CA2264429A1 - Preparation of 9-hydrocarbyl-9-phosphabicyclononanes - Google Patents
Preparation of 9-hydrocarbyl-9-phosphabicyclononanes Download PDFInfo
- Publication number
- CA2264429A1 CA2264429A1 CA 2264429 CA2264429A CA2264429A1 CA 2264429 A1 CA2264429 A1 CA 2264429A1 CA 2264429 CA2264429 CA 2264429 CA 2264429 A CA2264429 A CA 2264429A CA 2264429 A1 CA2264429 A1 CA 2264429A1
- Authority
- CA
- Canada
- Prior art keywords
- cod
- isomer
- rph2
- symmetric
- adduct
- 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
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
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6568—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus atoms as the only ring hetero atoms
- C07F9/65683—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus atoms as the only ring hetero atoms the ring phosphorus atom being part of a phosphine
-
- 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
- C07F9/5059—Preparation; Separation; Purification; Stabilisation by addition of phosphorus compounds to alkenes or alkynes
Abstract
9-Hydrocarbyl-9-phosphabicyclnonanes are prepared by reacting a primary hydrocarbylphosphine with 1,5-cyclooctadiene in a free radical reaction at a temperature below 100°C.
Description
t Preparation of 9-Hydrocarbyl-9-Phosphabicyclononanes Background of the Invention United States Patent No. 3,501,515 (Van Winkle et al) discloses the use of 9-alkyl-9-phosphabicylononanes as superior ligands when combined with cobalt for the hydroformylation of olefins. The 9-alkyl-9-phosphabicyclononane is currently prepared in a two step reaction process. In a first step, phosphine is added in a free radical reaction to 1, 5-cyclooctadiene (COD), to form a 9-phosphabicyclononane.In a subsequent step an olefin is added to the 9-phosphabicyclo-nonane in a free radical reaction, to form 9-alkyl-9-phosphabicyclononane.
The product of the first step is a mixture of 9-phosphabicyclononane isomers, 9-phosphabicyclo [3.3.1] nonane (the symmetrical isomer) and 9-phosphabicyclo [4.2.1] nonane (the unsymmetrical isomer). These are obtained in a mixture that is approximately 60 parts symmetrical isomer and 40 parts unsymmetrical isomer. The desired isomer is the symmetrical one, as it is more hindered at the phosphorus atom and therefore more sensitive when used as a ligand in a catalyst.
Otherbyproducts of this reaction are several 1:2 adducts of phosphine and cyclooctadiene and some 2:2and 2:3 adducts of phosphine and cyclooctadiene.. Also formed is a small amount (usually about 1.5 to 1.8~, based on the two main isomers) of trans 5-phosphinocyclooctene.
In the subsequent step the mixture of the symmetrical and the unsymmetrical 9-phosphanonanes and other byproducts obtained from the first step is allowed to react with an olefin under free radical conditions. Unwanted higher oligomers of phosphine and cyclooctadiene are then removed by vacuum stripping. The mixture of the symmetrical and unsymmetrical 9-alkyl-9-phosphabicyclononanes is then combined with Co2+ to form a catalyst system for the hydroformylation of long chain olefins.
As stated the symmetrical isomer is believed to be the active component of the mixture. Efforts to increase the content of the symmetrical isomer at the expense of the unsymmetrical isomer have been unsuccessful, however. In practice the symmetrical isomer has constituted between about 58~ and about 61~ of the isomer mixture, and obtaining the value of about 61~ has necessitated some loss of yield when calculated on the amount of cyclooctadiene used.
United States Patent No. 3,400,163 (Mason et al) discloses some bicyclic heterocyclic phosphines and their production. In Example IV eicosylphosphine is reacted with 1, 5-cyclooctadiene at a temperature of 135°C-145°C in the presence of di-(tert.-butyl) peroxide. The product is said to be a mixture of 9-eicosyl-9-phosphabicyclo[4.2.1]nonane and 9-eicosyl-9-phosphabicyclo[3.3.1]nonane. The relative proportion of these two isomers is not stated.
Summary of the Invention The present invention provides a process for preparing a 9-hydrocarbyl-9-phosphabicyclo[3.3.1]-nonane which comprises the addition of a primary hydrocarbyl phosphine to 1,5-cyclooctadiene in the presence of a free radical initiator at a temperature not greater than 100°C.
The reaction of the hydrocarbyl phosphine with the 1,5-cyclooctadiene still results in a mixture of the desired symmetrical[3.3.1] isomer and the undesired unsymmetrical [4.2.1] isomer. The ratio of the isomers is shifted markedly in favour of the desired isomer, however. In some instances the mixture has had a symmetrical content of 74~. This is a 25~ improvement in yield over the approximately 60~ that was the best that could previously be achieved. Furthermore, the amount of other undesired byproducts is reduced.
Description of the Preferred Embodiments The process is preferably carried out in a reactor under autogenous pressure in the presence of a free radical initiator that is an azo compound. The reaction is carried out at a relatively low temperature, preferably below say 80°C, more preferably below about 60°C and most preferably below about 40°C. It has been found that as the reaction temperature is reduced the quantity of undesired byproducts, particularly the traps 1:1 phosphine:COD adduct, is much reduced and the ratio of the desired symmetrical isomer to the undesired unsymmetrical isomer is much enhanced. At lower temperature, however, the reaction does take longer.
The free radical initiator can be, for example a peroxide or an azo radical initiator, or it can be radiation, for example W radiation or gamma radiation. The peroxide and azo initiators are temperature sensitive. Furthermore peroxides, for example di-(tert.-butyl)peroxide, tend to require a higher reaction temperature, and also to cause formation of phosphine oxide, so their use is not preferred.
Radiation is not temperature sensitive, but phosphine is not a good UV or gamma radiation absorber, so, on their own, the use of these radical sources is not preferred. The preferred initiators are azo compounds, for instance 2,2'-azobis-(2-methylbutyronitrile) (also known as azobis isovaleronitrile) and 2,2'-azobis-(2,4-dimethylvaleronitrile), available from Du Pont under the trademarks Vazo 67 and Vazo 52, respectively. These normally decompose thermally to yield free radicals that initiate the desired reaction. Different compounds, of course, decompose at different temperatures and different rates, and the number following the trademark indicates the temperature at which the compound has a half life of 10 hours. Thus Vazo 67 has a half life of 10 hours at 67°C
and Vazo 52 has the same half life at 52°C. Other suitable azo free radical initiators are commercially available under the trade-marks Vazo 88 and Vazo 64 and have 10 hour half lives of 88°C and 64°C, respectively. The initiator should be selected with the intended reaction temperature in mind, so that for reactions in the vicinity of 70 to 100°C Vazo 67 is preferred and for reactions in the range of 40 to 70°C Vazo 52 is preferred.
It is possible to use a combination of an initiator and radiation. Because the azo initiators are good W
absorbers, the radiation causes decomposition of the azo initiator to yield free radicals to initiate the desired reaction. In this embodiment the rate of decomposition of the azo initiator and hence the rate of reaction, are not temperature dependent. This advantage must of course be balanced against the cost of providing both initiator and a suitable W reactor.
