US 7,507,853 B2
Process for the preparation of phenolic carboxylic acid derivatives by enzymatic catalysis
Reinhold Öhrlein, Rheinfelden-Herten (Germany); Gabriele Baisch, Binzen (Germany); Kai-Uwe Schöning, Oberwil (Switzerland); Jemima Schmidt, Schopfheim (Germany); and Sandra Franziska Mayer, Hetzendorf (Austria)
Assigned to Ciba Specialty Chemicals Corporation, Tarrytown, N.Y. (US)
Appl. No. 10/529,802
PCT Filed Oct. 02, 2003, PCT No. PCT/EP03/10967
§ 371(c)(1), (2), (4) Date Mar. 30, 2005,
PCT Pub. No. WO2004/033699, PCT Pub. Date Apr. 22, 2004.
Claims priority of application No. 02405869 (EP), filed on Oct. 10, 2002.
Prior Publication US 2006/0110807 A1, May 25, 2006
Int. Cl. C12P 7/42 (2006.01); C12P 7/62 (2006.01); C12P 7/22 (2006.01); C12P 13/02 (2006.01); C07C 69/88 (2006.01); C07C 69/76 (2006.01)
U.S. Cl. 560—67  [560/65; 560/75; 560/55; 560/87; 560/89; 560/95] 10 Claims
 
1. A process for the preparation of a compound of the formula:

OG Complex Work Unit Drawing
wherein
one of R1 and R2 independently of one another represents hydrogen, a substituent selected from the group consisting of C1-C18alkyl, phenyl, (C1-C4alkyl)1-3phenyl, phenyl-C1-C3alkyl, (C1-C4alkyl)1-3phenyl-C1-C3alkyl, C5-C12cycloalkyl and (C1-C4alkyl)1-3C5-C12cycloalkyl or a group of the partial formula:

OG Complex Work Unit Drawing
wherein
Ra represents hydrogen or a substituent selected from the group consisting of C1-C4alkyl, halogen and sulpho;
and the other one of R1 and R2 represents a substituent selected from the group consisting of C4-C18alkyl, phenyl, (C1-C4alkyl)1-3phenyl, phenyl-C1-C3alkyl, (C1-C4alkyl)1-3phenyl-C1-C3alkyl, C5-C12cycloalkyl and (C1-C4alkyl)1-3C5-C12cycloalkyl or a group of the partial formula (A);
R3 represents hydrogen or methyl;
m represents zero or 1; and
n represents a numeral from 1 to 4; and,
if n represents 1,
m represents zero or 1, Y represents the monovalent groups —O—Y1 or —N(—Y2)2, wherein Y1 is selected from the group consisting of C5-C45alkyl, C3-C45alkyl interrupted by at least one O-heteroatom, C5-C12cycloalkyl, C2-C12alkenyl,
—CH2—CH(OH)—CH2—O—C(═O)—Rb  (B),
wherein
Rb represents hydrogen or a substituent selected from the group consisting of C1-C8alkyl, C3-C5alkenyl and benzyl and
—CH2—CH2—O—Rc  (C),
wherein
Rc represents hydrogen or a substituent selected from the group consisting of C1-C24alkyl, C5-C12cycloalkyl, phenyl,
—CHRd—CHRe—C(═O)—O—Rt  (C1),
wherein
one of Rd and Re represents methyl and the other one represents methyl and Rf represents hydrogen or C1-C24alkyl,

OG Complex Work Unit Drawing
wherein R1 and R2 are as defined above, and
—CH2—C(═O)—O—Rf  (C3),
wherein Rf is as defined above; and,
Y2 represents hydroxy-C2-C4alkyl;
if n represents 2,
m represents zero, Y represents a bivalent group selected from the group consisting of
—O—CxH2x—O—
wherein x is a numeral from 2 to 20,
—O—(CH2—CH2—O)y—CH2—CH2—O—  (E),
wherein y is a numeral from 1 to 30,
—O—CH2—CH2—S—CH2—CH2—O—
—O—CH2—CH═CH—CH2—O—  (G)
—NH—(CH2)z—NH—  (H),
wherein z represents zero or a numeral from 2 to 10; and
if n represents 3,
m represents zero and Y represents a trivalent group selected from the group consisting of

OG Complex Work Unit Drawing
wherein Rg represents C1-C24alkyl or phenyl, and

OG Complex Work Unit Drawing
and, if n represents 4,
m represents zero and Y represents a tetravalent group of the partial formula:

OG Complex Work Unit Drawing
characterised in that in a compound of the formula:

OG Complex Work Unit Drawing
wherein
R1, R2, R3 and m are as defined above and —X represents C1-C4 alkoxy, the group —X is replaced by enzymatic catalysis with a mono-, bi-, tri- or tetravalent group —Y that corresponds to the value of the numeral n,
if n represents 1 with the monovalent group —O—Y1 or —N(—Y2)2; or,
if n represents 2, with one of the bivalent groups (D), (E), (F), (G) or (H); or,
if n represents 3, with the trivalent group of the partial formulae (K) or (L); or,
if n represents 4, with the tetravalent group of the partial formula (M).