CN1816513B - Process for the hydroformylation of ethylenically unsaturated compounds - Google Patents

Process for the hydroformylation of ethylenically unsaturated compounds Download PDF

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CN1816513B
CN1816513B CN200480018581.6A CN200480018581A CN1816513B CN 1816513 B CN1816513 B CN 1816513B CN 200480018581 A CN200480018581 A CN 200480018581A CN 1816513 B CN1816513 B CN 1816513B
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group
desired method
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alkyl
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CN1816513A (en
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G·埃斯特姆
D·科尔-哈密尔顿
C·吉米内茨
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Mitsubishi Chemical UK Ltd
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Lucite International UK Ltd
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Abstract

The present invention provides a process for the hydroformylation of ethylenically unsaturated compounds, which process comprises reacting said ethylenically unsaturated compound with carbon monoxideand 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, the processcharacterised in that a chlorine moiety is present in at least one of the said Group VIII metal compound or said solvent.

Description

The hydroformylation process of alefinically unsaturated compounds
The present invention relates in the presence of catalyst system alefinically unsaturated compounds by with the hydroformylation of carbon monoxide and hydrogen reaction.
In the presence of hydrogen and catalyzer, use the carbonylation and the hydroformylation of the alefinically unsaturated compounds of carbon monoxide to have been described in many patents and the patent application; above-mentioned catalyzer comprises the group VIII metal; as rhodium; with the phosphine part, as alkylphosphines, cycloalkyl phosphine, aryl phosphine, pyridyl phosphine or bidentate phosphine.
WO96/19434 discloses that the specific bidentate phosphine compound of a class can provide stable catalyst in carbonylation reaction system, and uses described catalyzer to produce the higher speed of reaction of the previous disclosed speed of reaction of obvious ratio.
WO01/68583 discloses the carbonylation method of the higher alkene of three or more carbon atoms.
For example, WO02/76996 discloses a kind of method of diphosphine and purposes that conduct makes the promotor of olefin hydroformylation thereof of producing.WO02/20448 discloses the preparation of the rhodium shortening formylation of alkene with aryl phosphine similarly.
Although researched and developed in hydroformylation process, show reasonable stability and produce higher speed of reaction and the aldehyde product of linear and branching between the catalyst system of higher regioselectivity, but still existence is for the needs of selectable and/or improved catalyst system.Suitably, the purpose of this invention is to provide a kind of selectable and/or improved catalyzer that is used to make the alefinically unsaturated compounds hydroformylation.In addition, the purpose of this invention is to provide the solvent that improves the catalyst system performance.
Surprisingly, found to obtain to use the improved linear aldehyde product of comparative catalyst's system of prior art than branching aldehyde product selectivity than passing through.
According to the present invention, provide a kind of hydroformylation process of alefinically unsaturated compounds, described in additional claims.According to additional claims and specification sheets, preferred feature of the present invention will become apparent.And according to the present invention; the purposes of medium, the catalyst system of the catalyst system of a kind of catalyst system, a kind of hydrogenation formyl reaction, a kind of reaction medium, a kind of hydrogenation formyl reaction, the purposes and the method for preparing catalyst system and reaction medium of reaction medium are provided, as hereinafter with described in additional claims.
According to a first aspect of the invention; a kind of hydroformylation process of alefinically unsaturated compounds is provided; this method is included in catalyst system and solvent and makes described alefinically unsaturated compounds and carbon monoxide and hydrogen reaction under existing, and described catalyst system can be by making following component in conjunction with acquisition:
A) group VIII metal or its compound; With
B) bidentate phosphine of general formula (Ia)
Figure G2004800185816D00021
Wherein R is the covalency bridged group;
R 1-R 12Represent hydrogen, low alkyl group, aryl or Het independently of one another, preferred low alkyl group, aryl or Het;
Q 1And Q 2Represent phosphorus (phosphorus), arsenic or antimony independently of one another, and correspondingly revise with reference to above phosphine or phosphorus under two kinds of situations in the back,
The method is characterized in that, have the chlorine structure division in one of at least at described group VIII metallic compound or described solvent.
Hereinafter, aforesaid method is called " method of the present invention ".Method of the present invention comprises embodiment hereinafter described.
In one group of embodiment, the radicals R in the formula (Ia) can be represented alkylidene group bridging group, preferred low-grade alkylidene.
In another group and embodiment preferred, bridged group R may be defined as-A-(K, D) Ar (E Z)-B-, makes general formula (Ia) become general formula (I):
Wherein:
Figure G2004800185816D00031
Ar is the bridged group that comprises the optional aryl structure division that replaces, and phosphorus atom is being connected on the available adjacent carbons on the above-mentioned aryl structure division;
A and B represent low-grade alkylidene independently of one another;
K, D, E and Z are the substituting group of aryl structure division (Ar) and represent hydrogen, low alkyl group, aryl, Het, halogen, cyano group, nitro, OR independently of one another 19, OC (O) R 20, C (O) R 21, C (O) OR 22, NR 23R 24, C (O) NR 25R 26, C (S) R 25R 26, SR 27, C (O) SR 27Or-J-Q 3(CR 13(R 14) (R 15)) CR 16(R 17) (R 18), wherein J represents low-grade alkylidene; Or two adjacent groups that are selected from K, Z, D and E form another phenyl ring with the carbon atom that they are connected the aromatic ring on it, and described phenyl ring is randomly by one or more hydrogen, low alkyl group, halogen, cyano group, nitro, OR of being selected from 19, OC (O) R 20, C (O) R 21, C (O) OR 22, NR 23R 24, C (O) NR 25R 26, C (S) R 25R 26, SR 27Or C (O) SR 27Substituting group replace;
R 1-R 18Represent hydrogen, low alkyl group, aryl or Het independently of one another, preferred low alkyl group, aryl or Het;
R 19-R 27Represent hydrogen, low alkyl group, aryl or Het independently of one another;
Q 1, Q 2And Q 3(when existing) represents inferior phosphorus (phosphorous), arsenic or antimony independently of one another, and correspondingly revises with reference to above phosphine or inferior phosphorus under two kinds of situations in the back.
Preferably, represent-J-Q as K, D, E or Z 3(CR 13(R 14) (R 15)) CR 16(R 17) (R 18) time, corresponding K, D, E or Z are on aryl carbon, and described aryl carbon is adjacent with the aryl carbon that is connected A or B, perhaps if not so adjacent, then with self expression-J-Q 3(CR 13(R 14) (R 15)) CR 16(R 17) (R 18) remaining K, D, E or Z group adjacent.
Preferably, R 1-R 18Represent low alkyl group or aryl independently of one another.More preferably, R 1-R 18Represent C independently of one another 1-C 6Alkyl, C 1-C 6Alkyl phenyl (wherein phenyl is optional replaces as defined herein) or phenyl (wherein phenyl is optional replaces as defined herein).Even more preferably, R 1-R 18Represent C independently of one another 1-C 6Alkyl, it is chosen wantonly and replaces as defined herein.Most preferably, R 1-R 18Represent unsubstituted C independently of one another 1-C 6Alkyl is as methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, amyl group, hexyl and cyclohexyl.
Alternatively or additionally, R 1-R 3, R 4-R 6, R 7-R 9, R 10-R 12, R 13-R 15Or R 16-R 18Each group can form ring texture independently together, as 1-norcamphyl (norbornyl) or 1-norbornadiene base.Another example of compound group is included in R 1-R 6, R 7-R 12And R 13-R 18Between the ring texture that forms.Alternatively, one or more above-mentioned groups can be represented the solid phase (solid phase) that part is connected thereto.
In addition, be connected to Q 1And/or Q 2On at least one (CR xR yR z) group, that is, and CR 1R 2R 3, CR 4R 5R 6, CR 7R 8R 9Or CR 10R 11R 12, replaceable is five rings adamantyl (congressyl) or adamantyl, or is connected to Q 1And/or Q 2Any or as above be defined as (CR on both xR yR z) two groups can with any Q that is fit to 1Or Q 2Alternatively form optional 2-phospha-three ring [3.3.1.1{3,7}] decyl or derivatives thereof that replaces together.But, in above-mentioned one group of specific embodiment, that is, when bridged group be defined as-A-(K, D) Ar (E, Z)-time, if any (CR xR yR z) group defines by this section, then they are preferably five rings adamantyl or adamantyl, and more preferably unsubstituted adamantyl or five rings adamantyl most preferably are unsubstituted adamantyl.
In a particularly preferred embodiment according to the invention, R 1, R 4, R 7, R 10, R 13And R 16Represent identical low alkyl group, aryl or Het structure division as herein defined separately, R 2, R 5, R 8, R 11, R 14And R 17Represent identical low alkyl group, aryl or Het structure division as herein defined separately, and R 3, R 6, R 9, R 12, R 15And R 18Represent identical low alkyl group, aryl or Het structure division as herein defined independently of one another.More preferably R 1, R 4, R 7, R 10, R 11And R 16Represent identical C independently of one another 1-C 6Alkyl, particularly unsubstituted C 1-C 6Alkyl is as methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, amyl group, hexyl or cyclohexyl; R 2, R 5, R 8, R 11, R 14And R 17Represent identical C as defined above independently of one another 1-C 6Alkyl; And R 3, R 6, R 9, R 12, R 15And R 18Represent identical C as defined above independently of one another 1-C 6Alkyl.For example, R 1, R 4, R 7, R 10, R 13And R 16Represent methyl separately; R 2, R 5, R 8, R 11, R 14And R 17Represent ethyl separately; And R 3, R 6, R 9, R 12, R 15And R 18Represent normal-butyl or n-pentyl separately.
In a particularly preferred embodiment according to the invention, R 1-R 18Group is represented identical low alkyl group, aryl or Het structure division as herein defined separately.Preferably, R 1-R 18Represent identical C separately 1-C 6Alkyl, particularly unsubstituted C 1-C 6Alkyl is as methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, amyl group, hexyl and cyclohexyl.Most preferably, each R 1-R 18The expression methyl.
In the compound of formula (I), preferred each Q 1, Q 2And Q 3(when existing) is identical.In addition, in the compound of formula (Ia), preferred Q 1And Q 2Identical.Most preferably, each Q 1, Q 2And Q 3(when existing) represents inferior phosphorus.
Preferably, in the compound of formula (I), A, B and J (when existing) represent C independently of one another 1-C 6Alkylidene group, it is chosen wantonly and for example adopts low alkyl group to replace as defined herein.In addition, in the compound of formula (Ia), R (when alkylidene group) represents C 1-C 6Alkylidene group, it is chosen wantonly and for example adopts low alkyl group to replace as defined herein.Preferably, the low-grade alkylidene of A, B and J (when existing) expression is not substituted.The particularly preferred low-grade alkylidene that A, B and J can represent independently is-CH 2-or-C 2H 4-.Most preferably, the identical low-grade alkylidene as herein defined of each expression of A, B and J (when existing), particularly-CH 2-.The particularly preferred low-grade alkylidene that R represents is replacement or unsubstituted, and can be selected from ethylidene (C 2H 4-) and replace variant, propylidene (C 3H 6-) and replace variant and butylidene (C 4H 8-) and replace variant, and wherein said replacement can be on any, some or all carbon atom of low-grade alkylidene, and described replacement can be adopted low alkyl group.More preferably, the low-grade alkylidene that R represents most preferably replaces or unsubstituted propylidene for replacing or unsubstituted ethylidene or propylidene.
Preferably, in the compound of formula (I), when K, D, E or Z do not represent-J-Q 3(CR 13(R 14) (R 15)) CR 16(R 17) (R 18) time, K, D, E or Z represent hydrogen, low alkyl group, phenyl or low alkyl group phenyl.More preferably, K, D, E or Z represent hydrogen, phenyl, C 1-C 6Alkyl phenyl or C 1-C 6Alkyl is as methyl, ethyl, propyl group, butyl, amyl group and hexyl.Most preferably, K, D, E or Z represent hydrogen.
Preferably, in the compound of formula (I), when the carbon atom that is connected the aromatic ring on it with them as K, D, E and Z did not form phenyl ring, K, D, E and Z represented hydrogen, low alkyl group, phenyl or low alkyl group phenyl independently of one another.More preferably, K, D, E and Z represent hydrogen, phenyl, C independently of one another 1-C 6Alkyl phenyl or C 1-C 6Alkyl is as methyl, ethyl, propyl group, butyl, amyl group and hexyl.Even more preferably, K, D, E and Z represent identical substituting group.Most preferably, their expression hydrogen.
Preferably, in the compound of formula (I), when K, D, E or Z do not represent-J-Q 3(CR 13(R 14) (R 15)) CR 16(R 17) (R 18) and K, D, E and the Z carbon atom that is connected the aromatic ring on it with them when not forming phenyl ring, each expression among K, D, E and the Z is identical is selected from hydrogen, low alkyl group, aryl or the group of Het as herein defined; Particularly be selected from hydrogen or C 1-C 6Alkyl (more especially unsubstituted C 1-C 6Alkyl), hydrogen especially.
Preferably, in the compound of formula (I), when two among K, D, E and the Z carbon atoms that are connected the aromatic ring on it with them formed phenyl ring, then phenyl ring was randomly by one or more aryl, low alkyl group (described alkyl itself can be chosen wantonly as being substituted or end-blocking with giving a definition), Het, halogen, cyano group, nitro, OR of being selected from 19, OC (O) R 20, C (O) R 21, C (O) OR 22, NR 23R 24, C (O) NR 25R 26, SR 27, C (O) SR 27Or C (S) NR 25R 26Substituting group replace R wherein 19-R 27Represent hydrogen or low alkyl group (described alkyl itself can be chosen wantonly and be substituted as defined herein or end-blocking) independently of one another.More preferably, phenyl ring is not replaced by any substituting group, that is, it only has hydrogen atom.
