ZA200510105B

ZA200510105B - Process for the hydroformylation of ethylenically unsaturated compounds

Info

Publication number: ZA200510105B
Application number: ZA200510105A
Authority: ZA
Inventors: Eastham Graham; Jimenez Christina; Cole-Hamilton David
Original assignee: Uk Lucite Internat Uk Ltd
Priority date: 2003-07-03
Filing date: 2005-12-12
Publication date: 2006-12-27
Also published as: CN1816513B; CN1816513A; GB0315536D0

Description

PROCESS FOR THE HYDROFORMYLATION OF ETHYLENICALLY

UNSATURATED COMPOUNDS

The present invention relates to the nydroformylation of ethylenically unsaturated compounds by reaction with carbon monoxide and hydrogen in the presence of a catalyst system. :

The carbonylation and hydroformylation of ethylenically unsaturated compounds using carbon monoxide in the presence of hydrogen and a catalyst comprising a group

VIII metal, example, rhodium, and a phosphine ligand, example an alkyl phosphine, cycloalkyl phosphine, aryl phosphine, pyridyl phosphine or bidentate phosphine, has been "described in ‘numerous ~~ patents and = patent applications.

WO 96/19434 disclosed that a particular group of bidentate phosphine compounds . can provide stable catalysts in carbonylation reaction systems, and the use of such catalysts leads to reaction rates which were significantly higher than those previously disclosed.

Wo 01/68583 discloses carbonylation processes for higher alkenes of three or more carbon atoms. : I

Wo -02/76996, for example, discloses a method for producing : diphosphines, and their use . as co-catalyst = for hydroformylating olefins. WO 02/20448 similarly discloses the preparation of . arylphosphines for the. rhodium- ‘catalysed nydroformylation of alkenes. E

PCT/GB2004/002859

Although catalyst systems have been developed which exhibit reasonable stability during the hydroformylation process and permit relatively high reaction rates and regioselectivity between linear and branched aldehyde products, there still exists a need for altermative and/or improved catalyst systems. Suitably, the present invention aims to provide an alternative and/or improved catalyst for hydroformylating ethylenically unsaturated compounds. Moreover, the present invention aims to provide solvents which improve the performance of the catalyst system.

Surprisingly, it has been found that improved selectivity of the linear aldehyde product compared to the branched aldehyde product can pe obtained than by using comparative catalyst systems of the prior art.

According to the present invention there is provided a process for the hydroformylation of ethylenically unsaturated compounds, as set forth in the appended claims. preferred features of the invention will be apparent from the dependent claims, and the description.

Also according to the present invention there is provided a catalyst system, & hydroformylation reaction catalyst gystem, a reaction medium, a hydroformylation reaction medium, use of a catalyst system, use of a reaction medium, and a process for preparing a catalyst system and reaction medium, as set forth hereinafter and in the appended claims.

According to the first aspect of the present invention there 1s provided a process for the hydroformylation of ethylenically unsaturated compcunds, which process comprises reacting said ethylenically unsaturated

AMENDED SHEET

PCT/GB2004/002859 ) 2a compound with carbon monoxide and hydrogen, in the presence of a catalyst system, the catalyst system obtainable by combining: a) a Group VIII metal compound; and b) a bidentate phosphine of general formula (Ia) (Ia)

R' R® }

R'I—cC c—R®

NN yar

R R

, Q*Rr—al

R R

NJ

R™—cC c—R’ x Re wherein:

R is a bridging group;

Rl to R}? each independently represent hydrogen, lower alkyl, aryl or Het;

Q' and Q? each independently represent phosphorus, arsenic or antimony and in the latter two cases references to phosphine or phosphorus above are amended accordingly, the process characterised in that a chlorine moiety is present in at least said Group VIII metal compound.

According to a second aspect of the present invention there is provided a process for the hydroformylation of ethylenically unsaturated compounds, which process

AMENDED SHEET

PCT/GB2004/002859 comprises reacting gaid ethylenically unsaturated compound with carbon monoxide and hydrogen, in the presence of a catalyst system and a solvent, the catalyst system obtainable by combining: a) a metal of Group VIII or a compound thereof; and b) a bidentate phosphine of general formula (1a) (Ia)

R' re

R'—cC c—R® [3 JL

R R

, QXR—Ql

T AN

R—C c—R’ ’ R wherein R is a bridging group;

R' to RY? each independently represent hydrogen, lower alkyl, aryl or Het,

Q' and Q* each independently represent phosphorus, arsenic or antimony and in the latter two cases references to phosphine or phosphorus above are amended accordingly, the process characterised in that a chlorine moiety is present in at least one of the said Group VIII metal compound or said solvent.

R! to R*? preferably represent lower alkyl, aryl or fet.

R may be a covalent bridging group.

AMENDED SHEET

PCT/GB2004/002859 ’ 3a

A process such as the first or second aspect of the invention is referred to hereinafter as "the process of the invention".

The process of the invention includes the embodiments set out hereinafter.

AMENDED SHEET

In one set of embodiments, the group R in formula (Ia) may represent an alkylene bridging group. preferably, a lower alkylene.

