Method for the hydroformylation of 2-substituted butadienes and the production of secondary products thereof, especially ambrox

A process for the preparation of compounds of the general formula (I) and of secondary products thereof,

• comprising reacting at least one compound of the general formula (II)
• in which
• R1 is in each case linear or branched C1-C24-alkyl or C2-C24-alkenyl having 1, 2, 3 or more than 3 C—C double bonds,
• with carbon monoxide and hydrogen in the presence of a hydroformylation catalyst comprising a rhodium complex with at least one phosphorus chelate compound as ligand, the hydroformylation catalyst comprising at least one phosphorus chelate compound of the general formula (VI)
• in which
• RA, RB, RC and RD, independently of one another, are alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl,
• where the alkyl radicals RA, RB, RC and RD are unsubstituted or carry 1, 2, 3, 4 or 5 identical or different substituents which are selected from cycloalkyl, heterocycloalkyl, aryl, hetaryl, alkoxy, cycloalkoxy, heterocycloalkoxy, aryloxy, hetaryloxy, hydroxy, mercapto, polyalkylene oxide, polyalkyleneimine, COOH, carboxylate, SO3H, sulfonate, NE1E2, NE1E2E3+X−, halogen, nitro, formyl, acyl and cyano, in which E1, E2 and E3 are in each case identical or different radicals selected from hydrogen, alkyl, cycloalkyl or aryl, and X− is an anion equivalent,
• and where the cycloalkyl, heterocycloalkyl, aryl and hetaryl radicals RA, RB, RC and RD are in each case unsubstituted or carry 1, 2, 3, 4 or 5 identical or different substituents which are selected from alkyl and the substituents specified above for the alkyl radicals RA, RB, RC and RD,
• or
• RA and RB and/or RC and RD, together with the phosphorus atom and, if present, the oxygen atoms to which they are bonded, are a 5- to 8-membered heterocycle which is optionally additionally annelated once, twice or three times with cycloalkyl, heterocycloalkyl, aryl or hetaryl, where the heterocycle and, if present, the annelated groups are, independently of one another, unsubstituted or carry one, two, three or four identical or different substituents which are selected from alkyl, cycloalkyl, heterocycloalkyl, aryl, hetaryl, hydroxy, mercapto, polyalkylene oxide, polyalkyleneimine, alkoxy, halogen, COOH, carboxylate, SO3H, sulfonate, NE4E5, NE4E5E6+X−, nitro, alkoxycarbonyl, formyl, acyl and cyano, in which E4, E5 and E6 are in each case identical or different radicals, selected from hydrogen, alkyl, cycloalkyl and aryl, and X− is an anion equivalent,
• a, b, c and d, independently of one another, are 0 or 1, and
• Y is selected from groups of the formula VII.a or VII.b
• in which
• RI, RII, RIII, RIV, RV and RVI, independently of one another, are hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl, hetaryl, hydroxy, mercapto, polyalkylene oxide, polyalkyleneimine, alkoxy, halogen, SO3H, sulfonate, NE7E8, alkylene-NE7E8, trifluoromethyl, nitro, alkoxycarbonyl, carboxyl, formyl, acyl or cyano, in which E7 and E8 are in each case identical or different radicals selected from hydrogen, alkyl, cycloalkyl and aryl,
• where two adjacent radicals RI to RVI, together with the carbon atoms of the benzene ring to which they are bonded, can also be a condensed ring system having 1, 2 or 3 further rings,
• A1 and A2, independently of one another, are O, S, SiRERF, NRG or CRHRK, where RE, RF, RG, RH and RK, independently of one another, are hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl, and
• D is a divalent bridging group of the general formula
• in which
• # is in each case a binding site to the 9,10-dihydroanthracene backbone, and
• Rd1, Rd2, Rd3 and Rd4, independently of one another, are hydrogen, alkyl, cycloalkyl, aryl, halogen, trifluoromethyl, carboxyl, carboxylate or cyano,
• where Rdl can also be, together with Rd3, the binding fraction of a double bond between the two carbon atoms to which Rdl and Rd3 are bonded, and/or Rd2 and Rd4, together with the carbon atoms to which they are bonded, can also be a 4- to 8-membered carbo- or heterocycle, which is optionally additionally annelated once, twice or three times with cycloalkyl, heterocycloalkyl, aryl or hetaryl, where the carbo- or heterocycle and, if present, the annelated groups are, independently of one another, unsubstituted or in each case carry one, two, three or four identical or different substituents which are selected from alkyl, cycloalkyl, heterocycloalkyl, aryl, hetaryl, COORd5, COO−M+, SO3Rd5, SO3−M+, NE9E10, alkylene-NE9E10, NE9E10E11+X−, alkylene-NE9E10E11+X−, ORd6, SRd6, (CHRfCH2O)yRd6, (CH2N(E9))yRd6, (CH2CH2N(E9))yRd6, halogen, trifluoromethyl, nitro, formyl, acyl or cyano, in which
• Rd5, E9, E10 and E11 are in each case identical or different radicals selected from hydrogen, alkyl, cycloalkyl or aryl,
• Rd6 is hydrogen, methyl or ethyl,
• M+ is a cation equivalent,
• X− is an anion equivalent, and
• Y is an integer from 1 to 120,
• wherein a reaction mixture is obtained which comprises at least 50.1% by weight, based on the total weight of the reaction mixture, of at least one compound of the general formula (I).