Pivalic acid

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Pivalic acid
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Names
Preferred IUPAC name
2,2-Dimethylpropanoic acid
Other names
Pivalic acid
Dimethylpropanoic acid
Neopentanoic acid
Neovaleric acid
Trimethylacetic acid
Identifiers
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3D model (JSmol)
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  • InChI=1S/C5H10O2/c1-5(2,3)4(6)7/h1-3H3,(H,6,7) checkY
    Key: IUGYQRQAERSCNH-UHFFFAOYSA-N checkY
  • O=C(O)C(C)(C)C
Properties
C5H10O2
Molar mass 102.133 g·mol−1
Density 0.905 g/cm3
Melting point 35 °C (95 °F; 308 K)
Boiling point 163.7 °C (326.7 °F; 436.8 K)
Acidity (pKa) 5.03
Hazards
Lethal dose or concentration (LD, LC):
2000 mg/kg (rat, oral)
Related compounds
Related compounds
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Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).

Template:Chembox Footer/trackingTemplate:Short description

Pivalic acid is a carboxylic acid with a molecular formula of (CH3)3CCO2H. This colourless, odoriferous organic compound is solid at room temperature. Two abbreviations for pivalic acid are t-BuC(O)OH and PivOH. The pivalyl or pivaloyl group is abbreviated t-BuC(O). Salts of the acid is called pivalates.

Pivalic acid is an isomer of valeric acid, the other two isomers of it are 2-methylbutanoic acid and 3-methylbutanoic acid.

Preparation

Pivalic acid is prepared on a commercial scale by hydrocarboxylation of isobutene via the Koch reaction:

(CH3)2C=CH2 + CO + H2O → (CH3)3CCO2H

Such reactions require an acid catalyst such as hydrogen fluoride. tert-Butyl alcohol and isobutyl alcohol can also be used in place of isobutene. Globally, several million kilograms are produced annually.[1] Pivalic acid is also economically recovered as a byproduct from the production of semisynthetic penicillins like ampicillin and amoxycillin.

It was originally prepared by the oxidation of pinacolone with chromic acid.[2] This necessitates the breaking of a C-C bond, which is usual for this reagent.

File:Acetone2pinacolone (cropped).svg

Alternative laboratory routes include the Haloform reaction of pinacolone,[3] hydrolysis of corresponding nitrile (Pivalonitrile),[4] and carbonation of the Grignard reagent formed from tert-butyl chloride:[5]

File:Carboxylation of alkyl magnesium halides.svg

Applications

Relative to esters of most carboxylic acids, esters of pivalic acid are unusually resistant to hydrolysis. Some applications result from this thermal stability. Polymers derived from pivalate esters of vinyl alcohol are highly reflective lacquers.[citation needed]

Use in the laboratory

Pivalic acid is sometimes used as an internal chemical shift standard for NMR spectra of aqueous solutions. While DSS is more commonly used for this purpose, the minor peaks from protons on the three methylene bridges in DSS can be problematic. The 1H NMR spectrum at 25 °C and neutral pH is a singlet at 1.08 ppm.[citation needed]

Pivalic acid is employed as co-catalyst in some palladium-catalyzed C-H functionalization reactions.[6][7]

Alcohol protection

The pivaloyl (abbreviated Piv or Pv) group is a protective group for alcohols in organic synthesis. Common protection methods include treatment of the alcohol with pivaloyl chloride (PvCl) in the presence of pyridine.[8]

File:PvProtectedAlcohol.png

Alternatively, the esters can be prepared using pivaloic anhydride in the presence of Lewis acids such as scandium triflate (Sc(OTf)3).

