CN1980883B - Method for the production of optically active alkyl succinic acid monoalkyl esters - Google Patents

Method for the production of optically active alkyl succinic acid monoalkyl esters Download PDF

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CN1980883B
CN1980883B CN2005800228341A CN200580022834A CN1980883B CN 1980883 B CN1980883 B CN 1980883B CN 2005800228341 A CN2005800228341 A CN 2005800228341A CN 200580022834 A CN200580022834 A CN 200580022834A CN 1980883 B CN1980883 B CN 1980883B
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hydrogenation
alkyl
catalyzer
succinic acid
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CN1980883A (en
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F·黑特歇
C·耶克尔
M·弗里德里克
R·帕切洛
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BASF SE
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    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
    • B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
    • B01J31/2419—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising P as ring member
    • B01J31/2428—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising P as ring member with more than one complexing phosphine-P atom
    • B01J31/2433—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising P as ring member with more than one complexing phosphine-P atom comprising aliphatic or saturated rings
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    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
    • B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
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    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/303—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by hydrogenation of unsaturated carbon-to-carbon bonds
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    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/60—Reduction reactions, e.g. hydrogenation
    • B01J2231/64—Reductions in general of organic substrates, e.g. hydride reductions or hydrogenations
    • B01J2231/641—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes
    • B01J2231/645—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes of C=C or C-C triple bonds
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    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/82—Metals of the platinum group
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    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/82—Metals of the platinum group
    • B01J2531/828—Platinum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/84—Metals of the iron group
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    • C07B2200/00—Indexing scheme relating to specific properties of organic compounds
    • C07B2200/07—Optical isomers

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Abstract

The invention relates to a method for producing optically active alkyl succinic acid monoalkyl esters of formula (I), wherein D and E independently represent H, C1-C10 alkyl, and R represents C1-C10 aryl or alkylaryl.

