Bioderived Acrylates from Alkyl Lactates via Pd-Catalyzed Hydroesterification

Gereon M. Yee; Marc A. Hillmyer; Ian A. Tonks

doi:10.1021/acssuschemeng.8b02359

Bioderived Acrylates from Alkyl Lactates via Pd-Catalyzed Hydroesterification

Gereon M. Yee, Marc A. Hillmyer, Ian A. Tonks

Chemistry (Twin Cities)

Research output: Contribution to journal › Article › peer-review

11 Scopus citations

Abstract

The conversion of methyl and ethyl lactate to their corresponding alkyl 2-(propionyloxy)propanoate esters was achieved by Pd catalyzed hydroesterificative coupling with carbon monoxide (CO) and ethylene (C₂H₄) at moderate temperatures and CO/C₂H₄ pressures. A screening of reaction conditions showed that the reaction could be carried out at low loadings of catalyst, which was generated in situ from inexpensive and commercially available reagents. High conversions and product yields were obtained in a variety of solvents and even under neat conditions. Product analysis identified transesterification to be the primary competing reaction, which could be mitigated by changing solvents, as well as minimizing the amount of excess acid present in solution. Pyrolysis of methyl and ethyl 2-(propionyloxy)propanoate transformed these esters into their respective acrylates suitable for subsequent polymerization, along with propionic acid as a valuable coproduct.

Original language	English (US)
Pages (from-to)	9579-9584
Number of pages	6
Journal	ACS Sustainable Chemistry and Engineering
Volume	6
Issue number	8
DOIs	https://doi.org/10.1021/acssuschemeng.8b02359
State	Published - Aug 6 2018

Bibliographical note

Funding Information:
Financial support for this work was provided by the Minnesota Corn Growers Association. M.A.H. acknowledges the Center for Sustainable Polymers at the University of Minnesota, a National Science Foundation supported center for Chemical Innovation (CHE-1413862). Equipment for the Chemistry Department NMR facility were supported through a grant from the National Institutes of Health (S10OD011952) with matching funds from the University of Minnesota. I.A.T. is an Alfred P. Sloan Fellow. X-ray diffraction experiments were performed using a crystal diffractometer acquired through NSF-MRI Award CHE-1229400.

Publisher Copyright:
Copyright © 2018 American Chemical Society.

Keywords

Acrylates
Alkoxycarbonylation
Alkyl lactates
Carbonylation
Catalysis
Hydroesterification
Lactic acid
Pyrolysis

Access

10.1021/acssuschemeng.8b02359

OpenUrl availability

Full text

Cite this

@article{b09648028b1341168e7ce10cbeafbee2,

title = "Bioderived Acrylates from Alkyl Lactates via Pd-Catalyzed Hydroesterification",

abstract = "The conversion of methyl and ethyl lactate to their corresponding alkyl 2-(propionyloxy)propanoate esters was achieved by Pd catalyzed hydroesterificative coupling with carbon monoxide (CO) and ethylene (C2H4) at moderate temperatures and CO/C2H4 pressures. A screening of reaction conditions showed that the reaction could be carried out at low loadings of catalyst, which was generated in situ from inexpensive and commercially available reagents. High conversions and product yields were obtained in a variety of solvents and even under neat conditions. Product analysis identified transesterification to be the primary competing reaction, which could be mitigated by changing solvents, as well as minimizing the amount of excess acid present in solution. Pyrolysis of methyl and ethyl 2-(propionyloxy)propanoate transformed these esters into their respective acrylates suitable for subsequent polymerization, along with propionic acid as a valuable coproduct.",

keywords = "Acrylates, Alkoxycarbonylation, Alkyl lactates, Carbonylation, Catalysis, Hydroesterification, Lactic acid, Pyrolysis",

author = "Yee, {Gereon M.} and Hillmyer, {Marc A.} and Tonks, {Ian A.}",

note = "Funding Information: Financial support for this work was provided by the Minnesota Corn Growers Association. M.A.H. acknowledges the Center for Sustainable Polymers at the University of Minnesota, a National Science Foundation supported center for Chemical Innovation (CHE-1413862). Equipment for the Chemistry Department NMR facility were supported through a grant from the National Institutes of Health (S10OD011952) with matching funds from the University of Minnesota. I.A.T. is an Alfred P. Sloan Fellow. X-ray diffraction experiments were performed using a crystal diffractometer acquired through NSF-MRI Award CHE-1229400. Publisher Copyright: Copyright {\textcopyright} 2018 American Chemical Society.",

