One step process for the hydroformylation of olefins

Abstract

A one-step process for hydroformylation of olefins can include iron-catalyzed hydroformylation of olefins. The process can result in the conversion of olefin in the range of 40 to 99%. A reaction mixture includes iron precursor, ligand, substrate and solvent. The reaction mixture can be pressurized with syngas (CO/H.sub.2) under constant stirring to obtain a desired aldehyde compound. The ligand can be a monodentate ligand of a phosphines or a phosphite, and the iron precursor can be [HFe(CO).sub.4].sup..

Claims

1. A one-step process for hydroformylation of olefins, comprising charging iron precursor, ligand, substrate, and solvent in a reaction vessel followed by pressurizing the reaction mixture with syngas (CO/H.sub.2) under constant stirring at temperature in the range of 70 to 100 C. for a period in the range of 16 to 48 hrs to produce a desired aldehyde compound, wherein the conversion of said olefin is in the range of 40 to 99%, the ligand is selected from a group consisting of monodentate ligands of phosphines and phosphites and the iron precursor is [HFe(CO).sub.4].sup..

2. The process as claimed in claim 1, wherein the process comprises addition of an acid to the reaction mixture.

3. The process as claimed in claim 2, wherein the acid is at least one selected from the group consisting of acetic acid and formic acid.

4. The process as claimed in claim 1, wherein the pressure of the syngas (CO/H.sub.2) is in the range of 10 to 30 bars.

5. The process as claimed in claim 1, wherein the ligand is selected from the group consisting of Triphenylphosphine (PPh.sub.3) and Triphenyl phosphite [P(OPh).sub.3].

6. The process as claimed in claim 1, wherein the solvent is selected from the group consisting of methanol, ethanol, isopropyl alcohol, and acetic acid.

7. The process as claimed in claim 1, wherein the olefin is at least one selected from the group consisting of linear olefin, terminal olefin, and internal olefin.

8. The process as claimed in claim 7, wherein the olefin is selected from the group consisting of 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-octadecene, trimethoxy(vinyl)silane, trimethyl(vinyl)silane, cardanol, 2, 3-dihydrofuran, allyl malonic acid, styrene, 4-methyl styrene, 4-iBu-styrene, 4-tBu-styrene, 4-methoxy styrene, 4-acetoxy styrene, 4-bromo styrene, 4-chloro styrene, 4-vinylbenzonitrile, 4-vinylbenzoic acid, and allyl benzene.

9. The process as claimed in claim 1, wherein the reaction is carried out in a batch mode or a continuous mode of operation.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1: .sup.1H NMR Spectrum of reaction mixture in CDCl.sub.3 showing peak for aldehydes in case of (trimethoxy)vinylsilane.

(2) FIG. 2: GC chromatogram for Hydroformylation of styrene showing regioselectivity 8:92.

(3) FIG. 3: GC chromatogram of 1-hexene

(4) FIG. 4: GC chromatogram of 1-octene

(5) FIG. 5: GC chromatogram of 1-decene

DETAILED DESCRIPTION OF THE INVENTION

(6) The invention will now be described in detail in connection with certain preferred and optional embodiments, so that various aspects thereof may be more fully understood and appreciated.

(7) In an embodiment, the present invention provides a one step process for the hydroformylation of olefin comprises charging iron precursor, ligand, olefin and solvent in a reaction vessel followed by pressurizing the reaction mixture with syngas (CO/H.sub.2) under constant stirring at temperature in the range of 70 to 100 C. for the period in the range of 16 to 48 hrs to afford desired aldehyde compound.

(8) In a preferred embodiment, the conversion of the olefin is in the range of 40 to 99%.

(9) In another preferred embodiment, the iron precursor is [HFe(CO).sub.4].sup. and the ligand is selected from group consisting of monodentate ligands preferably phosphines and phosphites, more preferably Triphenylphosphine (PPh.sub.3) or Triphenyl phosphite [P(OPh).sub.3].

(10) The solvent is selected from protic solvents, wherein the protic solvent is selected from group consisting of methanol, ethanol, isopropyl alcohol, and acetic acid.

(11) The reaction is carried out in stainless steel autoclave equipped with pressure regulator and an employed safety valve. The autoclave is charged with iron precursor, ligand, solvent, olefin along with teflon stirring bars. In preferred embodiment, before starting the catalytic reaction said charged autoclave is purged three to four times with syngas (CO: H.sub.2=1:1) and pressurizing to the desired pressure in the range of 10 bar to 30 bars.

