Methoxycarbonylation with formic acid and methanol

1. A process for the methoxycarbonylation of alkenes to form a methyl ester of an acid that corresponds to the alkene comprising the process steps of:

a) adding an olefin to form a reaction mixture;

b) introducing to the mixture a compound comprising Pd, wherein the Pd is capable of forming a complex;

c) introducing to the mixture a compound of general formula (I):

wherein R 1 , R 2 , R 3 and R 4 are each independently selected from the group consisting of: -H, -(C 1 -C 12 )-alkyl, -O-(C 1 -C 12 )-alkyl, -(C 4 -C 14 )-aryl, -O-(C 4 -C 14 )-aryl, cycloalkyl, -(C 1i -C 12 )-heteroalkyl, -O-(C 1 -C 12 )- heteroalkyl, -(C 3 -C 14 ) heteroaryl, -O-(C 3 -C 1 4)-heteroaryl, -COO-alkyl, -COO-aryl, -C-O-alkyl, C-O-aryl, NH 2 , and halogen;

wherein the recited alkyl groups, aryl groups, cycloalkyl, heteroalkyl groups and heteroaryl groups may be substituted with:

-(C 1 -C 12 )-alkyl, -O-(C 1 -C 12 )-alkyl or halogen; and at least one of the radicals R 1 , R 2 , R 3 and R 4 does not represent phenyl;

d) introducing to the mixture MeOH;

e) introducing to the mixture HCOOH,

wherein the employed volume of HCOOH based on 2 mmol of olefin is in the range from 0.3 ml to 0.8 ml:

f) heating of the reaction mixture to convert the olefin, MeOH and HCOOH into the methyl ester where no CO gas is supplied to the reaction mixture.

2. The process according to claim 1 , wherein HCOOH serves as the only CO source for the reaction.

3. The process according to claim 1 , wherein the compound in process step b) is Pd(acac) 2 , PdC1 2 , Pd(dba) 3 *CH 3 C1(dba=dibenzylideneacetone), Pd(OAc) 2 , Pd(TFA) 2 , or Pd(CH 3 CN)C1 2 .

4. The process according to claim 1 , wherein the process comprises an additional process step g):

g) adding an acid to the reaction mixture.

5. The process according to claim 4 , wherein the acid is H 2 SO 4 , CH 3 SO 3 H, CF 3 SO 3 H, or PTSA.

6. The process according to claim 1 , wherein the employed volume of HCOOH based on 2 mmol of olefin is in the range from 0.4 ml to 0.6 ml.

7. The process according to claim 1 , wherein R 1 , R 2 , R 3 and R 4 are -(C 1 -C 12 )-alkyl, -O-(C 1 -C 12 )- alkyl, -(C 4 -C 14 )-aryl, -O-(C 4 -C 14 )-cycloalkyl, -(C 1 -C 12 )-heteroalkyl, -O-(C 1 -C 12 )- heteroalkyl, -(C 3 -C 14 )-heteroaryl, -O-(C 3 -C 14 )-heteroaryl, -COO-alkyl, -COO-aryl, -C-O-alkyl, -C-O-aryl, NH 2 , or halogen;

wherein the recited alkyl groups, aryl groups, cycloalkyl, heteroalkyl groups and heteroaryl groups may be substituted with:

-O-(C 1 -C 12 )-alkyl -O-(C 1 -C 12 )-alkyl or halogen;

and at least one of the radicals R 2 , R 3 , R 2 , and R 4 does not represent phenyl.

8. The process according to claim 1 , wherein R 1 , R 2 , R 3 and R 4 are -(C 1 -C 12 )-alkyl, -(C 4 -C 14 )-aryl, cycloalkyl, -(C 1 -C 12 )-heteroalkyl, -(C 3 -C 14 )-heteroaryl, or halogen;

wherein the recited alkyl groups, aryl groups, cycloalkyl, heteroalkyl groups and heteroaryl groups may be substituted with as follows:

-(C 1 -C 12 )-alkyl, -O-(C 1 -C 12 )-alkyl or halogen;

and at least one of the radicals R 1 , R 2 , R 3 and R 4 does not represent phenyl.

9. The process according to claim 1 ,

wherein R 1 , R 2 , R 3 and R 4 are -(C 1 -C 12 )-alkyl, cycloalkyl, or -(C 3 -C 14 )-heteroaryl;

wherein the recited alkyl groups, cycloalkyl and heteroaryl groups may be substituted:

with -(C 1 -C 12 )-alkyl, -O-(C 1 -C 12 )-alkyl, halogen, and at least one of the radicals R 1 , R 2 , R 3 and R 4 does not represent phenyl.

10. The process according to claim 1 ,

wherein R 1 , R 4 are -(C 1 -C 12 )-alkyl or cycloalkyl;

wherein the recited alkyl groups and cycloalkyl may be substituted with:

-O -(C 1 -C 12 )-alkyl or halogen.

11. The process according to claim 1 ,

wherein R 2 , R 3 each independently represent -(C 3 -C 14 )-heteroaryl,

wherein the recited heteroaryl groups may be substituted with:

-O-(C 1 -C 12 )-alkyl, -O-(C 1 -C 12 )-alkyl or halogen.

12. The process according to claim 1 ,

wherein the compound of general formula (I) has the structure (II):