The reaction is carried out in an inert, e.g., nitrogen, atmosphere.
The substituent at the 9-position of the product is determined by the primary phosphine reactant. The primary phosphine reactant can be represented by the formula so that the reaction yielding the desired symmetrical product can be represented by the equation -RPH2 +
R can be alkyl, straight chained or branched, suitably containing up to about 36 carbon atoms, or cycloalkyl or arylalkyl. A preferred alkylphosphine is eicosylphosphine.
The group R can be substituted provided that the substituents do not interfere with the reaction. As possible substituents there are mentioned hydroxyl, amino, monoalkyl, dialkylamino, alkanoyloxy, alkoxycarbonyl, cycloalkyl, phenyl and pyridyl groups. The group R can be cycloalkyl containing from 3 to 8, preferably 5 or 6, carbon atoms.
The reaction is normally carried out in the liquid phase. Depending upon the value of R, this may require the use of pressure or the use of a solvent. If R is a lower alkyl group, for instance, a methyl, ethyl or propyl group, then increased pressure, up to about 100 psig or possibly higher, may be used. COD is itself a liquid but as-the desired product is formed the melting point of the reaction mixture may increase and the reaction mixture may freeze or crystallize.
This is undesirable, so a solvent, or mixture of solvents, may be used to lower the freezing point of the reaction mixture.
Examples of suitable solvents include aliphatic hydrocarbons z such as octane or kerosene, alkylaromatic hydrocarbons such as toluene, xylene, ethylbenzene, tert.-butyl-toluene and the corresponding halogenated aromatic hydrocarbons in which the halogen, e.g., chlorine, atom is attached to a carbon atom of the aromatic ring, alcohols such as isopropanol and ethers such as tetrahydrofuran (THF). The hydrocarbyl primary phosphine or COD may be used in excess and this excess may serve as solvent.
Hence, in its broad aspect R can be hydrocarbyl. The term "hydrocarbyl" is used in its accepted meaning as representing a radical formed from a hydrocarbon by removal of a hydrogen atom. The hydrocarbyl groups represented by R in the formula above may be any non-acetylenic organic radical composed solely of carbon and hydrogen. The widest variation is possible in that the (non-acetylenic) hydrocarbyl group may be alkyl, alkenyl, cycloalkyl, cycloalkenyl, aryl, aralkyl, alkaryl, single ring, mufti-ring, straight chain, branched chain, large or small. Representative hydrocarbyl groups include methyl, ethyl, methallyl, n-butyl, hexyl, hexenyl, isooctyl, dodecyl, oleyl, octadecyl, eicosyl, hexacosyl, octacosyl, triacontyl, hexatriacontyl, tetracontyl, cyclohexyl, cyclooctyl, cyclooctenyl, phenyl, naphthyl, benzyl, styryl, phenethyl, and the like. Thus, a particularly useful class of bicyclic heterocyclic tert-phosphines is that containing only carbon, hydrogen, and phosphorus atoms.
Substituted hydrocarbyl groups are also operable and may contain a functional group such as the carboxyl, nitro, amino and hydroxy (e. g. hydroxyethyl) groups. A particularly useful group of ligands consists of those in which R is hydrocarbyl of from 1 to 36 carbon atoms; especially preferred are those in which R is hydrocarbyl of from 3 to 30 carbons.
The invention is further illustrated in the following Examples and in the accompanying figures, which are a graphical representation of results obtained in Examples 8, 9 & 10.
Example 1 Addition of Cyclohexylphosphine to 1,5-cyclooctadiene at 95°C. A stirred jacketed glass reactor was inerted with nitrogen and was then charged with 499 g of cyclohexyl-phosphine.- After heating the reactor contents to 95°C, 208.3 g of a mixture containing 3.65 g of azobisisovaleronitrile in 204.7 g of 1,5-cyclooctadiene was added over a three hour period. This was followed by the addition of 266 g of a solution containing 4.6 g of azobisisovaleronitrile in toluene over three hours. Gas chromatographic analysis of the product mixture indicated the presence of 37.9% toluene, 11.8%
cyclohexylphosphine, 2.4% 1,5-cyclooctadiene, 6.7% of the 1:1 RPH2/COD trans adduct, 10.9% unsymmetric 9-cyclohexyl-9-phosphabicyclo[4.2.1]nonane, 25.6% symmetric 9-cyclohexyl-9-phosphabicyclo[3.3.1]nonane and a total of 2.4% of byproduct 1:2 RPH2/COD isomers. Based on symmetric and unsymmetric isomer content, the product mixture contains 70.1% symmetric.
The weight ratios of byproduct 1:1 RPH2/COD trans adduct and 1:2 RPH2/COD adduct isomers to the desired bicyclo nonanes are 0.184 and 0.065 respectively.
The phosphorus NMR spectrum of the product mixture contained three major signals with the following chemical shifts: 13.21, -25.71 and -110.92 ppm. The relative areas were 16.13, 36.02, and 25.41 respectively. The signals at 13.21 and -25.71 ppm are due to the unsymmetric and symmetric products. The signal at -110.92 is from unconverted cyclohexylphosphine. A minor signal at -33.80 ppm is due to the 1:1 RPH2/COD trans adduct. In a corresponding proton coupled phosphorus NMR spectrum, the signals at 13.21 and -25.71 ppm remained as ringlets while thecorresponding signals at -33.81 and -110.92 became a doublet and a triplet respectivelythus confirming that the assignments corresponded to the expected tertiary, secondary and primary phosphines.
The symmetric content based on the peak areas is 69.1% which is consistent with the G.C. data.
Example 2 Addition of cyclohexylphosphine to 1,5-cyclooctadiene ~t 60°C. Similar to Example 1, a reactor was charged with 484.5 g of cyclohexylphosphine, 202.2 g of 1,5-cyclooctadiene and 3.6 g of azobisisovaleronitrile. After five hours at 60°C, a further 3.5 g of radical initiator was added. Sixteen hours _ 7 later the reaction mixture was cooled and analyzed by G.C. The mixture contained 23.1% unconverted cyclohexylphosphine, <0.1%
COD, 5.19% byproduct 1:1 RPH2/COD traps adduct, 19.1%
unsymmetric isomer, 51.6% symmetric isomer and <0.3% byproduct 1:2 RPH2/COD adducts. The symmetric isomer thus made up 73.0%
of the desired bicyclic nonanes. The weight ratios of byproduct 1:1 RPH2/COD traps adduct and 1:2 RPH2/COD isomers to desired products were 0.074 and <0.004 respectively.
Example 3 Addition of cyclohexylphosphine to 1,5-cyclooctadiene at 40°C. Similar to Example 1, a reactor was charged with 495.3 g of cyclohexylphosphine, 241.3 g of 1,5-cyclooctadiene and 4.2 g of azobisisovaleronitrile. After 15 hours at 40°C, a further 4.0 g of radical initiator was added. The mixture was allowed to digest for a further 48 hours. At that time it was analyzed by G.C. The product mixture contained 33.5%
cyclohexylphosphine, 1.3% COD, 1.8% 1:1 RPH2/COD traps adduct, 15.2% unsymmetric isomer, 44.4% symmetric isomer and 1.2% 1:2 RPH2/COD adducts. The symmetric isomer thus made up 74.5% of the desired products. The weight ratios of byproduct 1:1 RPH2/COD traps adduct and 1:2 RPH2:COD isomers to desired products were 0.030 and 0.020 respectively. Examples 1-3 clearly demonstrate the effect of low reaction temperature on reducing the byproduct 1:1 RPH2/COD traps adduct. An added benefit from lower reaction temperatures is an increase in symmetric isomer content.