In another and preferred get of embodiments, the bridging group R may pe defined as ~-A- (K,D)Ar (RE, 2) -B-, guch that general formula (Ia) becomes general formula (I), (1) rR" rE

Rg EF

KON / Re o JATIRERTETE

B RG CR? lL f wherein: ar is a bridging | group. comprising an optionally gubstituted aryl moiety to which the phosphorus atoms are linked on available adjacent carbon atoms;

A and B each independently represent lower alkylene;

K, D, E and Z are substituents of the aryl moiety (Ar) and each independently represent hydrogen, lower alkyl, aryl,

Het, halo, cyano, nitro, OR?*?, oc (0) R?®, C(O)R®, C(O)OR*,

NRZR?*, Cc (0)NR*R*, Cc (S) R¥R?, sr??, C(O) ar?’, or -J- o? (CR¥ (RM) (RS) ) CR*¢ (RY) (rR). where J represents lower alkylene; OY two adjacent groups gelected from XK, Z, D and

E together with the carbon atoms of the aryl ring to which they are attached form a further phenyl ring, which is optionally" substituted by one OF more substituents gelected from hydrogen, lower alkyl, halo, cyano, nitro,

ORY, OC(O)R*’, c(O)R®, C(O)OR™, NRZR*, c (0) NR**R*, c(S)RP°R*, SR? or c (0) SRY;

R! to R!*® each independently represent hydrogen, lower alkyl, aryl, or Het, preferably, lower alkyl, aryl or Het;.

RY? to R? each independently represent hydrogen, lower alkyl, aryl or Het; Co : : ot, Q* and Q® (when present) each independently represent phosphorous, arsenic or antimony and in the latter two cases references to phosphine ox phosphorous above are amended accordingly. oo preferably, when K, "p, E or 2 represent ~J-

Q® (CR* (R™) (R*®)) CR* (RY) (R*) , the respective K, D, E or Z is on the aryl carbon adjacent the aryl carbon to which A or B is connected or, if not 80 adjacent, is adjacent a remaining K, D, E oF Z group which itself represents -J-

Q? (CRY? (R*) (RY5) ) CR*® (R*") (R'®) . . . preferably, R' to R*® each independently represent lower alkyl -or aryl. " More preferably, rR? to RY? each independently represent Cc, to Ce alkyl, C,-Cs . alkyl phenyl (wherein the phenyl group is optionally ‘substituted as defined herein) or phenyl (wherein the phenyl group is optionally substituted as defined herein) . - Even more preferably, R* to R*® each independently represent Ci tO Cs alkyl, which is optionally substituted as defined herein.

Most preferably, R* to R!® each represent non-substituted c, to Ce alkyl such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, tert-butyl, pentyl, hexyl and cyclohexyl. Co Cl :

Alternatively, OT additionally, each of the groups R* to

R®, R* to Rf, R’ to r%, R*® to RY, R*® to R® or RY to R*® together independently may form cyclic structures such as 1-norbornyl or 1 -norbornadienyl. Further examples of composite groups include cyclic gtructures formed between

R* to RS, R’ to R¥, and rR? to R™. Alternatively, one OY more of the groups may represent a solid phase to which the ligand is attached.

Moreover, at least one (CR*RYR®) group attached to Q' and/or Q°, i.e. CRIR?R®, CRR°R®, CR'R®R®, or CRIPRMR'?, may instead be congressyl or adamantyl, or both groups defined above as (CR*R'R?) attached to either or both Q' and/or Q*, may, together with either o' or Q* as appropriate, instead form an optionally substituted 2-phospha- tricyclo(3.3.1.1{3,7}]decyl group OY derivative thereof.

However, in this particular set of embodiments, i.e. when the bridging group is defined as -A- (K,D)Ar(E,Z)-, if any (CR*RYR®) groups are defined as per this paragraph, they are preferably congressyl OY adamantyl, more preferably non-substituted adamantyl or congressyl, most preferably a non-substituted adamantyl group. :

In a particularly preferred embodiment of the present invention RY, g*, R’, RY, RY and R'¢ each represent the game lower alkyl, aryl or Het moiety as defined herein, »?, ®°, R®, R*, R* and RY’ each represent the same lower alkyl, aryl or Het moiety as defined herein, and R3, RS, r?, RY, R and R'® each independently represent the same lower alkyl, aryl or Het moiety as defined herein. More preferably rR}, R', R', rR, rR and RY each independently represent the same c,-Cs alkyl, ' particularly non-

substituted Ci-Cs alkyl, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, tert-butyl, pentyl, hexyl or cyclohexyl; r?, R°, FR’, rR, R¥ and RY? each independently represent the same c,-C¢ alkyl as defined above; and R®, R°, rR’, R*?, RY and R*® each independently represent the same C1-Cs alkyl as defined above. For example: RY, RY, rR’, R*°, R® and R® each represent methyl; 'R?, ®R°, R®, RY, R* and RY each represent ethyl; and, R’,

RS, R®, R*, R' and R*® each represent n-butyl or n-pentyl.