Preferred compound in this group embodiment Chinese style (I) comprises those compounds, wherein:
A and B represent unsubstituted C independently of one another 1-C 6Alkylidene group;
K, D, E and Z represent hydrogen, C independently of one another 1-C 6Alkyl, phenyl, C 1-C 6Alkyl phenyl or-J-Q 3(CR 13(R 14) (R 15)) CR 16(R 17) (R 18), wherein J represents unsubstituted C 1-C 6Alkylidene group; Or among K, D, Z and the E two carbon atoms that are connected the aromatic ring on it with them form phenyl ring, and described phenyl ring is optional to be replaced by one or more substituting groups that are selected from low alkyl group, phenyl or low alkyl group phenyl;
R 1-R 18Represent C independently of one another 1-C 6Alkyl, phenyl or C 1-C 6Alkyl phenyl.
Comprise those compounds at the further preferred compound of this group embodiment Chinese style (I), wherein:
A and B all represent-CH 2-or C 2H 4, CH particularly 2
K, D, Z and E represent hydrogen, C independently of one another 1-C 6Alkyl phenyl or C 1-C 6Alkyl or-J-Q 3(CR 13(R 14) (R 15)) CR 16(R 17) (R 18), wherein J is identical with A; Or among K, D, E and the Z two carbon atoms that are connected the aromatic ring on it with them form unsubstituted phenyl ring;
R 1-R 18Represent C independently of one another 1-C 6Alkyl.
Comprise those compounds at the further preferred compound of this group embodiment Chinese style (I), wherein:
R 1-R 18Identical and represent C separately 1-C 6Alkyl, particularly methyl.
Comprise those compounds at the still further preferred compound of this group embodiment Chinese style (I), wherein:
K, D, Z and E are selected from hydrogen or C independently of one another 1-C 6Among alkyl, particularly K, D, Z and the E each is represented each the expression hydrogen among identical group, especially K, D, Z and the E; Or
K represents-CH 2-Q 3(CR 13(R 14) (R 15)) CR 16(R 17) (R 18), and D, Z and E are selected from hydrogen or C independently of one another 1-C 6Identical group, especially D, Z and the E of the two expression of alkyl, particularly D and E represents hydrogen.
Comprise those compounds in the particularly preferred particular compound of this group embodiment Chinese style (I), wherein:
R 1-R 22Identical separately and the expression methyl;
A and expression-CH identical with B 2-;
Identical and the expression hydrogen of K, D, Z and E.
In the embodiment of this particular group, Ar may be defined as " Ar " and " aryl " hereinafter, but preferred Ar is defined as and comprises six to ten yuan carbocyclic aromatic group, as phenyl and naphthyl, described group is one or more aryl, low alkyl group (described alkyl itself can be chosen wantonly as being substituted or end-blocking with giving a definition), Het, halogen, cyano group, nitro, the OR of being selected from of also optional employing except K, D, E or Z 19, OC (O) R 20, C (O) R 21, C (O) OR 22, NR 23R 24, C (O) NR 25R 26, SR 27, C (O) SR 27Or C (S) NR 25R 26Substituting group replace R wherein 19-R 27Represent independently of one another hydrogen, aryl or low alkyl group (described alkyl itself can choose wantonly such as hereinafter definition be substituted or end-blocking).
In another group embodiment, in formula (I) or compound (Ia), be connected to Q 1And/or Q 2On at least one (CR xR yR z) group, that is, and CR 1R 2R 3, CR 4R 5R 6, CR 7R 8R 9Or CR 10R 11R 12, replaceable is five rings adamantyl or adamantyl, or is connected to Q 1And/or Q 2Any or as above be defined as (CR on both xR yR z) two groups can with the Q that is fit to 1Or Q 2Alternatively form optional 2-phospha-three ring [3.3.1.1{3,7}] decyl or derivatives thereof, preferably at least one (CR that replaces together xR yR z) group is five rings adamantyl or adamantyl.
Except hydrogen atom, adamantyl randomly can comprise one or more be selected from low alkyl group ,-OR 19,-OC (O) R 20, halogen, nitro ,-C (O) R 21,-C (O) OR 22, cyano group, aryl ,-N (R 23) R 24,-C (O) N (R 25) R 26,-C (S) (R 27) R 28,-CF 3,-P (R 56) R 57,-PO (R 58) (R 59) ,-PO 3H 2,-PO (OR 60) (OR 61) or-SO 3R 62Substituting group, R wherein 19, R 20, R 21, R 23, R 24, R 25, R 26, R 27, R 28, R 28(R as mentioned 19-R 27Equally define), low alkyl group, cyano group and aryl as defined herein, and R 56-R 62Represent hydrogen, low alkyl group, aryl or Het independently of one another.But in one embodiment, adamantyl is not substituted.
Suitably, when adamantyl was replaced by one or more substituting groups as defined above, substituting group very preferably comprised unsubstituted C 1-C 8Alkyl ,-OR 19,-OC (O) R 20, phenyl ,-C (O) OR 22, fluorine ,-SO 3H ,-N (R 23) R 24,-P (R 56) R 57,-C (O) N (R 25) R 26With-PO (R 58) (R 59) ,-CF 3, R wherein 19Expression hydrogen, unsubstituted C 1-C 8Alkyl or phenyl, R 20, R 22, R 23, R 24, R 26, R 26Represent hydrogen or unsubstituted C independently of one another 1-C 8Alkyl, R 56-R 59Represent unsubstituted C independently of one another 1-C 8Alkyl or phenyl.
Suitably, except hydrogen atom, adamantyl can comprise 10 of as many as substituting group as defined above, and 5 of preferred as many as are substituting group as defined above, more preferably 3 of as many as substituting group as defined above.Suitably, except hydrogen atom, when adamantyl comprised one or more substituting group as herein defined, preferably each substituting group was identical.Preferred substituted is unsubstituted C 1-C 8Alkyl and trifluoromethyl, particularly unsubstituted C 1-C 8Alkyl is as methyl.Adamantyl very preferably only comprises hydrogen atom, and promptly adamantyl is not substituted.
Preferably, when existing more than one adamantyl in formula (Ia) or compound (I), each adamantyl is identical.
Except hydrogen atom, 2-phospha-three ring [3.3.1.1{3,7}] decyl (this paper is called 2-phospha-adamantyl) randomly can comprise one or more substituting groups.The substituting group that is fit to comprises that this paper is about defined those substituting groups of adamantyl.Substituting group very preferably comprises low alkyl group (particularly unsubstituted C 1-C 8Alkyl, especially methyl), trifluoromethyl ,-OR 19(R wherein 19As defined herein, particularly unsubstituted C 1-C 8Alkyl or aryl) and the 4-dodecylphenyl.When 2-phospha-adamantyl comprised more than a substituting group, preferably each substituting group was identical.
Preferably, 2-phospha-adamantyl is replaced by substituting group defined herein on one or more positions of 1,3,5 or 7.More preferably, 2-phospha-adamantyl is substituted on each position of 1,3 and 5.Suitably, the meaning of above-mentioned arrangement is that the inferior phosphorus atom of 2-phospha-adamantyl is keyed on the carbon atom that does not have hydrogen atom in the adamantyl skeleton.Most preferably, 2-phospha-adamantyl is substituted on each position of 1,3,5 and 7.When 2-phospha-adamantyl comprised more than 1 substituting group, preferably each substituting group was identical.Particularly preferred substituting group is unsubstituted C 1-C 8Alkyl and trifluoromethyl, particularly unsubstituted C 1-C 8Alkyl is as methyl.
Preferably, 2-phospha-adamantyl is represented unsubstituted 2-phospha-adamantyl or by one or more unsubstituted C 1-C 82-phospha-adamantyl or its combination that alkyl substituent replaces.
Preferably, except the inferior phosphorus atom of 2-, 2-phospha-adamantyl also comprises other heteroatoms in 2-phospha-adamantyl skeleton.The other heteroatoms that is fit to comprises oxygen and sulphur atom, particularly Sauerstoffatom.More preferably, 2-phospha-adamantyl comprises one or more other heteroatomss at 6,9 and 10.Even more preferably, 2-phospha-adamantyl comprises other heteroatoms each position of 6,9 and 10.Most preferably, when 2-phospha-adamantyl comprised two or more other heteroatoms in 2-phospha-adamantyl skeleton, each other heteroatoms was identical.Particularly preferred 2-phospha-adamantyl comprises Sauerstoffatom in each position of 6,9 and 10 of 2-phospha-adamantyl skeleton, and described 2-phospha-adamantyl can randomly be replaced by one or more substituting groups as herein defined.
Preferably, 2-phospha-adamantyl comprises one or more Sauerstoffatoms in 2-phospha-adamantyl skeleton.
2-phospha-adamantyl very preferably comprises 2-phospha-1,3,5 as herein defined, 7-tetramethyl--6,9,10-trioxa adamantyl, 2-phospha-1,3,5-trimethylammonium-6,9,10-trioxa adamantyl, 2-phospha-1,3,5,7-four (trifluoromethyl)-6,9,10-trioxa adamantyl and 2-phospha-1,3,5-three (trifluoromethyl)-6,9,10-trioxa adamantyl.Most preferably, 2-phospha-adamantyl is selected from 2-phospha-1,3,5,7-tetramethyl--6,9,10-trioxa adamantyl or 2-phospha-1,3,5 ,-trimethylammonium-6,9,10-trioxa adamantyl.
Preferably, when having 2-phospha more than one-adamantyl in formula (I) or compound (Ia), each 2-phospha-adamantyl is identical.
2-phospha-adamantyl can be by well known to a person skilled in the art the method preparation.Suitably, some 2-phospha-adamantyl compound can be available from 901Garner Road, NiagaraFalls, Ontario, the Cytec Canada Inc of Canada L2E 6T4.2-phospha-adamantyl the compound etc. of formula (I) can prepare by similar approach equally, accordingly.
In addition, CR 13(R 14) (R 15) and CR 16(R 17) (R 18) at least one, replaceable for five rings adamantyl or adamantyl (can choose wantonly as mentioned above and replace) when existing, or be connected to Q 3On be defined as CR 13(R 14) (R 15) and CR 16(R 17) (R 18) two groups can with Q 3Alternatively form optional 2-phospha-three ring that replaces [3.3.1.1{3,7)] decyl or derivatives thereof together, preferred CR 13(R 14) (R 15) and CR 16(R 17) (R 18) at least one, when existing, be five rings adamantyl or adamantyl.
Preferably, in the compound of formula (I), when K represents-J-Q 3(CR 13(R 14) (R 15)) CR 16(R 17) (R 18) and E represent-J-Q 3(CR 13(R 14) (R 15)) CR 16(R 17) (R 18) time, then D represents-J-Q 3(CR 13(R 14) (R 15)) CR 16(R 17) (R 18).
Term 2-phospha-three ring [3.3.1.1{3,7}] decyl is represented by being connected to Q 1On two groups be connected Q on it with them 1Together in conjunction with the 2-phospha-adamantyl that forms, by being connected to Q 2On two groups be connected Q on it with them 2Together in conjunction with the 2-phospha-adamantyl that forms, by being connected to Q 3On two groups be connected Q on it with them 3Together in conjunction with the 2-phospha-adamantyl that forms, wherein Q 1, Q 2Or Q 3At adamantyl (wherein, Q 1, Q 2Or Q 3An integral part of formation adamantyl) on the 2-position, and Q 1, Q 2And Q 3Each the expression phosphorus.
In this group embodiment and wherein exist the preferred compound of at least one 2-phospha-adamantyl to comprise compound with following feature:
Group CR 1(R 2) (R 3) and CR 4(R 5) (R 6) be connected to Q 1On, and be connected to Q 2On group and Q 2Form 2-phospha-adamantyl together;
Group CR 1(R 2) (R 3) and adamantyl be connected to Q 1On, and be connected to Q 2On group and Q 2Form 2-phospha-adamantyl together;
Group CR 1(R 2) (R 3) and congressyl be connected to Q 1On, and be connected to Q 2On group and Q 2Form 2-phospha-adamantyl together;
Two adamantyls are connected to Q 1On, and be connected to Q 2On group and Q 2Form 2-phospha-adamantyl together;
Two congressyl groups are connected to Q 1On, and be connected to Q 2On group and Q 2Form 2-phospha-adamantyl together;
Be connected to Q 1On group and Q 1Form 2-phospha-adamantyl together, and be connected to Q 2On two groups and Q 2Form 2-phospha-adamantyl together;
Certainly, in above-mentioned preferred compound, Q 1And Q 2And it is interchangeable together with the group that is connected thereto.Therefore, first for example listed preferred compound can be preferably equally:
Group CR 7(R 8) (R 9) and CR 10(R 11) (R 12) be connected to Q 2On, and be connected to Q 1On group and Q 1Form 2-phospha-adamantyl together.
Compound very preferably comprises the compound with following feature in this embodiment:
Be connected to Q 1On group and Q 1Form 2-phospha-adamantyl together, and be connected to Q 2On two groups and Q 2Form 2-phospha-adamantyl together.
Preferably, be connected to Q 1On group identical.
Preferably, be connected to Q 1On group identical, be connected to Q 2On group identical, and be connected to Q 3On group identical, more preferably all above-mentioned groups identical or its form identical group with Q that they connect on it.
Particularly preferred in the present invention combination comprises the combination of the formula (I) with following feature:
(1) (CR 7R 8R 9) and (CR 10R 11R 12) be connected the Q on it with them 2Represent 2-phospha-adamantyl together;
(CR 4R 5R 6) and (CR 1R 2R 3) be connected the Q on it with them 1Represent 2-phospha-adamantyl together;
A and expression-CH identical with B 2-;
K, D and expression hydrogen or unsubstituted C identical with E 1-C 6Alkyl, particularly hydrogen;
Q 1And Q 2All represent phosphorus.