The above product was subjected to vacuum distillation to recover the bicyclic products. A 236 g fraction distilled over with a vapour temperature of 142°C at 0.4 mmHg. The fraction solidified on cooling to room temperature. (m. pt. approximately 50°C). G.C. analysis indicated the fraction contained 2.8% 1:1 RPH2/COD traps adduct, 24.3% unsymmetric isomer and 72.0% symmetric isomer.
The symmetric isomer made up 74.8% of the desired product.
Example 4 (Comparative) Addition of phosphine to 1,5-cyclooctadiene at 95°C.
A 3.7 litre autoclave was charged with 1378 g of 1,5-_ g _ cyclooctadiene and 400 g of toluene. The mixture was heated to 95°C under 550 psig of phosphine pressure. A mixture containing 19.5 g of azobisisovaleronitrile in 250 g of toluene was added over seven hours while maintaining the autoclave temperature and pressure. G.C. analysis of the product mixture indicated the presence of 0.25% COD, 26.8% toluene, 1.15% 1:1 PH3/COD trans adduct, 38.2% symmetric isomer, 26.0% unsymmetric isomer and 4.65% 1:2 PH3/COD isomers. The symmetric isomer makes up only 59.5% of the desired bicyclic nonanes. The weight ratios of byproduct 1:1 PH3/COD trans adduct and 1:2 PH3/COD isomers to desired product are 0.018 and 0.072. The above 9-phosphabicyclic nonanes can be converted to 9-alkyl-9-phosphabicyclic nonanes by the free radical addition of an olefin such an octene-1, cyclohexene or isobutylene. The product mixture will only contain at best 59.5% symmetric isomer. Examples 1 and 4 demonstrate that the vast increase in symmetric isomer content which can be obtained by adding a primary phosphine to 1,5-cyclooctadiene vs the two step process of phosphine addition to COD followed by further reaction with an olefin. In addition, while the yield losses of COD to 1:1 P/COD trans adducts are comparable, the COD yield losses to 1:2 P/COD adducts are much less.
Example 5 Addition of isobutylphosphine to 1,5-cyclooctadiene at 60°C. As per Example 2, a reactor was charged with 462 g of 85% isobutylphosphine (remainder is isopropanol), 232 g of COD
and 3.7 g of azobisisovaleronitrile. After six hours at 60°C, a further 3.9 g of radical initiator was added. After a further sixteen hours at 60°C, the mixture was cooled and analyzed by G.C. The mixture contained 2.2% IPA, 17.6%
isobutylphosphine, 3.1% 1:1 RPH2/COD trans adduct, 18.4%
unsymmetric isomer, 54.7% symmetric isomer and <0.3% 1:2 RPH2/COD isomers. The symmetric isomer formed 74.8% of the desired product. The weight ratios of 1:1 RPH2/COD trans adduct and 1:2 RPH2/COD isomers to the desired products are 0.042 and < 0.004 respectively.
Components of the reaction mixture were confirmed by _ g _ G.C./M.S. analysis. The mass spectra of the symmetric and unsymmetric 9-isobutyl-9-phosphabicyclononane isomers are virtually identical and had the same molecular ion (198) as the spectrum of the 1:1 RPH2/COD trans adduct. However the bicyclic products are distinguished from the 1:1 RPH2/COD trans-adduct by the rather large abundance (base peak) of the stable 142 ion. The corresponding 142 ion for the trans adduct is only 35% of the base peak.
Example 6 Addition of isobutylphosphine to 1,5-cyclooctadiene at 40°C. A reactor was charged with 490 g of 85%
isobutylphosphine (remainder is isopropanol), 309 g of COD and 4.0 g of azobisisovaleronitrile. After 6 hours at 40°C, an additional 3.6 g of radical initiator was added. Two additional charges (3.7 and 2.0 g) of initiator were made after 24 and 30 hours respectively. Finally after 48 hours the mixture was analyzed by G.C. The mixture contained 5.5%
isobutylphosphine, 3.3% COD, 1.97% 1:1 RPH2/COD trans adduct, 19.47% unsymmetric isomer, 63.0% symmetric isomer and 0.9% 1:2 RPH2/COD isomers. The desired products have 76.4% symmetric content. The weight ratios of 1:1 RPH2/COD trans adduct and 1:2 RPH2/COD isomers to the desired product are 0.024 and 0.011 respectively.
The above product mixture was sujected to vacuum distillation to recover the bicyclononane isomers. A 290 g fraction distilled over with a vapour temperature of 126°C at 9 mmHg. The fraction (a viscous liquid) contained 2.45% 1:1 RPH2/COD trans adduct, 21.2% unsymmetric isomer and 72.9%
symmetric isomer. The desired bicyclic components contain 77.4% of the symmetric isomer. A phosphorus NMR of this fraction indicated two major signals at -2.66 and -38.99 ppm which had relative areas of 21.07 and 72.15. The area of the symmetric component is 77.4% of the total. This is consistent with the G.C. data.
Example 7 Addition of cyclopentylphosphine to 1,5 cyclooctadiene at 35°C. A reactor was charged with 615 g of cyclopentylphosphine, 271 g of COD and 4.0 g of azobis-isovaleronitrile. Additional 4.0 g charges of radical initiator were made after 24 and 48 hours at 35°C. Finally after 72 hours the mixture was analysed by G.C. The mixture contained 7.9% cyclopentylphosphine, 1.6% COD, 1.9% 1:1 RPH2/COD trans adduct, 18.9% unsymmetric isomer, 54.4%
symmetric isomer. The symmetric content of the desired products was 74.2%. The weight ratio of the 1:1 RPH2/COD trans adduct to desired product was 0.026.
Examples 5, 6 and 7 further demonstrate that 74-76%
symmetric 9-alkyl-9-phosphabicyclicnonanes can be obtained by the addition of primary phosphines to 1,5-cyclooctadiene whether they be hindered or non hindered.
Examples 8, 9 and 10 Three reactions were carried out using eicosylphosphine as the hydrocarbylphosphine. The reactions were carried out at 37°, 70° and 92°C, using Vazo 52 at the two lower temperatures and Vazo 67 at the higher temperature. A
10-15% molar excess of COD was charged to a stirred jacketed and inerted reactor containing eicosylphosphine. After heating the reaction mixture to the desired reaction temperature the initiator was added as a solution in toluene over a 4-5 hour time period. Due to the half life of Vazo 52 at 37°C Example 8 required an additional 23 hours to convert the eicosylphosphine, whereas the other two reactions were over within 1-3 hours of adding the initiator.