Common deprotection methods involve hydrolysis with a base or other nucleophiles.[9][10][11][12]

File:PvProtection.png

References

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  1. ^ Page Module:Citation/CS1/styles.css has no content.Kubitschke, Jens; Lange, Horst; Strutz, Heinz (2014). "Carboxylic Acids, Aliphatic". Ullmann's Encyclopedia of Industrial Chemistry. pp. 1–18. doi:10.1002/14356007.a05_235.pub2. ISBN 9783527306732.
  2. ^ Page Module:Citation/CS1/styles.css has no content."A. Henninger, aus Paris 10. Februar 1873". Berichte der Deutschen Chemischen Gesellschaft. 6: 144–147. 1873. doi:10.1002/cber.18730060154.
  3. ^ Page Module:Citation/CS1/styles.css has no content.S. V. Puntambeker; E. W. Zoellner (1928). "Trimethylacetic acid from Pinacolone". Organic Syntheses. 8: 104. doi:10.15227/orgsyn.008.0104.
  4. ^ Butlerow, Ann. 165, 322 (1873).[full citation needed]
  5. ^ Page Module:Citation/CS1/styles.css has no content.S. V. Puntambeker; E. A. Zoellner; L. T. Sandborn; E. W. Bousquet (1941). "Trimethylacetic acid from tert-Butyl Chloride". Organic Syntheses. doi:10.15227/orgsyn.008.0104; Page Module:Citation/CS1/styles.css has no content.Collected Volumes, vol. 1, p. 524.
  6. ^ Page Module:Citation/CS1/styles.css has no content.Lafrance, Marc; Fagnou, Keith (2006-12-27). "Palladium-catalyzed benzene arylation: incorporation of catalytic pivalic acid as a proton shuttle and a key element in catalyst design". Journal of the American Chemical Society. 128 (51): 16496–16497. doi:10.1021/ja067144j. ISSN 0002-7863. PMID 17177387.
  7. ^ Page Module:Citation/CS1/styles.css has no content.Zhao, Dongbing; Wang, Weida; Lian, Shuang; Yang, Fei; Lan, Jingbo; You, Jingsong (2009-01-26). "Phosphine-Free, Palladium-Catalyzed Arylation of Heterocycles through C-H Bond Activation with Pivalic Acid as a Cocatalyst". Chemistry – A European Journal. 15 (6): 1337–1340. doi:10.1002/chem.200802001. ISSN 0947-6539. PMID 19115287.
  8. ^ Page Module:Citation/CS1/styles.css has no content.Robins, Morris J.; Hawrelak, S. D.; Kanai, Tadashi; Siefert, Jan Marcus; Mengel, Rudolf (1979). "Nucleic acid related compounds. 30. Transformations of adenosine to the first 2',3'-aziridine-fused nucleosides, 9-(2,3-epimino-2,3-dideoxy-.beta.-D-ribofuranosyl)adenine and 9-(2,3-epimino-2,3-dideoxy-.beta.-D-lyxofuranosyl)adenine". The Journal of Organic Chemistry. 44 (8): 1317–22. doi:10.1021/jo01322a026.
  9. ^ Page Module:Citation/CS1/styles.css has no content.Van Boeckel, C.A.A.; Van Boom, J.H. (1979). "Synthesis of glucosylphosphatidylglycerol via a phosphotriester intermediate". Tetrahedron Letters. 20 (37): 3561–4. doi:10.1016/S0040-4039(01)95462-0.
  10. ^ Page Module:Citation/CS1/styles.css has no content.Griffin, B.E.; Jarman, M.; Reese, C.B. (1968). "The Synthesis of oligoribonucleotides—IV". Tetrahedron. 24 (2): 639–62. doi:10.1016/0040-4020(68)88015-9. PMID 5637486.
  11. ^ Page Module:Citation/CS1/styles.css has no content.Ogilvie, Kelvin K.; Iwacha, Donald J. (1973). "Use of the tert-butyldimethylsilyl group for protecting the hydroxyl functions of nucleosides". Tetrahedron Letters. 14 (4): 317–9. doi:10.1016/S0040-4039(01)95650-3.
  12. ^ Page Module:Citation/CS1/styles.css has no content.Paquette, Leo A.; Collado, Iván; Purdie, Mark (1998). "Total Synthesis of Spinosyn A. 2. Degradation Studies Involving the Pure Factor and Its Complete Reconstitution". Journal of the American Chemical Society. 120 (11): 2553–62. doi:10.1021/ja974010k. INIST 10388970.
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