Diglycolic acid

Diglycolic acid is an aliphatic dicarboxylic acid, its acidity is between the one of acetic acid and oxalic acid.[1] It is formed in the oxidation of diethylene glycol in the body and can lead to severe complications with fatal outcome.[2]

Diglycolic acid
Names
Preferred IUPAC name
2,2′-Oxydiacetic acid
Identifiers
3D model (JSmol)
ChemSpider
ECHA InfoCard 100.003.476
EC Number
  • 203-823-5
UNII
  • InChI=1S/C4H6O5/c5-3(6)1-9-2-4(7)8/h1-2H2,(H,5,6)(H,7,8) ☒N
    Key: QEVGZEDELICMKH-UHFFFAOYSA-N ☒N
  • InChI=1/C4H6O5/c5-3(6)1-9-2-4(7)8/h1-2H2,(H,5,6)(H,7,8)
    Key: QEVGZEDELICMKH-UHFFFAOYAA
  • C(C(=O)O)OCC(=O)O
Properties
C4H6O5
Molar mass 134.09 g/mol
Melting point 140-144°C
Acidity (pKa) 2.79, 3.93 (20°C)
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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Infobox references

Preparation

Oxidation of diethylene glycol with concentrated nitric acid was described by A. Wurtz in 1861[3]

Diglycolsäure durch Oxidation von DEG

In parallel, W. Heintz reported the synthesis of diglycolic acid from chloroacetic acid by heating with sodium hydroxide solution.[4]

Diglycolsäure aus Monochloressigsäure

In a version with barium hydroxide solution as an alkaline medium, diglycolic acid is obtained in 68% yield after acidification.[5]

The yields of the described reactions are unsatisfactory for use on a technical scale.

The single-stage nitric acid process gives even in the presence of an oxidation catalyst (vanadium(V)oxide) yields of only 58-60%.[6] In a multi-stage process of nitric acid oxidation at 70 °C and multiple crystallization steps, evaporation of the residues and return of the diethylene glycol-containing mother liquor, product yields of up to 99% (based on diethylene glycol) can be achieved.[7]

The oxidation of diethylene glycol with air, oxygen or ozone avoids the use of expensive nitric acid and prevents the inevitable formation of nitrous gases.[8] In the presence of a platinum catalyst, yields of 90% can be obtained by air oxidation.[9]

On a bismuth platinum contact catalyst, yields of 95% are to be achieved under optimized reaction conditions.[10]

The oxidation of 1,4-dioxan-2-one (p-dioxanone, a lactone which is used as a comonomer in biodegradable polyesters with nitric acid or dinitrogen tetroxide) is also described with yields of up to 75%.[11]

Diglycolsäuresynthese aus 1,4-Dioxan-2-on
Diglycolsäuresynthese aus 1,4-Dioxan-2-on

Properties

Diglycolic acid is readily water soluble and crystallizes from water in monoclinic prisms as a white, odorless solid. At an air humidity of more than 72% and 25 °C the monohydrate is formed. The commercial product is the anhydrous form as a free-flowing flakes.[12]

Application

Diesters of diglycolic acid with (branched) higher alcohols can be used as softeners for polyvinyl chloride (PVC) with comparable properties as di-n-octyl phthalate (DOP).[13]

Basic solutions of diglycolic acid are described for the removal of limescale deposits in gas and oil bores, as well as in systems such as heat exchangers or steam boilers.[14]

Diglycolic acid can be used as a diester component in homo- and copolymeric polyesters (so-called polyalkylene diglycolates) which are biocompatible and biodegradable and can be used alone or in blends with aliphatic polyesters as tissue adhesives, cartilage substitutes or as implant materials:[15]

Vernetzte Polyalkylenglycolate
Vernetzte Polyalkylenglycolate

References
  1. L. Bhattacharyya, J. Rohrer, ed. (2012), Appendix 1: DISSOCIATION CONSTANTS (pKa) OF ORGANIC ACIDS (AT 20 °C), in Applications of Ion Chromatography for Pharmaceutical and Biological Products, John Wiley & Sons, Inc., doi:10.1002/9781118147009.app1
  2. A.A. Roscher, E. Jussek, T. Noguchi, S. Franklin (1975), "Fatal Accidental Diglycolic Acid Intoxication" (PDF), Bull. Soc. Pharm. Environ. Pathol., vol. III, no. 4, archived from [PDF the original] on 2017-06-29, retrieved 2017-02-04 {{citation}}: Check |url= value (help)CS1 maint: multiple names: authors list (link)
  3. A. Wurtz (1861), "Umwandlung des Aethylens zu complicirten organischen Säuren", Liebigs Ann. Chem. (in German), vol. 117, no. 1, pp. 136–140, doi:10.1002/jlac.18611170114
  4. W. Heintz (1862), "Ueber die Diglycolsäure (Paraäpfelsäure)", Ann. Phys. (in German), vol. 191, no. 2, pp. 280–295, doi:10.1002/andp.18621910206
  5. K.E. Füger (1959), [PDF Synthese und katalytische Reduktion von Glykolsäure und Glykolsäureestern, Promotionsarbeit ETH Zürich] (in German), Juris-Verlag {{citation}}: Check |url= value (help)
  6. C. Erk (1991), "Condensation of diglycolic acid dichloride with polyglycols, 5. An improved synthesis of cyclic polyether-esters by cyclization", Liebigs Ann. Chem., vol. 1991, no. 10, pp. 1083–1084, doi:10.1002/jlac.1991199101186
  7. US 4066691, M. Schröder, "Process for the production of pure diglycolic acid by oxidation if diethylene glycol with nitric acid", published 1978-1-3, assigned to Chemische Werke Hüls AG
  8. US 3879452, G.E. Brown, Jr., "Method for making diglycolic acid, dipropionic acid and the salts there f", published 1975-4-22, assigned to Conen Corp.
  9. US 4256916, D.L. Morris, W.J. Gammans, J.D. Holmes, "Oxidation of polyethylene glycols to dicarboxylic acids", published 1981-3-17, assigned to Eastman Kodak Co.
  10. Y-Y. Zhang, Z.-Y. Liang, Y.-D. Zhang (May 2012), [PDF "Preparation of Diglycolic Acid via Oxidation of Diethylene Glycol with Molecular Oxygen"], Fine Chemicals {{citation}}: Check |url= value (help)CS1 maint: multiple names: authors list (link)
  11. US 3952054, C.Y. Shen, "Process for preparing diglycolic acid", published 1976-4-20, assigned to Monsanto Co.
  12. W.M. Bruner, L.T. Sherwood, Jr. (1949), "Diglycolic acid – a new commercial dibasic acid", Ind. Eng. Chem., vol. 41, no. 8, pp. 1653–1656, doi:10.1021/ie50476a032{{citation}}: CS1 maint: multiple names: authors list (link)
  13. US 3173888, P.T. von Bramer, R.M. Simons, "Diesters of diglycolic acid and vinyl chloride polymers plastized therewith", published 1965-3-16, assigned to Eastman Kodak Co.
  14. US 3639279, T.R. Gardner, R.M. Lasater, J.A. Knox, "Scale removal composition and method using salt of diglycolic acid and base at pH above 5", published 1972-2-1, assigned to Halliburton Co.
  15. US 5696178, K. Cooper, A. Scopelianos, "Absorbable polyalkylene diglycolates", published 1997-12-9, assigned to Ethicon, Inc.
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