Description

The method for preparing optically active alkyl succinic acid monoalkyl esters
The present invention relates to a kind of novel method for preparing optically active alkyl succinic acid monoalkyl esters.
Prior art
Up to now, can't obtain a kind of direct unsaturated precursor by them directly optionally forms III type system and optically active enantiomorph thereof by asymmetric hydrogenation path satisfactorily.
Figure G2005800228341D00011
This can be by for example confirming that by methylene-succinic acid monomethyl ester 3 preparation (2R)-methylsuccinic acid 4-methyl ester 4 wherein methylene-succinic acid monomethyl ester 3 can easily obtain with low cost.
K.Achiwa, Y.Ohga, Y.Itaka, Tetrahedron Lett.1978,19,4683 in methyl alcohol, obtained the to have 60% enantiomeric excess compound 4 of (=ee=[enantiomorph 1 content-enantiomorph 2 content]/[enantiomorph 1 content+enantiomorph 2 content]).
W.C.Christopfel, B.D.Vineyard, J.Am.Chem.Soc.1979,101,4406 have obtained to have the compound 4 of 55%ee in methyl alcohol.
S.Saito, Y.Nakamura, Y.Morita, Chem.Pharm.Bull.1985,33,5284 have obtained to have the compound 4 of 90%ee in benzene/MeOH 1/4.
H.Kawano, Y.Ishii, T.Ikariya, M.Saburi, S.Yoshikawa, TetrahedronLett.1987,28,1905 have obtained to have the compound 4 of 60%ee in toluene/THF.
D.Carmichael, H.Doucet, J.M.Brown, Chem.Commun.1999,261 H.Kawano, T.Ikariya, Y.Ishii, M.Saburi, S.Yoshikawa et al., J.Chem.Soc.Perkin Trans.1 1989,1571 have obtained to have the compound 4 of 94%ee in methyl alcohol.
U.Berens, M.Burk, (WO 00/27855 for A.Gerlach; EP 1 127 061 B1) in methyl alcohol, obtained to have the compound 4 of 95%ee.
Therefore, under the situation of not having additional enriching step, the optical purity that aforesaid method reaches can not satisfy the requirement of activeconstituents aspect, and requirement in most cases is enantiomeric excess 〉=98%ee.
Other method that can reach higher optical purity is used a large amount of catalyzer, just low substrate/catalyst ratio (s/c), and this is uneconomic for industrial production; Perhaps selected reaction conditions (particularly solvent) is had in mind or is in-problem for the reason of Occupational safety from environmental.
M.Ostermeier, B.Brunner, C.Korff, G.Helmchen, Eur.J.Org.Chem.2003,3453 obtain to have the compound 4 of 97.3%ee with 200/1 s/c ratio in methylene dichloride, at C 6H 5CF 3In equally reached 98.3%ee with 200/1 s/c ratio.In ethylene dichloride, the s/c ratio with 1000/1 reaches purity 99.3%ee.
For the above reasons, all these methods all are not suitable on technical scale by directly synthesizing optically-active succsinic acid alkyl ester in one step of alkene precursor that obtains with low-cost and easy-to.
Goal of the invention
The purpose of this invention is to provide a kind of novel method for preparing optically active alkyl succinic acid monoalkyl esters, this method is used a spot of catalyzer (s/c 〉=20,000/1), have simultaneously with the reaction conditions of environmental harmony, completely reaction conversion ratio and high optical yield (〉=98%ee), therefore can carry out efficient, environmentally acceptable, effectively industry is synthetic for cost.
Summary of the invention
We have found that the method for a kind of preparation formula (I) optically active alkyl succinic acid monoalkyl esters,
Wherein D and E are H, C independently of one another 1-C 10Alkyl,
R is C 1-C 10Alkyl, aryl or alkylaryl,
This method in the presence of the catalyzer that comprises formula (L) phospholane part (phospholane ligand),
Figure G2005800228341D00032
(L)
Wherein:
R 1And R 2Be C independently of one another 1-C 6Alkyl, aryl, alkylaryl,
R 1Be hydrogen in addition,
A is R 1Or
Condition is B=has 1-5 carbon atom between two P atoms connection base (Iinker) or Cp-Fe-Cp,
Enantioselectivity ground hydrogenation of formula (II) compound:
Figure G2005800228341D00041
Wherein D, E and R have meaning mentioned above.
Formula (I) compound is the optically-active compound that is used for representing a kind of enantiomorph (R or S) in all cases.
Enantioselective hydrogenation is used to refer to following hydrogenation hereinafter: this hydrogenation can not obtain two kinds of enantiomorphs of same degree, and wherein a kind of enantiomorph (R or S) forms with high purity, the particularly purity with enantiomeric excess 98%, 99%, 99.5%.
The initial compounds of formula (II) can by document know and can be easily by the traditional method preparation (for D=E=H; R=Me, referring to for example, A.R.Devi, S.Rajaram, Ind.J.Chem.2000,39B, 294-296 or R.C.Anand, V.A.Milhotra, J.Chem.Res. (S) 1999,378-379 or R.N.Ram, I.Charles, Tetrahedron 1997,53,7335-7340).Preferred initial compounds (II) is those wherein D and E compounds of having following meaning independently of one another: H, methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, wherein said alkyl comprise the not isomer of branching and branching.Particularly preferred initial compounds is that wherein D and E are those of H and methyl, and especially wherein D and E are that H or D and E are those of methyl.Further preferred initial compounds (II) is that wherein D is that H and E are those of butyl.