In an especially preferred embodiment of the present invention each R' to R'® group represents the same lower alkyl, aryl, or Het moiety as defined herein. Preferably, each R* to R*® represents the same Cc, to Cs alkyl group, particularly non-substituted C,-Cs alkyl, such as methyl, _ ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, tert- butyl, pentyl, hexyl and cyclohexyl. Most preferably, each

R* to R*® represents methyl. -

In the compound of formula (I), preferably each 0, Q° and 0? (when present) is the same. Moreover, in a compound of formula (Ia), preferably o' and Q* are the same. Most preferably, each OF, Q* and Q° (when present) represents phosphorous. Co Copreferably. in the compound of formula (I), A, B and J. (when present) each independently represent Ci to Ce alkylene which is optionally substituted as defined herein, for example with lower alkyl groups. Moreover, in the compound of formula (Ia), R (when alkylene) represents ¢, to Ce alkylene which is optionally gubstituted as defined herein, for example with lower alkyl groups. preferably, the lower alkylene groups which A, B and J

(when present) represent are non-substituted. A particular preferred lower alkylene which A, B and J may independently represent ig -CHz- Or -CoH,- Most preferably, each of A, B and J (when present) represent the same lower alkylene as defined herein, particularly -

CHz-. particularly preferred lower alkylenes which R represents are substituted or non-substituted and may be gelected from ethylene (-CoHs-), and gubstituted. variants thereof, propylene (-CyHs-), and substituted variants thereof, and butylene (-CHs-), and aubstituted variants thereof, and wherein such substitution may be on any, some or all of the carbon atoms of the lower alkylene and such gubstitution may be with lower alkyl groups. More preferably, the lower alkylenes which R represents are substituted or non-substituted ethylene or propylene, most preferably, substituted or non-substituted propylene. preferably, in the compound of formula (I) when K, D, E or 7 does not represent -J-0° (CR* (R*) (R™) yCR* (RY) (R*®), KX,

D, BE or Z represents hydrogen, lower alkyl, phenyl or lower alkylphenyl. More preferably, K. D, E or 2 represent hydrogen, phenyl, Ci-Ce alkylphenyl or C;-Cs alkyl, such as methyl, ethyl, propyl, puryl, pentyl and hexyl. Most preferably, K, D, E or Z represents hydrogen. preferably, in the compound of formula (I) when K, D, E and 2 together with the carbon atoms of the aryl ring to which they are attached do not form a phenyl ring, XK, D, E and Z each independently represent hydrogen, lower alkyl, phenyl or lower alkylphenyl. More preferably, K, D, E and

Zz each independently represent hydrogen, phenyl, Ci-Ce alkylphenyl or Ci-Ce alkyl, such as methyl, ethyl, propyl, putyl, pentyl and hexyl. Even more preferably, K, D, E and

S

Zz represent the same substituent. Most preferably, they represent hydrogen. preferably, in the compound of formula (I) when XK, D. E or

Z does not represent 3-0 (CR*® (R**) (RS) ) CR (R*) (R*®) and

K, D, BE and 7 together with the carbon atoms of the aryl ring to which they are attached do not form 2a phenyl ring, " each of XK, D, E and 2 represent the same group gelected from hydrogen, lower alkyl, aryl, or Het as defined herein; particularly hydrogen OF C,-Cs alkyl (more particularly unsubstituted C1-Cs alkyl). especially hydrogen. preferably, in the ‘compound of formula (I) when two of K,

D, E and Z together with the carbon atoms of the aryl ring to which they are attached form a phenyl rind, then the phenyl ring is optionally substituted with one ‘or more substituents selected from aryl, lower alkyl (which alkyl group way itself be optionally gubstituted or terminated as defined below), Het, halo, cyano, nitro, ORY, OC(0)R*’, c(0)R®, C(O)OR*, NRPR?, C(O)NR**R*, gr?’, C(0)srR* or . c(S)NR**R?*® wherein RY? to R* each independently represent hydrogen or lower alkyl (which alkyl group may itself be optionally substituted or terminated as defined herein).

More preferably, the phenyl ring is not substituted by any substituents i.e. it bears hydrogen atoms only. preferred compounds of formula (1) within this set of embodiments include those wherein:

A and B each independently represent unsubstituted Ci to

Ce alkylene; oo

K, D, 2 and E each independently represent hydrogen, C1-Cs alkyl, phenyl, C1-Cs alkylphenyl or -J- 0? (CR*? (R*) (R*®) ) CRS (RY) (R*) where J represents unsubstituted CG to Cs alkylene; OY two of K, D, Z and E together with the carbon atoms of the aryl ring to which they are attached form a phenyl xing which is optionally substituted by one Or more substituents gelected from "lower alkyl, phenyl or lower alkylphenyl. :

R* to R® each independently represent ¢, to Cs alkyl, phenyl or Ci to C¢ alkylphenyl.

Further preferred compounds of formula (I) within this set of embodiments include those wherein:

A and B both represent -CH,~ or CgHg, particularly CH;;

K, D, Z and E each independently represent hydrogen, C1-Ce . alkyl phenyl or C;-Cs alkyl or -J-

Q® (CRY? (RM) (R*®) ) CR* (RY) (R*®) where J is the same as A; or two of XK, D, E and 2 together with the carbon atoms of the aryl ring to which they are attached form an unsubstituted phenyl ring;

R® to R'® each independently represent Ci to Ce alkyl; still further preferred compounds of formula (I) within this set of embodiments include those wherein: EE

R* to R*® are the same and each represents Cc, to Ce alkyl, particularly methyl. E oo still further preferred compounds of formula I within this get of embodiments include those wherein:

K, D, 2 and E are each independently selected from the group consisting of hydrogen or c, to GCs alkyl, particularly where each of K, Dp, Z and E represent the game Jroup, especially where each of XK, Dp, 2 and E represent hydrogen; oT :

K represents _CH,-Q® (CR® (R*) (R*®) ) CR* (RY) (R*®) and D, 2 and E are each independently gelected from the group consisting of hydrogen OT Cc, to Cs alkyl, particularly where both D and E represent the same droup. especially where D, Z and E represent hydrogen. N

Especially prefexred specific compounds of formula (I) within this set of embodiments include those wherein: each R* to R*? is the same and represents methyl; _

A and B are the same and represent -CH,-;

K, D, Z and E are the same and represent hydrogen.