The reactions were followed by gas chromatographic (GC) analysis of the product mixtures with time. The actual charges and reaction conditions are given in Table 1, and the results are given in Tables 2A and 2B, below, the figures given in Table 2A being based on data from GC analysis and the data given in Table 2B being based on data from 31P NMR analysis.
Data from Table 2A are plotted in Figures 1, 2 and 3.
Figure 1 is a graph of the fraction of the symmetrical isomer, based on the symmetrical plus unsymmetrical isomer, versus the reaction temperature, Figure 2 is a graph showing the amount of the undesired trans 1:1 adduct versus the reaction temperature reaction temperature and Figure 3 is a graph of the product purity i.e., the amount of the symmetrical plus unsymmetrical isomer, based on the amount of alkylphosphine reactant RPH2, versus the reaction temperature. Figure 1 clearly demonstrates that as the reaction temperature is lowered the amount of the desired symmetrical isomer obtained is increased at the expense of the undesired unsymmetrical isomer. Figure 2 clearly shows that as the reaction temperature is lowered the amount of the undesired trans 1:1 adduct is reduced. Figure 3 clearly shows that as the reaction temperature is lowered the amount of symmetrical plus unsymmetrical isomers obtained is increased.
(t3 O di N ~ I~Jl ~
~
'7--1 Cp -,1 \ u1 W
~
,~
O
~ N ~
H
O N O
lD N
N
O
N N
FC c7 ~ d~ ~ ~ c~
H
y O
U
N
. N d~ l0 L~.a' . ~4 lflO
~,' Ln d' W ~ -~- I~ l0 l0 H ~ ~ . O O O
~
l L mn oo ~ O
\ ~ d' d''di O U1 rl rl rl C~ M rl xN _ O H H -I N N
H W
o\o rl ~ ~ L(1t17 ~'-I +~ J> U~
O
..~ U
~1 rIi II~ ~ M M O iQ,' O O
~
O ~-I61 M ~ H l0 N '-I
N
-rl ~ CO l0 C~ ~ O q CO 01 L(1 o\o Wit'LflLf1 N N N
H ''-~ ~C
~
O J-U
H
O N ~ ~ 1~ H
-ra ,.."~C~ m t U tI1 J-~ Pa o1 lflL~ o ~ 61 N l l l ~ o\ ' ~
U r r r ~ M C
~ ~
U] ~ r~ r-i ~ FC
-r~- W ~,1 H
O
(~ N N L~ ''-~ N Lf700 di "I N N l0 ' l!1117l0 ~ o\o "
, N~ ~ O O O O O rl O
H ~ ~ ~
W Ul H
L~ 01 ~-1 O O rl L~ O N N
W
o~ M L~ 01 ~U L~ O N
~ 0 H
o r-t ~z ~, w w n '~ ~ o ~
c ~
o ~ ~ mo U +
u~
z U
'~3 M ''tj N ,-I aoto ~O
~-1 N
.!-~ Lc7v-IN
N cd ~i H
N
H o~
N
O
-rl ri .!-~
,.Q
U
cti rd H N
P
4-a O
O
C~O N
.~..) M C~ Ol N
w E-~
O
J-~
U
O
p., O
z U O
[) r~ 0001 N
Pa ?C
tx W
In the example reactants and products were characterized by GC/MS data and 31P NMR. While the unsymmetric and symmetric isomers have almost identical mass spectra, the spectra are both somewhat different from that of the undesired traps 1.1 RPH2/COD adduct. However with additional data from 31p ~R spectra, the symmetric and unsymmetric isomers as well as the traps 1:1 RPH2/COD adduct can be identified. The proton coupled 31P NMR of a -secondary phosphine (the traps l:l RPH2/COD adduct) is a well defined "doublet" with a chemical shift in the -50 to -60 ppm range while the proton coupled 31p NMR of the symmetric and unsymmetric isomers, because they are tertiary phosphines, shows ringlets for each isomer with chemical shifts in the +10 to -40 ppm range. The 31P NMR
spectra of the three product mixtures of Examples 8, 9 and 10 each. have a pair of ringlets and two doublets with peak areas corresponding roughly to the GC peak areas of the symmetric and unsymmetric isomers and the traps 1:1 RPH2/COD adduct. Table 2B contains the traps 1:1 adduct concentrations and the symmetric isomer fraction calculated from the 31P NMR spectra.
The data are comparable to the GC results.
The product of the first step is a mixture of 9-phosphabicyclononane isomers, 9-phosphabicyclo [3.3.1] nonane (the symmetrical isomer) and 9-phosphabicyclo [4.2.1] nonane (the unsymmetrical isomer). These are obtained in a mixture that is approximately 60 parts symmetrical isomer and 40 parts unsymmetrical isomer. The desired isomer is the symmetrical one, as it is more hindered at the phosphorus atom and therefore more sensitive when used as a ligand in a catalyst.
Otherbyproducts of this reaction are several 1:2 adducts of phosphine and cyclooctadiene and some 2:2and 2:3 adducts of phosphine and cyclooctadiene.. Also formed is a small amount (usually about 1.5 to 1.8~, based on the two main isomers) of trans 5-phosphinocyclooctene.
In the subsequent step the mixture of the symmetrical and the unsymmetrical 9-phosphanonanes and other byproducts obtained from the first step is allowed to react with an olefin under free radical conditions. Unwanted higher oligomers of phosphine and cyclooctadiene are then removed by vacuum stripping. The mixture of the symmetrical and unsymmetrical 9-alkyl-9-phosphabicyclononanes is then combined with Co2+ to form a catalyst system for the hydroformylation of long chain olefins.
As stated the symmetrical isomer is believed to be the active component of the mixture. Efforts to increase the content of the symmetrical isomer at the expense of the unsymmetrical isomer have been unsuccessful, however. In practice the symmetrical isomer has constituted between about 58~ and about 61~ of the isomer mixture, and obtaining the value of about 61~ has necessitated some loss of yield when calculated on the amount of cyclooctadiene used.
United States Patent No. 3,400,163 (Mason et al) discloses some bicyclic heterocyclic phosphines and their production. In Example IV eicosylphosphine is reacted with 1, 5-cyclooctadiene at a temperature of 135°C-145°C in the presence of di-(tert.-butyl) peroxide. The product is said to be a mixture of 9-eicosyl-9-phosphabicyclo[4.2.1]nonane and 9-eicosyl-9-phosphabicyclo[3.3.1]nonane. The relative proportion of these two isomers is not stated.
Summary of the Invention The present invention provides a process for preparing a 9-hydrocarbyl-9-phosphabicyclo[3.3.1]-nonane which comprises the addition of a primary hydrocarbyl phosphine to 1,5-cyclooctadiene in the presence of a free radical initiator at a temperature not greater than 100°C.
The reaction of the hydrocarbyl phosphine with the 1,5-cyclooctadiene still results in a mixture of the desired symmetrical[3.3.1] isomer and the undesired unsymmetrical [4.2.1] isomer. The ratio of the isomers is shifted markedly in favour of the desired isomer, however. In some instances the mixture has had a symmetrical content of 74~. This is a 25~ improvement in yield over the approximately 60~ that was the best that could previously be achieved. Furthermore, the amount of other undesired byproducts is reduced.
