GB2085874A

GB2085874A - Hydroformylation of olefins

Info

Publication number: GB2085874A
Application number: GB8125581A
Authority: GB
Original assignee: Johnson Matthey PLC
Current assignee: Johnson Matthey PLC
Priority date: 1980-09-04
Filing date: 1981-08-21
Publication date: 1982-05-06
Also published as: NL8103989A; JPS57114545A; CA1211467A; DE3135127A1; SE462528B; DE3135127C2; US4399312A; JPS6332342B2; BE890210A; GB2085874B; FR2489308A1; FR2489308B1; SE8104987L

Description

1

SPECIFICATION

Catalytic process GB 2 085 874 A 1 This invention relates to the hydroformylation of olefins, and provides a two phase catalytic process therefor which operates under mild conditions and in which separation and recovery of catalyst is facilitated.

Hydroformylation of olefins to yield alclehydes and/or alcohols is a wellknown and useful industrial process which may use as catalyst a complex of a precious metal such as rhodium and is carried out in the organic phase. The catalyst complex is soluble in the organic phase, with the result that diff iculties ensue in separation and recovery of rhodiurn or other precious metal catalyst. 10 One proposed solution to this problem is to carry out the reaction in the presence of an aqueous solution of rhodiurn or a rhodium compound and a sulphonated tri-aryl phosphine, such that the organic phase containing the reaction starting materials and/or products can readily be separated from the aqueous phase containing the catalyst. Such a reaction however requires very high reactor pressures, typically 40 bars (4000 kPa) or greater, and often requires an unacceptably long reaction time. Furthermore, it is difficult to achieve a 15 high n:iso ratio of product aldehydes, which is desirable from the point of view of usefulness in further processes.

We have now found that these disadvantages in the use of a two-phase system may be mitigated or avoided by including in the reaction mixture a reagent which has an aff inity for both the organic and aqueous phases. Such reagents may be classified either as phase transfer reagents or as surfactants. For 20 convenience, we refer to such agents generically as "amphiphilic reagents". We have found that these reagents enable the hydroformylation reaction to proceed smoothly under mild conditions and preferably do not interfere with separation and recovery of catalyst from the aqueous phase.

According to the invention, therefore, we provide a catalytic piocess for the hydroformylation of olefins which comprises reacting together at elevated temperature and pressure an olefin, hydrogen and carbon 25 monoxide in the presence of a catalyst comprising a water-soluble complex of a platinum group metal in a reaction medium comprising an aqueous phase and an organic phase and in the further presence of an amphiphiliG reagent.

The organic phase consists essentially of the substrate olefin and/or the hydroformylation reaction product preferably with one or more organic solvents. The substrate olefin may be a terminal or internal 30 olefin having a carbon chain length Of C3-C20, Preferably CTC14- If a solvent is used, it may be selected from common inert aliphatic solvents such as alkanes or aromatic solvents such as toluene or chlorobenzene. We prefer to use C5 to c9 alkanes such as cyclohexane and n-pentane.

The aqueous phase contains the water-soluble complex of platinum group metal. By "platinum group metal" we mean platinum, rhodium, palladium, ruthenium, iridium and osmium. We prefer to use as catalyst 35 a water-soluble complex of rhodium, platinum, ruthenium or palladium, especially rhodiurn which operates under the mildest conditions. The catalytic complex is preferably formed in situ from a water-soluble precursor compound or complex of platinum group metal and a water-soluble phosphine. The choice of precursor compound or complex is not critical. Examples includes [Rh(acac)(CO)21, [RhC133H201, [RhCl(diene)12, [Rh(diene)21'A-, [Rh2(C5Me5)2(OH)31'A-, [RU2(OH)3(arene)21'A-, [Pd(allyl)dienel'A-, [Pd2(dba)31, K2[PdCI41, K2(PtCI41, [RuC133H201, Na3[RuCI61 and [RU2CI4(arene)21, where acac represents acetylacetonato, a suitable diene is 1,5-cyclooctadiene, suitable arenes include p-cymene (ie isopropylto luene) and hexamethylbenzene, A is a non-comp(exing anion such as tetra phenyl borate ortetrafluoroborate, and dba represents clibenzylidene acetone.