(2) (CR 7R 8R 9) and (CR 10R 11R 12) be connected the Q on it with them 2Represent 2-phospha-adamantyl together;
(CR 4R 5R 6) and (CR 1R 2R 3) be connected the Q on it with them 1Represent 2-phospha-adamantyl together;
K represents-CH 2-Q 3(X 5) X 6, X wherein 5And X 6Be connected the Q on it with them 3Represent 2-phospha-adamantyl together;
A and expression-CH identical with B 2-;
Q 1, Q 2And Q 3Represent phosphorus separately;
D and expression hydrogen or unsubstituted C identical with E 1-C 6Alkyl, particularly hydrogen.
(3) (CR 7R 8R 9) and (CR 10R 11R 12) be connected the Q on it with them 2Represent 2-phospha-adamantyl together;
(CR 4R 5R 6) and (CR 1R 2R 3) be connected the Q on it with them 1Represent 2-phospha-adamantyl together;
K represents-CH 2-Q 3(X 5) X 6, X wherein 5And X 6Be connected the Q on it with them 3Represent 2-phospha-adamantyl together;
A and expression-CH identical with B 2-;
Q 1, Q 2And Q 3Represent phosphorus separately.
In another group embodiment, in formula (I), Ar is a cyclopentadienyl, and Z can be by-M (L 1) n(L 2) mExpression and Z are connected on the cyclopentadienyl through the metal-complexing key, and M represents VIB or VIIIB family metal or its metallic cation; With
L 1Representative ring pentadienyl, indenyl or aryl, each of above-mentioned group can be randomly by one or more hydrogen, low alkyl group, halogen, cyano group, nitro, OR of being selected from 19, OC (O) R 20, C (O) R 21, C (O) OR 22, NR 23R 24, C (O) NR 25R 26, C (S) R 25R 26, SR 27, C (O) SR 27Or the substituting group of ferrocenyl replaces;
L 2Represent one or more parts, each of described part is independently selected from hydrogen, low alkyl group, alkaryl, halogen, CO, PR 43R 44R 45Or NR 46R 47R 48
R 43-R 48Represent hydrogen, low alkyl group, aryl or Het independently of one another;
N=0 or 1;
And m=0-5;
Condition is when n=1, and m equals 0 and when n equals 0, and m is not equal to 0.
Preferably, A, B, Q 1, Q 2, K, D, E and R 1-R 27Define and describe as mentioned, comprise its preferred embodiment.
In the compound of formula (I), term " M represents VIB or VIIIB family metal " expression comprises the metal such as Cr, Mo, W, Fe, Co, Ni, Ru, Rh, Os, Ir, Pt and Pd.Preferably, metal is selected from Cr, Mo, W, Fe, Co, Ni, Ru and Rh.For avoiding query, VIB or VIIIB metal should be referring to the 6th, 8,9 and 10 families that comprise in the modern periodictable nomenclature herein.
Term " its metallic cation " meaning is that VIB or VIIIB family metal (M) in formula (I) compound has positive charge as herein defined.Suitably, the form that metallic cation can be salt maybe can comprise weakly coordinating anion, and described weakly coordinating anion is derived from halogen; Nitric acid; Sulfuric acid; Lower alkane (as many as C 12) sour as acetate and propionic acid; Sulfonic acid such as methylsulfonic acid, chlorsulfonic acid, fluosulfonic acid, trifluoromethanesulfonic acid, Phenylsulfonic acid, naphthene sulfonic acid, toluenesulphonic acids (as, tosic acid), tertiary butyl sulfonic acid and 2-hydroxy-propanesulfonic acid; Sulfonated ion exchange resin; High hydracid is as perchloric acid; Perfluorinated carboxylic acid is as trichoroacetic acid(TCA) and trifluoroacetic acid; Ortho-phosphoric acid; Phosphonic acids such as phosphenylic acid; And the acid that obtains by the interaction between Lewis acid and the Bronsted acid.Can provide suitable anionic other source to comprise the tetraphenyl borate salts derivative.
Preferred M represents VIB or VIIIB family metal.In other words, total electronic number of metal M is 18.
Halogen group comprises fluorine, chlorine, bromine and iodine, L 2Can represent that halogen and above-mentioned group can adopt halogen to replace or end-blocking.
Suitably, if A representative ring pentadienyl and n=1, then the compound of formula (I) can contain or two cyclopentadienyl rings, two indenyl rings or an indenyl and a cyclopentadienyl rings (each of described member ring systems can be chosen wantonly as described herein and be substituted).Above-claimed cpd can be called " sandwich compound ", and wherein metal M or its metallic cation are sandwiched between two member ring systems.Each cyclopentadienyl and/or indenyl rings system be copline or they can incline towards each other (so-called bending metals is luxuriant) basically each other.
Alternatively, when n=1, compound of the present invention can contain a cyclopentadienyl or an indenyl rings (each of described member ring systems can be chosen wantonly as described herein and be substituted) and an aromatic ring (that is L, 1The expression aryl), described aromatic ring can be chosen wantonly as defined herein and be substituted.Suitably, as n=1 and L 1Expression is during aryl, and then the metal M of formula (I) compound is the form of metallic cation usually as herein defined.
Suitably, when n=0, compound of the present invention only contains a cyclopentadienyl or indenyl rings (each of described member ring systems can be chosen wantonly as described herein and be substituted).Above-claimed cpd can be called " half sandwich compound ".Preferably, when n=0, m represents 1-5 so that the metal M of formula (I) compound has 18 electronic numbers.In other words, when the metal M of formula (I) compound is iron, by ligand L 2The electronics sum of being contributed is generally 5.
Suitably, the metal M in the cyclopentadienyl compounds of formula (I) or its metallic cation are keyed on the cyclopentadienyl structure division of cyclopentadienyl rings (one or more) or indenyl rings (one or more) usually.Usually, the cyclopentadienyl structure division of cyclopentadienyl rings or indenyl rings shows the pentahapto keyed jointing mode with metal; But,, close coordination as three and be also included within the scope of the present invention in the cyclopentadienyl structure division of cyclopentadienyl rings or indenyl rings and other keyed jointing mode between the metal.
Preferably, be that M represents Cr, Mo, Fe, Co or Ru or its metallic cation in formula (I) compound of cyclopentadienyl at Ar.Even more preferably, M represents Cr, Fe, Co or Ru or its metallic cation.Most preferably, M is selected from VIIIB family metal or its metallic cation.Particularly preferred VIIIB family's metal (M) is Fe.Although metal M can be cationic form as herein defined, preferably it since with L defined herein 1And/or L 2Coordination and do not have residual charge basically.
Preferably, when n=1 in the compound of formula (I), L 1Representative ring pentadienyl, indenyl or aryl, the ring of each above-mentioned group can be randomly by one or more hydrogen, low alkyl group, halogen, cyano group, OR of being selected from 19, OC (O) R 20, C (O) R 21, C (O) OR 22, NR 23R 24, SR 27Or ferrocenyl (its meaning is L 1Cyclopentadienyl, indenyl or the aryl rings of expression directly are keyed on the cyclopentadienyl rings of metallocenes group) substituting group replace.More preferably, if L 1Cyclopentadienyl, indenyl or the aryl rings of expression are substituted, the one or more C that are selected from of then preferred employing 1-C 6Alkyl, halogen, cyano group, OR 19, OC (O) R 20, C (O) R 21, C (O) OR 22, NR 23R 24Substituting group replace R wherein 19, R 20, R 21, R 22, R 23And R 24Represent hydrogen or C independently of one another 1-C 6Alkyl.
Preferably, when n=1, L 1Optional as defined herein cyclopentadienyl, indenyl, the phenyl or naphthyl that replaces of expression.Preferably, cyclopentadienyl, indenyl, phenyl or naphthyl are not substituted.More preferably, L 1Representative ring pentadienyl, indenyl or phenyl, the ring of each above-mentioned group is not substituted.Most preferably, L 1Represent unsubstituted cyclopentadienyl.
In a particularly preferred embodiment according to the invention, in the compound of formula (I), n=1, L 1As defined herein, and m=0.
Alternatively, equal zero and m when being not equal to zero L as n in the compound of formula (I) 2Represent one or more parts, each part is independently selected from low alkyl group, halogen, CO, PR 43R 44R 45Or NR 46R 47R 48More preferably, L 2Represent one or more parts, each part is independently selected from C 1-C 4Alkyl, halogen (particularly chlorine), CO, PR 43R 44R 45Or NR 46R 47R 48, R wherein 43-R 48Be independently selected from hydrogen, C 1-C 6Alkyl or aryl is as phenyl.
In particularly preferred optional embodiment of the present invention, in the compound of formula (I), n=0, L 2As defined herein, and m=3 or 4, particularly 3.
M represents to be selected from metal or its metallic cation of Cr, Mo, Fe, Co or Ru;
L 1Representative ring pentadienyl, indenyl, naphthyl or phenyl, the ring of each above-mentioned group can be randomly by one or more C that are selected from 1-C 6Alkyl, halogen, cyano group, OR 19, OC (O) R 20, C (O) R 21, C (O) R 22, NR 23R 24Substituting group replace;
L 2Represent one or more parts, each described part is independently selected from C 1-C 6Alkyl, halogen, CO, PR 43R 44R 45Or NR 46R 47R 48
N=0 or 1;
And m=0-4;
Condition is when n=1, m=0 and and be not equal to when zero n=0 as m.
The in addition preferred compound of formula (I) comprises those compounds with following feature:
M represents iron or its positively charged ion;
L 1Representative ring pentadienyl, indenyl or phenyl, each above-mentioned group can be randomly by one or more C that are selected from 1-C 6Alkyl, halogen, cyano group, OR 19, OC (O) R 20, C (O) R 21, C (O) R 22Substituting group replace;
L 2Represent one or more parts, each part is independently selected from C 1-C 6Alkyl, halogen, CO, PR 43R 44R 45Or NR 46R 47R 48, R wherein 43-R 48Be independently selected from hydrogen, C 1-C 6Alkyl or phenyl;
N=0 or 1; And m=0-4.
Still the preferred compound of formula (I) comprises those compounds with following feature:
L 1Represent unsubstituted cyclopentadienyl, indenyl or phenyl, particularly unsubstituted cyclopentadienyl; And n=1 and m=0.
The optional preferred compound of formula (I) comprises those compounds with following feature:
n＝0；
L 2Represent one or more parts, each part is independently selected from C 1-C 6Alkyl, halogen, CO, PR 43R 44R 45Or NR 46R 47R 48, R wherein 43-R 48Be independently selected from hydrogen, C 1-C 6Alkyl or phenyl; And m=1-4, particularly 3 or 4.For example, when m=3, L 2Three parts of expression comprise (CO) 2Halogen, (PR 43R 44R 45) 2Halogen or (NR 46R 47R 48) 2Halogen.
In above-mentioned embodiment of the present invention and wherein exist the particularly preferred combination of at least one 2-phospha-adamantyl to comprise the combination of formula (I) with following feature:
(4) (CR 7R 8R 9) and (CR 10R 11R 12) be connected the Q on it with them 2Represent 2-phospha-adamantyl together;
(CR 4R 5R 6) and (CR 1R 2R 3) be connected the Q on it with them 1Represent 2-phospha-adamantyl together;
A and expression-CH identical with B 2-;
Q 1And Q 2All represent phosphorus;
K represents hydrogen or unsubstituted C 1-C 6Alkyl, particularly hydrogen;
D forms unsubstituted phenyl ring with E with the carbon atom that they are connected the cyclopentadienyl rings on it;
M represents Fe;
N=1 and L 1The representative ring pentadienyl, particularly unsubstituted cyclopentadienyl, and m=0.
(5) (CR 7R 8R 9) and (CR 10R 11R 12) be connected the Q on it with them 2Represent 2-phospha-adamantyl together;
(CR 4R 5R 6) and (CR 1R 2R 3) be connected the Q on it with them 1Represent 2-phospha-adamantyl together;
A and expression-CH identical with B 2-;
K, D and expression hydrogen or unsubstituted C identical with E 1-C 6Alkyl, particularly hydrogen;
Q 1And Q 2All represent phosphorus;
M represents Fe;
N=1 and L 1The representative ring pentadienyl, particularly unsubstituted cyclopentadienyl, and m=0.
(6) (CR 7R 8R 9) and (CR 10R 11R 12) be connected the Q on it with them 2Represent 2-phospha-adamantyl together;
(CR 4R 5R 6) and (CR 1R 2R 3) be connected the Q on it with them 1Represent 2-phospha-adamantyl together;
K represents-CH 2-Q 3(X 5) X 6, X wherein 5And X 6Be connected the Q on it with them 3Represent 2-phospha-adamantyl together;
A and expression-CH identical with B 2-;
Q 1, Q 2And Q 3Represent phosphorus separately;
D and expression hydrogen or unsubstituted C identical with E 1-C 6Alkyl, particularly hydrogen;
M represents Fe;
N=1 and L 1The representative ring pentadienyl, particularly unsubstituted cyclopentadienyl, and m=0.
(7) (CR 7R 8R 9) and (CR 10R 11R 12) be connected the Q on it with them 2Represent 2-phospha-adamantyl together;
(CR 4R 5R 6) and (CR 1R 2R 3) be connected the Q on it with them 1Represent 2-phospha-adamantyl together;
K represents-CH 2-Q 3(X 5) X 6, X wherein 5And X 6Be connected the Q on it with them 3Represent 2-phospha-adamantyl together;
A 1And A 2Identical and expression-CH 2-;
Q 1, Q 2And Q 3Represent phosphorus separately;
D forms unsubstituted phenyl ring with E with the carbon atom that they are connected the cyclopentadienyl rings on it;
M represents Fe;
N=1 and L 1The representative ring pentadienyl, particularly unsubstituted cyclopentadienyl, and m=0.