Description of the Preferred Embodiments The process is preferably carried out in a reactor under autogenous pressure in the presence of a free radical initiator that is an azo compound. The reaction is carried out at a relatively low temperature, preferably below say 80°C, more preferably below about 60°C and most preferably below about 40°C. It has been found that as the reaction temperature is reduced the quantity of undesired byproducts, particularly the traps 1:1 phosphine:COD adduct, is much reduced and the ratio of the desired symmetrical isomer to the undesired unsymmetrical isomer is much enhanced. At lower temperature, however, the reaction does take longer.
The free radical initiator can be, for example a peroxide or an azo radical initiator, or it can be radiation, for example W radiation or gamma radiation. The peroxide and azo initiators are temperature sensitive. Furthermore peroxides, for example di-(tert.-butyl)peroxide, tend to require a higher reaction temperature, and also to cause formation of phosphine oxide, so their use is not preferred.
Radiation is not temperature sensitive, but phosphine is not a good UV or gamma radiation absorber, so, on their own, the use of these radical sources is not preferred. The preferred initiators are azo compounds, for instance 2,2'-azobis-(2-methylbutyronitrile) (also known as azobis isovaleronitrile) and 2,2'-azobis-(2,4-dimethylvaleronitrile), available from Du Pont under the trademarks Vazo 67 and Vazo 52, respectively. These normally decompose thermally to yield free radicals that initiate the desired reaction. Different compounds, of course, decompose at different temperatures and different rates, and the number following the trademark indicates the temperature at which the compound has a half life of 10 hours. Thus Vazo 67 has a half life of 10 hours at 67°C
and Vazo 52 has the same half life at 52°C. Other suitable azo free radical initiators are commercially available under the trade-marks Vazo 88 and Vazo 64 and have 10 hour half lives of 88°C and 64°C, respectively. The initiator should be selected with the intended reaction temperature in mind, so that for reactions in the vicinity of 70 to 100°C Vazo 67 is preferred and for reactions in the range of 40 to 70°C Vazo 52 is preferred.
It is possible to use a combination of an initiator and radiation. Because the azo initiators are good W
absorbers, the radiation causes decomposition of the azo initiator to yield free radicals to initiate the desired reaction. In this embodiment the rate of decomposition of the azo initiator and hence the rate of reaction, are not temperature dependent. This advantage must of course be balanced against the cost of providing both initiator and a suitable W reactor.
The reaction is carried out in an inert, e.g., nitrogen, atmosphere.
The substituent at the 9-position of the product is determined by the primary phosphine reactant. The primary phosphine reactant can be represented by the formula so that the reaction yielding the desired symmetrical product can be represented by the equation -RPH2 +
R can be alkyl, straight chained or branched, suitably containing up to about 36 carbon atoms, or cycloalkyl or arylalkyl. A preferred alkylphosphine is eicosylphosphine.
The group R can be substituted provided that the substituents do not interfere with the reaction. As possible substituents there are mentioned hydroxyl, amino, monoalkyl, dialkylamino, alkanoyloxy, alkoxycarbonyl, cycloalkyl, phenyl and pyridyl groups. The group R can be cycloalkyl containing from 3 to 8, preferably 5 or 6, carbon atoms.
The reaction is normally carried out in the liquid phase. Depending upon the value of R, this may require the use of pressure or the use of a solvent. If R is a lower alkyl group, for instance, a methyl, ethyl or propyl group, then increased pressure, up to about 100 psig or possibly higher, may be used. COD is itself a liquid but as-the desired product is formed the melting point of the reaction mixture may increase and the reaction mixture may freeze or crystallize.
This is undesirable, so a solvent, or mixture of solvents, may be used to lower the freezing point of the reaction mixture.
Examples of suitable solvents include aliphatic hydrocarbons z such as octane or kerosene, alkylaromatic hydrocarbons such as toluene, xylene, ethylbenzene, tert.-butyl-toluene and the corresponding halogenated aromatic hydrocarbons in which the halogen, e.g., chlorine, atom is attached to a carbon atom of the aromatic ring, alcohols such as isopropanol and ethers such as tetrahydrofuran (THF). The hydrocarbyl primary phosphine or COD may be used in excess and this excess may serve as solvent.
Hence, in its broad aspect R can be hydrocarbyl. The term "hydrocarbyl" is used in its accepted meaning as representing a radical formed from a hydrocarbon by removal of a hydrogen atom. The hydrocarbyl groups represented by R in the formula above may be any non-acetylenic organic radical composed solely of carbon and hydrogen. The widest variation is possible in that the (non-acetylenic) hydrocarbyl group may be alkyl, alkenyl, cycloalkyl, cycloalkenyl, aryl, aralkyl, alkaryl, single ring, mufti-ring, straight chain, branched chain, large or small. Representative hydrocarbyl groups include methyl, ethyl, methallyl, n-butyl, hexyl, hexenyl, isooctyl, dodecyl, oleyl, octadecyl, eicosyl, hexacosyl, octacosyl, triacontyl, hexatriacontyl, tetracontyl, cyclohexyl, cyclooctyl, cyclooctenyl, phenyl, naphthyl, benzyl, styryl, phenethyl, and the like. Thus, a particularly useful class of bicyclic heterocyclic tert-phosphines is that containing only carbon, hydrogen, and phosphorus atoms.
Substituted hydrocarbyl groups are also operable and may contain a functional group such as the carboxyl, nitro, amino and hydroxy (e. g. hydroxyethyl) groups. A particularly useful group of ligands consists of those in which R is hydrocarbyl of from 1 to 36 carbon atoms; especially preferred are those in which R is hydrocarbyl of from 3 to 30 carbons.
The invention is further illustrated in the following Examples and in the accompanying figures, which are a graphical representation of results obtained in Examples 8, 9 & 10.
Example 1 Addition of Cyclohexylphosphine to 1,5-cyclooctadiene at 95°C. A stirred jacketed glass reactor was inerted with nitrogen and was then charged with 499 g of cyclohexyl-phosphine.- After heating the reactor contents to 95°C, 208.3 g of a mixture containing 3.65 g of azobisisovaleronitrile in 204.7 g of 1,5-cyclooctadiene was added over a three hour period. This was followed by the addition of 266 g of a solution containing 4.6 g of azobisisovaleronitrile in toluene over three hours. Gas chromatographic analysis of the product mixture indicated the presence of 37.9% toluene, 11.8%
cyclohexylphosphine, 2.4% 1,5-cyclooctadiene, 6.7% of the 1:1 RPH2/COD trans adduct, 10.9% unsymmetric 9-cyclohexyl-9-phosphabicyclo[4.2.1]nonane, 25.6% symmetric 9-cyclohexyl-9-phosphabicyclo[3.3.1]nonane and a total of 2.4% of byproduct 1:2 RPH2/COD isomers. Based on symmetric and unsymmetric isomer content, the product mixture contains 70.1% symmetric.
The weight ratios of byproduct 1:1 RPH2/COD trans adduct and 1:2 RPH2/COD adduct isomers to the desired bicyclo nonanes are 0.184 and 0.065 respectively.