The aqueous phase also contains a water-soluble phosphine which reacts in situ with the catalyst 45 precursor compound or complex and also with hydrogen and/or carbon monoxide to form the catalytic complex. The water-soluble phosphine is preferably a sulfonated or carboxylated triarylphosphine having the formula Ar XX1 50 Ry 1 __,.,X x 2 P-Ar Ry2 55 \ XX 3 Ar Ry 3 60 in which the Ar groups are the same or different aryl groups, for example phenyl and naphthyl; the substituent R groups are the same or different and are selected from Cl to C4 linear or branched chain alkyl or alkoxy groups, for example methyl, ethyl, propyl, isopropyl, butyl, methoxy, ethoxy, propoxy or butoxy groups; halogen; hydroxy; nitrile; nitro; amino and Cl to C4 alkyl- substituted amino; the substituent X groups are the same or different and are selected from carboxylic acid, sulphonic acid and salts thereof; xl, 65 2 GB 2 085 874 A 2 x2 and x3 are the same or different integers from 0 to 3 inclusive, provided that at least xl is equal to or greater than 1; and yj,V2 and y3 are the same or different integers from 0 to 5 inclusive. Preferably Ar is phenyl, X is either COOH or S03Na, xl is 1, X2 and x3 are 0 and Y1, Y2 and Y3 are 0. When x is an acid salt, the cation thereof is preferably Na', although other alkali metal cations such as K+ may alternatively be utilised. 5 Quaternary ammonium cations, for example NH4+, may also be used.

Preferred water-soluble phosphines include the following compounds:- 503Na COOH 10 p AND p p 20 Another example is P(C6H4CO2H6 Phosphinites of commercial ly-available polyoxyethylene detergents, for example PPhACH2CHAnOC12H25, where n=23, may also be used.

Optionally, the catalyst precursor compound or complex may be reacted in advance with the water-soluble phosphine to form an intermediate precursor compound of the catalytic hydrido/carbonyl-containing complex. Generally speaking, however, it is more convenient to form the catalytic hydridolcarbonyl complex 25 direct from precursor and water-souble phosphine in situ in the hydroformylation reactor.

The aqueous phase should preferably include free water-soluble phosphines in addition to that required to form the catalytic complex. The free phosphine may be the same or different from that used to form the catalytic complex although it is preferred to utilise the same phosphine. Conveniently, a stoichiometric excess of the phosphine is added to the reactor both to form the catalytic complex and to provide the free 30 phosphine.

The free phosphine should be present in a mole ratio to precious metal of up to 150:1 although it is generally possible to operate satisfactorily at a ratio of 20:1 or lower, or even 10:1 or lower. The concentration of amphiphilic reagent has an effect on the reaction, however, independently of the phosphine: precious metal ratio.

The ratio of the aqueous to organic phases should be in the range 0.33:1 to 5A, preferably 0.5:1 to 3: 1.

Good results have been obtained at ratios of approximately 2:1 and 1: 1. Lower ratios of aqueous to organic tend to slow the reaction rate whereas higher ratios tend to cause a greater quantity of precious metal to accumulate in the organic phase.

The concentrations of precious metal in the reaction medium is expressed in terms of parts per million 40 (ppm) of metal based on the aqueous phase. We have found that both the rate of reaction and the selectivity for straight-chain products are increased with increasing precious metal (rhodium) concentration to maxima, after which either a decrease or a tendency to remain the same is observed. Efficiency (that is, percentage conversion to aldehydes) is substantially unaffected by rhodium concentration. Precious metal concentra tion should be in the range 100 to 500 ppm; preferably 200-400 ppm, a level of 300 ppm being the optimum 45 in many reactions.

The pH of the aqueous phase should preferably be buffered at 7 or greater although there is no intrinsic objection to operating under acid conditions provided that the buffer and the catalyst are compatible and mutually inert.

The purpose of the amphiphilic reagent is to enable the substrate olefin to cross smoothly into the aqueous phase and to enable product aldehyde to cross back to the organic phase. Exceptionally, the amphiphilic reagent may promote inter-phase transfer of catalyst. Desirably, it should contain polar and non-polar moieties to provide the required affinity for both aqueous and organic phases, and should preferably be distributed principally in the aqueous phase with a minor portion in the organic phase. More preferably, the amphiphilic reagent should be substantially soluble in the aqueous and substantially insoluble in the organic, its effectiveness in operation being due, we believe, to its tendency to transport species across the phase boundary in view of the polar and non-polar moieties. An approximate analogy may be drawn between this tendency and the preferred position and orientation of a detergent molecule, at an aqueouslorganic phase boundary, generally expressed in terms of "HLB", thehyd ro phobic-] ipophobic 60 balance. Such a quantitative definition is not appropriate as a classification for amphiphilic reagents, however, since the necessary determinations cannot, at least for the most effective ones, be made. The amphiphilic reagent may be anionic, cationic or neutral. Many suitable reagents are available commercially as phasetransfer reagents or surfactants. An example of a suitable anionic reagent is sodium dodecyl sulphate; a neutral reagent is commercially available "Brij 35---(ie [C12H25(OCH2CH2)230H1) and a cationic 65 reagent is atetra-alkyl ammonium salt such as cetVltrimethylammonium bromide. Also useful as examples 65 3 GB 2 085 874 A 3 1 of cationic reagents are other complex ammonium salts such as cetylpyridinium bromide, lauryl and myristyl ammonium bromides and cetyltrimethylammonium acetate. Generally, we prefer to use cationic reagents, or neutral reagents such as polyoxyethylenes, such as "Brij 35". The concentration of amphiphilic reagent relative to precious metal should be up to 100:1 on a molar basis, preferably from 1:1 to 25A, for example 5:1 or 20: 1. We have found in general that increasing quantities of amphiphilic reagent reduce the 5 loss of precious metal to the organic phase.