(12) The process may optionally comprise addition of acid to the reaction mixture, wherein the acid is selected from acetic acid or formic acid.

(13) The olefin is selected from linear olefin or terminal olefin or internalolefin. More preferably, the olefin is selected from group consisting of 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-octadecene, trimethoxy(vinyl)silane, trimethyl(vinyl)silane, cardanol, 2, 3-dihydrofuran, allyl malonic acid, styrene, 4-methyl styrene, 4-iBu-styrene, 4-tBu-styrene, 4-methoxy styrene, 4-acetoxy styrene, 4-bromo styrene, 4-chloro styrene, 4-vinylbenzonitrile, 4-vinylbenzoic acid and allyl benzene.

(14) The reaction is carried out in either batch mode or continuous mode of operation.

(15) The hydroformylation of various olefins using [HFe(CO).sub.4].sup. as shown in following scheme 1:

(16) ##STR00001##

(17) The scope of the iron catalyzed hydroformylation is examined and about 20 substrates are evaluated. Both aliphatic and aromatic substrates are hydroformylated with good to excellent conversion to aldehydes. The aromatic substrates exhibited slightly lower reactivity. A short chain olefin, 1-hexene, is hydroformylated under further milder conditions with 50% exclusive conversion to heptanal along with 72% linear selectivity. Hydroformylation of long-chain olefins is even more challenging, as their reactivity decreases with increasing carbon number and the possibility of internal isomers and corresponding aldehyde products increases. With increasing chain length of the olefin, the reactivity is found to decrease. Thus, at 15 bars syngas pressure and 100 C., a C10 olefin 1-decene led to only 47% yield, whereas increasing the CO/H.sub.2 pressure to 30 bars led to an improved yield of 97%. Along the same lines, 1-dodecene and 1-octadecene displayed 97% and 87% yield respectively under identical conditions.

(18) The catalyst is further examined by subjecting functional olefins to iron catalyzed hydroformylation. The catalyst is found to tolerate trimethoxy group without any hindrance and 75% conversion to aldehyde is observed. A slight change in the silane to trimethyl(vinyl)silane led to 49% conversion to aldehyde. A cardanol, which is a non-edible plant oil derived substrate, is tested in the iron catalyzed hydroformylation. Although only 11% aldehyde product could be observed, the fact that such a mixture (cardanol is mixture of three different internal olefins) could be hydroformylated indicates the potential that the iron catalyst holds. A highly challenging heterocyclic olefin, 2, 3-dihydrofuran, is hydroformylated to yield (62%) a highly regioseletive 3-carbaldehyde with 97% selectivity. Hydroformylation of 1, 1-disubstituted difunctional olefin allyl malonic acid lead to reduced activity and only 10% aldehyde could be observed, clearly indicating the limited functional group tolerance of the current catalytic system. On an average, aliphatic olefins are hydroformylated in 24 hours, whereas aromatic substrates required 48 or more hours. Styrene is chosen as a representative benchmark substrate and iron catalyzed hydroformylation is examined, a quantitative conversion is observed at 20 bars syngas pressure at 100 C., with the preferred branched aldehyde formed with 92% selectivity. The reversal of regioselectivity is very commonly observed in styrenic substrates and monodentate phosphine ligands are known to preferably deliver the branched product. Both electron donating and electron withdrawing substituents are tolerated. The electron donating substrates 4-methyl styrene, 4-tertbutyl styrene demanded 30 bars syngas pressure for 45-50% conversion.

(19) The results for the hydroformylation of various olefins using [HFe(CO).sub.4].sup. (via in-situ generated catalyst in presence of different ligands as catalyst are presented in table 1 and 2 below:

(20) TABLE-US-00001 TABLE 1 Iron (1) catalyzed hydroformylation of 1-octene in the presence of L1.sup.a L CO/H.sub.2 Time Conv. Run (equiv.) Solvent (bars) (h) (%).sup.b L:B.sup.b 1 L1 (1) MeOH 20 24 47 73:27 2 L1 (2.5) MeOH 20 24 95 66:34 3 L1 (3) MeOH 20 24 95 64:36 4 L1 (4) MeOH 20 24 92 64:36 5 L1 (2.5) THF 20 24 3 NA 6 L1 (2.5) DXN 20 24 66 73:27 7 L1 (2.5) DCM 20 24 24 63:37 8 L1 (2.5) EtOH 20 24 17 67:33 9 L1 (2.5) iPrOH 20 24 20 70:30 10 L1(2.5) MeOH 30 48 90 60:40 11 L1(2.5) MeOH 30 24 76 70:30 12 L1(2.5) MeOH 15 24 62 67:33 13.sup.c L1(2.5) MeOH 20 24 85 67:33 14.sup.d L1(2.5) MeOH 20 24 3 74:26 15 NA MeOH 35 24 0 NA 16 L2(1) MeOH 20 48 18 68:32 17 L2(2.5) MeOH 20 48 47 70:30 18 L2(3) MeOH 20 48 27 65:35 19 L2(2.5) MeOH 30 48 92 63:37 20 L2(2.5) MeOH 30 24 5 76:24 21 L2(2.5) MeOH 20 24 2 NA 22.sup.e L2(2.5) MeOH 20 24 23 68:32 .sup.aConditions: 1: 0.0077 mmol, Ligand/Metal: 2.5, L1 = PPh.sub.3, L2 = P(OPh).sub.3; Sub/Fe: 100, Solvent: 1 ml, NA: Not applicable; MeOHMethanol, THFTetrahydrofuran, DXN1,4-dioxane, DCMDichloromethane, EtOHEthanol, iPrOHIsopropanol, hardly any (~1%) hydrogenation product was detected. .sup.bDetermined by GC. .sup.cPerformed at 120 C. .sup.dPerformed at 80 C. .sup.eL2 was incubated for 24 hours before addition of 1-octene.

(21) TABLE-US-00002 TABLE 2 Iron (1) catalyzed hydroformylation of alkenes in the presence of L1.sup.a Temp. CO/H.sub.2 Time Conv. Run Substrate ( C.) (bars) (h) (%)b L:B .sup.b 1 S2 80 10 48 50 72:28 2 S3 100 30 24 97 61:39 3 S4 100 30 24 97 61:39 4 S5 100 30 24 87 48:52 5 S6.sup.c 100 30 24 75 5:95 6.sup.d S7.sup.c 100 30 24 99 67:33 7.sup.e S8.sup.c 100 30 48 43 45:55 8 S9 70 25 24 62 3:97 9.sup.f S10.sup.c 100 30 48 82 50:50 10 S11 100 20 48 99 8:92 11 S12 100 30 48 45 13:87 12 S13 100 30 48 15 28:72 13 S14 100 30 48 46 7:93 14 S15 100 30 48 96 11:89 15 S16 100 25 48 68 2:98 16 S17 100 20 48 97 4:96 17 S18 100 30 48 72 8:92 18 S19 100 25 48 19 10:90 19.sup.g S20.sup.c 100 30 48 99 0:99 20 S21 100 35 48 22 64:36 .sup.aConditions: 1: 0.0077 mmol, Ligand/Metal: 2.5, Sub/Fe: 100, Solvent: 1 ml methanol; S2: 1-hexene, S3: 1-decene, S4: 1-dodecene, S5: 1-octadecene, S6: trimethoxy(vinyl) silane, S7: trimethyl(vinyl)silane, S8: Cardanol, S9: 2,3-dihydrofuran, S10: Allyl malonic acid, S11: styrene, S12: 4-methyl styrene, S13: 4-iBu-styrene, S14: 4-tBu-styrene, S15: 4-methoxy styrene, S16: 4-acetoxy styrene, S17: 4-bromo styrene, S18: 4-chloro styrene, S19: 4-vinylbenzonitrile, S20: 4-vinylbenzoic acid, S21: allyl benzene; NA: Not applicable .sup.b Determined by GC. .sup.cYields determined by .sup.1H NMR with CH.sub.2Br.sub.2 as an internal standard, .sup.dconversion to aldehyde is 49%; .sup.econversion to aldehyde is 11%; .sup.fconversion to aldehyde is 10%; .sup.gconversion to aldehyde is 26%.

(22) In one embodiment of the present invention, the process may optionally addition of acid to the reaction mixture; preferably the acid is selected from acetic acid or formic acid.