The phosphorus NMR spectrum of the product mixture contained three major signals with the following chemical shifts: 13.21, -25.71 and -110.92 ppm. The relative areas were 16.13, 36.02, and 25.41 respectively. The signals at 13.21 and -25.71 ppm are due to the unsymmetric and symmetric products. The signal at -110.92 is from unconverted cyclohexylphosphine. A minor signal at -33.80 ppm is due to the 1:1 RPH2/COD trans adduct. In a corresponding proton coupled phosphorus NMR spectrum, the signals at 13.21 and -25.71 ppm remained as ringlets while thecorresponding signals at -33.81 and -110.92 became a doublet and a triplet respectivelythus confirming that the assignments corresponded to the expected tertiary, secondary and primary phosphines.
The symmetric content based on the peak areas is 69.1% which is consistent with the G.C. data.
Example 2 Addition of cyclohexylphosphine to 1,5-cyclooctadiene ~t 60°C. Similar to Example 1, a reactor was charged with 484.5 g of cyclohexylphosphine, 202.2 g of 1,5-cyclooctadiene and 3.6 g of azobisisovaleronitrile. After five hours at 60°C, a further 3.5 g of radical initiator was added. Sixteen hours _ 7 later the reaction mixture was cooled and analyzed by G.C. The mixture contained 23.1% unconverted cyclohexylphosphine, <0.1%
COD, 5.19% byproduct 1:1 RPH2/COD traps adduct, 19.1%
unsymmetric isomer, 51.6% symmetric isomer and <0.3% byproduct 1:2 RPH2/COD adducts. The symmetric isomer thus made up 73.0%
of the desired bicyclic nonanes. The weight ratios of byproduct 1:1 RPH2/COD traps adduct and 1:2 RPH2/COD isomers to desired products were 0.074 and <0.004 respectively.
Example 3 Addition of cyclohexylphosphine to 1,5-cyclooctadiene at 40°C. Similar to Example 1, a reactor was charged with 495.3 g of cyclohexylphosphine, 241.3 g of 1,5-cyclooctadiene and 4.2 g of azobisisovaleronitrile. After 15 hours at 40°C, a further 4.0 g of radical initiator was added. The mixture was allowed to digest for a further 48 hours. At that time it was analyzed by G.C. The product mixture contained 33.5%
cyclohexylphosphine, 1.3% COD, 1.8% 1:1 RPH2/COD traps adduct, 15.2% unsymmetric isomer, 44.4% symmetric isomer and 1.2% 1:2 RPH2/COD adducts. The symmetric isomer thus made up 74.5% of the desired products. The weight ratios of byproduct 1:1 RPH2/COD traps adduct and 1:2 RPH2:COD isomers to desired products were 0.030 and 0.020 respectively. Examples 1-3 clearly demonstrate the effect of low reaction temperature on reducing the byproduct 1:1 RPH2/COD traps adduct. An added benefit from lower reaction temperatures is an increase in symmetric isomer content.
The above product was subjected to vacuum distillation to recover the bicyclic products. A 236 g fraction distilled over with a vapour temperature of 142°C at 0.4 mmHg. The fraction solidified on cooling to room temperature. (m. pt. approximately 50°C). G.C. analysis indicated the fraction contained 2.8% 1:1 RPH2/COD traps adduct, 24.3% unsymmetric isomer and 72.0% symmetric isomer.
The symmetric isomer made up 74.8% of the desired product.
Example 4 (Comparative) Addition of phosphine to 1,5-cyclooctadiene at 95°C.
A 3.7 litre autoclave was charged with 1378 g of 1,5-_ g _ cyclooctadiene and 400 g of toluene. The mixture was heated to 95°C under 550 psig of phosphine pressure. A mixture containing 19.5 g of azobisisovaleronitrile in 250 g of toluene was added over seven hours while maintaining the autoclave temperature and pressure. G.C. analysis of the product mixture indicated the presence of 0.25% COD, 26.8% toluene, 1.15% 1:1 PH3/COD trans adduct, 38.2% symmetric isomer, 26.0% unsymmetric isomer and 4.65% 1:2 PH3/COD isomers. The symmetric isomer makes up only 59.5% of the desired bicyclic nonanes. The weight ratios of byproduct 1:1 PH3/COD trans adduct and 1:2 PH3/COD isomers to desired product are 0.018 and 0.072. The above 9-phosphabicyclic nonanes can be converted to 9-alkyl-9-phosphabicyclic nonanes by the free radical addition of an olefin such an octene-1, cyclohexene or isobutylene. The product mixture will only contain at best 59.5% symmetric isomer. Examples 1 and 4 demonstrate that the vast increase in symmetric isomer content which can be obtained by adding a primary phosphine to 1,5-cyclooctadiene vs the two step process of phosphine addition to COD followed by further reaction with an olefin. In addition, while the yield losses of COD to 1:1 P/COD trans adducts are comparable, the COD yield losses to 1:2 P/COD adducts are much less.
Example 5 Addition of isobutylphosphine to 1,5-cyclooctadiene at 60°C. As per Example 2, a reactor was charged with 462 g of 85% isobutylphosphine (remainder is isopropanol), 232 g of COD
and 3.7 g of azobisisovaleronitrile. After six hours at 60°C, a further 3.9 g of radical initiator was added. After a further sixteen hours at 60°C, the mixture was cooled and analyzed by G.C. The mixture contained 2.2% IPA, 17.6%
isobutylphosphine, 3.1% 1:1 RPH2/COD trans adduct, 18.4%
unsymmetric isomer, 54.7% symmetric isomer and <0.3% 1:2 RPH2/COD isomers. The symmetric isomer formed 74.8% of the desired product. The weight ratios of 1:1 RPH2/COD trans adduct and 1:2 RPH2/COD isomers to the desired products are 0.042 and < 0.004 respectively.
Components of the reaction mixture were confirmed by _ g _ G.C./M.S. analysis. The mass spectra of the symmetric and unsymmetric 9-isobutyl-9-phosphabicyclononane isomers are virtually identical and had the same molecular ion (198) as the spectrum of the 1:1 RPH2/COD trans adduct. However the bicyclic products are distinguished from the 1:1 RPH2/COD trans-adduct by the rather large abundance (base peak) of the stable 142 ion. The corresponding 142 ion for the trans adduct is only 35% of the base peak.
Example 6 Addition of isobutylphosphine to 1,5-cyclooctadiene at 40°C. A reactor was charged with 490 g of 85%
isobutylphosphine (remainder is isopropanol), 309 g of COD and 4.0 g of azobisisovaleronitrile. After 6 hours at 40°C, an additional 3.6 g of radical initiator was added. Two additional charges (3.7 and 2.0 g) of initiator were made after 24 and 30 hours respectively. Finally after 48 hours the mixture was analyzed by G.C. The mixture contained 5.5%
isobutylphosphine, 3.3% COD, 1.97% 1:1 RPH2/COD trans adduct, 19.47% unsymmetric isomer, 63.0% symmetric isomer and 0.9% 1:2 RPH2/COD isomers. The desired products have 76.4% symmetric content. The weight ratios of 1:1 RPH2/COD trans adduct and 1:2 RPH2/COD isomers to the desired product are 0.024 and 0.011 respectively.
