chromatography to determine the effects of temperature on the reaction kinetics.
The rate of disappearance of 1,2-dibromoethane is a~sumed to be pseudo-first order because an exces~ of secondary phosphine is u~ed in each reaction. The fir~t 3S order rate equations are;
' :,.
, .
~8~2~
-d r BrCH~CHzBrl = k[BrCH2CH2Br~ or ln([lBBrcCN2cC~B ~ ~ kt By plotting ln(~BrCH2CH2Br]) vs. time, the rate constant k can be determined. The plot for Example 10 was linear. The plot for Example 9 and 11 were slightly curved and the slopes were greater than the slope of the plot for Example 10. Because the reaction for Example 11 was only run for 5.5 hours, the plot is curved and not a true indication of the rate constant, but by extending the plot of Example 11 using the last few points the slope of Sxample 11 ~s greater than the slope of'Example 9. The rate constants (k) for Examples 9 to 11 are reported in Table 6.
lS ExamPle k 9 1.7E-4 minl ~
3.5E-3 min ;
11 3.4E-l min~
This data indicates that the reaction rate i~
very temperature sensitive. It is believed that by running the reaction under slight pressure, the reaction temperature can be increased allowing the reaction to be completed within eight ~8) hourg.
The procedure of Example 1 is repeated, substituting 1,2-dibromopropane for 1,2-dibromoethane. The corresponding product is obtained. The product i~ a racemate of two optically-active enantiomers by virtue of the prochiral - CH(CH3J - group in the starting material.
The product can be resolved into its respective optical lsomers in Xnown ways, e.g., by formlng a complex salt with an optically active acid and fractlonal crystallization, or by chromatography on an optically-active adsorbent or by other procedures.
The procedure of Example 1 is repeated, substituting 2,3-dlbromopentane for 1,2-dibromoethane. The corre~ponding product iCi obtained. The pro~uct i~ a S racemate of four optically-active enantiomers by virtue of the prochiral - CH(CH3) - and - CH(C2~s) - groups in the starting material. The product can be resolved into its respective optical isomers in known ways, e.g., by forming a complex salt with an optically active acid and fractional cry~tallization, or by chromatography on an optically-active adsorbent or by other procedures.
The procedure of Example 1 is repeated, su~stituting 1,2-di~romoethene for 1,2-dibromoethane The corresponding 1,2 bis(dialkylphosphino) alkene product 1 obtained.
The procedure of Example 1 is repeated, substituting 1,2-dibromopropene-1 for 1,2-dibromoethane.
The corresponding 1,2 bis(dialkylphosphino) alkene prodùct is obtained.
The procedure of Example 1 is repeated, substituting 1,2-dibromobenzene for 1,2-dibromoethane. The corresponding 1,2 bi~(dialkylphosphino) arene product i~
obtained.
~ he procedure of Example 1 ic repeated, substituting 1,2-dichloroethane for 1,2-dibromoethane. ~he same 1,2 bis(dialkylphosphino) alkane product is obtained.
The procedure of Example 1 is repeated, substituting 1,2-diiodoethane for 1,2-dibromoethane. The same 1,2 bis(dialkylphosphino) alkane product is obtained.
The above mentioned patent(s), any publication(~) and any test method(s) are incorporated herein by reference.
~' 20~2~
Many variations in the present invention w$11 suggest themselves to those skilled in this art in light of the above detailed descript$on. All such obvious modifications are within the full intended scope of the appended claims.
~'" ,,, ' ' :''
Claims (16)
1. A process for preparing a vicinally-disubstituted bis(diorganophosphino)-alkane, -alkene, or -arene which comprises reacting a secondary phosphine with a vicinally-disubstituted dihalo-alkane, -alkene or -arene at a molar ratio of at least about 2 to 1 of said secondary phosphine to said disubstituted dihalo compound to form a halide salt of said vicinally-disubstituted bis(diorganophosphino)-compound, and treating said salt with a base to convert the salt to the free vicinally-disubstituted bis(diorganophosphino)-alkane, -alkene, or -arene base.