Suitably, method of the present invention is used in carbon monoxide and there is the hydroformylation of catalysis alefinically unsaturated compounds down in hydrogen, that is, but method catalysis alefinically unsaturated compounds of the present invention changes into corresponding aldehyde.Aptly, do not compare with wherein there not being the similar approach of chlorine structure division, method of the present invention will show the selectivity that linear aldehyde product (than the aldehyde product of branching) is increased.The preferred linearity that is obtained by hydroformylation method of the present invention: the ratio of branched product is higher when using the comparable catalyst system that wherein there is not the chlorine structure division/solvent; promptly; this ratio is partial to linear product; more preferably should linearity: the ratio of branching be higher than 1: 1; more preferably be higher than 1.25: 1; even more preferably be higher than 1.5: 1, and more preferably be higher than 2: 1 again, most preferably be higher than 3: 1.
Aptly, method of the present invention can be used highly stable compound under typical hydrogenation formyl reaction condition so that they need or do not need to add hardly.Aptly, with currently known methods relatively, method of the present invention can have the speed of reaction of hydroformylation of the alefinically unsaturated compounds of increase.Aptly, method of the present invention can promote the high conversion of alefinically unsaturated compounds, thereby produces the required product of high yield under the situation that does not almost have or do not have impurity.Aptly, by adopting method of the present invention can improve the commercial viability of hydroformylation method (as the hydroformylation of alefinically unsaturated compounds).
If not indicated otherwise, be applicable to described and all embodiment groups under usable condition before to give a definition.
When using in this article and not pointing out in addition, term " Ar " or " aryl " comprise 5-10 unit, the carbocyclic aromatic or the false aromatic group of preferred 6-10 unit, as phenyl, ferrocenyl and naphthyl, preferred phenyl and naphthyl, described group can be randomly except K, D, E or Z by one or more aryl, low alkyl group (described alkyl itself can choose wantonly as to be substituted or end-blocking), Het, halogen, cyano group, nitro, OR of being selected from with giving a definition 19, OC (O) R 20, C (O) R 21, C (O) OR 22, NR 23R 24, C (O) NR 25R 26, SR 27, C (O) SR 27Or C (S) NR 25R 26Substituting group replace R wherein 19-R 27Represent independently of one another hydrogen, aryl or low alkyl group (described alkyl itself can choose wantonly such as following definition be substituted or end-blocking).
Suitably, when the carbon atom that Ar or aryl are cyclopentadienyl and D with E is connected the cyclopentadienyl rings on it with them formed phenyl ring, metal M or its positively charged ion were connected on the indenyl rings system.In a preferred embodiment, Ar represents phenyl or naphthyl, more preferably phenyl, and under any situation, and they can choose as described above that paragraph is substituted describedly wantonly.
When using in this article, term " Het " comprises 4-12 unit, the member ring systems of preferred 4-10 unit, described ring comprises one or more heteroatomss that are selected from nitrogen, oxygen, sulphur and composition thereof, and described ring can contain one or more pairs of keys or can be non-aromatics, partially aromatic or Wholly aromatic in nature.Member ring systems can be monocycle, dicyclo or condensed ring.Each of defined " Het " group can be randomly by one or more halogen, cyano group, nitro, oxo, low alkyl group (described alkyl itself can be chosen wantonly as following and be substituted or end-blocking with defining), OR of being selected from herein 19, OC (O) R 20, C (O) R 21, C (O) OR 22, NR 23R 24, C (O) NR 25R 26, SR 27, C (O) SR 27Or C (S) NR 25R 26Substituting group replace R wherein 19-R 27Represent independently of one another hydrogen, aryl or low alkyl group (described alkyl itself can choose wantonly such as following definition be substituted or end-blocking).Therefore, term " Het " comprises the group such as optional azetidine, pyrrolidyl, imidazolyl, indyl, furyl, oxazolyl, isoxazolyl, oxadiazole base, thiazolyl, thiadiazolyl group, triazolyl, oxatriazole base, thiatriazole base, pyridazinyl, morpholinyl, pyrimidyl, pyrazinyl, quinolyl, isoquinolyl, piperidyl, pyrazolyl and the piperazinyl that replaces.Replacement on Het can be at the carbon atom place of Het ring, or under the suitable situation, can be at one or more heteroatomss place.
" Het " group also can be the form of oxynitride.
When using in this article, term " low alkyl group " meaning is C 1-C 10Alkyl and comprise methyl, ethyl, propyl group, butyl, amyl group, hexyl and heptyl.If regulation in addition, when having enough carbonatomss, alkyl can be linearity or branching, saturated or unsaturated, ring-type, acyclic or part ring-type/acyclic, and/or by one or more halogen, cyano group, nitro, OR of being selected from 19, OC (O) R 20, C (O) R 21, C (O) OR 22, NR 23R 24, C (O) NR 25R 26, SR 27, C (O) SR 27, C (S) NR 25R 26, aryl or Het substituting group replace or end-blocking, and/or or at interval by silylation (silano) or dialkyl silicon group institute by one or more oxygen or sulphur atom; R wherein 19-R 27Represent hydrogen, aryl or low alkyl group independently of one another.
When having enough carbonatomss, R 1, R 2, R 3, R 4, R 5, R 6, R 7, R 8, R 9, R 10, R 11, R 12, R 13, R 14, R 15, R 16, R 17, R 18, R 19, R 20, R 21, R 22, R 23, R 24, R 25, R 26, R 27, R 28, K, D, E and Z is denotable and aryl and Het can be linearity or branching, saturated or unsaturated, ring-type, acyclic or part ring-type/acyclic by the low alkyl group of its replacement, and/or or at interval, and/or by one or more halogen, cyano group, nitro, OR of being selected from by silylation or dialkyl silicon group institute by one or more oxygen or sulphur atom 19, OC (O) R 20, C (O) R 21, C (O) OR 22, NR 23R 24, C (O) NR 25R 26, SR 27, C (O) SR 27, C (S) NR 25R 26, aryl or Het substituting group replace; R wherein 19-R 27Represent hydrogen, aryl or low alkyl group independently of one another.
Similarly, when using herein, the term " low-grade alkylidene " that R represents in A, B and J (when existing) compound expression and formula (Ia) in the compound of formula (I) comprises C 1-C 10Group, described group two positions on group are carried out keyed jointing and employing and " low alkyl group " same way as and are defined in addition.
Above-mentioned group can be comprised fluorine, chlorine, bromine and iodine group by its replacement or end capped halogen group.
Contain under the situation of alkenyl in formula (I) or compound (Ia), cis (E) and trans (Z) isomery also can take place.The present invention includes under each steric isomer and suitable situation of formula (I) compound its various tautomeric forms and composition thereof.Separating of diastereomer or cis and trans-isomer(ide) can be passed through routine techniques, and for example fractional crystallization, chromatogram or the H.P.L.C. of the stereoisomer mixture of through type (I) compound or its salt that is fit to or derivative obtain.Each enantiomer of formula (I) compound also can be by corresponding optically pure intermediate preparation, or use the chiral support that is fit to by (for example splitting, passing through H.P.L.C.) corresponding racemoid prepares, or prepare by the fractional crystallization of diastereoisomeric salt of forming by corresponding racemoid and optically active acid that is fit to or alkali reaction.
All steric isomers all are included in the scope of the inventive method.
It should be appreciated by those skilled in the art that the compound of formula (I) or the compound of formula (Ia) (that is, above-mentioned (b)) can be used as with group VIII metal or its compound (that is, above-mentioned (a)) coordinate part to be formed for compound of the present invention.Usually, group VIII metal or its compound (that is, above-mentioned (a)) are coordinated on one or more inferior phosphorus, arsenic and/or the antimony atoms of formula (I) compound.
Details hereinafter and embodiment are applicable to all embodiment groups mentioned above.
As indicated above, the invention provides a kind of hydroformylation process of alefinically unsaturated compounds, this method comprises makes alefinically unsaturated compounds and carbon monoxide and hydrogen contact in the presence of defined catalyst system and the solvent as the present invention.
Suitably, this hydrogenation formyl reaction is 20 ℃-180 ℃ in temperature, more preferably 35 ℃-165 ℃; more preferably 50 ℃-150 ℃ again, even more preferably 55 ℃-115 ℃, most preferably 60 ℃-95 ℃; under for example about 80 ℃; and the dividing potential drop at carbon monoxide/hydrogen is the 1-700 crust, preferred 1-600 crust, more preferably 1-300 crust; even more preferably 15-100 clings to; even more preferably 20-45 crust again, most preferably the 25-40 crust carries out under for example about 30 crust.
Suitably, alefinically unsaturated compounds can comprise the carbon-to-carbon double bond more than, and wherein two keys are conjugated or unconjugated.Preferred this alefinically unsaturated compounds contains only 1 or 2 carbon-to-carbon double bond of per molecule 1-3 a carbon-to-carbon double bond, particularly per molecule, and common per molecule is a carbon-to-carbon double bond only.
In the method according to the invention, for example nitrogen, carbonic acid gas or rare gas argon-dilution for example of rare gas element is used or adopted to carbon monoxide and hydrogen can be pure form.
The catalyst consumption of the present invention that is used for the hydroformylation process of alefinically unsaturated compounds is not crucial.But when the consumption of preferred group VIII metal is 10 -7-10 -1The moles/mole alefinically unsaturated compounds, more preferably 10 -6-10 -2The moles/mole alefinically unsaturated compounds, most preferably 10 -5-10 -2During the moles/mole alefinically unsaturated compounds, can obtain good result.The bidentate compound of preferred formula (I) or formula (Ia) is 10 with respect to the consumption of unsaturated compound -7-10 -1, more preferably 10 -6-10 -2, most preferably 10 -5-10 -2The moles/mole alefinically unsaturated compounds.
Catalyst compound of the present invention can be used as " heterogeneous " catalyzer or " homogeneous phase " catalyzer.
Term " homogeneous phase " catalyzer is represented a kind of catalyzer; promptly; compound of the present invention; the not load of described catalyzer; but with the reactant of hydrogenation formyl reaction (for example; alefinically unsaturated compounds, hydrogen and carbon monoxide) simply mix or original position formation, preferably in suitable solvent as described herein.
Term " heterogeneous " catalyzer represents to load to supported catalyst (that is compound of the present invention).
Therefore, according to another aspect, the invention provides a kind of hydroformylation process of alefinically unsaturated compounds as herein defined, wherein this method utilization comprises carrier, and the catalyzer of preferred soluble carrier carries out.
Preferably, carrier comprises polymkeric substance for example polyolefine, polystyrene and polystyrene copolymer such as divinyl benzene copolymer or polymkeric substance or multipolymer that other is fit to well known by persons skilled in the art; Silicon-dioxide, siloxanes or silicon rubber that silicon derivative is for example functionalized; Or other porous prilled material for example inorganic oxide and butter.
Preferred carrier materials is a porous silica, and the surface-area that described porous silica has is 10-700m 2/ g, total pore volume are 0.1-4.0cc/g, and mean particle size is 10-500 μ m.More preferably, surface-area is 50-500m 2/ g, pore volume are 0.5-2.5cc/g, and mean particle size is 20-200 μ m.Most desirably, surface-area is 100-400m 2/ g, pore volume are 0.8-2.0cc/g, and mean particle size is 30-100 μ m.The mean pore size of typical porous carrier materials is Preferably, use mean pore size to be And be desirably most Solid support material.It is desirable to especially in temperature is under 100 ℃-800 ℃ silicon-dioxide to be dewatered 3-24 hour.
Suitably, carrier can be a flexibility or rigidity, and insoluble carrier can adopt the compound of the inventive method by well known to a person skilled in the art technology coating and/or dipping.
Alternatively, the compound of the inventive method randomly is fixed on the surface of soluble carrier through covalent linkage, and this layout comprises that randomly difunctionality spacer molecule is with spaced apart with compound and soluble carrier.
The functional group that exists in the compound by promotion formula (I) (or formula (Ia)), for example substituting group K, D, Z and the E of aryl structure division and be present on the carrier or the complementary interaction radical reaction that is inserted in advance in the carrier can be fixed to compound of the present invention on the surface of soluble carrier.The reactive group of carrier provides a kind of heterogeneous catalyst with complementary substituent combination of The compounds of this invention, and compound wherein of the present invention and carrier couple together via the key such as ether, ester, acid amides, amine, urea, ketone group.
The characteristic of the group of the substituting group (one or more) of compound and carrier is depended in the selection that the compound of the inventive method is connected to the reaction conditions on the carrier.For example, can adopt for example carbodiimide, 1 of reagent, 1 '-carbonyl, three imidazoles and technology are for example used mixed acid anhydride, reductive amination.
According to another aspect, the invention provides the purposes of the inventive method, wherein catalyzer is connected on the carrier.
Preferred especially organic radicals R 1, R 2, R 3, R 4, R 5, R 6, R 7, R 8, R 9, R 10, R 11And R 12When the time forming sterically hindered at least as the compound group of the tertiary butyl with its carbon atom associating separately.About this point, described in the 14th page of sterically hindered " Homogenous TransitionMetal Catalysis-A Gentle Art " as C Masters (Chapman and Hall publish, 1981) and the following pages.