The above product mixture was sujected to vacuum distillation to recover the bicyclononane isomers. A 290 g fraction distilled over with a vapour temperature of 126°C at 9 mmHg. The fraction (a viscous liquid) contained 2.45% 1:1 RPH2/COD trans adduct, 21.2% unsymmetric isomer and 72.9%
symmetric isomer. The desired bicyclic components contain 77.4% of the symmetric isomer. A phosphorus NMR of this fraction indicated two major signals at -2.66 and -38.99 ppm which had relative areas of 21.07 and 72.15. The area of the symmetric component is 77.4% of the total. This is consistent with the G.C. data.
Example 7 Addition of cyclopentylphosphine to 1,5 cyclooctadiene at 35°C. A reactor was charged with 615 g of cyclopentylphosphine, 271 g of COD and 4.0 g of azobis-isovaleronitrile. Additional 4.0 g charges of radical initiator were made after 24 and 48 hours at 35°C. Finally after 72 hours the mixture was analysed by G.C. The mixture contained 7.9% cyclopentylphosphine, 1.6% COD, 1.9% 1:1 RPH2/COD trans adduct, 18.9% unsymmetric isomer, 54.4%
symmetric isomer. The symmetric content of the desired products was 74.2%. The weight ratio of the 1:1 RPH2/COD trans adduct to desired product was 0.026.
Examples 5, 6 and 7 further demonstrate that 74-76%
symmetric 9-alkyl-9-phosphabicyclicnonanes can be obtained by the addition of primary phosphines to 1,5-cyclooctadiene whether they be hindered or non hindered.
Examples 8, 9 and 10 Three reactions were carried out using eicosylphosphine as the hydrocarbylphosphine. The reactions were carried out at 37°, 70° and 92°C, using Vazo 52 at the two lower temperatures and Vazo 67 at the higher temperature. A
10-15% molar excess of COD was charged to a stirred jacketed and inerted reactor containing eicosylphosphine. After heating the reaction mixture to the desired reaction temperature the initiator was added as a solution in toluene over a 4-5 hour time period. Due to the half life of Vazo 52 at 37°C Example 8 required an additional 23 hours to convert the eicosylphosphine, whereas the other two reactions were over within 1-3 hours of adding the initiator.
The reactions were followed by gas chromatographic (GC) analysis of the product mixtures with time. The actual charges and reaction conditions are given in Table 1, and the results are given in Tables 2A and 2B, below, the figures given in Table 2A being based on data from GC analysis and the data given in Table 2B being based on data from 31P NMR analysis.
Data from Table 2A are plotted in Figures 1, 2 and 3.
Figure 1 is a graph of the fraction of the symmetrical isomer, based on the symmetrical plus unsymmetrical isomer, versus the reaction temperature, Figure 2 is a graph showing the amount of the undesired trans 1:1 adduct versus the reaction temperature reaction temperature and Figure 3 is a graph of the product purity i.e., the amount of the symmetrical plus unsymmetrical isomer, based on the amount of alkylphosphine reactant RPH2, versus the reaction temperature. Figure 1 clearly demonstrates that as the reaction temperature is lowered the amount of the desired symmetrical isomer obtained is increased at the expense of the undesired unsymmetrical isomer. Figure 2 clearly shows that as the reaction temperature is lowered the amount of the undesired trans 1:1 adduct is reduced. Figure 3 clearly shows that as the reaction temperature is lowered the amount of symmetrical plus unsymmetrical isomers obtained is increased.
(t3 O di N ~ I~Jl ~
~
'7--1 Cp -,1 \ u1 W
~
,~
O
~ N ~
H
O N O
lD N
N
O
N N
FC c7 ~ d~ ~ ~ c~
H
y O
U
N
. N d~ l0 L~.a' . ~4 lflO
~,' Ln d' W ~ -~- I~ l0 l0 H ~ ~ . O O O
~
l L mn oo ~ O
\ ~ d' d''di O U1 rl rl rl C~ M rl xN _ O H H -I N N
H W
o\o rl ~ ~ L(1t17 ~'-I +~ J> U~
O
..~ U
~1 rIi II~ ~ M M O iQ,' O O
~
O ~-I61 M ~ H l0 N '-I
N
-rl ~ CO l0 C~ ~ O q CO 01 L(1 o\o Wit'LflLf1 N N N
H ''-~ ~C
~
O J-U
H
O N ~ ~ 1~ H
-ra ,.."~C~ m t U tI1 J-~ Pa o1 lflL~ o ~ 61 N l l l ~ o\ ' ~
U r r r ~ M C
~ ~
U] ~ r~ r-i ~ FC
-r~- W ~,1 H
O
(~ N N L~ ''-~ N Lf700 di "I N N l0 ' l!1117l0 ~ o\o "
, N~ ~ O O O O O rl O
H ~ ~ ~
W Ul H
L~ 01 ~-1 O O rl L~ O N N
W
o~ M L~ 01 ~U L~ O N
~ 0 H
o r-t ~z ~, w w n '~ ~ o ~
c ~
o ~ ~ mo U +
u~
z U
'~3 M ''tj N ,-I aoto ~O
~-1 N
.!-~ Lc7v-IN
N cd ~i H
N
H o~
N
O
-rl ri .!-~
,.Q
U
cti rd H N
P
4-a O
O
C~O N
.~..) M C~ Ol N
w E-~
O
J-~
U
O
p., O
z U O
[) r~ 0001 N
Pa ?C
tx W
In the example reactants and products were characterized by GC/MS data and 31P NMR. While the unsymmetric and symmetric isomers have almost identical mass spectra, the spectra are both somewhat different from that of the undesired traps 1.1 RPH2/COD adduct. However with additional data from 31p ~R spectra, the symmetric and unsymmetric isomers as well as the traps 1:1 RPH2/COD adduct can be identified. The proton coupled 31P NMR of a -secondary phosphine (the traps l:l RPH2/COD adduct) is a well defined "doublet" with a chemical shift in the -50 to -60 ppm range while the proton coupled 31p NMR of the symmetric and unsymmetric isomers, because they are tertiary phosphines, shows ringlets for each isomer with chemical shifts in the +10 to -40 ppm range. The 31P NMR
spectra of the three product mixtures of Examples 8, 9 and 10 each. have a pair of ringlets and two doublets with peak areas corresponding roughly to the GC peak areas of the symmetric and unsymmetric isomers and the traps 1:1 RPH2/COD adduct. Table 2B contains the traps 1:1 adduct concentrations and the symmetric isomer fraction calculated from the 31P NMR spectra.
The data are comparable to the GC results.
Claims (8)
1. A process for preparing a 9-hydrocarbyl-9-phosphabicyclo[3.3.1]nonane which comprises allowing a primary hydrocarbylphosphine to react with 1,5-cyclooctadiene in the presence of a free radical initiator and at a temperature not greater than 100°C.
