Tetrolic acid

Tetrolic acid
Names
	Preferred IUPAC name But-2-ynoic acid
	Other names 2-Butynoic acid; But-2-ynoic acid; Butynoic acid
Identifiers
CAS Number	590-93-2;
3D model (JSmol)	Interactive image;
ChemSpider	61810 ;
ECHA InfoCard	100.008.815
PubChem CID	68535;
CompTox Dashboard (EPA)	DTXSID4060444 ;
	InChI InChI=1S/C4H4O2/c1-2-3-4(5)6/h1H3,(H,5,6) Key: LUEHNHVFDCZTGL-UHFFFAOYSA-N;
	SMILES CC#CC(=O)O;
Properties
Chemical formula	C4H4O2
Molar mass	84.074 g·mol−1
Density	0.9641 g/cm3[1]
Melting point	78 °C (172 °F; 351 K)[1]
Boiling point	203 °C (397 °F; 476 K)[1]
	Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
	Infobox references

Tetrolic acid (2-butynoic acid) is a short-chain unsaturated carboxylic acid, described by the formula CH₃-C≡C-CO₂H. Salts and esters of tetrolic acid are known as tetrolates.

History

The first reported synthesis[2] of tetrolic acid is believed to be by German chemist Johann Georg Anton Geuther in 1871 as part of his work investigating the derivatives of ethyl acetoacetate.

Production

Tetrolic acid is manufactured[3] on a commercial scale by treatment of propyne with a strong base (to form an acetylide), followed by carbon dioxide:

Scheme2

Strong bases such as n-BuLi[4] and NaNH₂[5] can be used.

Properties

Tetrolic acid is highly soluble in polar solvents (water, ethanol) and may be recrystallized from non polar solvents (such as heptane, toluene). The compound is a white crystalline solid which can exist in two polymorphous crystalline forms.[6]

The proton nuclear magnetic resonance (¹H-NMR) spectrum in deuterated dimethyl sulfoxide shows a characteristic singlet peak at 1.99 ppm corresponding to the -CH₃ protons.

Tetrolic acid sublimes at temperatures above 20°C, and should ideally be stored in a sealed container in a refrigerator.[7]

Safety

Tetrolic acid is thermally unstable at high temperatures. Testing using accelerated rate calorimetry (ARC) showed exothermic onset from 135 °C, precluding short-path distillation as a means of purification.[7]

References

Haynes, William M., ed. (2011). CRC Handbook of Chemistry and Physics (92nd ed.). Boca Raton, FL: CRC Press. p. 3.88. ISBN 1439855110.
Geuther, A. (1871). "Ethyldiacetic Acid and some of its Derivatives". J. Chem. Soc. 24: 812–837. doi:10.1039/JS8712400808.
Smith, W. (1973) "Preparation of tetrolic acid" U.S. Patent 3,752,848A
Hartzoulakis, Basil; Gani, David (1994). "Synthesis of (2S, 3R)- and (2S, 3S)-3-methylglutamic acid". J. Chem. Soc., Perkin Trans. 1. 1994 (18): 2525–2531. doi:10.1039/P19940002525.
Kauer, J. C.; Brown, M. (1962). "Tetrolic Acid (2-Butynoic Acid)". Organic Syntheses. 42: 97. doi:10.15227/orgsyn.042.0097.; Collective Volume, 5, p. 1043
Flakus, Henryk T.; Hachuła, Barbara (2008). "Effects of "excessive" exciton interactions in polarized IR spectra of the hydrogen bond in 2-butynoic acid crystals: Proton transfer induced by dynamical co-operative interactions involving hydrogen bonds". Chemical Physics. 345 (1): 49–64. Bibcode:2008CP....345...49F. doi:10.1016/j.chemphys.2008.01.035.
Golden, M. (2019). "Thermal Stability of 2-Butynoic Acid (Tetrolic acid)". Org. Process Res. Dev. 23, (5) (5): 1101–1104. doi:10.1021/acs.oprd.9b00106.

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[b92-1] Haynes, William M., ed. (2011). CRC Handbook of Chemistry and Physics (92nd ed.). Boca Raton, FL: CRC Press. p. 3.88. ISBN 1439855110.

[2] Geuther, A. (1871). "Ethyldiacetic Acid and some of its Derivatives". J. Chem. Soc. 24: 812–837. doi:10.1039/JS8712400808.

[3] Smith, W. (1973) "Preparation of tetrolic acid" U.S. Patent 3,752,848A

[4] Hartzoulakis, Basil; Gani, David (1994). "Synthesis of (2S, 3R)- and (2S, 3S)-3-methylglutamic acid". J. Chem. Soc., Perkin Trans. 1. 1994 (18): 2525–2531. doi:10.1039/P19940002525.

[5] Kauer, J. C.; Brown, M. (1962). "Tetrolic Acid (2-Butynoic Acid)". Organic Syntheses. 42: 97. doi:10.15227/orgsyn.042.0097.; Collective Volume, 5, p. 1043

[6] Flakus, Henryk T.; Hachuła, Barbara (2008). "Effects of "excessive" exciton interactions in polarized IR spectra of the hydrogen bond in 2-butynoic acid crystals: Proton transfer induced by dynamical co-operative interactions involving hydrogen bonds". Chemical Physics. 345 (1): 49–64. Bibcode:2008CP....345...49F. doi:10.1016/j.chemphys.2008.01.035.

[stability-7] Golden, M. (2019). "Thermal Stability of 2-Butynoic Acid (Tetrolic acid)". Org. Process Res. Dev. 23, (5) (5): 1101–1104. doi:10.1021/acs.oprd.9b00106.