These space steric hindrance groups can be ring-type, part ring-type or acyclic, and are preferably acyclic.When being ring-type or part ring-type, this group can be replacement or unsubstituted, perhaps can be saturated or undersaturated.This ring-type or part cyclic group comprise tertiary carbon atom can comprise C interior in ring texture 4-C 30, more preferably C 6-C 20, C most preferably 10-C 15Individual carbon atom.Ring texture can be by one or more halogen, cyano group, nitro, OR of being selected from 19, OC (O) R 20, C (O) R 21, C (O) OR 22, NR 23R 24, C (O) NR 25R 26, SR 27, C (O) SR 27, C (S) NR 25R 26, aryl or Het substituting group replace, and/or or at interval by silylation or dialkyl silicon group institute by one or more oxygen or sulphur atom; R wherein 19-R 27Represent hydrogen, aryl or low alkyl group independently of one another.
As mentioned above, in certain embodiments, bridged group Ar is the aryl structure division, phenyl for example, and it can be chosen wantonly and be substituted, and condition is that two phosphorus atom are connected on the adjacent carbon atom, for example on 1 and 2 of phenyl.In addition, this aryl structure division can be the fused polycycle group, as naphthalene, biphenylene or indenes.But the preferred aryl groups structure division is phenyl or naphthalene, more preferably phenyl.
The bidentate ligand that is fit to the concrete but example of indefiniteness is 1,2-two (di-t-butyl phosphinomethyl) benzene, 1,2-two (two tert-pentyl phosphinomethyl) benzene, 1,2-two (di-t-butyl phosphinomethyl) naphthalene, 1,2-two (two adamantyl phosphinomethyl) benzene, 1,2-two (two-3,5-dimethyladamantane base phosphinomethyl) benzene, 1,2-two (two 5-tertiary butyl adamantyl phosphinomethyl) benzene, 1,2-two (1-adamantyl tertiary butyl phosphinomethyl) benzene, 1,2-two (two-1-, two amantane phosphinomethyl) benzene, 1-[(two adamantyl phosphinomethyl)-and 2-(di-t-butyl phosphinomethyl)] benzene, 1-(di-t-butyl phosphinomethyl)-2-(two (five rings adamantyl) phosphinomethyl) benzene, 1-(di-t-butyl phosphinomethyl)-2-(phospha-adamantyl phosphinomethyl) benzene, 1-(two adamantyl phosphinomethyl)-2-(phospha-adamantyl phosphinomethyl) benzene, 1-(tertiary butyl adamantyl)-2-(two adamantyls)-(phosphinomethyl) benzene, 1-[(P-(2,2,6,6-tetramethyl-phosphine (phosphinan)-4-ketone) phosphinomethyl)]-2-(phospha-adamantyl phosphinomethyl) benzene, 1,2-two (di-t-butyl phosphinomethyl) ferrocene, 1,2-two (di-t-butyl phosphinomethyl) ferrocene, 1,2,3-three (di-t-butyl phosphinomethyl) ferrocene, 1,2-two (dicyclohexyl phosphinomethyl) ferrocene, 1,2-two (diisobutyl phosphinomethyl) ferrocene, 1,2-two (dicyclopentyl group phosphine ylmethyl) ferrocene, 1,2-two (diethyl phosphinomethyl) ferrocene, 1,2-two (di-isopropyl phosphinomethyl) ferrocene, 1,2-two (dimethyl phosphine ylmethyl) ferrocene, 1,2-two (two (1,3,5,7-tetramethyl--6,9,10-trioxa-2-phospha-adamantyl methyl)) ferrocene, 1,2-two-α, α-(P-(2,2,6,6,-tetramethyl-phosphine-4-ketone)) dimethyl ferrocene and 1,2-two (two-1,3,5,7-tetramethyl--6,9,10-trioxa-2-phospha-adamantyl methyl)) benzene, be preferably selected from two (di-t-butyl phosphino-)-o-Xylols (also being called 1,2-two (di-t-butyl phosphinomethyl) benzene); 1,2-two (two adamantyl phosphinomethyl) benzene; 1,2-two (two adamantyl phosphinomethyl) naphthalene; 1,2-two (two tert-pentyl phosphino-s) o-Xylol (also being called 1,2-two (two tert-pentyl phosphinomethyl) benzene); With two-1,2-(di-t-butyl phosphinomethyl) naphthalene.In addition, bidentate phosphine can be in bridged group Ar, linking group A or linking group B at least one be keyed on the suitable polymeric substrate, for example, two (di-t-butyl phosphino-) o-Xylol can be keyed on the polystyrene to produce the fixed heterogeneous catalyst through the dimethylbenzene group.
The consumption of the bidentate ligand that uses can change in wide region.Preferably, bidentate ligand is so that the ratio of the mole number of the bidentate ligand that exists and the mole number of the group VIII metal of existence is 1-50,1-10 for example, and particularly the consumption of 1-5 moles/mole metal exists.More preferably, formula (I) or (Ia), the compound of preferred formula (I) is with respect to the mol of group VIII metal: the mol scope is 1: 1-3: 1, most preferably 1: 1-1.25: 1.Aptly, it may be favourable using these low mol ratios because it has avoided using excessive formula (I) or (Ia), the compound of preferred formula (I), therefore make these usually the consumption of very expensive compound minimize.Suitably, the catalyzer of the inventive method is used in its original position adopting independent step preparation before the hydrogenation formyl reaction of alefinically unsaturated compounds.
Carbon monoxide and hydrogen can use in the presence of other gas (being inert in reaction).The example of described gas comprises for example argon gas of nitrogen, carbonic acid gas and rare gas.
Group VIII metal (also being called VIIIB family metal) or its compound that can be fit to the compound bonded of formula (I) comprise cobalt, nickel, palladium, rhodium, ruthenium and platinum.Preferably, (a) be rhodium or its compound.The compound that is fit to of above-mentioned group VIII metal comprises described metal and nitric acid; Sulfuric acid; Lower alkane (as many as C 12) acid for example acetate and propionic acid; Sulfonic acid is methylsulfonic acid, chlorsulfonic acid, fluosulfonic acid, trifluoromethanesulfonic acid, Phenylsulfonic acid, naphthene sulfonic acid, toluenesulphonic acids (such as, tosic acid), tertiary butyl sulfonic acid and 2-hydroxy-propanesulfonic acid for example; Sulfonated ion exchange resin; High hydracid is perchloric acid for example; Halogenated carboxylic acid is trichoroacetic acid(TCA) and trifluoroacetic acid for example; Ortho-phosphoric acid; Phosphonic acids is phosphenylic acid for example; And derived from the salt of the interactional acid between Lewis acid and the Bronsted acid, or comprise compound derived from the weakly coordinating anion of above-mentioned acid.Other alternative comprises halogen (halo salt).Can provide suitable anionic other source to comprise optional halogenated tetraphenyl borate salts derivative, for example perfluor tetraphenyl borate salts.In addition, can use metal complex, particularly with the complex compound of unstable part.Certainly, method of the present invention need be by combining group VIII metal or its compound the catalyst system of acquisition with bidentate phosphine, has the chlorine structure division at group VIII metallic compound or solvent in one of at least; Therefore, if solvent does not contain the chlorine structure division, then the group VIII metallic compound must contain the chlorine structure division, and is understandable therefore.Certainly, if the chlorine structure division is present in the solvent, then this structure division can be present in any part of solvent system, for example wherein solvent system can comprise solvent and for example chlorine structure division source, preferred this chlorine structure division is present in the chemical structure of solvent molecule itself, for example in chlorinated hydrocarbon solvent, chloro-containing fluorocarbon solvent etc.
Catalyst system of the present invention preferably constitutes in liquid phase, and described liquid phase can form or form by the solvent that use is fit to by one or more reactants.Significantly, under the former situation, the reference for solvent among the present invention should correspondingly be explained, and this chlorine structure division must be present in the group VIII metallic compound in this case.
Choice of Solvent is not crucial, except according to according to the present invention following true: if the group VIII metallic compound does not comprise the chlorine structure division then solvent must comprise the chlorine structure division.Certainly, selected solvent should be harmful to catalyst system, reactant or product.In addition, solvent can be the mixture of the more high boiling product (for example, aldol condensation product) of reactant (for example, alefinically unsaturated compounds), product and/or any by product and its secondary reaction.In addition, can exist more than a kind of solvent, for example, the mixture of solvent.
When existing, suitable solvent comprises stable hydrocarbon for example kerosene, mineral oil or hexanaphthene; Ether is diphenyl ether, methyl phenyl ether, Anaesthetie Ether, Di Iso Propyl Ether, tetrahydrofuran (THF) or polyoxyethylene glycol for example; Ketone is acetone, methylethylketone, methyl butyl ketone and pimelinketone for example; Nitrile is methyl cellosolve acetate glutaronitrile, valeronitrile and benzonitrile for example; Aromatic substances (comprising the halo variant), for example toluene, benzene and dimethylbenzene; Ester is ritalin, methyl valerate and caprolactone for example; Dimethyl formamide; With sulfone tetramethylene sulfone and comprise the variant of any above-mentioned substance of at least one chlorine structure division for example.
Other solvent that is fit to comprises for example mixture of toluene (as mentioned above), hydrocarbon or hydrocarbon of aromatic substance.Can also make water and alcohol for example methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol and isopropylcarbinol.The variant that comprises the above-mentioned substance of at least one chlorine structure division also is fit to.
As previously mentioned, the chlorine structure division be present in the group VIII metallic compound of the inventive method or solvent one of at least in.Therefore, suitably, the group VIII metallic compound as defined above and comprise the chlorine structure division.The specific examples of the group VIII compound that is fit to comprises rhodium complex (containing and do not contain the complex compound of at least one chlorine structure division) and is [RhCl (CO) for example 2] 2, [RhCl (Cod) 2] 2(wherein " Cod " expression " 1, the 5-cyclooctadiene "), RhCl 3XH 2O, [Rh (CO) 2(acac)] 2(wherein " acac " expression " methyl ethyl diketone root "), [Rh (acetate moiety) 2] 2, [RhCl (norbornadiene)] 2, Rh 2(OAc) 4, [RhCl (cyclooctene) 2] 2, chlorine (1, the 5-hexadiene)-rhodium (I) dipolymer, two (1, the 5-cyclooctadiene)-rhodium (I) Tetrafluoroboric acid salt hydrate, μ-dichloro tetrem alkene-two rhodium (μ-dichlorotetraethylene-dirhodium), (dicyclo [2,2,1] heptan-2, the 5-diene) chlorine rhodium (I) dipolymer, (1, the 5-cyclooctadiene) (2,4-diacetylmethane root closes) rhodium (I), (dicyclo [2,2,1] heptan-2,5-diene) (2,4-diacetylmethane root closes) rhodium (I), acetylacetonate rhodium (III), (dicyclo [2,2,1] heptan-2, the 5-diene) chlorine rhodium (I) dipolymer, more especially [RhCl (CO) 2] 2, [RhCl (Cod) 2] 2, RhCl 3XH 2O, [Rh (CO) 2(acac)] 2, [Rh (acetate moiety) 2] 2, [RhCl (norbornadiene)] 2, [RhCl (cyclooctene) 2] 2, chlorine (1, the 5-hexadiene)-rhodium (I) dipolymer, the most particularly [RhCl (CO) 2] 2, [RhCl (Cod) 2] 2, RhCl 3XH 2O, [Rh (CO) 2(acac)] 2, [Rh (acetate moiety) 2] 2Therefore, comprise at rhodium complex under the situation of at least one chlorine structure division, the complex compound that is fit to comprises [RhCl (CO) 2] 2, [RhCl (Cod) 2] 2, RhCl 3XH 2O, [RhCl (norbornadiene)] 2, [RhCl (cyclooctene) 2] 2, chlorine (1, the 5-hexadiene)-rhodium (I) dipolymer, μ-dichloro tetrem alkene-two rhodium, (dicyclo [2,2,1] heptan-2,5-diene) chlorine rhodium (I) dipolymer, more especially [RhCl (CO) 2] 2, [RhCl (Cod) 2] 2, RhCl 3XH 2O, [RhCl (norbornadiene)] 2, [RhCl (cyclooctene) 2] 2, chlorine (1, the 5-hexadiene)-rhodium (I) dipolymer, the most particularly [RhCl (CO) 2] 2, [RhCl (Cod) 2] 2, RhCl 3XH 2O.In addition, suitably, the solvent of the inventive method as previously mentioned and comprise the chlorine structure division.This specific examples that comprises the solvent of at least one chloro structure division comprises methylene dichloride, chlorobenzene, orthodichlorobenzene, a chlorobenzene, tetracol phenixin, trichloroethane, ethylene dichloride, chlorofluorocarbon (CFC), tetrachloroethane, zellon, more especially methylene dichloride.Even more preferably, group VIII metallic compound and solvent all contain the chlorine structure division.
Reaction product can be separated with other component by any suitable method.But an advantage of the inventive method has been to form obvious less by product, thereby has reduced the initially-separate product needs to being further purified afterwards, and it is confirmed by the usually obvious higher selectivity and the linear lag.Another advantage is other component that contains catalyst system can be carried out recirculation and/or utilization again in further reacting, and adding of live catalyst minimized.
Preferably, this hydroformylation is 20 ℃-180 ℃ in temperature, more preferably 35 ℃-165 ℃, more preferably 50 ℃-150 ℃ again, even more preferably 55 ℃-115 ℃, most preferably under 60 ℃-95 ℃, for example carries out under about 80 ℃.Advantageously, this hydroformylation can carry out under moderate temperature.Particularly advantageous is to carry out this hydrogenation formyl reaction under the room temperature being higher than.
