| US 7,615,645 B2 | ||
| Method for the continuous production of aldehydes | ||
| Martin Volland, Heidelberg (Germany); Thomas Mackewitz, Römerberg (Germany); Wolfgang Ahlers, Worms (Germany); Ansgar Schäfer, Karlsruhe (Germany); Wolfgang Richter, Wachenheim (Germany); and Rocco Paciello, Bad Dürkheim (Germany) | ||
| Assigned to BASF Aktiengesellschaft, (Germany) | ||
| Appl. No. 10/575,843 PCT Filed Oct. 14, 2004, PCT No. PCT/EP2004/011530 § 371(c)(1), (2), (4) Date Apr. 13, 2006, PCT Pub. No. WO2005/042458, PCT Pub. Date May 12, 2005. |
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| Claims priority of application No. 103 49 482 (DE), filed on Oct. 21, 2003; and application No. 10 2004 041 144 (DE), filed on Aug. 24, 2004. | ||
| Prior Publication US 2007/0004939 A1, Jan. 04, 2007 | ||
| Int. Cl. C07C 45/50 (2006.01); C07D 207/00 (2006.01) | ||
| U.S. Cl. 548—400 [568/8; 568/451; 568/453] | 12 Claims |
1. A process for the continuous preparation of an aldehyde having from 5 to 21 carbon atoms by isomerizing hydroformylation
in the homogeneous phase of an olefin composition having from 4 to 20 carbon atoms and comprising an α-olefin or an olefin
having internal double bonds by means of a synthesis gas in the presence of a homogeneous rhodium catalyst complexed with
an oxygen- and/or nitrogen-containing organophosphorus ligand and free ligand at elevated temperature and elevated pressure
in a multistage reaction system comprising at least two reaction zones, wherein the olefin composition is firstly reacted
with the synthesis gas having a CO/H2 molar ratio of from 4:1 to 1:2 at a total pressure of from 10 to 40 bar in a group of one or more first reaction zones to
a conversion of the α-olefin of from 40 to 95% and the hydroformylation mixture from this group of one or more first reaction
zones is reacted with the synthesis gas having a CO/H2 molar ratio of from 1:4 to 1:1000 at a total pressure of from 5 to 30 bar in a group of one or more downstream reaction zones,
where the total pressure in the one or more downstream reaction zones is in each case from 1 to (T1−Tf) bar lower than in
the preceding reaction zone, where T1 is the total pressure in the preceding reaction zone and Tf is the total pressure in
the reaction zone downstream of the one or more first reaction zones, with the proviso that the difference T1−Tf is greater
than 1 bar, and the CO partial pressure in the one or more downstream reaction zones is in each case lower than in the reaction
zone preceding this reaction zone wherein the catalyst used is a complex of rhodium with a phosphoramidite ligand of the formula
I
 where
Q is a bridging group of the formula
 where
A1 and A2 are each, independently of one another, O, S, SiRaRb, NRc or CRdRe, where
Ra, Rb and Rc are each, independently of one another, hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl,
Rd and Re are each, independently of one another, hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl or together with the
carbon atom to which they are bound form a cycloalkylidene group having from 4 to 12 carbon atoms or the group Rd together with a further group Rd or the group Re together with a further group Re forms an intramolecular bridging group D,
D is a divalent bridging group selected from group consisting of
 where
R9 and R10 are each, independently of one another, hydrogen, alkyl, cycloalkyl, aryl, halogen, trifluoromethyl, carboxyl, carboxylate
or cyano or are joined to one another to form a C3- to C4-alkylene bridge,
R11, R12, R13 and R14 are each, independently of one another, hydrogen, alkyl, cycloalkyl, aryl, halogen, trifluoromethyl, COOH, carboxylate, cyano,
alkoxy, SO3H, sulfonate, NE1E2, alkylene-NE1E2E3+X−, acyl or nitro,
c is 0 or 1,
Y is a chemical bond,
R5, R6, R7 and R8 are each, independently of one another, hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl, hetaryl, COORf, COO−M+, SO3Rf, SO−3M+, NE1E2, NE1E2E3+X−, alkylene-NE1E2E3+X−, ORf, SRf, (CHRgCH2O)xRf, (CH2N(E1))xRf, (CH2CH2N(E1))xRf, halogen, trifluoromethyl, nitro, acyl or cyano,
where
Rf, E1, E2 and E3 are identical or different radicals selected from among hydrogen, alkyl, cycloalkyl and aryl,
Rg is hydrogen, methyl or ethyl,
M+ is a cation,
X− is an anion and
x is an integer from 1 to 120,
or
R5 and/or R7 together with two adjacent carbon atoms of the benzene ring to which they are bound form a fused ring system having 1, 2 or
3 further rings,
a and b are each, independently of one another, 0 or 1,
P is a phosphorus atom,
and
R1, R2, R3, R4 are each, independently of one another, hetaryl, hetaryloxy, alkyl, alkoxy, aryl, aryloxy, cycloalkyl, cycloalkoxy, heterocycloalkyl,
heterocycloalkoxy or an NE1E2 group, with the proviso that R1 and R3 are bound via the nitrogen atom of pyrrole groups bound to the phosphorus atom P or R1 together with R2 and/or R3 together with R4 form a divalent group E which contains at least one pyrrole group bound via the pyrrole nitrogen to the phosphorus atom P
and has the formula
Py-I-W
where
Py is a pyrrole group,
I is a chemical bond or O, S, SiRaRb, NRc or CRhRi,
W is cycloalkyl, cycloalkoxy, aryl, aryloxy, hetaryl or hetaryloxy,
and
Rh and Ri are each, independently of one another, hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl,
or form a bispyrrole group which is bound via the nitrogen atoms to the phosphorus atom P and has the formula
Py-I-Py.
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