The reaction conditions of temperature and pressure are mild. The temperature should be in the range 400 - 150'C. Below about 400C, the rate of reaction is unacceptable slow whereas catalyst deactivation tends to occur at temperatures in excess of 1150'C. A preferred range is 70 120'C, for example 80'C or 1 00'C, since these temperatures yield the best results in terms of efficiency to aldehydes and selectivity to n-aldehydes, 10 coupled with an acceptable rate of reaction.

The total (H2 + CO) initial pressure should be within the broad range 300 - 10000 Wa, depending on the precious metal used. For rhodium catalyst, the range is 300 - 3000 Wa, more preferred ranges being 500 - 2500 Wa and 800 - 1700 Wa. The H2:CO ratio should preferably be 1: 1 although ratios of up to about 5:1 may be selected if desired. Complete absence of hydrogen is undesirable.

We have found that under the various conditions discussed above we can achieve a high conversion of olefin with a high efficiency to aldehydes, the selectivity to n- aldehydes also being usefully high, the precious metal being readily recoverable from the aqueous phase. In particular, the experimental data for the hydroformylation of hex-1 -ene and hexadec-1 -ene in the presence and absence of amphiphilic reagent illustrates three important roles that the amphiphilic reagent plays:

(a) Rate An the absence of amphiphilic reagent the rate of hydroformylation is lower by an order of magnitude. The amphiphilic reagent therefore provides a mechanism by which the reaction is rendered more favourable, for example by transferring the olefin to the aqueous phase.

(b) Selectivity -The presence of amphiphilic reagent increases the selectivity to the n-aldehyde.

(c) Efficiency -The presence of amphiphilic reagent increases the efficiency to the aldehyde.

Embodiments of the invention will now be described with reference to the following Examples and Figure which illustrates graphically the results of Examples 15 to 21.

A Preparation of water-solublephosphines 1. 4-Ph2PC6H4CO2H was prepared according to the method of Schiemenz (G Schiemenz, Chem. Ber., 30 1966,99,504).

4-BrC61-1413r+Mg ---> 4-BrMgC6H4Br Ph2PCI+4-BrMgC6H4Br---, 4Ph2P-C6H413r 35 4-Ph2PC6H413r ---> 4-Ph2PC6H4CO2H 2. 3-Ph2PC6H4S03Na was prepared according to the method of Ahriand and Chatt (S. Ahriand and V Chatt,J Chem. Soc., 1958,276).

- 40 TH2S04-SO3 PPh3 (DNaOH 3-Ph2PC61-14S03Na 45 B Process Examples Examples 1 to 10 show the general effectiveness of the use of an amphiphilic reagent according to the invention.

Example 1 (Comparative example) A mixture of acetylacetonate-dicarbonyl rhodiumM (0.015 g) and PPh2(C6H4CO2H) (0.177g) was placed together with 20 mis of pH 10 buffer (NaNC03-NaOH), hex-l-ene (5 g) and heptane (5 g) in a glass pressure vessel which was flushed with nitrogen and pressurised to 560 Wa at 80'c with magnetic stirring. The reactor 55 was left at this pressure for 3 h. GC analysis of the organic layer indicated that there had been a 2.4% conversion of hex-1 -ene to heptaldehydes and that the ratio of n- heptaldehyde to i-heptaldehyde was 20: 1.

Example 2

The same procedure was adopted as in Example 1 except that lauryltrimethylammonium bromide (0.355 60 g) was added to the reaction mixture. Analysis of the organic phase after 1 hour indicated that 28% of the hex-1 -ene had been converted to products. 98% of the products were present as heptaidehydes and the by products were internal olefins. The ratio of n-heptaldehyde to i- heptaldehyde was 87 to 1.