In this particular set of embodiments, Ar may be defined as are “Ar” and varyl” hereinafter, but preferably, Ar is defined as “including gix-to-ten-membered “carbocyclic aromatic groups, such as phenyl and naphthyl, which groups are optionally substituted with, in addition to K, D, E or 7, one Or more substituents gelected from aryl, lower alkyl (which alkyl group may itself Dbe optionally substituted or terminated as defined below), Het, halo, cyano, nitro, ORY, oC (0)R®, C(O)R*, C(O)OR®, NRZR?*, c (O)NR**R?*®, SRY, c (0) sr” or C(S)NR®*R?*® wherein RY to RY each independently represent hydrogen, aryl or lower alkyl’

(which alkyl group may itself be optionally substituted or terminated as defined hereinafter) .

In a further set of embodiments, in a compound of either formula (I) or (Ia) at least one (CR™R'R®) group attached to O* and/or Q?, i.e. CR'R?R®, CR'R°R®, CR'R'R’, or CRYR*R*, may instead be congressyl Or adamantyl, oT both groups defined above as (CR*RYR®) attached to either or both Qt and/or ©Q°, may, together with either og! or Q° as appropriate, instead form an optionally substituted 2- phospha-tricyclo(3.3.1.1{3,7}]decyl group Or derivative thereof, preferably the at 1east one (CR*R'R?) group being congressyl or adamantyl. :

The adamantyl group may optionally comprise, besides hydrogen atoms, one or more substituents selected from lower alkyl, -OR™, -0C(0)R*°, halo, nitro, _c(0)R*, -C (0) OR, cyano, aryl, -N(R®)R¥, Cc (0)N (R®)R?, ci) (RFR®, CFR, -R(RFIRT, pO (R%®) (R®®), -POsHz, _po(OR®®) (ORY), or -SO;R®, wherein: RY, R¥®, R®, R¥?, R¥,

R?, R®, R¥*, RY, R?® (defined as are R*® to RY hereinbefore), lower alkyl, cyano and aryl are as defined herein and R*® to R$? each independently represent hydrogen, lower alkyl, aryl or Het. However, in one embodiment, the adamantyl groups are not substituted . :

Suitably, when the adamantyl group is substituted with one or more substituents as defined above, highly preferred substituents include unsubstituted Cp to Cs alkyl, -ORY?, - - oc(0)R?®, phenyl, _C(0)OR??, fluoro, =-SOsH, -N(R**)R*, _p(®*F)RS7, -C(O)N(R**)R* and -pO(R®®) (R®®), ~CF;, wherein RY represents hydrogen, unsubstituted Ci-Cs alkyl or phenyl,

R?°, R**, R®, R*, R?®, R¥* each independently ‘represent hydrogen OF unsubstituted Ci-Cs alkyl, R*® to R3® each independently represent unsubstituted c,-Ce alkyl or phenyl. suitably, the adamantyl group may comprise, besides nydrogen atoms, Up to 10 substituents as defined above, preferably up to 5 substituents as defined above, more preferably up to 3 gubstituents as defined above. suitably, when the adamantyl g¥oup comprises, besides hydrogen atoms, one Or more substituents as defined herein, preferably each substituent is identical.

Preferred substituents are unsubstituted C1-Cs alkyl and trifluoromethyl, particularly unsubstituted Ci-Cs alkyl "such as methyl. A highly preferred adamantyl group comprises hydrogen atoms only i.e. the adamantyl group is not substituted.

Preferably, ‘when more than one adamantyl group is present in a compound of formula (1a) or (I), each adamantyl group ig identical.

The »-phospha-tricyelo[3.3.1.1.{3,7}]decy! group (referred to as .2-phospha-adamantyl group herein) may optionally ‘comprise, beside hydrogen atomsg, one Or more substituents.

Suitable substituents include, those substituents as defined herein in respect of the adamantyl group. ‘Highly preferred substituents include lower alkyl, particularly unsubstituted c,-Cs . alkyl, especially methyl, trifluoromethyl, _OR'® wherein RY is as defined herein particularly unsubstituted Ci-Cs alkyl or aryl, and 4- ‘dodecylphenyl. When the 2-phospha-adamantyl group includes ‘more than one substituent, preferably each substituent is identical. SEE preferably, the 2-phospha-adamantyl group is gubstituted on one Or wore of the 1, 3, 5s or 7 positions with a substituent as defined herein.

More preferably, the 2- phospha-adamantyl group is substituted on each of the 1, 3 and 5 positions. guitably, such an arrangement means the phosphorous atom of the 2-phospha-adamantyl group is " ponded to carbon atoms in the adamantyl gkeleton having no hydrogen atoms.

Most preferably, the 2-phospha-adamantyl group is gubstituted on each of the 1, 3, 5 and 7 positions.

When the 2 -phospha- adamantyl group includes more than 1 substituent preferably each substituent is identical.