(23) The results of acetic acid promoted iron {[HFe(CO).sub.4][PPN]+} catalyzed hydroformylation 1-hexene, styrene, 4-methoxy styrene and 4-methyl styrene are presented in table 3 below:

(24) TABLE-US-00003 TABLE 3 Acetic acid promoted iron (1) catalyzed hydroformylation of 1-hexene, styrene, 4- methoxy styrene and 4-methyl styrene.sup.a Sr. AcOH CO/H.sub.2 Time Conv. No. Substrate (equiv.) b bars (h) (%)c L:Bc 1 1-hexene 1 20 16 49 72:28 2 1-hexene 2 20 16 25 73:27 3 1-hexene 5 20 16 1 NA 4 styrene 1 20 24 94 14:76 5 4-methoxy styrene 1 20 24 32 16:84 6 4-methyl styrene 1 20 24 64 16:84 7 4-methoxy styrene 1 20 24 80 8:92 .sup.aConditions: 1-0.0077 mmol, Ligand/Metal: 2.5, Sub/Fe: 100, Solvent: 1 ml Methanol, NA: Not determined, b equivalent of acetic acid as compared to the catalyst, cDetermined by GC.

(25) FIG. 1 shows .sup.1H NMR Spectrum of reaction mixture in CDCl.sub.3 showing peak for aldehydes in case of (trimethoxy)vinylsilane.

(26) FIG. 2 shows GC chromatogram for HF of styrene showing regioselectivity 8:92.

EXAMPLES

(27) Following examples are given by way of illustration therefore should not be construed to limit the scope of the invention.

Example 1

Synthesis of Iron Complexes [Fe(CO).SUB.5.] and [HFe(CO)4].SUP..[PPN].SUP.+

(28) We began with the synthesis of [Fe(CO).sub.5] following a known literature procedure. 42.01 g (0.0137 mol) of benzylideneacetone, 5 g (0.0137 mol) of [Fe.sub.2(CO).sub.9] were suspended in dry toluene (30 ml) in a Schlenk flask. The above suspension was heated at 60 C. for 5 hours, after which volatiles were evaporated under vacuum. The resultant volatiles were collected and subjected to low temperature precipitation at 45 C. to obtain [Fe(CO).sub.5] as straw yellow colored precipitate. The supernatant toluene was syringed out and the resultant solid (64% yield) was used for next step. Subsequently, the solid was allowed to warm up to room temperature, leading to a straw yellow color liquid.

(29) 5 g (0.0255 mol) of [Fe(CO).sub.5] was treated with 2.86 g (0.051 mol) of KOH in methanol (40 ml) to obtained the desired metal precursor [HFe(CO)4][K]+. 2 A saturated solution of bis-triphenylphosphine iminium chloride (1 g in 10 ml methanol) was added to above [HFe(CO).sub.4][K]+ salt to obtain pale yellow colored precipitate. The thus obtained precipitate was further recrystallized from 1:1 hot solution of ethanol:ethyl acetate to obtain [HFe(CO).sub.4][PPN]+(1) [where [PPN]+=Bis(triphenylphosphine)iminium cation] in 46% yield.

(30) .sup.1H NMR (500 MHz in CD.sub.3OD): =8.52 (s, 1H, FeH). .sup.13C NMR (125 MHz in CD.sub.3OD): =161.5 (CO), 135.0, 133.6, 130.8, 128.3.31P NMR (500 MHz in CD.sub.3OD): =21.02. IR (cm.sup.1)=1870 (CO). ESI-MS (ve mode): m/z=168.91 [M].sup..

Example 2

General Procedure for Hydroformylation

(31) In a typical hydroformylation experiment a stainless steel autoclave (450 mL) equipped with 50 ml high pressure liquid charging chamber, pressure regulator and a safety valve was used. Individual vials were charged with metal precursor [HFe(CO).sub.4].sup.[PPN]+(1) (5.5 mg, 0.0077 mmol), ligand (as in Table 1-3), solvent (1 ml), substrate (100 equiv.) and stirring bars in a glove box. The vials were transferred to autoclave and the autoclave was purged three times with syngas (CO:H.sub.2=1:1) before pressurizing it to the desired pressure. Suitable temperature and pressure was maintained during the reaction. After completion of the reaction, the autoclave was cooled to 0 C., and excess gas was vented off in a well-ventilated fume-hood. The conversion and regio-selectivity were determined by using gas chromatography (GC).