2. A process according to claim,1 wherein the reaction temperature is not greater than about 80°C.
3. A process according to claim 1 wherein the reaction temperature is not greater than about 40°C.
4. A process according to claim 1, 2 or 3 wherein the free radical initiator is 2,2'-azobis-(2-methylbutyronitrile).
5. A process according to claim 1, 2 or 3 wherein the free radical initiator is 2,2'-azobis-(2,4-dimethylvaleronitrile).
6. A process according to any one of claims 1 to 5 wherein the primary hydrocarbylphosphine is a C1-36 alkylphosphine or a C3-8 cycloalkylphosphine.
7. A process according to claim 6 wherein the primary hydrocarbylphosphine is a C3-30 alkylphosphine or cyclohexylphosphine.
8. A process according to claim 6 wherein the primary hydrocarbylphosphine is eicosylphosphine.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA 2264429 CA2264429A1 (en) | 1999-03-03 | 1999-03-03 | Preparation of 9-hydrocarbyl-9-phosphabicyclononanes |
| AU29820/00A AU2982000A (en) | 1999-03-03 | 2000-02-03 | Preparation of 9-hydrocarbyl-9-phosphabicyclononanes |
| PCT/US2000/002944 WO2000052017A1 (en) | 1999-03-03 | 2000-02-03 | Preparation of 9-hydrocarbyl-9-phosphabicyclononanes |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA 2264429 CA2264429A1 (en) | 1999-03-03 | 1999-03-03 | Preparation of 9-hydrocarbyl-9-phosphabicyclononanes |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2264429A1 true CA2264429A1 (en) | 2000-09-03 |
Family
ID=4163359
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2264429 Abandoned CA2264429A1 (en) | 1999-03-03 | 1999-03-03 | Preparation of 9-hydrocarbyl-9-phosphabicyclononanes |
Country Status (3)
| Country | Link |
|---|---|
| AU (1) | AU2982000A (en) |
| CA (1) | CA2264429A1 (en) |
| WO (1) | WO2000052017A1 (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2291503A1 (en) * | 1999-12-03 | 2001-06-03 | Allan James Robertson | Synthesis of organic phosphines |
| WO2002000669A2 (en) | 2000-06-26 | 2002-01-03 | Basf Aktiengesellschaft | Phosphacyclohexanes and the use thereof in the hydroformylation of olefins |
| CN1535180A (en) * | 2001-01-31 | 2004-10-06 | 国际壳牌研究有限公司 | Process for carbonylation of ethylenically unsaturated compounds, bidentate diphosphine composition used in this process and processes for preparaton of this bidentate diphosphine composition |
| AU2003245725A1 (en) * | 2002-02-13 | 2003-09-04 | Cytec Technology Corp | Phosphine compounds |
| US6806391B2 (en) | 2002-07-31 | 2004-10-19 | Shell Oil Company | Process for the carbonylation of ethylenically unsaturated compounds and bidentate diphosphine composition used in this process |
| US7084089B2 (en) | 2002-07-31 | 2006-08-01 | Shell Oil Company | Process for the carbonylation of ethylenically unsaturated compounds, bidentate diphosphine composition used in this process and a process for preparation of this bidentate diphosphine composition |
| EP2100885A1 (en) | 2008-03-14 | 2009-09-16 | Bayer MaterialScience AG | Production of trimeric polyisocyanates |
| US7767862B2 (en) | 2008-08-11 | 2010-08-03 | Shell Oil Company | Ligand, catalyst and process for hydroformylation |
| WO2012072594A1 (en) | 2010-11-30 | 2012-06-07 | Shell Internationale Research Maatschappij B.V. | Ligand, catalyst and process for hydroformylation |
| US20160016860A1 (en) * | 2013-03-14 | 2016-01-21 | Dublin City University | Methods for phosphine oxide reduction in catalytic wittig reactions |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3400163A (en) * | 1965-06-30 | 1968-09-03 | Shell Oil Co | Bicyclic heterocyclic sec- and tert-phosphines |
| BE732031A (en) * | 1969-04-24 | 1969-10-01 | ||
| JPS55122792A (en) * | 1979-03-15 | 1980-09-20 | Nippon Chem Ind Co Ltd:The | Preparation of 9-eicosyl-9-phosphabicyclononane |
-
1999
- 1999-03-03 CA CA 2264429 patent/CA2264429A1/en not_active Abandoned
-
2000
- 2000-02-03 WO PCT/US2000/002944 patent/WO2000052017A1/en active Application Filing
- 2000-02-03 AU AU29820/00A patent/AU2982000A/en not_active Abandoned
Also Published As
| Publication number | Publication date |
|---|---|
| WO2000052017A1 (en) | 2000-09-08 |
| AU2982000A (en) | 2000-09-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA2264429A1 (en) | Preparation of 9-hydrocarbyl-9-phosphabicyclononanes | |
| AU741245B2 (en) | Method of manufacturing phosphine compound | |
| Schwartz et al. | Silica-supported zirconium hydrides as isomerization or hydrogenation catalysts for long-chain olefins | |
| US5488169A (en) | Method of producing tetrakis(pentafluorophenyl)borate derivatives using pentafluorophenylmagnesium derivatives | |
| US6376715B1 (en) | Process for the preparation of bisphosphines | |
| US3400163A (en) | Bicyclic heterocyclic sec- and tert-phosphines | |
| US4620021A (en) | Organic nickel compounds, production and use thereof as catalysts in the polymerization of olefins | |
| Allcock et al. | Dicobalt-hexacarbonyl complexes of acetylenic phosphazenes | |
| Torres et al. | Evidence for a Dinuclear Mechanism in Alkyne Hydrogenations Catalyzed by Pyrazolate‐Bridged Diiridium Complexes | |
| US7250535B2 (en) | Process for producing tertiary phosphine | |
| KR102000754B1 (en) | Bicyclic Bridgehead Phosphoramidite Derivatives, Preparation Method and Uses Thereof | |
| US20030109380A1 (en) | Catalytic boronate ester synthesis from boron reagents and hydrocarbons | |
| Imamoto et al. | Synthesis of organic phosphorus compounds containing a linear PB bond chain | |
| CA1082217A (en) | Process for the production of phosphite chlorides | |
| KR100245203B1 (en) | Co-oligomerisation process | |
| GB1578584A (en) | Couble ylide complexes of metals and process for making them | |
| US4618719A (en) | Addition of phosphines to alpha-olefins | |
| KR101450359B1 (en) | Process for Preparing Dialkyl Oxide Methallocenes or Diaryl Oxide metallocenes | |
| GB2089790A (en) | Preparation of ethylene glycol and ethers thereof | |
| GB1135248A (en) | Diaza-sila-cycloalkanes | |
| US5021380A (en) | Catalyst for preparation of biaryl compounds | |
| US3125594A (en) | Process for the preparation of halo- | |
| RU2146259C1 (en) | Method of preparing 2-alkyl-1,4-bis(diethylalum)butanes | |
| May et al. | [3+ 1] Cycloaddition: reaction of dichlorogermylene with hexafluoro-2-propanethione 1-adamantylimide | |
| US3818057A (en) | Dimethyl-w-carboxyalkylphosphines and their alkyl esters |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| FZDE | Dead |