Suitably, this hydroformylation is depressed at the branch of reaction gas mixtures under selected temperature of reaction and is carried out.Usually, this dividing potential drop is that 1-700 clings to, and preferably 1-600 clings to, and more preferably 1-300 clings to, even more preferably 15-100 clings to, and more preferably 20-45 clings to again, and most preferably 25-40 clings to, and for example about 30 cling to.But according to the activity of employed hydroformylation catalysts, dividing potential drop can be different with above-mentioned scope.Under the situation of catalyst system of the present invention, for example reaction also can for example be carried out in the 1-100 crust in the area of low pressure.
Although there is not the linear lag advantage as adopting ethene, this reaction can be carried out at any alefinically unsaturated compounds that comprises ethene.Preferably, therefore this reaction is suitable for sub-C 3-C 20Alefinically unsaturated compounds, more preferably C 3-C 18, C most preferably 3-C 12Compound.
This method can be at containing 2 or more a plurality of carbon atom (for example, C 2-C 20Individual atom or C 3-C 20Individual atom or C 4-C 20Individual atom) alefinically unsaturated compounds carries out.The optional upper limit of carbon atom is along with increasing progressively of preferred property can be C in described compound 18Or C 15Or C 12The optional lower limit of carbon atom can be C in any above-mentioned scope of alefinically unsaturated compounds 3, C 4, C 5Or C 6Preferred alefinically unsaturated compounds is that per molecule contains 1,2 or 3 or the alkene of more a plurality of carbon-to-carbon double bonds.
Any above-mentioned alkene can be substituted or not be substituted.The substituting group that is fit to comprises C 1-8Alkyl and C 1-22Aryl.If do not stipulate in addition, alefinically unsaturated compounds can be linearity or branching, that replace, ring-type, acyclic or part ring-type/acyclic when having enough carbonatomss, and/or by one or more low alkyl group, aryl, alkaryl, Het, alkyl Het, halogen, OR of being selected from 19, OC (O) R 20, C (O) R 21, C (O) OR 22, NR 23R 24, C (O) NR 25R 26, NO 2, CN, SR 27Substituting group randomly replace or end-blocking; R wherein 19-R 27Represent hydrogen or low alkyl group independently of one another.So the alkene that replaces comprises the alkyl ester of vinylbenzene and unsaturated carboxylic acid, for example methacrylic ester.Suitably, alefinically unsaturated compounds can demonstrate cis (E) and trans (Z) isomery.
The example of the alefinically unsaturated compounds that is fit to can be independently selected from isomer, 1-hexene and its isomer, 1-heptene and its isomer, 1-octene and its isomer, 1-nonene and its isomer, 1-decene and its isomer, the C of ethene, propylene, 1-butylene, 2-butylene, iso-butylene, 1-amylene, 2-amylene, 3-amylene and its branching 11-C 20Alkene and its known isomer, 3 pentene nitrile, 3-amylene-4 acid methyl ester, 1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, 1,2,4-heptadiene and 2-methyl isophthalic acid, 3-diene.Preferably, alefinically unsaturated compounds is C 2-C 20Alkene more preferably has the C of carbon-to-carbon double bond in the 1-position 3-C 20Alkene most preferably has the C of carbon-to-carbon double bond in the 1-position 3-C 12Or C 6-C 12Alkene.
Using stable compound in catalyst system also is useful aspect the recovery that improves the metal that has lost from catalyst system.When utilizing this catalyst system in liquid reaction medium, described stable compound can help the recovery of VIIIB family metal.
Therefore, preferred catalyst systems comprises the polymeric dispersant that is dissolved in the liquid vehicle in liquid reaction medium, described polymeric dispersant can be in liquid vehicle the colloidal suspension of particle of the group VIII metal of rugged catalyst system or metallic compound.
Liquid reaction medium can be that reaction is with solvent or can comprise one or more reactants or reaction product itself.It is can be with solvent or liquid diluent miscible or be dissolved in solvent or the liquid diluent to be the reactant of liquid form and reaction product.
Polymeric dispersant is soluble in liquid reaction medium, but should significantly not increase the viscosity of reaction medium, and this will or conduct heat harmful to reaction kinetics to a certain extent.Under the reaction conditions of temperature and pressure the solubleness of dispersion agent in liquid medium should be too not high so that significantly suppress dispersant molecule and be adsorbed onto on the metallics.
Polymeric dispersant can be stablized the colloidal suspension of the particle of described group VIII metal or metallic compound in liquid reaction medium, so that, prepare the more catalyzer of volume from reactor to be used to reclaim and choose wantonly to be reused for because the metallics that catalyst degradation forms is the form of suspensoid is retained in the liquid reaction medium and together with liquid and discharges.Although may form in some cases than macroparticle, metallics has the colloid size usually, for example the 5-100nm mean particle size.The partial polymer dispersant adsorption is to the surface of metallics, simultaneously the dispersant molecule of residual content still to small part by the liquid reaction medium solvation and therefore make dispersive group VIII metallics stabilization, prevent on its wall that deposits to reactor or deposit in the dead angle of reactor and prevent to form the aggregation of metallics that described aggregation is grown by particle encounter and be finally coalescent.Even also some aggregation of particles may take place under the situation that has the dispersion agent that is fit to, but when the type of optimizing dispersion agent and concentration, then above-mentioned gathering should be in lower level and only may form aggregation so that they can be smashed and make the particle redispersion by stirring by loosely.
Polymeric dispersant can comprise homopolymer or multipolymer, comprises the polymkeric substance such as graft copolymer and star polymer.
Preferably, polymeric dispersant has the functionality of enough acidity or alkalescence to stablize the colloidal suspension of described group VIII metal or metallic compound basically.
" basically stable " meaning is to have avoided the group VIII metal to be precipitated out mutually from solution basically.
Particularly preferred dispersion agent comprises acidity or alkaline polymer with regard to above-mentioned purpose, comprises carboxylic acid, sulfonic acid, amine and acid amides, for example polyacrylic ester; Or heterocycle, particularly nitrogen heterocyclic ring; The polyvinyl polymkeric substance that replaces, for example Polyvinylpyrolidone (PVP); Or the multipolymer of aforementioned substances.
The example of described polymeric dispersant is optional from Polyvinylpyrolidone (PVP), polyacrylamide, polyacrylonitrile, polymine, polyglycine, polyacrylic acid, polymethyl acrylic acid, poly-(3-hydroxybutyric acid), poly--the L-leucine, poly--the L-methionine(Met), poly--the L-proline(Pro), poly--the L-Serine, poly--L-tyrosine, poly-(vinylbenzenesulfonic acid) and poly-(vinyl sulfonic acid).
Preferably, polymeric dispersant on the side group or in main polymer chain in conjunction with acidity or alkaline structure part.Preferably, the dissociation constant (pK that has of acid structure division a) less than 6.0, be more preferably less than 5.0, most preferably less than 4.5.Alkali dissociation constant (the pK that preferred alkaline structure division has b) less than 6.0, be more preferably less than 5.0, and most preferably less than 4.5, pK aAnd pK bUnder 25 ℃, in dilute aqueous, measure.
The polymeric dispersant that is fit to except dissolving in the reaction medium, also contains at least one acidity or alkaline structure part in main polymer chain or as side group under reaction conditions.We find, and particularly suitable is to be combined with acid and amide structure polymkeric substance partly, for example Polyvinylpyrolidone (PVP) (PVP) and polyacrylic ester polyacrylic acid (PAA) for example.The molecular weight that is suitable for polymkeric substance used in this invention depends on the characteristic of reaction medium and the solubleness of polymkeric substance wherein.We find that molecular-weight average is less than 100,000 usually.Preferably, molecular-weight average is 1,000-200, and 000, more preferably, and 5,000-100,000, most preferably, and 10,000-40,000.For example when using PVP, Mw is preferably 10,000-80,000, more preferably 20,000-60,000; And it is about 1 under the situation of PAA, 000-10,000.
The effective concentration of dispersion agent in reaction medium should be determined at each reaction/catalyst system to be used.
Dispersive group VIII metal can for example reclaim by filtering from liquid stream (taking out from reactor), then its processing or processing is used for again as catalyzer or other application.In continuous processing, liquid stream can circulate through external heat exchanger, and under described situation, is easily for the palladium particle is provided with strainer in these circulation devices.
Preferably, polymkeric substance: metal quality is 1 than (in g/g): 1-1000: 1, more preferably 1: 1-400: 1, most preferably 1: 1-200: 1.Preferably, polymkeric substance: metal quality than (in g/g) but as many as 1000, more preferably as many as 400, most preferably as many as 200.
In one aspect of the method; the invention provides a kind of catalyst system; preferred wherein said system is used for the hydroformylation process of alefinically unsaturated compounds and this method and comprises described alefinically unsaturated compounds and carbon monoxide and hydrogen are reacted in the presence of described system, and this catalyst system can be by making following component in conjunction with acquisition:
A) as previously described or defined group VIII metallic compound; With
B) as previously described or defined bidentate phosphine,
And wherein catalyst system is characterised in that in described at least group VIII metallic compound and has the chlorine structure division.
In a further aspect; the invention provides a kind of catalyst system of hydrogenation formyl reaction; this catalyst system is used for catalysis alefinically unsaturated compounds and carbon monoxide and hydrogen in the presence of described system, and this catalyst system can be by making following component in conjunction with acquisition:
A) as previously described or defined group VIII metallic compound; With
B) as previously described or defined bidentate phosphine,
And wherein catalyst system is characterised in that in described at least group VIII metallic compound and has the chlorine structure division.
In a further aspect; the invention provides a kind of reaction medium that comprises catalyst system and solvent; preferred wherein said medium is used for the hydroformylation process of alefinically unsaturated compounds; and described method is included under described system and the existence of described solvent and makes described alefinically unsaturated compounds and carbon monoxide and hydrogen reaction; wherein said solvent as previously described or define, this catalyst system can be by making following component in conjunction with acquisition:
A) as previously described or defined group VIII metal or its compound; With
B) as previously described or defined bidentate phosphine,
And wherein reaction medium is characterised in that at described group VIII metallic compound or described solvent and has the chlorine structure division in one of at least, is included in the possibility that all exists among both.
In a further aspect; the invention provides a kind of hydrogenation formyl reaction medium; wherein said medium comprises catalyst system and solvent; preferred wherein said system is used for the hydroformylation process of alefinically unsaturated compounds; and described method is included under described system and the existence of described solvent and makes described alefinically unsaturated compounds and carbon monoxide and hydrogen reaction; wherein said solvent as previously described or define, this catalyst system can be by making following component in conjunction with acquisition:
A) as previously described or defined group VIII metal or its compound; With
B) as previously described or defined bidentate phosphine,
And wherein reaction medium is characterised in that at described group VIII metallic compound or described solvent and has the chlorine structure division in one of at least, is included in the possibility that all exists among both.
In another aspect of the present invention; provide as the front to define or described catalyst system is used for the purposes of the hydroformylation of alefinically unsaturated compounds, described purposes is included in described catalyst system and has the step that makes described alefinically unsaturated compounds and carbon monoxide and hydrogen reaction down.
In another aspect of the present invention; provide as the front to define or described reaction medium is used for the purposes of the hydroformylation of alefinically unsaturated compounds, described purposes is included in described reaction medium and has the step that makes described alefinically unsaturated compounds and carbon monoxide and hydrogen reaction down.
In another aspect of the present invention, provide a kind of preparation to define or the method for described catalyst system or reaction medium as the front, described method comprises to be made a) as previously described or defined group VIII metal or its compound, and b) as previously described or defined bidentate phosphine combination.
The feature of first aspect of the present invention and embodiment are equally applicable to as described herein any or all respects of the present invention, unless described feature/embodiment does not conform to particular aspects or be mutually exclusive.
Following indefiniteness and pure illustrative embodiment further explain the present invention.
All synthetic Schlenk glasswares of the drying and the degassing that use carry out in vacuum argon gas Schlenk pipeline.
1-octene and 1-hexene (all available from Aldrich) are outgased by distillation purifying and by employing argon gas bubbling.Toluene carries out drying by adopting the distillation of diphenylketone acetal sodium.THF (tetrahydrofuran (THF)) carries out drying by adopting the distillation of sodium and benzophenone.DCM (methylene dichloride) carries out drying by adopting the hydrolith distillation.
[RhCl (CO) 2] 2, Rh 2(OAc) 4And RhCl 3XH 2O (Strem) is owing to its air sensitive is stored in the glove box.1,2-two (di-t-butyl phosphinomethyl) benzene is storage and the operation in glove box owing to its air sensitive also.
1,2-two (di-t-butyl phosphinomethyl) benzene is available from Strem Chemicals (catalogue 19 numbering 15-0072, CAS numbers 121954-50-5), perhaps can prepare according to embodiment 18 according to WO-A-99/47528, PCT/GB99/00797 in these embodiments, the detail file of preparation are introduced with for referencial use.
1, the preparation detail file of 2-two (two adamantyl phosphinomethyl) benzene and other diamantane base class part provide in the disclosed application of applicant WO-A-04/014552, PCT/GB03/003419, be incorporated herein by reference at this, particularly at described preparation detail file.
1, the preparation detail file of 2-two (di-t-butyl phosphinomethyl) ferrocene and other ferrocene class part provide in the disclosed application of applicant WO-A-04/024322, PCT/GB03/003936, be incorporated herein by reference at this, particularly at described preparation detail file.
Catalytic solution is prepared as follows.
For containing [RhCl (CO) 2] 2As the catalyst system of rhodium precursor, in glove box with 9mg (0.023mmol) [RhCl (CO) 2] 2And 20mg (0.046mmol) 1,2-two (di-t-butyl phosphinomethyl) benzene joins in the Schlenk pipe.Adopt syringe to add corresponding solvent (10ml usually) then.When all solids dissolved, with 1-octene or 1-hexene (2ml), hydroformylation matrix joined in the solution.