2. A process as claimed in Claim 1 wherein said secondary phosphine compound is of the formula:
R1R2 - P ;
said disubstituted dihalo compound is of the formula:
X - CH(R3) - CH(R4) - X ; and said vicinally-disubstituted bis(diorganophosphino)-alkane, -alkene, or -arene base is of the formula:
R1R2 - P - CH(R3) - CH(R4) - P - R1R2 wherein R1 and R2, independently, are selected from alkyl, aryl, alkaryl, aralkyl, cycloalkyl, alkylcycloalkyl, alkoxyalkyl, cycloalkylaryl, aminoalkyl, heterocyclyl and heterocyclylalkyl groups, non-terminal alkenyl groups, or inertly-substituted such groups;
X is selected from Cl, Br, or I; and R3 and R4, independently, are selected from the same groups as defined for R1 and R2, and, in addition, hydrogen, and, when taken together with the carbon atoms to which they are attached, R1 and R2 form a single bond, or part of a three- to seven- membered ring comprising a cycloalkyl, an alkylcycloalkyl, a cyclolalkylaryl, a heterocyclyl, a heterocyclylalkyl, an aryl, an alkylaryl group, a ring-fused-, or an inertly-substituted- such group.
R1R2 - P ;
said disubstituted dihalo compound is of the formula:
X - CH(R3) - CH(R4) - X ; and said vicinally-disubstituted bis(diorganophosphino)-alkane, -alkene, or -arene base is of the formula:
R1R2 - P - CH(R3) - CH(R4) - P - R1R2 wherein R1 and R2, independently, are selected from alkyl, aryl, alkaryl, aralkyl, cycloalkyl, alkylcycloalkyl, alkoxyalkyl, cycloalkylaryl, aminoalkyl, heterocyclyl and heterocyclylalkyl groups, non-terminal alkenyl groups, or inertly-substituted such groups;
X is selected from Cl, Br, or I; and R3 and R4, independently, are selected from the same groups as defined for R1 and R2, and, in addition, hydrogen, and, when taken together with the carbon atoms to which they are attached, R1 and R2 form a single bond, or part of a three- to seven- membered ring comprising a cycloalkyl, an alkylcycloalkyl, a cyclolalkylaryl, a heterocyclyl, a heterocyclylalkyl, an aryl, an alkylaryl group, a ring-fused-, or an inertly-substituted- such group.
3. A process as claimed in Claim 1 wherein said secondary phosphine is reacted with a vicinally-disubstituted dibromo-alkane, -alkene or -arene.
4. A process as claimed in Claim 3 wherein said secondary phosphine is reacted with a vicinally disubstituted dibromo-alkane.
5. A process as claimed in Claim 4 wherein the vicinally disubstituted dibromo-alkane is 1,2-dibromoethane.
6. A process as claimed in Claim 1 wherein the secondary phosphine is di-iso-butylphosphine or di-sec-butylphosphine.
7. A process as claimed in Claim 1 wherein the base is sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium ethoxide, potassium ethoxide, ammonium carbonate, ammonium hydrogen carbonate, calcium oxide, calcium hydroxide, magnesium oxide or magnesium hydroxide
8. A process as claimed in Claim 1 wherein the reaction is carried out in an organic solvent.
9. A process as claimed in Claim 8 wherein the reaction is carried out in an organic solvent whose boiling point is about 20 to 30°C higher than the boiling point of the required vicinally-di-substituted dihalo-alkane, -alkene, or -arene.
10. A process as claimed in Claim 9 wherein the reaction is carried out in tetradecane, hexadecane, octadecane, docosane, or eicosane.
11. A process as claimed in Claim 1 wherein water is added to the reaction mixture after addition of the dihalo -alkane, -alkene, or -arene but before addition of the base.
12. A process as claimed in Claim 1 wherein the base is sodium hydrogen carbonate.
13. A process as claimed in Claim 1 wherein the base is sodium hydroxide.
14. A process as claimed in Claim 1 wherein acetonitrile is also present in the reaction mixture.
15. A process as claimed in Claim 1 wherein the vicinally-disubstituted dihalo-alkane, -alkene, or -arene is a prochirally-substituted compound whereby the product of the process is a racemic mixture comprising a chiral bidentate ligand adapted to be combined with a metal to prepare a catalyst for use in hydroformylation, decarbonylation and hydrogenation reactions.