Especially preferred gubstituents are unsubstituted C1-Cs alkyl and trif 1uoromethyl, particularly unsubstituted c,-Cs alkyl such as methyl. preferably, 2-phospha-adamantyl represents unsubstituted 2-phospha-adamantyl or 2-phospha-adamantyl substituted with one or more unsubstituted Ci-Ce alkyl substituents, or a combination thereof. preferably, the 2-phospha- adamantyl group includes additional heteroatoms, other than the 2-phosphorous atom, in the 2-phospha-adamantyl skeleton.

Suitable additional heteroatoms include oxygen and sulphur atoms, especially oxygen atoms.

More preferably, the 2-phospha-adamantyl group includes one. or more additional heteroatoms in the 6, 9 and 10 positions.

Even more preferably, the 2- phospha-adamantyl group ‘includes an additional heteroatom in each of the 6, 9 and 10 positions.

Most preferably, when the 2-phospha-adamantyl group ‘includes two or more additional heteroatoms in the 2-phospha- adamantyl skeleton, each of the additional heteroatoms are identical. An especially preferred 2-phospha -adamantyl group, which may optionally pe substituted with one or more substituents as defined herein, includes an oxygen atom in each of the 6, 9 and 10 positions of the 2- phospha-adamantyl skeleton. preferably, the 2-phospha-adamantyl includes one or more oxygen atoms in the 2-phospha-adamantyl gkeleton. -

Highly preferred 2-phospha-adamantyl groups as defined herein include 2-phospha-1, 3, 5, 7-tetramethyl-6,9, 10- trioxadamantyl group: 2-phospha-1,3, 5-trimethyl-6 ,9,10- trioxadamantyl group, 2-phospha-1,3,5, 7- tetra (trifluoromethyl) -6,9,10-trioxadamantyl group, and 2- phospha-1 ,3,5-tri (trifluoromethyl) -6,9,10 _trioxadamantyl group. Most preferably, the 2 -phospha-adamantyl is selected from 2-phospha-1,3, 5,7 -tetramethyl-6,9,10- trioxadamantyl group OY 2-phospa-1,3,5, -trimethyl-6,9,10- trioxadamantyl group. : preferably, when more than one 2 -phospha-adamantyl group is present in a compound of formula (1) or (Ia), each 2- phospha-adamantyl group is identical.

The 2-phospha-adamantyl group may be prepared by methods well known to those skilled. in the art. Suitably, certain 2-phospha-adamantyl compounds are obtainable -from Cytec

Canada Inc of 901 Garner Road, Niagara Falls, Ontario,

Canada L2E 6T4. Likewise corresponding 2-phospha-adamantyl compounds of formula (I) etc may be prepared by analogous ‘methods. E

Moreover, at least one of CRM (RY) (R*®) and CR (RY) (R'™®) , when present, may instead be congressyl OY adamantyl, optionally substituted as described above, OT both groups defined as CRM (RM) (RY) and CR (RY) (R!®) attached to Q® , may together with -Q*, instead form an optionally substituted 2-phospha-tricyclo [3.3.1.1{3,7}1 decyl group or derivative thereof, preferably the at least one of

CR? (R*) (R?®) and CR (RY) (R'®), when present, being congressyl or adamantyl. preferably, in a compound of formula (I) when both K represents -J-0% (CR®® (R*) (R*®)) CRY (RY) (R™) and BE represents _J-Q® (CR® (R™) (R*®) ) CR (R*") (R*®), then D represents -J-0° (CR (RY) (R') ) CR* (RYT) (R™)

By the term 2-phospha-tricyclo(3.3.1.1{3,7}1decyl group we mean a 2-phospha-adamantyl group formed by the combination of the two groups attached. to Q, together with Q' to which they are attached, a 2-phospha-adamantyl -group formed by the combination of the two groups attached’ to 02, together with 0° to which they are attached, a 2- phospha-adamantyl group formed by the combination of the two groups’ attached to Q°, together. with Q° to which they are attached, wherein of, @*, or Q is in the 2-position of the adamantyl group of which it forms an integral part and each of op 0?, and Q° represents phosphoxus. preferred compounds within the present set of embodiments and wherein at least one '2-phospha-adamantyl group is present include those wherein:

Claims

PCT/GB2004/002859 ° 63 CLAIMS

1. A process for the hydroformylation of ethylenically unsaturated compounds, which process comprises reacting said ethylenically unsaturated compound with carbon monoxide and hydrogen, in the presence of a catalyst system, the catalyst system obtainable by combining: aj a Group VIII metal compound; and b) a bidentate phosphine of general formula (Ia) (Ia) R%? rE RIL ¢ rR’

LN. pyar R R os Q*-R—Q! In va NJ RC c—R’ LL a wherein: R is a bridging group; rR! to R*? each independently represent hydrogen, lower alkyl, aryl or Het; gt and @Q° each independently represent phosphorus, arsenic or antimony and in the latter two cases references to phosphine or phosphorus above are amended accordingly, the process characterised in that a chlorine moiety is present in at least said Group VIII metal compound. AMENDED SHEET

PCT/GB2004/0028589 ® os

2. A process as claimed in claim 1 in which rR! to RY? each independently represent lower alkyl, aryl or

Het.