(32) The results for the hydroformylation of various olefins using [HFe(CO).sub.4].sup. in presence of different ligands as catalyst are presented in table 1 and 2 below:

(33) 1-hexene. GC analysis for 1-hexene was carried out on an Agilent 7890B GC system using HP-05 column (30 m320 m0.25 m), split ratio 30:1, column pressure 10 psi, injector temperature of 260 C., detector temperature of 330 C., argon carrier gas. Temperature program: Initial temperature 50 C., hold for 1 min.; ramp 1:4 C./min. to 120 C.; ramp 2:20 C./min. to 250 C.; ramp 3:20 C./min. to 320 C., hold for 2 min. Retention time for 1-hexene=2.05 min hydrogenated product (n-hexane)=2.07 min.; branched aldehydes=4.74 min.; linear aldehyde=5.65 minute. (FIG. 3)

(34) 1-octene. Temperature program: Initial temperature 70 C., hold for 1 min.; ramp 1: 4 C./min. to 120 C.; ramp 2: 10 C./min. to 250 C.; ramp 3: 20 C./min. to 320 C., hold for 2 min. Retention time for 1-octene=2.7 min.; hydrogenated product (n-octane)=2.8 min.; branched aldehydes=7.02 min.; linear aldehyde=8.1 minute. (FIG. 4)

(35) 1-decene, 1-dodecene, 1-octadecene. Temperature program: Initial temperature 70 C., hold for 1 min.; ramp 1: 4 C./min. to 120 C.; ramp 2: 10 C./min. to 250 C.; ramp 3: 20 C./min. to 320 C., hold for 2 min. Retention time for 1-decene=5.4 min. hydrogenated product (n-decane)=5.7 min.; branched aldehydes=13.1 min.; linear aldehyde=14.4 minute (FIG. 5). Retention time for 1-dodecene=9.9 min. hydrogenated product (n-dodecane)=11.2 min.; branched aldehydes=18.0 min.; linear aldehyde=18.8 min. Retention time for 1-octadecene=22.4 min.; branched aldehydes=26.0 min.; linear aldehyde=26.5 min.

(36) Styrene, 4-methyl styrene. GC analysis for styrene and 4-methyl styrene was carried out on an Agilent 7890B GC system using Supelco -dex 225 (30 m*0.25 mm*0.25 m), split ratio 30:1, column pressure 10 psi., injector temperature of 220 C., detector temperature of 300 C., argon carrier gas. Temperature program: Initial temperature 100 C., hold for 2 min.; ramp 1: 2 C./min. to 160 C.; ramp 2: 20 C./min. to 210 C.; hold for 2 min. Retention time R.sub.t for styrene=7.3 mins. for hydrogenated product (Ethyl benzene)=6.3 mins, n-dodecane=14.7 min. (internal standard), for branched aldehydes=17.0 mins. for linear aldehyde=23.2 mins. Retention time R.sub.t for 4-methylstyrene=10.3 mins. for branched aldehydes=22.0 mins. for linear aldehyde=22.7 mins.

(37) 4-methoxy styrene, 4-bromo styrene, 4-iBu-styrene, 4-tBu-styrene, 4-acetoxy styrene, 4-bromo styrene, 4-chloro styrene, 4-vinylbenzonitrile and allyl benzene.

(38) GC analyses for above styrenic substrates was carried out on an Agilent 7890B GC system using Supelco -dex 225 (30 m*0.25 mm*0.25 m), split ratio 30:1, column pressure 10 psi., injector temperature of 220 C., detector temperature of 300 C., argon carrier gas. Temperature program: Initial temperature 100 C., hold for 2 min.; ramp 1: 2 C./min. to 160 C.; ramp 2: 10 C./min. to 210 C.; hold for 2 min. Retention time R.sub.t for 4-methoxy styrene=20.5 mins. for branched aldehydes=33.3 mins, for linear aldehyde=36.0 mins. Retention time R.sub.t for 4-bromo styrene=19.3 mins. for branched aldehydes=35.4 mins. for linear aldehyde=38.5 mins. Retention time R.sub.t for 4-iso-butyl styrene=20.7 mins. for branched aldehydes=32.6 mins. for linear aldehyde=37.1 mins. Retention time R.sub.t for 4-tertbutyl styrene=19.9 mins. for branched aldehydes=33.3 mins. for linear aldehyde=36.2 mins. Retention time R.sub.t for 4-acetoxy styrene=30.0 mins. for branched aldehydes=32.9 mins. for linear aldehyde=38.44 mins. Retention time R.sub.t for 4-chloro styrene=14.4 mins. for branched aldehydes=31.4 mins. for linear aldehyde=36.0 mins. Retention time R.sub.t for 4-vinylbenzonitrile=28.3 mins. for branched aldehydes=37.0 mins. for linear aldehyde=38.5 mins. Retention time R.sub.t for Allyl benzene=8.4 mins. for branched aldehydes=24.3 mins. for linear aldehyde=29.2 mins.