16. A process as defined in Claim 2 wherein the dihaloalkane is of the formula X - CH(R3) - CH(R4) - X
wherein at least one of R3 and R4 is other than hydrogen or both R3 and R4 are not the same, one or both of groups - CH(R3) - and - CH(R4) - being chiral groups, whereby the product of the process comprises a racemic mixture of the corresponding chiral bidentate ligand.
wherein at least one of R3 and R4 is other than hydrogen or both R3 and R4 are not the same, one or both of groups - CH(R3) - and - CH(R4) - being chiral groups, whereby the product of the process comprises a racemic mixture of the corresponding chiral bidentate ligand.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA 2086285 CA2086285A1 (en) | 1992-12-24 | 1992-12-24 | Process for the preparation of vicinally-disubstituted bis(diorganophosphino) compounds |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA 2086285 CA2086285A1 (en) | 1992-12-24 | 1992-12-24 | Process for the preparation of vicinally-disubstituted bis(diorganophosphino) compounds |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2086285A1 true CA2086285A1 (en) | 1994-06-25 |
Family
ID=4150910
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2086285 Abandoned CA2086285A1 (en) | 1992-12-24 | 1992-12-24 | Process for the preparation of vicinally-disubstituted bis(diorganophosphino) compounds |
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| Country | Link |
|---|---|
| CA (1) | CA2086285A1 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000024752A1 (en) * | 1998-10-24 | 2000-05-04 | Albright & Wilson Uk Limited | Organophosphines |
| WO2001087899A1 (en) * | 2000-05-17 | 2001-11-22 | Shell Internationale Research Maatschappij B.V. | Bidentate ligands useful in catalyst system |
| WO2002064250A2 (en) * | 2001-01-31 | 2002-08-22 | Shell Internationale Research Maatschappij B.V. | Process for the carbonylation of ethylenically unsaturated compounds, bidentate diphosphine composition used in this process and processes for preparation of this bidentate diphosphine composition |
| EP2213645A1 (en) | 2009-01-28 | 2010-08-04 | Hexion Specialty Chemicals Research Belgium S.A. | Process for the preparation of an allyl aryl ether by catalytic o-allylation |
| EP2213644A1 (en) | 2009-01-28 | 2010-08-04 | Hexion Specialty Chemicals Research Belgium S.A. | Process for the preparation of an allyl alkyl ether by catalyic allylation |
| EP2213643A1 (en) | 2009-01-28 | 2010-08-04 | Hexion Specialty Chemicals Research Belgium S.A. | Process for the preparation of an allyl aryl ether by catalytic o-allylation |
-
1992
- 1992-12-24 CA CA 2086285 patent/CA2086285A1/en not_active Abandoned
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000024752A1 (en) * | 1998-10-24 | 2000-05-04 | Albright & Wilson Uk Limited | Organophosphines |
| US6476272B1 (en) | 1998-10-24 | 2002-11-05 | Rhodia Consumer Specialties Limited | Organophosphines |
| WO2001087899A1 (en) * | 2000-05-17 | 2001-11-22 | Shell Internationale Research Maatschappij B.V. | Bidentate ligands useful in catalyst system |
| US6639091B2 (en) | 2000-05-17 | 2003-10-28 | Shell Oil Company | Bidentate ligand, catalyst system containing such ligand and a process for the carbonylation of ethylenically or acetylenically unsaturated compounds using such a catalyst system |
| WO2002064250A2 (en) * | 2001-01-31 | 2002-08-22 | Shell Internationale Research Maatschappij B.V. | Process for the carbonylation of ethylenically unsaturated compounds, bidentate diphosphine composition used in this process and processes for preparation of this bidentate diphosphine composition |
| WO2002064250A3 (en) * | 2001-01-31 | 2003-01-30 | Shell Int Research | Process for the carbonylation of ethylenically unsaturated compounds, bidentate diphosphine composition used in this process and processes for preparation of this bidentate diphosphine composition |
| EP2213645A1 (en) | 2009-01-28 | 2010-08-04 | Hexion Specialty Chemicals Research Belgium S.A. | Process for the preparation of an allyl aryl ether by catalytic o-allylation |
| EP2213644A1 (en) | 2009-01-28 | 2010-08-04 | Hexion Specialty Chemicals Research Belgium S.A. | Process for the preparation of an allyl alkyl ether by catalyic allylation |
| EP2213643A1 (en) | 2009-01-28 | 2010-08-04 | Hexion Specialty Chemicals Research Belgium S.A. | Process for the preparation of an allyl aryl ether by catalytic o-allylation |
| WO2010086137A1 (en) | 2009-01-28 | 2010-08-05 | Resolution Research Nederland B.V. | Process for the preparation of an allyl aryl ether by catalytic o-allylaton |
| WO2010086138A1 (en) | 2009-01-28 | 2010-08-05 | Resolution Research Nederland B.V. | Process for the preparation of an allyl aryl ether by catalytic o-allylation |
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