3. A process for the hydroformylation of ethylenically unsaturated compounds, which process comprises. reacting said ethylenically unsaturated compound with carbon monoxide and hydrogen, in the presence of a catalyst system and a solvent, the catalyst aystem obtainable by combining: a) a metal of Group VIII or a compound thereof; and b) a bidentate phosphine of general formula (Ia) (Ia) Rr"? r® R''—c c—R’ AN Se i» a-r—a! R F NJ R—C c—R? Il if wherein: R is a bridging group; R! to R'? each independently represent hydrogen, lower alkyl, aryl or Het; o* and 0? each independently represent phosphorus, arsenic or antimony and in the latter two cases references to phosphine or phosphorus above are amended accordingly, the process characterised in that a chlorine moiety is present in at least one of the said Group VIII metal compound Or said solvent. AMENDED SHEET

PCT/GB2004/002859 ® cs

4. A process as claimed in claim 3 in which rR! to RY? each independently represent lower alkyl, aryl or

Het.

5. The process as claimed in claim 3, wherein a chlorine moiety is present in both said Group VIII metal compound and said solvent.

6. The process as claimed in any of claims 1 to 4, wherein R! to RY? each independently represent C, to Ce alkyl, C; to Cs alkyl phenyl or phenyl.

7. The process as claimed in claim 6, wherein R* to R™ each independently represent methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, tert-butyl, pentyl, hexyl and cyclohexyl.

8. The process as claimed in any preceding claim, wherein RY, R*, R’ and RY each independently represent the same C;-Cs alkyl; R%, R®, R® and RY, each independently represent the same Ci-¢ alkyl; and R®, RS, R® and R'?, each independently represent the same C;.¢ alkyl.

9. The process as claimed in any preceding claim, wherein RY to R*? each represents the same C;-Ce alkyl group.

10. The process as- claimed in claim 9, wherein the said C;-¢ alkyl group is non-substituted and selected from the list comprising: methyl, ethyl, n-propyl, iso- AMENDED SHEET

PCT/GB2004,/002859 ® & propyl, n-butyl, iso-butyl, tert-butyl, pentyl, hexyl and cyclohexyl.

it. The process as claimed in claim 10, wherein the said Ci-¢ alkyl group is methyl.

12. The process as claimed in any preceding claim, wherein Q and Q® represents phosphorus.

13. The process as claimed in any one of claims 1 to5 wherein R is defined as -A-(X,D)Ar(E,Z)-B- and the bidentate phosphine is of general formula (I) (I) 7 ® R''—c c—R® RN ) / rR* , Q*A—(KD)ArEZ)—B—Q . v ANG R—C C—R° rR’ R’ wherein: Ar is a bridging group comprising an optionally substituted aryl moiety to which .the phosphorus atoms are linked on available adjacent carbon atoms; A and B each independently represent lower alkylene; K, D, E and Z are substituents of the aryl moiety (a¥) and each independently represent hydrogen, lower alkyl, aryl, Het, halo, cyano, nitro, OR, 0C{0) R??, AMENDED SHEET

PCT/GB2004/002859 C(O)R®, C(O)OR®, NR¥®R?, C(O)NR®R*, C(S)R¥R*, SRY, C(O) SRY’, or -J-QF(CR™ (RY) (R*®))CR (RY) (R'®) where J represents lower alkylene; or two adjacent groups selected from K, Z, D and E together with the carbon : atoms of the aryl ring to which they are attached form a further phenyl ring, which is optionally substituted by one or more substituents selected from hydrogen, lower alkyl, halo, cyano, nitro, OR'?, oC(0)R®®, C(O)R®, C(O)OR*?*, NR®R™, C(O)NR™R®, C(S)R*R?*®, sR?’ or C(0)SR*’; R* to R!® each independently represent lower alkyl, aryl, or Het; R* to R?*’ each independently represent hydrogen, lower alkyl, aryl or Het; o', ©* and Q° (when present) each independently represent phosphorous, arsenic or antimony and in the latter two cases references to phosphine or phosphorous above are amended accordingly.

14. The process as claimed in claim 13, wherein R' to R® each independently represent C, to Cg alkyl, Ci; te Cg alkyl phenyl or phenyl.

15. The process as claimed in claim 14, wherein R! to R*® each independently represent methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, tert-butyl, pentyl, hexyl and cyclohexyl.

16. The process as claimed in any of claims 13 to 15 wherein RY, R*, R’, RY, R'® and R'® each independently AMENDED SHEET

PCT/GB2004/002859 ° represent the same C;-Cg alkyl; ®?, R®, R®, R*, R* and RY? each independently represent the same Cy.¢ alkyl; and R®, RS, R°, RY; RY and R" each independently represent the same Cig alkyl.

17. The process as claimed in any of claims 13 to 16, wherein R' to R*® each represents the same C1-Cs alkyl group.

18. The process as claimed in claim 17, wherein the said

Ci. alkyl group is non-substituted and selected from the list comprising: methyl, ethyl, n-propyl, iso- propyl, n-butyl, iso-butyl, tert-butyl, pentyl, hexyl

. and cyclohexyl.

19. The process as claimed in claim 18, wherein the said

C,.¢ alkyl group is methyl.

20. The process as claimed in any of claims 13 to 19, wherein OY, 0? and @*® (when present) represents phosphorus.

21. The process as claimed in any of claims 13 te 20,

. wherein A, B and J (when present) each independently represent C; to Cs alkylene.