The autoclave that is used for described embodiment is the hastelloy autoclave of 250ml.After the baking oven inner drying, autoclave adopts argon cleaning 3 times.In case, solution is shifted through sleeve pipe with its degassing.Adopt the synthetic gas of 30 crust that it is pressurizeed then, and be heated to 80 ℃ and continue 3 hours, it is cooled off, exhaust then in air.Adopt GC-MS to analyze the solution that obtains.
Adopt method preparation same as described above to use Rh 2(OAc) 4Or RhCl 3Catalyst system as the rhodium precursor.
Conversion percentage is represented the amount by the matrix of this reaction conversion.
Selectivity is optionally measuring for specific hydro formylation products.
L: b represents the linearity of hydro formylation products: the branching ratio.
Embodiment 1
The hydroformylation of 1-hexene: the chlorine structure division is present in the rhodium precursor
With 9.0mg (0.00383 mol) [RhCl (CO) 2] 2Join 18mg (0.00383 mol) bidentate phosphine part, 1, in 2-two (di-t-butyl phosphinomethyl) benzene.In mixture, add 10ml toluene then.Add 2.0ml (16.0mmol) 1-hexene then, and pass through to add CO: H down at 80 ℃ 21: 1 mixture pressure be 30 the crust under carried out hydroformylation 3 hours.
Found that under these conditions after 3 hours, 1-hexene 100% is converted into the aldehyde product, for branched product, is 84% selectivity for linear enanthaldehyde; L: the b ratio is 5.25: 1.
Comparative Examples 1
The hydroformylation of 1-hexene: do not have the chlorine structure division
With 10mg (0.00383 mol) [Rh (OAc) 2] 2Join 40mg (0.00846 mol) bidentate phosphine part, 1, in 2-two (di-t-butyl phosphinomethyl) benzene.In mixture, add 10ml toluene then.Add 2.0ml (16.0mmol) 1-hexene then, and pass through to add CO: H down at 80 ℃ 21: 1 mixture pressure be 30 the crust under carried out hydroformylation 3 hours.
Found that under these conditions after 3 hours, 1-hexene 100% is converted into the aldehyde product, for branched product, is 55% selectivity for linear enanthaldehyde; L: b is 1.22: 1 than only.
Hydroformylation according to the 1-hexene; with do not have the chlorine structure division and compare; when having the chlorine structure division in the rhodium compound precursor of catalyst system, Comparative Examples 1 and embodiment 1 clearly show for branched product, the raising of linear selectivity of product.
Embodiment 2
The hydroformylation of vinyl carbinol: the chlorine structure division is present in the rhodium precursor
With 9.0mg (0.00383 mol) [RhCl (Cod) 2] 2Join 18.0mg (0.00383 mol) bidentate phosphine part, 1, in 2-two (di-t-butyl phosphinomethyl) benzene.In mixture, add 10ml toluene then.Add 2.0ml (29.0mmol) vinyl carbinol then, and pass through to add CO: H down at 80 ℃ 21: 1 mixture pressure be 30 the crust and in the presence of 0.072mmol NaOAc, carried out hydroformylation 3 hours.
Having found under these conditions after 3 hours have 86.6% vinyl carbinol to transform, is 73.8% selectivity for hydroxyl tetrahydrofuran; It for the methylol propionic aldehyde 12.9% selectivity.Make above-mentioned two kinds of product hydrogenations then, obtain 1 respectively, 4-butyleneglycol and 2-methyl isophthalic acid, ammediol.L in this case: the b ratio is 5.72: 1.
Embodiment 3
The hydroformylation of vinyl carbinol: the chlorine structure division is present in the solvent
Repeat embodiment 2, but in this case, rhodium compound is [Rh (OAc) 2] 2And the solvent that uses is methylene dichloride.
In this case, 100% vinyl carbinol transforms, and is 75% selectivity for hydroxyl tetrahydrofuran; For the methylol propionic aldehyde is 17% selectivity, and the hydrogenated products of generation is with l: the b ratio is counted 4.41: 1.
Hydroformylation according to vinyl carbinol; when the chlorine structure division was present in the rhodium compound precursor of catalyst system in (embodiment 2) or the solvent (embodiment 3), embodiment 2 showed the relative high selectivity of linear product (opposite with branched product) with embodiment 3.
Embodiment 4
The hydroformylation of 1-octene: the chlorine structure division is present in the solvent
[Rh (acac) (CO) with 5.0mg (0.0016 mol) 2] 2Join 18.0mg (0.00383 mol) bidentate phosphine part, 1, in 2-two (di-t-butyl phosphinomethyl) benzene.In mixture, add the 10ml methylene dichloride then.Add 2.5ml (16mmol) 1-octene then, and pass through to add CO: H down at 80 ℃ 21: 1 mixture pressure be 30 the crust under carried out hydroformylation 3 hours.
Having found under these conditions had 29% to be converted into the aldehyde product after 3 hours, for branched product, was 80% selectivity for linear aldehyde C-9; L: the b ratio is 4: 1.
Embodiment 5
The hydroformylation of 1-octene: the chlorine structure division is present in rhodium precursor and the solvent
The same in details and the foregoing description 4, except using 9.0mg (0.00383 mol) [RhCl (C0) 2] 2As the rhodium precursor.
Finding again, have 29% to be converted into the aldehyde product, for branched product, is 80% selectivity for linear aldehyde C-9; L: the b ratio is 4: 1.
Embodiment 6
The hydroformylation of 1-octene: the chlorine structure division is present in the rhodium precursor
The same in details and the foregoing description 5, except using the OctMiMTfN of 10ml, 1-octyl group-3-methylimidazole salt di-trifluoromethyl sulphonamide, a kind of not chloride solvent is as solvent.
Finding in this case, have 10% to be converted into the aldehyde product, for branched product, is 80% selectivity for linear aldehyde C-9; L: the b ratio is 4: 1.
Embodiment 7
The hydroformylation of 1-octene: the chlorine structure division is present in the rhodium precursor
The same in details and the foregoing description 5, except using 10ml toluene as solvent.
Finding in this case, have 11% to be converted into the aldehyde product, is 100% selectivity for linear aldehyde C-9.
Comparative Examples 2
The hydroformylation of 1-octene: do not have the chlorine structure division
The same in details and the foregoing description 4, except using 10ml toluene as solvent.
Finding in this case, have 89% to be converted into the aldehyde product, only is 50% selectivity for linear aldehyde C-9; L: the b ratio is 1: 1.
Hydroformylation according to the 1-octene; compare with Comparative Examples 2 (wherein in rhodium precursor or solvent, all not having the chlorine structure division); when the chlorine structure division is present in solvent (embodiment 4), rhodium precursor (embodiment 6 and 7) or solvent and the rhodium precursor (embodiment 5); embodiment 4-7 clearly shows for branched product, the raising of linear selectivity of product.
Although listed and described certain preferred embodiments, those skilled in the art should understand that and can carry out various changes and improvements and do not deviate from scope of the present invention, such as in additional claims definition.
Reader's attention relates to all papers and document, described paper is submitted to simultaneously with this specification sheets (relevant with the application) with document or was submitted to before it and examines to carry out the public with this specification sheets is open, and introduces with for referencial use in this content with described above-mentioned paper and document.
In this specification sheets (comprising any additional claims, summary and accompanying drawing) disclosed all features and/or so disclosed any method or technology in steps can arbitrary combination form make up the combination of repelling mutually except wherein at least some described features and/or step.
If specially do not point out in addition, disclosed each feature can replaceable feature identical with satisfying, equivalent or similar purpose replace in this specification sheets (comprising any additional claims, summary and accompanying drawing).Therefore, if specially do not point out in addition, disclosed each feature only is an example of a series of equivalences or similar characteristics.
The present invention is not limited to the details of previous embodiments.The present invention may extend to any new feature or any new combination of disclosed feature in this specification sheets (comprising any additional claims, summary and accompanying drawing), or any new step or any new combination of the step of disclosed any method like this or technology.

Claims (57)

1. the hydroformylation process of an alefinically unsaturated compounds, described method are included in catalyst system and make described alefinically unsaturated compounds and carbon monoxide and hydrogen reaction under existing, and described catalyst system can be by making following component in conjunction with acquisition:
A) group VIII metallic compound; With
B) bidentate phosphine of general formula (Ia);
Wherein R is the covalency bridged group;
R 1-R 12Represent hydrogen, low alkyl group, aryl or Het independently of one another; Wherein said low alkyl group is meant C 1-C 10Alkyl; Described aryl comprises the carbocyclic aromatic or the false aromatic group of 5-10 unit; Described Het comprises the member ring systems of 4-12 unit, and described member ring systems comprises one or more heteroatomss that are selected from nitrogen, oxygen, sulphur and composition thereof;
Q 1And Q 2Represent phosphorus separately;
The method is characterized in that, in described at least group VIII metallic compound, have the chlorine structure division.
2. the hydroformylation process of an alefinically unsaturated compounds; described method is included in catalyst system and solvent and makes described alefinically unsaturated compounds and carbon monoxide and hydrogen reaction under existing, and described catalyst system can be by making following component in conjunction with acquisition:
A) group VIII metal or its compound; With
B) bidentate phosphine of general formula (Ia);
Wherein R is the covalency bridged group;
R 1-R 12Represent hydrogen, low alkyl group, aryl or Het independently of one another; Wherein said low alkyl group is meant C 1-C 10Alkyl; Described aryl comprises the carbocyclic aromatic or the false aromatic group of 5-10 unit; Described Het comprises the member ring systems of 4-12 unit, and described member ring systems comprises one or more heteroatomss that are selected from nitrogen, oxygen, sulphur and composition thereof;
Q 1And Q 2Represent phosphorus separately;
The method is characterized in that, have the chlorine structure division in one of at least at described group VIII metallic compound or described solvent.
3. as desired method in the claim 2, wherein in described group VIII metallic compound and described solvent, all there is the chlorine structure division.
4. as desired method, wherein R in each of claim 1-3 1-R 12Represent C independently of one another 1-C 6Alkyl, C 1-C 6Alkyl phenyl or phenyl, wherein when having enough carbonatomss, described alkyl can be linearity or branching, saturated or unsaturated, ring-type, acyclic or part ring-type/acyclic, and/or by one or more halogen, cyano group, nitro, OR of being selected from 19, OC (O) R 20, C (O) R 21, C (O) OR 22, NR 23R 24, C (O) NR 25R 26, SR 27, C (O) SR 27, C (S) NR 25R 26, aryl or Het substituting group replace or end-blocking, wherein R 19-R 27Represent hydrogen, aryl or C independently of one another 1-C 10Alkyl.
5. as desired method, wherein R in the claim 4 1-R 12Represent methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, amyl group, hexyl and cyclohexyl independently of one another.
6. as desired method, wherein R in each of claim 1-3 and 5 1, R 4, R 7And R 10Represent identical C independently of one another 1-C 6Alkyl; R 2, R 5, R 8And R 11Represent identical C independently of one another 1-C 6Alkyl; And R 3, R 6, R 9And R 12Represent identical C independently of one another 1-C 6Alkyl.
7. as desired method, wherein R in each of claim 1-3 and 5 1-R 12Represent identical C separately 1-C 6Alkyl.
8. as desired method in the claim 7, wherein said C 1-C 6Alkyl is unsubstituted and is selected from methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, amyl group, hexyl and cyclohexyl.
9. as desired method in the claim 8, wherein said C 1-C 6Alkyl is a methyl.
10. as desired method in each of claim 1-3, wherein R be defined as-A-(K, D) Ar (E, Z)-B-and bidentate phosphine have general formula (I)
Figure F2004800185816C00031
Wherein:
Ar is the bridge linkage group that comprises the optional aryl structure division that replaces, and phosphorus atom is being connected on the available adjacent carbons on the above-mentioned aryl structure division;
A and B represent low-grade alkylidene independently of one another;
K, D, E and Z are the substituting group of aryl structure division Ar, and represent hydrogen, low alkyl group, aryl, He t, halogen, cyano group, nitro, OR independently of one another 19, OC (O) R 20, C (O) R 21, C (O) OR 22, NR 23R 24, C (O) NR 25R 26, C (S) R 25R 26, SR 27, C (O) SR 27Or-J-Q 3(CR 13(R 14) (R 15)) CR 16(R 17) (R 18), wherein J represents low-grade alkylidene; Or two adjacent groups that are selected from K, Z, D and E form another phenyl ring with the carbon atom that they are connected the aromatic ring on it, and described phenyl ring is randomly by one or more hydrogen, low alkyl group, halogen, cyano group, nitro, OR of being selected from 19, OC (O) R 20, C (O) R 21, C (O) OR 22, NR 23R 24, C (O) NR 25R 26, C (S) R 25R 26, SR 27Or C (O) SR 27Substituting group replace; Or Z is by-M (L 1) n(L 2) mExpression and Z are connected on the aryl structure division Ar through the metal-complexing key, and wherein M represents VIB or VIIIB family metal or its metallic cation; And L 1Representative ring pentadienyl, indenyl or aryl, each of above-mentioned group are randomly by one or more hydrogen, low alkyl group, halogen, cyano group, nitro, OR of being selected from 19, OC (O) R 20, C (O) R 21, C (O) OR 22, NR 23R 24, C (O) NR 25R 26, C (S) R 25R 26, SR 27, C (O) SR 27Or the substituting group of ferrocenyl replaces; L 2Represent one or more parts, each of described part is independently selected from hydrogen, low alkyl group, alkaryl, halogen, CO, PR 43R 44R 45Or NR 46R 47R 48N=0 or 1; And m=0-5; Condition is when n=1, and m equals 0 and when n equals 0, and m is not equal to 0;
R 1-R 18Represent low alkyl group, aryl or Het independently of one another;
R 19-R 27Represent hydrogen, low alkyl group, aryl or Het independently of one another;
R 43-R 48Represent hydrogen, low alkyl group, aryl or Het independently of one another; And
Q 1, Q 2If with the Q that exists 3Represent phosphorus separately;
Wherein said low alkyl group is meant C 1-C 10Alkyl; Described low-grade alkylidene comprises C 1-C 10Group, described group two positions on group are carried out keyed jointing and employing and low alkyl group same way as and are defined in addition; Described aryl comprises the carbocyclic aromatic or the false aromatic group of 5-10 unit; Described Het comprises the member ring systems of 4-12 unit, and described member ring systems comprises one or more heteroatomss that are selected from nitrogen, oxygen, sulphur and composition thereof.