4 GB 2 085 874 A 4 Example 3 (Comparative example) The same procedure was adopted as in Example 1, except that hexadec-l-ene was used instead of hex-l-ene. Analysis of the organic phase after 3 hours indicated that 0.5% of the hexadec-l-ene had been converted to heptadecaldehydes.

Example 4

The same procedure was adopted as in Example 3 exceptthat lauryl trimethylammonium bromide (0.355 g) was added to the reaction mixture. Analysis after 1 hour indicated that 73% of the hexadec-l-ene had been converted to products of which 89% was heptadecylaidehydes (nheptadecyladehyde and 1lo heptadecylal dehyde). The ratio of n-heptadecyl aldehyde to i-heptadecyla Idehyde was 22: 1.

Example 5 (Comparative example) The same procedure was adopted as in Example 1 except that dodec-1 -ene was used instead of hex-1 -ene. Analysis after 3 hours indicated that 2. 2% of the dodec-l-ene had been converted to tridecanals and that the 15 ratio of n-tridecanal to i-tridecanal was 6A.

Example 6

The same procedurewas adopted as in Example 5 exceptthat cetyltrimethylammonium bromide (0.442 g) was added to the reaction mixture. Analysis of the organic phase after 1 hour indicated that 78% of 20 dodec-l-ene had been converted to products with an efficiency of 91%to tridecanals. The ratio of n-tridecanal to i-tridecanal was 20 to 1.

15, Example 7

The same procedure was adopted as in Example 5 except that lauryl trimethylammonium bromide (0.355 g) was added to the reaction mixture. Analysis of the organic phase after 1 hour indicated that 64% of the 25 dodec-l-ene had been converted to products with an efficiency of 94% to tridecanals. The ratio of n-tridecanal to i-tridecanal was 16 to 1.

Example 8 (Comparative example) The same procedure was adopted as in Example 5 except that neat dodec-1 - ene (10 g) was used as the 30 organic phase. Analysis of the organic phase after 3 hours indicated that 2.2% of the dodec-1 -ene had been converted to tridecanals and that the ratio of n-tridecanal to i- tridecanal was 7: 1.

Example 9

The same procedure was adopted as in Example 6 except that neat dodec-lene (10 9) was used as the 35 organic phase. Analysis of the organic phase after 1 hour indicated that 440/6 of the dodec-l-ene had been converted to products with an efficiency of 85% to tridecanals. The ratio of n-tridecanal to i-tridecanal was 73 to 1.

Example 10

The same procedure was adopted as in Example 7 except that neat dodec-lene (10 g) was used as the organic phase. Analysis of the organic phase after 1 hour indicated that 43% of the dodec-l-ene had been converted to products with an efficiency of 82% to tridecanals and the ratio of n-tridecanal to i-tridecanal was to 1.

The above Examples demonstrate the dramatic improvement in rate, conversion of olefin, efficiency to 45 aldehydes and selectivity to n-aldehydes obtained from the use of an amphiphilic reagent.

Examples 11 - 14 indicate that a range of rhodium complexes can be used as catalyst precursors with similar activities, selectivities and efficiencies and with low rhodium loss to the organic phase. Results are given in Table 1 below. Conditions were as in Example 9.

c TABLE 1

Example Rhodium Precursor GB 2 085 874 A Hydroformylation of dodec-l-ene Conversion Selectivity % to n-tridecanal (n/i) Efficiency [Rh] org 5 to ppm aldehydes % 11 [Rh(aca0C0)21 67 22 91 0.3 0 12 [RhCI3.3H201 86 27 87 0.3 13 [Rh2C12 (T14 C81-112)21 89 29 83 0.3 is 15 14 [Rh(T,4_CBH12)2]BF4 78 26 88 1.8 [RH]aq = 300 ppm Examples 15 - 21 illustrate that the hydroformylation of dodec-i-ene can be carried out at a range of rhodium concentrations. Results are quoted graphically in Figure 1, in which the rate is quoted as the time taken for the pressure to drop from 560 to 520 kPa after the fifth successive pressurisation to 560 Wa.

Examples 22 - 35 illustrate that the hydroformylation may be performed with a range Of C3 - C20 olefins 25 under mild conditions. Results appear in Table 2 below, Conditions were as in Example 1.