22. The process as claimed in claim 21, wherein each of a, B-and'J (when present) represent -CHa-.

23. The process as claimed in any of claims 13 to 22, wherein K, D, E and Z each represent hydrogen, phenyl, Ci1-C¢ alkylphenyl or Ci-Cs alkyl. AMENDED SHEET

PCT/GB2004/002859 ® os

24. The process as claimed in claim 23, wherein XK, D, E and Z each represent hydrogen.

25. The process as claimed in claim 13 wherein in formula (I): A and B each independently represent unsubstituted C, to Cg alkylene; K, D, 2 and E each independently represent hydrogen, ¢,-C¢ alkyl, phenyl, C,-C¢ alkylphenyl or -Jd- 0? (CR? (RM) (R®®)) CRY (RY?) (R'®) where J represents unsubstituted C; to Ces alkylene; or two.of K, D, Z and E together with the carbon atoms of the aryl ring to which they are attached form a phenyl ring which is optionally substituted by one or more substituents selected from lower alkyl, phenyl or lower alkylphenyl; R! to R*® each independently represent Ci to Cs alkyl, phenyl or C, to Cs alkylphenyl.

26. The process as claimed in claim 13 wherein in formula (I): A and B both represent -CHz- or CHy; K, D, Z and E each independently represent hydrogen, C,-Cs alkyl phenyl or C,-Cg alkyl or -J- 0? (CR* (RM) (R*S) ) CR*® (RY") (R*®) where J is the same as A; or two .of K, D, E and Z together with the carbon atoms of the aryl. ring to which they are attached form an unsubstituted phenyl ring; AMENDED SHEET

PCT/GB2004/002859 o 70 R to R'® each independently represent Ci to Cs alkyl;

27. The process as claimed in claim 26, wherein A and B both represent -CHa-.

28. The process as claimed in claim 13, wherein in formula (I): each R' to R'? is the same and represents methyl; A and B are the same and represent -CHa-; K, D, Z and E are the same and represent hydrogen.

29. The process as claimed in any of claims 13 to 28, wherein the reaction is carried out at a temperature of between 20°C and 180°C.

30. The process as claimed in claim 29, wherein the temperature is in the range 50°C to 150°C.

31. The process as claimed in any of claims 13 to 30, wherein the reaction is carried out under a partial pressure of carbon monoxide/hydrogen in the range of 1 to 700 bar.

32. The process as claimed in claim 31, wherein the partial pressure is in the range 1 to 300 bar.

33. The process .as claimed in. any of claims 13 to 32, wherein said ethylenically unsaturated compound has 1 to 3 carbon-carbon double bonds per molecule. AMENDED SHEET

PCT/GB2004/002859 @® 71

34. The process as claimed in claim 33, wherein said compound has 1 carbon-carbon double bond per molecule.

35. The process as claimed in any of claims 13 to 34, wherein the amount of bidentate compound of formula (I) to unsaturated compound is in the range 10"° to 102 moles per mole of unsaturated compound.

36. The process as claimed in any of claims 13 to 35, wherein said catalyst system further comprises a support.

37. The process as claimed in any of claims 13 to 36, wherein said bidentate phosphine is selected from the group comprising bis (di-t-butyl phosphino) -o-xylene; 1,2 bis (diadamantylphosphinomethyl) benzene; 1,2 bis (diadamantylphosphinomethyl) naphthalene; 1,2 bis (di-t-pentyl phosphino)-o-xylene; and bis 1,2 (di-t- butyl phosphino) naphthalene.

38. The process as claimed in any of claims 13 to 37, wherein the mol:mol range of compounds of formula (I) to Group VIII metal is in the range of 1:1 to 3:1.

39. The process as claimed in claim 38, wherein said mol:mol range is in the range of 1:1 to 1.25:1.

40. The process as claimed in any of claims 13 to 39, wherein the Group VIII metal is selected from the group: cobalt, nickel, palladium, rhodium, ruthenium and platinum. AMENDED SHEET

PCT/GB2004/002859 ® 72

41. The process as claimed in claim 40, wherein said Group VIII metal is rhodium.

42. The process as claimed in any of claims 13 to 41, wherein said chlorine moiety is present in at least said Group VIII metal compound and said compound is selected from the group comprising: [RhC1 (CO) ala, [RhC1 (Cod) 2] 2, RhCl,;.xH20, [RhC1 (Norbornadiene)]:, [RhC1 (Cyclooctene)z] a, Chloro(1l,5-hexadiene) - rhodium (I) dimer, p-dichlorotetraethylene- dirhodium, (bicyclo(2,2,1]lhepta-2-5-diene) chlororhodium(I)dimer.

43. The process as claimed in any of claims 13 to 42, wherein said chlorine moiety is present in at least said Group VIII metal compound and said compound is selected from the group comprising: [RhC1(CO):l2, [RhC1 (Cod) ;]2 and RhCl;.xH0.

44. The process as claimed in any of claims 13 to 43, wherein said chlorine moiety is present in at least said solvent and said solvent is selected from the group comprising dichloromethane, chlorobenzene, ©O- dichlorobenzene, m-chlorobenzene, carbon tetrachloride, trichloroethanes, dichloroethanes, chlorofluorocarbons (CFC’s), tetrachloroethanes and tetrachloroethene.