11. as desired method, wherein R in the claim 10 1-R 18Represent C independently of one another 1-C 6Alkyl, C 1-C 6Alkyl phenyl or phenyl, wherein when having enough carbonatomss, described alkyl can be linearity or branching, saturated or unsaturated, ring-type, acyclic or part ring-type/acyclic, and/or by one or more halogen, cyano group, nitro, OR of being selected from 19, OC (O) R 20, C (O) R 21, C (O) OR 22, NR 23R 24, C (O) NR 25R 26, SR 27, C (O) SR 27, C (S) NR 25R 26, aryl or Het substituting group replace or end-blocking, wherein R 19-R 27Represent hydrogen, aryl or C independently of one another 1-C 10Alkyl.
12. as desired method, wherein R in the claim 11 1-R 18Represent methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, amyl group, hexyl and cyclohexyl independently of one another.
13. as desired method, wherein R in each of claim 10-12 1, R 4, R 7, R 10, R 13And R 16Represent identical C independently of one another 1-C 6Alkyl; R 2, R 5, R 8, R 11, R 14And R 17Represent identical C independently of one another 1-C 6Alkyl; And R 3, R 6, R 9, R 12, R 15And R 18Represent identical C independently of one another 1-C 6Alkyl.
14. as desired method, wherein R in the claim 10 1-R 18Represent identical C separately 1-C 6Alkyl.
15. as desired method in the claim 14, wherein said C 1-C 6Alkyl is unsubstituted and is selected from methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, amyl group, hexyl and cyclohexyl.
16. as desired method in the claim 15, wherein said C 1-C 6Alkyl is a methyl.
17. as desired method in the claim 10, if wherein A, B and the J that exists represent C independently of one another 1-C 6Alkylidene group.
18. as desired method in the claim 17, if each expression-CH wherein among A, B and the J that exists 2-.
19. as desired method in the claim 10, wherein K, D, E and Z represent hydrogen, phenyl, C separately 1-C 6Alkyl phenyl or C 1-C 6Alkyl.
20. as desired method in the claim 19, wherein K, D, E and Z represent hydrogen separately.
21. as desired method in the claim 10, wherein in formula (I):
A and B represent unsubstituted C independently of one another 1-C 6Alkylidene group;
K, D, E and Z represent hydrogen, C independently of one another 1-C 6Alkyl, phenyl, C 1-C 6Alkyl phenyl or-J-Q 3(CR 13(R 14) (R 15)) CR 16(R 17) (R 18), wherein J represents unsubstituted C 1-C 6Alkylidene group; Or among K, D, Z and the E two carbon atoms that are connected the aromatic ring on it with them form phenyl ring, and described phenyl ring is randomly replaced by one or more substituting groups that are selected from low alkyl group, phenyl or low alkyl group phenyl; Described low alkyl group is meant C 1-C 10Alkyl;
R 1-R 18Represent C independently of one another 1-C 6Alkyl, phenyl or C 1-C 6Alkyl phenyl.
22. as desired method in the claim 10, wherein in formula (I):
A and B all represent-CH 2-or C 2H 4
K, D, Z and E represent hydrogen, C independently of one another 1-C 6Alkyl phenyl or C 1-C 6Alkyl or-J-Q 3(CR 13(R 14) (R 15)) CR 16(R 17) (R 18), wherein J is identical with A; Or among K, D, E and the Z two carbon atoms that are connected the aromatic ring on it with them form unsubstituted phenyl ring;
R 1-R 18Represent C independently of one another 1-C 6Alkyl.
23. as desired method in the claim 22, wherein A and B all represent-CH 2-.
24. as desired method in the claim 10, wherein in formula (I):
R 1-R 12Each identical and expression methyl;
A and expression-CH identical with B 2-;
Identical and the expression hydrogen of K, D, Z and E.
25. as desired method in the claim 10, wherein this to be reflected at temperature be to carry out under 20 ℃-180 ℃.
26. as desired method in the claim 25, wherein temperature is 50 ℃-150 ℃.
27. as desired method in the claim 10, wherein this dividing potential drop that is reflected at carbon monoxide/hydrogen is to carry out under the 1-700 crust.
28. as desired method in the claim 27, wherein dividing potential drop is the 1-300 crust.
29. as desired method in the claim 10, wherein said alefinically unsaturated compounds per molecule contains 1-3 carbon-to-carbon double bond.
30. as desired method in the claim 29, wherein said alefinically unsaturated compounds per molecule contains 1 carbon-to-carbon double bond.
31. as desired method in the claim 10, the bidentate compound of its Chinese style (I) is 10 with respect to the amount of unsaturated compound -5-10 -2The moles/mole unsaturated compound.
32. as desired method in the claim 10, wherein said catalyst system further comprises carrier.
33. as desired method in the claim 10, wherein said bidentate phosphine is selected from two (di-t-butyl phosphino-)-o-Xylols; 1,2-two (two adamantyl phosphinomethyl) benzene; 1,2-two (two adamantyl phosphinomethyl) naphthalene; 1,2-two (two tert-pentyl phosphino-s)-o-Xylol; With two-1,2-(di-t-butyl phosphino-) naphthalene.
34. as desired method in the claim 10, the compound of its Chinese style (I) is with respect to the mol of group VIII metal: the mol scope is 1: 1-3: 1.
35. as desired method in the claim 34, wherein said mol: the mol scope is 1: 1-1.25: 1.
36. as desired method in the claim 10, wherein the group VIII metal is selected from cobalt, nickel, palladium, rhodium, ruthenium and platinum.
37. as desired method in the claim 36, wherein said group VIII metal is a rhodium.
38. as desired method in the claim 10, wherein said chlorine structure division is present in the described group VIII metallic compound at least, and described compound is selected from [RhCl (CO) 2] 2, [RhCl (Cod) 2] 2, RhCl 3XH 2O, [RhCl (norbornadiene)] 2, [RhCl (cyclooctene) 2] 2, chlorine (1, the 5-hexadiene)-rhodium (I) dipolymer, μ-dichloro tetrem alkene-two rhodium, (dicyclo [2,2,1] heptan-2,5-diene) chlorine rhodium (I) dipolymer.
39. as desired method in the claim 10, wherein said chlorine structure division is present in the described group VIII metallic compound at least, and described group VIII metallic compound is selected from [RhCl (CO) 2] 2, [RhCl (Cod) 2] 2And RhCl 3XH 2O.
40. as desired method in the claim 10, wherein said chlorine structure division is present in the described solvent at least, and described solvent is selected from methylene dichloride, chlorobenzene, orthodichlorobenzene, a chlorobenzene, tetracol phenixin, trichloroethane, ethylene dichloride, chlorofluorocarbon and tetrachloroethane.
41. as desired method in the claim 40, wherein said solvent is a methylene dichloride.
42. as desired method in the claim 10, wherein said alefinically unsaturated compounds contains 2-20 carbon atom.
43. as desired method in the claim 42, wherein said alefinically unsaturated compounds contains 5-15 carbon atom.
44. as desired method in the claim 42, wherein said alefinically unsaturated compounds contains 6-12 carbon atom.
45. as desired method in the claim 10, wherein said alefinically unsaturated compounds is selected from isomer, 1-hexene and its isomer, 1-heptene and its isomer, 1-octene and its isomer, 1-nonene and its isomer, 1-decene and its isomer, the C of ethene, propylene, 1-butylene, 2-butylene, iso-butylene, 1-amylene, 2-amylene, 3-amylene and its branching 11-C 20Alkene and their known isomer, 3 pentene nitrile, 3-amylene-4 acid methyl ester, 1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, 1,2,4-heptadiene and 2-methyl isophthalic acid, 3-divinyl.
46. as desired method in the claim 10, wherein said catalyst system further comprises the polymeric dispersant that is dissolved in the liquid vehicle, described polymeric dispersant can be in liquid vehicle the colloidal suspension of particle of the group VIII metal of rugged catalyst system or metallic compound.
47. as desired method in the claim 46, wherein said polymeric dispersant is selected from Polyvinylpyrolidone (PVP), polyacrylamide, polyacrylonitrile, polymine, polyglycine, polyacrylic acid, polymethyl acrylic acid, poly-(3-hydroxybutyric acid), poly--the L-leucine, poly--the L-methionine(Met), poly--the L-proline(Pro), poly--the L-Serine, poly--L-tyrosine, poly-(vinylbenzenesulfonic acid) and poly-(vinyl sulfonic acid).
48. as desired method in the claim 47, wherein said polymeric dispersant is selected from Polyvinylpyrolidone (PVP) and polyacrylic acid.
49. as desired method in the claim 10, wherein when having solvent, this solvent forms by one or more reactants, product or the by product of this method, rather than independent entity.
50. as desired method in the claim 10, wherein Ar is defined as the carbocyclic aromatic group that comprises 6-10 unit, described group except K, D, E or Z randomly by one or more aryl, low alkyl group, Het, halogen, cyano group, nitro, OR of being selected from 19, OC (O) R 20, C (O) R 21, C (O) OR 22, NR 23R 24, C (O) NR 25R 26, SR 27, C (O) SR 27Or C (S) NR 25R 26Substituting group replace R wherein 19-R 27Represent independently of one another hydrogen, aryl or or low alkyl group;
Wherein said low alkyl group is meant C 1-C 10Alkyl; Described aryl comprises the carbocyclic aromatic or the false aromatic group of 5-10 unit; Described Het comprises the member ring systems of 4-12 unit, and described member ring systems comprises one or more heteroatomss that are selected from nitrogen, oxygen, sulphur and composition thereof.
51., wherein be connected to Q as desired method in claim 1 or 2 1And/or Q 2On at least one CR xR yR zGroup, that is, and CR 1R 2R 3, CR 4R 5R 6, CR 7R 8R 9Or CR 10R 11R 12, replaceable is five rings adamantyl or adamantyl, or is connected to Q 1And/or Q 2Any or as above be defined as CR on both xR yR zTwo groups can with the Q that is fit to 1Or Q 2Alternatively form optional 2-phospha-three ring [3 that replaces together.3。1。1{3,7}] the decyl or derivatives thereof.
52. as desired method in the claim 10, wherein Ar is a cyclopentadienyl, and Z can be by-M (L 1) n(L 2) mExpression, and Z is connected on the cyclopentadienyl through the metal-complexing key, and M represents VIB or VIIIB family metal or its metallic cation; With
L 1Representative ring pentadienyl, indenyl or aryl, each of above-mentioned group are randomly by one or more hydrogen, low alkyl group, halogen, cyano group, nitro, OR of being selected from 19, OC (O) R 20, C (O) R 21, C (O) OR 22, NR 23R 24, C (O) NR 25R 26, C (S) R 25R 26, SR 27, C (O) SR 27Or the substituting group of ferrocenyl replaces;
L 2Represent one or more parts, each of described part is independently selected from hydrogen, low alkyl group, alkaryl, halogen, CO, PR 43R 44R 45Or NR 46R 47R 48
R 43-R 48Represent hydrogen, low alkyl group, aryl or Het independently of one another;
N=0 or 1;
And m=0-5;
Condition is when n=1, and m equals 0 and when n equals 0, and m is not equal to 0;
Wherein said low alkyl group is meant C 1-C 10Alkyl; Described aryl comprises the carbocyclic aromatic or the false aromatic group of 5-10 unit; Described Het comprises the member ring systems of 4-12 unit, and described member ring systems comprises one or more heteroatomss that are selected from nitrogen, oxygen, sulphur and composition thereof.
53. as claim 1-3,5,8 and 9 each in desired method, wherein R represents alkylidene group bridging group.
54. a catalyst system, this catalyst system can be by making following component in conjunction with acquisition:
A) as defined group VIII metallic compound in each of claim 1-53; With
B) as defined bidentate phosphine in each of claim 1-53,
And wherein catalyst system is characterised in that, has the chlorine structure division in described at least group VIII metallic compound.
55. a reaction medium, this reaction medium comprises catalyst system and solvent, wherein said solvent in each of claim 2-53 definition, this catalyst system can be by making following component in conjunction with acquisition:
A) as defined group VIII metal or its compound in each of claim 1-53; With
B) as defined bidentate phosphine in each of claim 1-53,
And wherein reaction medium is characterised in that, has the chlorine structure division at described group VIII metallic compound or described solvent in one of at least, is included in the possibility that all exists among both.
56. be used for the purposes of the hydroformylation of alefinically unsaturated compounds as defined catalyst system in the claim 54, wherein said purposes is included in described catalyst system and has the step that makes described alefinically unsaturated compounds and carbon monoxide and hydrogen reaction down.
57. be used for the purposes of the hydroformylation of alefinically unsaturated compounds as defined reaction medium in the claim 55, described purposes is included in described reaction medium and has the step that makes described alefinically unsaturated compounds and carbon monoxide and hydrogen reaction down.
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