TABLE 2

Examples 22 - 35 Example Substrate Amphiphilic A:P:Rh % Selectivity Efficiency reagent (A) Conversion n/i % 22 PROPYLENE C7AB 20:10:1 - 13 23 HEX-1-ENE CTAB 5:3A 51 11 89 24 HEX-1-ENE CTAB 20:10:1 95 45 98 HEX-1-ENE + heptane CTAB 20:10:1 52 34 100 26 HEX-1-ENE + heptane LTAB 20:10:1 28 87 98 27 HEXADEC-1-ENE CTAB 5:3A 18 8 95 28 OCT-1-ENE + heptane CTAB 20:10:1 33 57 92 29 NON-1-ENE CTAB 20:10:1 51 50 91 NON-1-ENE + heptane LTAB 20:10:1 50 81 80 31 DEC-1-ENE LTAB 20:10:1 33 38 89 32 TRIDEC-1-ENE CTAB 20:10:1 38 43 70 33 TETRADEC-1-ENE CTAB 20:10:1 30 40 73 34 OCTADEC-1-ENE + heptane LTAB 20:10:1 54 19 100 E:CPS-1-ENE + heptane LTAB 20:10:1 64 25 95 1 1 (7) G) W N) C) W al W j Ph (3) 7 GB 2 085 874 A 7 Examples 36 - 41 indicate that the reaction can be carried out under a range of pressures with low Rh losses, good rates and good selectivities. Results are quoted in Table 3 below.

TABLE 3 5

Hydroformylation of dodec-l-ene: The effect of pressure variation Example Pressure Rate Selectivity Efficiency [Rh] in kPa AP (min) n:i aldehydes % organic layer pp.m 36 544-510 2 4.7 78.5 2.29 15 37 884-850 1.25 8.4 91.3 2.6 38 1360-1326 0.7 7.8 90.0 - 20 39 1701-1667 0.5 5.5 92.4 5.0 2041-2006 0.3 7 90.0 - 41 2448-2414 3 3.6 85.6 3.6 25 80', under 1:1 H2/CO, CTAB:P:1Rh = 20:10:1,[Rh] = 30Oppm organic:aqueous =-1:2,orgbnic = 40gdodec-1-ene Example 42 - showing a H2: CO ratio of 5:1 A glass reactor was charged with a mixture of Rhacac(C0)2 (0.015 g), 4, Ph2PC61-14COOH (0.0709 g), cetyl trimethylammonium bromide (0.106 g) with a pH 7 buffer (20 m]), hexane (10 g) and dodec-l-ene (10 g). The 35 reactor was flushed with nitrogen and pressurised to 700 kPa hydrogen- carbon monoxide (5:1) at 800C with stirring. The reactor was periodically pressurised to 700 kPa with hydrogen-carbon monoxide (M) over 4 h.

After this period the reactor was cooled down to room temperature. Analysis of the organic phase indicated that 96% of the dodec-l-ene had been consumed and that 83% of the product was present as n- or i-tridecanal. The ratio of n to i tridecanal was 26A. Rhodium was detected in the organic phase at levels of 5 40 13pm.

Examples 43 - 51 indicate that the reaction proceeds under a range of temperatures. Results are given in Table 4 below. Conditions were as in Example 36.

8 G8 2 085 874 A TABLE 4 Hydroformylation of dodec-l-ene - Temperature Variation 8 Example Temperature Selectivity Efficiency to 5 to tridecanals n-tridecanal (n/i) 43 20 5 100 10 44 40 5 98 - 60 5 97 15 46 80 6 92 47 1000 5 87 48 1100 3 64 20 49 120 4 73 130' 3 66 25 51 160, NO REACTION Examples 52 - 56 indicate that the reaction proceeds under a variety of aqueous: organic phase ratios.

Results are given in Table 5 below. Conditions were as in Example 9.

ti c CD TABLE 5

Hydroformylation of dodec-l-ene Example Volume Wt of wt Conversion Selectivity Efficiency [Rh] org ofaqueous dodec-l-ene heptane % to to pPm layer (mi) (9) (9) n-tridecanals tridecanals 52 20 5 5 78 23 92 0.9 53 20 10 10 48 25 78 0.2 54 20 20 20 19 3.4 87 0.5 20 30 30 No reaction 56 7 10 10 13 3 80 0.3 G) W N3 0 CO UI 00 4.D.

(D GB 2 085 874 A Examples 57 to 76 illustrate the effect of various amphiphilic reagents. All reagents gave an improvement in rate, conversion, efficiency, selectivity andlor retention of rhodium in the aqueous phase, although some reagents are preferred over other in terms of overall activity. Examples 58 and 60, although having a rate of greater than 60 mins, were nevertheless proceeding faster than the corresponding reaction in the absence of 5 amphiphilic reagent (for which see Example 8).