45. The process as claimed in claim 44, wherein said solvent is dichloromethane.

46. The process as claimed in any of claims 13 to 45, wherein said ethylenically unsaturated compound has 2 to 20 carbon atoms. AMENDED SHEET

PCT/GB2004/002859 @® 73

47. The process as claimed in claim 46, wherein said compound has 5 to 15 carbon atoms.

48. The process as claimed in claim 46, wherein said compound has 6 to 12 carbon atoms. 49, The process as claimed in any of claims 13 to 48, wherein said ethylenically unsaturated compound is selected from the group comprising ethene, propene, 1-butene, 2-butene, isobutene, l-pentene, 2-pentene, 3-pentene and branched isomers thereof, 1l-hexene and its isomers, l-heptene and its isomers, 1-octene. and its isomers, 1-nonene and its isomers, 1-decene and its isomers, the C;1-Cz alkenes and their known isomers, 3-pentenenitrile, methyl-3-penteneoate, 1,3 butadiene, 1, 3-pentadiene, 1,3 hexadiene, 1,3 cyclohexadiene, 2,4-leptadiene, and 2-methyl 1,3 butadiene.

50. The process as claimed in any of claims 13 to 49, wherein the said catalyst system further comprises a polymeric dispersant dissolved in a liquid carrier, said polymeric dispersant being capable of stabilising a colloidal suspension of particles of the Group VIII metal or metal compound of the catalyst system within the said liquid carrier.

5]. The process as claimed in claim 50, wherein said polymeric dispersant is selected from the list comprising: polyvinylpyrrolidone, polyacrylamide, polyacrylonitrile, polyethylenimine, polyglycine, polyacrylic acid, polymethacrylic acid, poly (3- AMENDED SHEET

PCT/GB2004/002859 hydroxybutyricacid), poly-L-leucine, poly-L- methionine, poly-L-proline, poly-L-serine, poly-L- tyrosine, poly (vinylbenzenesulphonic acid) and poly (vinylsulphonic acid).

52. The process as claimed in claim 51, wherein said polymeric dispersant is selected from the list comprising: polyvinylpyrrolidone and polyacrylic acid.

53. The process as claimed in any of claims 13 to 52, wherein the solvent is formed by one or more of the reactants, products or by-products of the process rather than being a separate entity.

54. A process as claimed in any of claims 13 to 53, wherein Ar is defined as including six-to-ten-membered carbocyclic aromatic groups, such as phenyl and naphthyl, which groups are optionally substituted with, in addition to K, D, E or Z, one or more substituents selected from aryl, lower alkyl, Het, halo, cyano, nitro, OR'?, OC(O)R*®, C(O)R**, C(0)OR™, NRZR?, C(O)NR*R?*, SR?*’, C(0)SR*’ or C(S)NR®R?*® wherein RY to R?? each independently represent hydrogen, aryl or lower alkyl.

55. A process as claimed in any preceding claim wherein at least one (CR*RYR?) group attached to 0! and/or Q?,

i.e. CR*R?R®, CR'R°R®, CR'R°R®, or CRRYR'?, may instead be congressyl or adamantyl, or both groups defined above as (CR*RYR*) attached to either or both ot and/or QF, may, together with either Q' or O° as appropriate, instead form an optionally substituted AMENDED SHEET

PCT/GB2004/002859 o 75 2-phospha-tricycle[3.3.1.1{3,7}]decyl group or derivative thereof.

56. A process as claimed in any of claims 13 to 53 and 55, wherein Ar is a cyclopentadienyl group, and Z may be represented by -M(In)a(l;)gs and Z is connected via a metal ligand bond to the cyclopentadienyl group, M represents a Group VIB or VIIIB metal or metal cation thereof; and L, represents a cyclopentadienyl, indenyl or aryl group each of which groups are optionally substituted by one or more substituents selected from hydrogen, lower alkyl, halo, cyano, nitro, OR, 0C(0)R?®, C(O)R**, C(0)OR*, NR**R*, C(0)NR**R?*®, C(S)R™R%*, SRY, C (0) SR?’ or ferrocenyl; L, represents one or more ligands each of which are independently selected from hydrogen, lower alkyl, alkylaryl, halo, CO, PR*R*R*S or NR*®R*'R*}; R*® to R*® each independently represent hydrogen, lower alkyl, aryl or Het; n=0o0r1; and m = 0 to 5; provided that when n = 1 then m equals 0, and when n equals 0 chen m does not equal 0. AMENDED SHEET

PCT/GB2004/002859 ® i:

57. A process as claimed in any of claims 1 to 12, wherein R represents an alkylene bridging group.

58. A process as claimed in claim 57 wherein R represents a lower alkylene.

59. A process for the hydroformylation of ethylenically unsaturated compounds as described hereinbefore with reference to the examples herein.

60. The use of a catalyst system as defined in any preceding claim for the hydroformylation of ethylenically unsaturated compounds, sald use comprising the step of reacting said ethylenically unsaturated compound with carbon monoxide and hydrogen, in the presence of said catalyst system.

61. The use of a reaction medium which comprises a solvent and a catalyst system as defined in any preceding claim for the hydroformylation of ethylenically unsaturated compounds, said use comprising the step of reacting said ethylenically unsaturated compound with carbon monoxide and hydrogen, in the presence of said reaction medium.

62. A process as claimed in any one of claims 1 to 59, substantially as herein described with reference to and as illustrated in any of the examples.

63. Use as claimed in claim 60 or claim 61, substantially as herein described with reference to and 2s illustrated in any of the examples. AMENDED SHEET