year = "2018",

month = aug,

day = "6",

doi = "10.1021/acssuschemeng.8b02359",

language = "English (US)",

volume = "6",

pages = "9579--9584",

journal = "ACS Sustainable Chemistry and Engineering",

issn = "2168-0485",

publisher = "American Chemical Society",

number = "8",

}

TY - JOUR

T1 - Bioderived Acrylates from Alkyl Lactates via Pd-Catalyzed Hydroesterification

AU - Yee, Gereon M.

AU - Hillmyer, Marc A.

AU - Tonks, Ian A.

N1 - Funding Information: Financial support for this work was provided by the Minnesota Corn Growers Association. M.A.H. acknowledges the Center for Sustainable Polymers at the University of Minnesota, a National Science Foundation supported center for Chemical Innovation (CHE-1413862). Equipment for the Chemistry Department NMR facility were supported through a grant from the National Institutes of Health (S10OD011952) with matching funds from the University of Minnesota. I.A.T. is an Alfred P. Sloan Fellow. X-ray diffraction experiments were performed using a crystal diffractometer acquired through NSF-MRI Award CHE-1229400. Publisher Copyright: Copyright © 2018 American Chemical Society.

PY - 2018/8/6

Y1 - 2018/8/6

N2 - The conversion of methyl and ethyl lactate to their corresponding alkyl 2-(propionyloxy)propanoate esters was achieved by Pd catalyzed hydroesterificative coupling with carbon monoxide (CO) and ethylene (C2H4) at moderate temperatures and CO/C2H4 pressures. A screening of reaction conditions showed that the reaction could be carried out at low loadings of catalyst, which was generated in situ from inexpensive and commercially available reagents. High conversions and product yields were obtained in a variety of solvents and even under neat conditions. Product analysis identified transesterification to be the primary competing reaction, which could be mitigated by changing solvents, as well as minimizing the amount of excess acid present in solution. Pyrolysis of methyl and ethyl 2-(propionyloxy)propanoate transformed these esters into their respective acrylates suitable for subsequent polymerization, along with propionic acid as a valuable coproduct.

AB - The conversion of methyl and ethyl lactate to their corresponding alkyl 2-(propionyloxy)propanoate esters was achieved by Pd catalyzed hydroesterificative coupling with carbon monoxide (CO) and ethylene (C2H4) at moderate temperatures and CO/C2H4 pressures. A screening of reaction conditions showed that the reaction could be carried out at low loadings of catalyst, which was generated in situ from inexpensive and commercially available reagents. High conversions and product yields were obtained in a variety of solvents and even under neat conditions. Product analysis identified transesterification to be the primary competing reaction, which could be mitigated by changing solvents, as well as minimizing the amount of excess acid present in solution. Pyrolysis of methyl and ethyl 2-(propionyloxy)propanoate transformed these esters into their respective acrylates suitable for subsequent polymerization, along with propionic acid as a valuable coproduct.

KW - Acrylates

KW - Alkoxycarbonylation

KW - Alkyl lactates

KW - Carbonylation

KW - Catalysis

KW - Hydroesterification

KW - Lactic acid

KW - Pyrolysis

UR - http://www.scopus.com/inward/record.url?scp=85051170195&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85051170195&partnerID=8YFLogxK

U2 - 10.1021/acssuschemeng.8b02359

DO - 10.1021/acssuschemeng.8b02359

M3 - Article

AN - SCOPUS:85051170195

SN - 2168-0485

VL - 6

SP - 9579

EP - 9584

JO - ACS Sustainable Chemistry and Engineering

JF - ACS Sustainable Chemistry and Engineering

IS - 8

ER -

Bioderived Acrylates from Alkyl Lactates via Pd-Catalyzed Hydroesterification

Abstract

Bibliographical note

Keywords

Access

OpenUrl availability

Other files and links

Fingerprint

Cite this