Radicals R can be C 1-C 10Alkyl, each H atom in the wherein said alkyl can so that by other group such as OH, NH 2, NO 2, CN, F, Cl, Br, I replace.In addition, R can also be aryl such as phenyl, naphthyl; With alkylaryl such as benzyl, aryl wherein can also and then be substituted.Preferred R is methyl, ethyl, propyl group, sec.-propyl and the tertiary butyl.R is preferably methyl especially.
Described catalyzer comprises the atoms metal that is selected from Pd, Pt, Ru, Rh, Ni, Ir.Particularly preferred catalyzer has Rh, Ru or the Ir as atoms metal, and the Rh catalyzer is particularly suitable for the inventive method.
The source metal that can be preferred for preparing described catalyzer is for example Pd of precursor 2(DBA) 3, Pd (Oac) 2, [Rh (COD) Cl] 2, [Rh (COD) 2]] X, Rh (acac) is (CO) 2, RuCl 2(COD), Ru (COD) (methylallyl) 2, Ru (Ar) Cl 2, the aryl that Ar=does not replace and replaces, [Ir (COD) Cl] 2, [Ir (COD) 2] X, Ni (allyl group) X.Also preferably use NBD (=norbornadiene) replaced C OD (=1, the 5-cyclooctadiene).
X can be that those skilled in the art are known and can be used for any negatively charged ion of asymmetric synthesis in these cases.The example of X is for example Cl of halogen -, Br -, I -, BF 4 -, ClO 4 -, SbF 6 -, PF 6 -, CF 3SO 3 -, BAr 4 -X is BF preferably 4 -, CF 3SO 3 -, SbF 6 -, ClO 4 -, BF particularly 4 -And CF 3SO 3 -
The catalyzer of the inventive method comprises the phospholane part of one or more formulas (L) in addition.Preferred substituted R 1And R 2Be H, methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, benzyl.R 1=H and R 2The substituting group combination of=methyl is particularly preferred.
Two R wherein further preferably in addition 1Form the R of bridge 1Group, for example isopropylidene or benzylidene.
Under the situation of bisphospholane (diphospholanes), preferably following formula represent those.
Figure G2005800228341D00051
The basic B of particularly preferred connection is n=1 or 2 or those of m=0 wherein.
Particularly preferred ligand L is that wherein A represents another one phospholane residue and is connected those of basic B, and wherein B can represent the bridge of two carbon atoms of the 1-5 between the phosphorus atom.1-5 carbon atom between described two phosphorus atom also do not mean that B comprises 5 carbon atoms at most, but the direct connection between two phosphorus atom comprises and is no more than 5 carbon atoms.B can be a phenyl ring for example, and condition is that two phosphorus atom are connected on the phenyl ring in contraposition.
But connecting basic B can also be ferrocene type compound, and it is by replacing or unsubstituted and form with the cyclopentadienyl (Cp) that sandwich form (Cp-Fe-Cp) comprises the Fe atom, and wherein the P Atom Bonding is to the Cp base.
Particularly preferred ligand L is:
Figure G2005800228341D00061
The present invention not only comprises the enantiomorph of being represented by these structural formulas, but also comprises their optically active enantiomorph.
About the Rophos Preparation of catalysts, with reference to EP 0889048, it is for reference to quote this patent at this.
Part-metal complexes can be by comprising unstable part ([RuCl for example 2(COD)] n, [Rh (COD) 2] BF 4, [Rh (COD) 2] CF 3SO 3, Rh (COD) 2ClO 4, [Ir (COD) Cl] 2, right-cymene ruthenium chloride dimer) rhodium, iridium, ruthenium, palladium, platinum, nickel complex reaction prepare with known manner synthesis catalytic labile coordination compound.But NBD also replaced C OD is used to prepare title complex, has good result.
As known to the those skilled in the art, title complex (=preformed catalyst precatalyst) can produce before using and separate, in time use then, or before actual hydrogenation generation (stating as follows) on the spot in reaction vessel.
Suitable solvent is the known solvents that are useful on asymmetric hydrogenation of those skilled in the art.Preferred solvent is a lower alkyl alcohol, for example methyl alcohol, ethanol, Virahol and toluene, THF, ethyl acetate.In the methods of the invention, methyl alcohol is preferably used as solvent especially.
Hydrogenation of the present invention is carried out under-20 ℃ to 150 ℃ usually, and preferred 0-100 ℃, preferred 10-80 ℃ especially.
The inventive method uses in all cases 〉=20,000/1 substrate/catalyst ratio (s/c), and result acquisition 〉=98%ee.Even the s/c ratio with 110,000/1 has also reached 98%ee.