Example 3

Hydroformylation of 1-Octene Using Fe Catalyst

(39) Hydroformylation of 1-octene was performed in a stainless steel autoclave (450 mL) equipped with pressure regulator and a safety valve. In a glove box the vials were charged with [(Ph.sub.3P).sub.2N].sup.+[HFe(CO).sub.4].sup. (0.0055 g, 1 eq.), PPh.sub.3 (0.0050 g, 2.5 eq.), dry MeOH (1 ml), 1-octene (0.12 ml, 100 eq.) along with Teflon stirring bars. Before starting the catalytic reactions, the charged autoclave was purged three times with syngas (CO:H.sub.2=1:1) and then pressurized to 30 bar syngas pressure. The autoclave was heated at 100 C. in an oil bath for 24 hours. After catalysis, the autoclave was cooled to 0 C., and excess gas was vented. The conversion and regioselectivity were determined by GC using mesitylene as an internal standard. GC method for 1-octene is as under:

(40) Column used: HP-5 (30 m*0.25 mm*320 m), Split ratio 30:1, Inlet temperature 260 C., Column pressure 10 psi,

(41) Temperature program: started at 1) 70 C., hold for 1 min 2) 4 C. to 120 C. 3) 10 C. to 250 C. 4) 20 C. to 320 C. hold for 2 mins.

(42) FID temperature: 330 C.

(43) Result is shown in following table:

(44) TABLE-US-00004 Retention time Area Area % Height Height % 2.775 10795405 16.40 3003949 19.60 7.113 16886492 25.65 4650727 30.35 8.275 38156662 57.95 7667703 50.04 Totals 65838559 100.00 15322379 100.00

Example 4

Acetic Acid Promoted Iron Catalyzed Hydroformylation

(45) Acetic acid promoted hydroformylation of olefins 1-hexene, styrene, 4-methyl styrene, 4-methoxy styrene and 4-bromo styrene was performed with some modification as under. In a typical hydroformylation experiment a stainless steel autoclave (450 mL) equipped with 50 ml high pressure liquid charging chamber, pressure regulator and a safety valve was used. Individual vials were charged with metal precursor {[HFe(CO).sub.4].sup.[PNP]+(5.5 mg, 0.0077 mmol)}, triphenyl phosphine and stirring bars in a glove box. The vials were transferred to a wide neck Schlenk container and methanol (1 ml), substrate (100 equiv.), and acetic acid was added. The vials were immediately transferred to autoclave and the autoclave was purged three times with syngas (CO:H.sub.2=1:1) before pressurizing it to the desired pressure. Suitable temperature and pressure was maintained during the reaction. After completion of the reaction, the autoclave was cooled to 0 C., and excess gas was vented off in a well-ventilated fume-hood. The conversion and regio-selectivity were determined by gas chromatography (GC).

(46) The results of acetic acid promoted iron {[HFe(CO).sub.4][PPN]+} catalyzed hydroformylation 1-hexene, styrene, 4-methoxy styrene and 4-methyl styrene are presented in table 3 below:

(47) TABLE-US-00005 TABLE Acetic acid promoted iron (1) catalyzed hydroformylation of 1-hexene, styrene, 4- methoxy styrene and 4-methyl styrene.sup.a Sr. AcOH CO/H.sub.2 Time Conv. No. Substrate (equiv.) b bars (h) (%)c L:Bc 1 1-hexene 1 20 16 49 72:28 2 1-hexene 2 20 16 25 73:27 3 1-hexene 5 20 16 1 NA 4 styrene 1 20 24 94 14:76 5 4-methoxy styrene 1 20 24 32 16:84 6 4-methyl styrene 1 20 24 64 16:84 7 4-methoxy styrene 1 20 24 80 8:92 .sup.aConditions: 1-0.0077 mmol, Ligand/Metal: 2.5, Sub/Fe: 100, Solvent: 1 ml Methanol, NA: Not determined; b equivalent of acetic acid as compared to the catalyst, cDetermined by GC.

ADVANTAGES OF THE INVENTION

(48) 1) Cheap iron metal is used.

(49) 2) Cheap and commercially available ligands have been used.

(50) 3) Hydroformylation is catalyzed under mild conditions.

(51) 4) Hydroformylation of 4-isobutyl styrene followed by its oxidation leads to Ibuprofen, a very popular, NSAID (Non-steroidal anti-inflammatory drug).