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# c12) United States Patent 

# Kanan et al. 

# (54) CARBONATE-PROMOTED CARBOXYLATION REACTIONS FOR THE SYNTHESIS OF VALUABLE ORGANIC COMPOUNDS 

(71) Applicant: The Board of 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) 

(73) Assignee: The Board of the Trustees of the Leland Stanford Junior University, Palo Alto, CA (US) 

( *) Notice: Subject to any disclaimer, the term ofthis patent is extended or adjusted under 35 U.S.C. 154(b) by O days. 

(21) Appl. No.: 16/195,434 

(22) Filed: Nov. 19, 2018 

## (65) Prior Publication Data 

US 2019/0084953 Al Mar. 21, 2019 

(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. 

(60) Provisional application No. 62/136,288, filed on Mar. 20, 2015. 

(51) Int. Cl. 

<img src='content_image/929409.jpg'>

(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 

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## Related U.S. Application Data 

## U.S. PATENT DOCUMENTS 

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# (IO) Patent No.: US 10,710,971 B2 

# (45) Date of Patent: Jul. 14, 2020 

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## FOREIGN PATENT DOCUMENTS 

<img src='content_image/929408.jpg'>

International Search Report from International Application No. PCT/US16/22969 dated Jun. 3, 2016. 

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. 

German Office Action from German Application No. 11 2016 001 317 .5 dated Feb. 20, 2018. 

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. 

* cited by examiner 

Primary Examiner - Timothy R Rozof (74) Attorney, Agent, or Firm - Beyer Law Group LLP 

## (57) ABSTRACT 

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. 

US010710971B2 

## OTHER PUBLICATIONS 

## 10 Claims, 3 Drawing Sheets 