The use of catalyzer can further be simplified by suitable stagnant catalyst.
For method for hydrogenation of the present invention, hydrogen pressure can change in the wide region of 0.1 crust-300 crust.In the pressure range of 1-200 crust, preferred 1-100 crust, obtain extraordinary result.
Reaction mixture utilizes the known step process of those skilled in the art.Product can for example be converted into carboxylate salt, precipitation and and then from catalyzer, remove, discharge again subsequently; Alternative possible method is by absorption that catalyzer is fixing in bed, can easily carry out chromatogram like this and purify.Can also catalyzer be shifted out from product by distillation.
By the product buffering be carboxylate salt and from reaction mixture, precipitating simply enantiomeric excess can be brought up to＞99.5%.To this suitable alkali is known all alkali of those skilled in the art, and wherein preferred amines and guanidine are as neutral alkali (neutral bases), and carboxylate salt, carbonate, oxyhydroxide, oxide compound are as metal base.Particularly preferred metal base is corresponding lithium compound.
Other is preferred embodiment described in appended claims and experimental section.
Experimental section
Embodiment 1
Preparation optically-active methylsuccinic acid methyl ester (s/c 20,000/1)
Under shielding gas with (RophosARhCOD) CF of 133mg (0.182mmol) 3SO 3(=preformed catalyst) is introduced in 4 liters of 21ml methyl alcohol in (enamel) Pfaudler autoclave, and adds 526g (3.65mol) the 2-methene succinic acid 4-mono-methyl (=substrate) that is dissolved in the 704ml methyl alcohol.Cling under the hydrogen at 40 ℃ and 5 then and carry out hydrogenation.Substrate conversion after 4 hours, finish ( 1H-NMR, 500MHz).Mapping by gas Chromatographic Determination product (2R)-methylsuccinic acid 4-mono-methyl is excessive＞98% (source: BGB-Analytik, column type: BGB-174, length 30m, internal diameter: 0.25ml, film thickness: 0.25 μ m, carrier gas: helium, inlet pressure: 2.35 crust, temperature: 135 ℃, heating rate: 1.2 ℃/min, the retention time of R enantiomorph: 23.3 minutes, the retention time of S enantiomorph: 22.6 minutes).The s/c ratio is 20,000: 1.
Embodiment 2
Preparation optically-active methylsuccinic acid methyl ester (s/c 40,000/1)
With 40,000: catalyzer/substrate ratio s/c of 1 carries out the reaction that embodiment 1 describes.Substrate conversion was finished after 4 hours.The enantiomeric excess of product＞98%.
Embodiment 3
Preparation optically-active methylsuccinic acid methyl ester (s/c 110,000/1)
Under shielding gas, 5.73g (39.8mmol) 2-methene succinic acid-4-mono-methyl is introduced in the 12ml methyl alcohol in the 50ml glass autoclave, and adds 6.6mg (RophosARhCOD) CF of 0.12ml 3SO 3(=preformed catalyst) solution (0.00036mmol preformed catalyst) in 3ml methyl alcohol.Cling under the hydrogen at 60 ℃, 5 then and carry out hydrogenation.The conversion of precursor was finished after 16 hours.The enantiomeric excess of this product is 98%.
Embodiment 4
Preparation optically-active methylsuccinic acid methyl ester then forms lithium salts on technical scale
Under shielding gas, 75kg methene succinic acid 4-mono-methyl (520.4mol) is introduced in 1m 3In 185 liters of methyl alcohol in the steel container.Adding 19.0g is dissolved in (RophosARhCOD) CF in 2 liters of methyl alcohol 3SO 3(=26mmol preformed catalyst, s/c 20,000/1) then clung under the hydrogen at 50 ℃, 4 and carried out hydrogenation.The conversion of substrate was finished after 4 hours.The enantiomeric excess of this hydrogenated products is determined as the 99.4% (manufacturers of post: Chiracel by chirality HPLC; Column type: OD-H; Moving phase: 95vol% normal heptane/5vol%2-propyl alcohol-this mixture of 0.1ml trifluoroacetic acid/1L; Retention time:
t R((R)-2-methylsuccinic acid 4-methyl ester)=7.4 minutes
t R((S)-2-methylsuccinic acid 4-methyl ester)=16.7 minutes).
In reaction soln, gradation adds total 22.2kg lithium hydroxide monohydrate, then adds the 375kg methyl tertiary butyl ether, is cooled to 0 ℃.By filtering the carboxylic acid lithium is removed (yield: 65.8kg) from the suspension that obtains.Its enantiomeric excess (after release, measuring)＞99.8%.
Embodiment 5
On-site preparation preformed catalyst (general step)
With 1.1 normal RophosA-Bistriflate salt (Rophos*2CF 3SO 3H) be dissolved in methyl alcohol with 1.1 equivalent alkali (preferred amines such as triethylamine, H ü nig ' s alkali etc.), and under-10 ℃, slowly splash into 1 normal source metal, preferred (Rh[COD] 2) in the solution of X, X=BF wherein 4, CF 3SO 3, SbF 6, PF 6, ClO 4, BAr 4Make this mixture reach room temperature then.If the use free ligand does not then add alkali.