In Table 6, which gives the results of Examples 57 to 76, a rough indication of the amount of rhodium in the respective phases is given by the colour of the phase.

i i TABLE 6

Hydroformylation of dodec-l-ene Example Amphiphilic reagent (A) A:P:11h Conversion % Selectivity to Efficiency to Rate (min) n-tridecanal n/i aldehydes % AP(5)560 520 kPA 57 18-crown-6 5:3A 40 3 88 9 58 PhCH2WI3UnCl 3 5:3A 3 7 76 >60 59 BUnNCl- 5:3:1 77 4 6 73 30 Bu4WO1-1- 5:3A 3 6 90 >60 61 C161-133PBu'Br- 5:3A 62 6 3 64 7 62 Aliquat336 5:3A 76 2 78 3 [C10H21)3NMeBr-1 63 Benzethonium chloride 5:3:1 28 5 82 16 64 Tween 41 5 M 41 4 72 5 Span 40 5:3A 30 5 80 7 66 Sodium dodecyl sulphate 5:3A 46 4 80 8 67 Brij 35 5:31 32 14 87 18 68 CTAB 5:3A 12 75 12 69 CTAB 20:10:1 36 115 76 7 C12H25We3Br- 20:10:1 38 76 69 9 71 tC12H25NW3Br- 20:10:1 73 28 80 9 72 C14H29NW3Br- 20:10:1 34 70 78 9 73 tCl4H29NW3Br- 20:10:1 63 13 84 18 a) ca N) cn CO (n 00 TABLE 6 (cont'd.) 74 C16H33NC5H5Br- 20.10:1 34 60 70 8 C16H33NC5b15Br- 20:10:1 83 20 81 5 76 C161133NIVIe3CH3C02- 20:10:1 53 71 73 8 In pH 10 KHC03 + KOH buffer tSubstrate: dodec-l-ene(5g)+heptane(5g) All runs at800,560-520 Wa 1:1 H2/CO, organic: aqueous = 11:2,organic = dodec-1-ene(10g) unless otherwise stated. Aqueous = pH 10 NaHC03 buffer. Benzethonium chloride has the formula cl X+(-)-0/\^/\N + 1 "'C M22 1. 1 c) W N) C) W M W ---4 r_% 1 11 1,- K) 13 TABLE 6 (Cont) Hydroformylation of dodec-l-ene Example Colour or org. phase (ppm Rh) Colour of aq, phase GB 2 085 874 A 13 57 yellow yellow 10 58 yellow brown 59 yellow brown yellow brown 15 61 deep purple colourless 62 deep purple colourless 20 63 yellow colourless 64 yellow colourless 65 yellow colourless 25 66 yellow brown 67 colourless brown 30 68 colourless brown (ca. 1 ppm) - 69 colourless yellow (0.55) 35 colourless clear orange (0.28) 71 colourless clear orange 40 (0.82 72 colourless clear orange (0.18) 45 73 colourless clear orange (0.92) 74 paleyellow yellow (0.64) 50 yellow yellow (1.95) 76 colourless yellow 55 Examples 77-86 illustrate phosphine variation. Results are given in Table 7 below. It is seen that an excess of amphiphilic reagent over phosphine is required for reaction to occur.

TABLE 7

Example Phosphine (P) Amphiphilic A:P:Rh Conversion Selectivity Efficiency Reagent (A) % to n-tridecanal to aldehydes (n/i) % 77 3-Ph2PC61-14S03Na None 0:3A 56 2.5 89 78 3,Ph2PC61-14S03Na Brij 35 5:3A 37 7 81 79 3-Ph2PC6H4S03Na CTAB 5:3A 37 4 86 3,Ph2PC6H4S03Na CTAB 5:8A No reaction 81 3-Ph2PC6H4S03Na CTAB 5:15:1 No reaction 82 4-Ph2PC6H4CO2H CTAB 5:2A 38 5 84 83 4-Ph2PC61-14CO2H CTAB 5:3A 39 8 67 84 4-Ph2PC61-14CO2H CTAB 20:10:1 45 49 85 4-Ph2PC6H4CO2H CTAB 20:12:1 67 18 86 P(C61-14COA3 CTAB 5:3A 28 9 70 86 P(C61-14COA3 CTAB 20:10:1 18 70 At 560 Wa, hydrogen-carbon monoxide (1: 1), 80' [Rh] = 300 ppm, Vol. of aqueous = 20mi(pHlobuffer) Vol.oforganic = 10ml(dodec-l-ene) 1 1) 1 11 11 1 G) W h) C) 00 ul 00 j.P.

