(45)  Date of Patent:  Jul.  14, 2020  (IO)  Patent No.:  US  10,710,971 B2  c12)  United States Patent  Kanan et al.  (54)  CARBONATE-PROMOTED  CARBOXYLATION REACTIONS FOR THE  SYNTHESIS OF VALUABLE ORGANIC  COMPOUNDS  1111111111111111 1111111111 1111111111 11111 1111111111 11111 111111111111111111  US010710971B2  3,359,310 A  12/1967 Raecke et al.  3,766,258 A  *  10/1973 Engelbrecht .......... C07C 51/416  2012/0059176 Al  3/2012 Walker et al.  2013/0345448 Al  12/2013 Shaikh et al.  2014/0364633 Al  12/2014 Janka et al.  562/481  DE  WO  WO  WO  60023335  01/016077  2010/070593  2014/099438  4/2006  3/2001  6/2010  6/2014  C07D 307168  C07C 51102  C07C 51115  (2006.01)  (2006.01)  (2006.01)  2,900,386 A  2,948,750 A  8/1959 Raecke et al.  8/ 1960 Blaser et al.  10 Claims, 3 Drawing Sheets  (57)  ABSTRACT  OTHER PUBLICATIONS  FOREIGN PATENT DOCUMENTS  (65)  Prior Publication Data  Related U.S. Application Data  (51)  Int. Cl.  (60)  Provisional application No. 62/136,288, filed on Mar.  20, 2015.  (63)  Continuation of application No. 15/558,528, filed as  application No. PCT/US2016/022969 on Mar. 17,  2016, now Pat. No. 10,160,740.  (22)  Filed:  Nov. 19, 2018  (21)  Appl. No.:  16/195,434  US 2019/0084953 Al  Mar. 21, 2019  (52)  U.S. Cl.  CPC ............  C07D 307168  (2013.01);  C07C 51102  (2013.01);  C07C 51115  (2013.01)  ( 58)  Field of Classification Search  CPC ........ C07D 307/68; C07C 51/02; C07C 51/15  See application file for complete search history.  (56)  References Cited  U.S. PATENT DOCUMENTS  A method for synthesizing a dicarboxylate containing an  aromatic heterocycle is provided. A carboxylic acid contain› ing a heterocycle is provided. A CO$_{3 }$ 2 - salt is provided to  form a mixture, which converts the carboxylic acid contain› ing an aromatic heterocycle to a carboxylate containing an  aromatic heterocycle. CO$_{2 }$ gas is provided to the mixture.  The mixture is heated to a temperature to at least partially  melt the carboxylate containing an aromatic heterocycle.  * cited by examiner  Brian D. Andresen "Synthesis of Sodium Formate C and Oxalic  Acid", Department of Pharmaceutical Chemistry, J. Org. Chem, vol.  42, No. 16, 1977, p. 2790.  German Office Action from German Application No. 11 2016 001  317 .5 dated Feb. 20, 2018.  Written Opinion from International Application No. PCT/US16/  22969 dated Jun. 3, 2016.  Kudo, Kiyoshi, "Carboxylation of Cesium, 2-Naphthoate in the  Alkali Metal Molten Salts of Carbonate and Formate with CO2  under High Pressure", Institute for Chemical Research, Kyoto  University, vol. 38, No. 1, pp. 40-47, Jun. 22, 1994.  Kudo, Kiyoshi, "Synthesis of oxalate from carbon monoxide and  carbon dioxide in the presence of caesium carbonate", Institute for  Chemical Research, Kyoto University, J. Chem. Soc., Perkin Trans.  2, pp. 679-682, 1997.  International Search Report from International Application No.  PCT/US16/22969 dated Jun. 3, 2016.  ( *)  Notice:  Subject to any disclaimer, the term ofthis  patent is extended or adjusted under 35  U.S.C. 154(b) by  O  days.  (73)  Assignee:  The Board of the Trustees of the  Leland Stanford Junior University,  Palo Alto, CA (US)  (72)  Inventors:  Matthew W. Kanan,  Palo Alto, CA  (US);  Aanindeeta Banerjee,  Stanford,  CA (US)  (71)  Applicant:  The Board of Trustees of the Leland  Stanford Junior University,  Palo Alto,  CA (US)  Primary Examiner  - Timothy R Rozof  (74)  Attorney, Agent, or Firm  - Beyer Law Group LLP 