Claims (17)

1. the method for a preparation formula (I) optically active alkyl succinic acid monoalkyl esters,
Figure F2005800228341C00011
Wherein D and E are H, C independently of one another 1-C 10Alkyl,
R is C 1-C 10Alkyl, phenyl or benzyl,
This method in the presence of the catalyzer that comprises formula (L) phospholane part,
Figure F2005800228341C00012
Wherein:
R 1Be hydrogen, C 1-C 6Alkyl or benzyl,
R 2Be C 1-C 6Alkyl or benzyl,
A is R 1Or
Condition be B=between two P atoms, have 1-5 carbon atom the connection base or
Cp-Fe-Cp，
Enantioselectivity ground hydrogenation of formula (II) compound
Figure F2005800228341C00021
Wherein D, E and R have above-mentioned meaning.
2. the method for claim 1, wherein D and E are that hydrogen and R are Me.
3. the method for claim 1 wherein is selected from part among Rophos A, the Rophos B as part (L):
Figure F2005800228341C00022
4. the method for claim 1, wherein said hydrogenation is carried out under the hydrogen pressure of 1-100 crust.
5. the method for claim 1, wherein said hydrogenation is carried out in methyl alcohol.
6. the method for claim 1, wherein said hydrogenation is carried out under 10 ℃-80 ℃.
7. the method for claim 1, use therein catalyzer is fixed.
8. the method for claim 1, wherein the reaction product that is obtained by hydrogenation (I) is converted into carboxylate salt and removes from this reaction mixture with this form.
9. method as claimed in claim 8, wherein said reaction product (I) precipitates from this reaction mixture with the form of carboxylic acid lithium.
10. the method for a preparation formula (I) optically active alkyl succinic acid monoalkyl esters,
Figure F2005800228341C00031
Wherein D and E are H, C independently of one another 1-C 10Alkyl,
R is C 1-C 10Alkyl, phenyl or benzyl,
This method in the presence of comprising the catalyzer that is selected from the part among Me-KetalPhos and the Me-f-KetalPhos,
Enantioselectivity ground hydrogenation of formula (II) compound
Wherein D, E and R have above-mentioned meaning.
11. method as claimed in claim 10, wherein D and E are that hydrogen and R are Me.
12. method as claimed in claim 10, wherein said hydrogenation is carried out under the hydrogen pressure of 1-100 crust.
13. method as claimed in claim 10, wherein said hydrogenation is carried out in methyl alcohol.
14. method as claimed in claim 10, wherein said hydrogenation is carried out under 10 ℃-80 ℃.
15. method as claimed in claim 10, use therein catalyzer is fixed.
16. method as claimed in claim 10, wherein the reaction product that is obtained by hydrogenation (I) is converted into carboxylate salt and removes from this reaction mixture with this form.
17. method as claimed in claim 16, wherein said reaction product (I) precipitates from this reaction mixture with the form of carboxylic acid lithium.
CN2005800228341A 2004-07-07 2005-07-06 Method for the production of optically active alkyl succinic acid monoalkyl esters Expired - Fee Related CN1980883B (en)

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DE200410032968 DE102004032968A1 (en) 2004-07-07 2004-07-07 Preparation of optically active alkyl succinic acid monoalkyl esters comprising enantioselective hydrogenation of ester compound in presence of catalyst, which carries phospholane ligand
DE102004032968.0 2004-07-07
DE102005007750.1 2005-02-18
DE200510007750 DE102005007750A1 (en) 2005-02-18 2005-02-18 Preparation of optically active alkyl succinic acid monoalkyl esters comprising enantioselective hydrogenation of ester compound in presence of catalyst, which carries phospholane ligand
PCT/EP2005/007289 WO2006002999A2 (en) 2004-07-07 2005-07-06 Method for the production of optically active alkyl succinic acid monoalkyl esters

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