45.

GB 2 085 874 A 15 Examples87-90: hydroformylation of internal olefins.

Example 87

A Baskerville-Lindsay autoclave (500 mi) was charged with a mixture of pH 10 bicarbonate buffer (0.1 M, 80 mi), [Rh(aca0C021 (0.06 g), Ph2PC6H4COOH (0.71 g), cetyltrimethylammonium bromide (1.69 trans-2- 5 heptene (5 g) and cyclohexane (40 g). The reacton was flushed with nitrogen and heated at WC under 4,400 Wa hydrogen-carbon monoxide for 212 h. The mixture was allowed to cool down to room temperature and the reactor was vented to atmospheric pressure. Centrifugation of the mixture gave a yellow aqueous phase and a colourless organic phase. GLC analysis of the organic phase indicated that 5% of the trans-hept-2-ene had been converted to octanals.

Example 88

The reactor was charged with reactants as in Example 87 except that the organic phase was composed of methyl oleate (10 g) and heptane (30 g). The reactor was heated at WC under 10 Wa hydrogencarbon is monoxide 0: 1). After the reaction the phases were separated by centrifugation to give a colourless organic phase and a yellow aqueous phase. Analysis of the organic phase 'H NIVIR indicated that 20% of the olefinic groups had been converted to aldehydes.

Example 89

The same conditions were used as in Example 88 except that the organic phase consisted of methyl linoleate (10 g) and heptane (30 g). After the reaction the phases were separated by centrifugation to give a colourless organic layer and a yellow aqueous phase. Analysis of the organic phase by 'H N MR indicated that 20% of the olefinic groups had been converted to aldehydes.

Example 90

The same conditions were used as in Example 88 except that the organic phase consisted of trans dec-5-ene (9 g) and heptane (31 g). GC analysis of the organic phase after reaction indicated that 10% of trans dec-5-ene had been converted to 2 butylheptanal. No by-products were observed.

Examples 91-106: use of complexes of Pd, Pt, Ru. Results are given in Table 8 below.

TABLE 8

Hydformylation of dodec-l-ene Example Complex Phosphine Amphiphilic (P) Reagent(A) 91 a-e [Pd2 (dba)31 Ph2PC61-14C021-1 40 92 a-e [Pd2(dba)31 Ph2PC61-14C021-1 C,6H33NMe3Br 93 a-e KA1Pc1C141 Ph2PC61-14C021-1 CirH33NW3Br 45 94 IPtCIAM3)21 As ligand b,d,e,g K21M141 4Ph2PCrH4COOH 96 b,d,e,g K21M141 4Ph2PC6H4COOH C161-133NIVIe3Br- 50 97 b,d,g,h K21M141 4Ph2PC6H4COOH C12H25NMe3Br 98 b,d,g,i [PtC12(Ph2PC6H4S03Na2)l As ligand + 55 99 b,d,g,i IPtCI2Ph2PC61-14S031Ma2)l As ligand C12H25NIVIe3Br b,d,j [PtC12(Ph2PC6H4S03Na)21 As ligand C16H33NMe3Br 101 b,d,i [RUC133H201 4-Ph2PC6H4CO2H 60 102 b,d,i [RuC133H201 4-Ph2PC61-14CO2H C16H33NMe3Br 103 b,d,i NaARUC161 4-Ph2PC6H4CO2H 16 GB 2 085 874 A 16 TABLE 8 (Cont'd) Hydroformylation of dodec-l-ene Example A:P:R Pressure Conversion Selectivity to 5 103 kPa % n-tridecanal 104 b,d,i NaARUC161 4-Ph2PC61-14CO2H C16H3Me3Br + 10 b,d,i [RU2C14(p-cymene)21 4-Ph2PC6H4C021-1 C161-133We3Br 106 b,d,i [RU2C14(p-cymene)21 4-Ph2PC6H4C021-1 C161-125S03-Na' 91 a-e 0:2A 5 4.0 4 92 a-e 5:2A 5 2 6 93 a-e 5:2A 5 2 7 20 94 0:2A 10 3.5 2 b,d,e,g 0:2A 10 0.4 2 96 b,d,e,g 20:2A 10 0.4 5 25 97 b,d,g,h 20:2A 10 3 3 98 b,d,g,i 0:2A 10 0.6 2 30 99 b,d,g,i 20:2A 10 0.6 4 b,d,j 20:2A 10 0.2 5 101 b,d,i 0:2A 10 90 3 35 102 b,d,i 5:2A 10 14 7 103 b,d,i 0:2A 10 8 4 40 104 b,d,i 10:2A 10 9 5 b,d,i 5:2:1 10 30 3 106 b,d,i 5:2A 10 31 3 45 c 17 GB 2 085 874 A 17 Notes to Examples 91 -106, Table 8.

a h e f 15, 9 dba = dibenzylidene acetone b [PGM1 = 300 ppm 5 c Cu:Pd = 1:1(asCu(0AcW d organic:aqueous = 1:2totalvolume = 120m] In pH 4 buffer In toluene-methanol (3-2) total volume = 120mi With added SnU2 (Sn:Pt = 5:1) h In pH 7 buffer In pH 10 buffer j In water

Claims

New Claims filed on 18 Nov. 81 New claims:25 20. A process according to

Claim 1 in which the catalyst comprises a complex of a platinum group metal 25 containing a water-soluble phosphine. 21. A process according to Claim 20 in which the catalyst comprises a carboyl complex of a platinum group metal. 22. A process according to Claim 21 in which the catalyst comprises a hydrido-carbonyl complex of a platinum group metal.

CLAIMS 1. A catalytic process for the hydroformylation of olefins comprising reacting together at elevated temperature and pressure an olefin, hydrogen and carbon monoxide in the presence of a catalyst comprising 35 a water-soluble complex of a platinum group metal in a reaction medium comprising an aqueous phase and an organic phase and in the further presence of an amphiphilic reagent.
2. A process according to claim 1 in which the organic phase comprises a reactant olefin and a solvent.
3. A process according to claim 1 or claim 2 in which the reactant olefin is a terminal olefin having a carbon chain length Of C3-C20.
4. A process according to claim 1 in which the platinum group metal is selected from rhodium, platinum, ruthenium and palladium.
5. A process according to any preceding claim in which the aqueous phase contains awater-soluble phosphine in complex combination with a platinum group metal catalyst precursor compound or complex.
6. A process according to claim 5 in which the water-soi uble phosphine is a su 1 phonated or carboxylated 45 triary] phosphine having the formula 50, r 1-11 XX1 50 " Ry 1 P-Ar "Ry2 55 Xx3 Ar "'RY3 60 in which the Ar groups are the same or different aryl groups, the substituent R groups are the same or different and are selected from Cl- C4 linear or branched chain alkyl or alkoxy groups, halogen, hydroxy, nitrile, nitro, amino and Cl-C4 alkyl-substituted amino; the substituent X groups are the same or different and 65 18 GB 2 085 874 A are selected from carboxylic acid, sulphonic acid and saitthereof; Xl, X2 and X3 are the same or different integersfrom 0-3 inclusive provided that at leastx, is equal to or greaterthan 1; and Y1, Y2 and Y3 are the same or different integers from 0-5 inclusive.
7. A process according to claim 6 in which the water-soluble phosphine has the formula either 18 5 S03Na C001-1 10 p 0 R p 15 20 20
8. A process according to claim 7 in which the water-soluble phosphine is present in excess.
9. A process according to any preceding claim in which the ratio of the aqueous to the organic phases is 25 in the range 0.33:1 to 5:1.
10. A process according to any preceding claim in which the precious metal is present in a concentration in the range 100 to 500 ppm based on the aqueous phase.
11. A process according to any preceding claim in which the amphiphilic reagent is selected from anionic, neutral, and cationic phase transfer reagents or surfactants.
12. A process according to claim 11 in which the cationic amphiphilic reagent is a complex ammonium 30 salt.
13. A process according to claim 11 in which the neutral amphiphilic reagent is a polyoxyethylene.
14. A process according to claim 11 in which the concentration of amphiphilic reagent relative to precious metal is up to 100:1 on a molar basis.
15. A process according to any preceding claim in which the temperature is in the range 40 - 150T.
16. A process according to any preceding claim in which the total initial pressure is in the range 300 - 10000 Wa.
17. A process according to any preceding claim in which the precious metal is rhodium and the total initial pressure is within the range 300 - 3000 Wa.
18. A process according to any preceding claim in which the H2:CO ratio is within the range 1: 1 to 5A. 40
19. A process as herein before described with reference to Examples 2, 4, 6, 9, 10, and 11 to 106.

Printed for Her Majesty's Stationery Office, by Croydon Printing Company Limited, Croydon, Surrey, 1982.

Published by The Patent Office, 25 Southampton Buildings, London, WC2A lAY, from which copies may be obtained.

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