Pivalic acid

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Pivalic acid
Pivalic acid.svg
Pivalic-acid-3D-balls.png
Names
Preferred IUPAC name
2,2-Dimethylpropanoic acid
Other names
Pivalic acid
Dimethylpropanoic acid
Neopentanoic acid
Neovaleric acid
Trimethylacetic acid
Identifiers
3D model (JSmol)
ChEBI
ChEMBL
ChemSpider
ECHA InfoCard 100.000.839 OOjs UI icon edit-ltr-progressive.svg
PubChem CID
UNII
  • InChI=1S/C5H10O2/c1-5(2,3)4(6)7/h1-3H3,(H,6,7) Yes check.svgY
    Key: IUGYQRQAERSCNH-UHFFFAOYSA-N Yes check.svgY
  • 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)
Related compounds
Related compounds
 neopentyl alcohol
neopentane
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
Yes check.svgY  verify  (what is  Yes check.svgYX mark.svgN ?)

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

Contents

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] and by the hydrolysis of tert-butyl cyanide. [3] Convenient laboratory routes proceed via tert-butyl chloride via carbonation of the Grignard reagent [4] and by oxidation of pinacolone. [5]

Pinacol rearrangement Acetone2pinacolone.svg
Pinacol rearrangement
t-Butylmagnesium bromide reacts with CO2 to form the pivalate salt. Addition of acid yields pivalic acid Carboxylation of alkyl magnesium halides.svg
t-Butylmagnesium bromide reacts with CO2 to form the pivalate salt. Addition of acid yields pivalic acid

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.

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 alcohol with pivaloyl chloride (PvCl) in presence of pyridine. [8]

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]

PvProtection.png

See also

Related Research Articles

<span class="mw-page-title-main">Ester</span> Compound derived from an acid

In chemistry, an ester is a compound derived from an acid in which the hydrogen atom (H) of at least one acidic hydroxyl group of that acid is replaced by an organyl group. Analogues derived from oxygen replaced by other chalcogens belong to the ester category as well. According to some authors, organyl derivatives of acidic hydrogen of other acids are esters as well, but not according to the IUPAC.

<span class="mw-page-title-main">Thioester</span> Organosulfur compounds of the form R–SC(=O)–R’

In organic chemistry, thioesters are organosulfur compounds with the molecular structure R−C(=O)−S−R’. They are analogous to carboxylate esters with the sulfur in the thioester replacing oxygen in the carboxylate ester, as implied by the thio- prefix. They are the product of esterification of a carboxylic acid with a thiol. In biochemistry, the best-known thioesters are derivatives of coenzyme A, e.g., acetyl-CoA. The R and R' represent organyl groups, or H in the case of R.

<span class="mw-page-title-main">Protecting group</span> Group of atoms introduced into a compound to prevent subsequent reactions

A protecting group or protective group is introduced into a molecule by chemical modification of a functional group to obtain chemoselectivity in a subsequent chemical reaction. It plays an important role in multistep organic synthesis.

In organic chemistry, an acyl chloride is an organic compound with the functional group −C(=O)Cl. Their formula is usually written R−COCl, where R is a side chain. They are reactive derivatives of carboxylic acids. A specific example of an acyl chloride is acetyl chloride, CH3COCl. Acyl chlorides are the most important subset of acyl halides.

<span class="mw-page-title-main">Sulfoxide</span> Organic compound containing a sulfinyl group (>SO)

In organic chemistry, a sulfoxide, also called a sulfoxide, is an organosulfur compound containing a sulfinyl functional group attached to two carbon atoms. It is a polar functional group. Sulfoxides are oxidized derivatives of sulfides. Examples of important sulfoxides are alliin, a precursor to the compound that gives freshly crushed garlic its aroma, and dimethyl sulfoxide (DMSO), a common solvent.

<span class="mw-page-title-main">Knorr pyrrole synthesis</span> Chemical reaction

The Knorr pyrrole synthesis is a widely used chemical reaction that synthesizes substituted pyrroles (3). The method involves the reaction of an α-amino-ketone (1) and a compound containing an electron-withdrawing group α to a carbonyl group (2).

<span class="mw-page-title-main">Trimethylsilyl chloride</span> Chemical compound

Trimethylsilyl chloride, also known as chlorotrimethylsilane is an organosilicon compound (silyl halide), with the formula (CH3)3SiCl, often abbreviated Me3SiCl or TMSCl. It is a colourless volatile liquid that is stable in the absence of water. It is widely used in organic chemistry.

<span class="mw-page-title-main">Dakin oxidation</span> Organic redox reaction that converts hydroxyphenyl aldehydes or ketones into benzenediols

The Dakin oxidation (or Dakin reaction) is an organic redox reaction in which an ortho- or para-hydroxylated phenyl aldehyde (2-hydroxybenzaldehyde or 4-hydroxybenzaldehyde) or ketone reacts with hydrogen peroxide (H2O2) in base to form a benzenediol and a carboxylate. Overall, the carbonyl group is oxidised, whereas the H2O2 is reduced.

<i>tert</i>-Butyloxycarbonyl protecting group Protecting group used in organic synthesis

The tert-butyloxycarbonyl protecting group or tert-butoxycarbonyl protecting group is a protecting group used in organic synthesis.

<span class="mw-page-title-main">Boronic acid</span> Organic compound of the form R–B(OH)2

A boronic acid is an organic compound related to boric acid in which one of the three hydroxyl groups is replaced by an alkyl or aryl group. As a compound containing a carbon–boron bond, members of this class thus belong to the larger class of organoboranes.

<span class="mw-page-title-main">2,6-Lutidine</span> Chemical compound

2,6-Lutidine is a natural heterocyclic aromatic organic compound with the formula (CH3)2C5H3N. It is one of several dimethyl-substituted derivative of pyridine, all of which are referred to as lutidines. It is a colorless liquid with mildly basic properties and a pungent, noxious odor.

In chemistry, carbonylation refers to reactions that introduce carbon monoxide (CO) into organic and inorganic substrates. Carbon monoxide is abundantly available and conveniently reactive, so it is widely used as a reactant in industrial chemistry. The term carbonylation also refers to oxidation of protein side chains.

<span class="mw-page-title-main">Oxazoline</span> Chemical compound

Oxazoline is a five-membered heterocyclic organic compound with the formula C3H5NO. It is the parent of a family of compounds called oxazolines, which contain non-hydrogenic substituents on carbon and/or nitrogen. Oxazolines are the unsaturated analogues of oxazolidines, and they are isomeric with isoxazolines, where the N and O are directly bonded. Two isomers of oxazoline are known, depending on the location of the double bond.

<span class="mw-page-title-main">Isovaleraldehyde</span> Chemical compound

Isovaleraldehyde organic compound, also known as 3-methylbutanal, with the formula (CH3)2CHCH2CHO. It is an aldehyde, a colorless liquid at STP, and found in low concentrations in many types of food. Commercially it is used as a reagent for the production of pharmaceuticals, perfumes and pesticides.

The Chan–Lam coupling reaction – also known as the Chan–Evans–Lam coupling is a cross-coupling reaction between an aryl boronic acid and an alcohol or an amine to form the corresponding secondary aryl amines or aryl ethers, respectively. The Chan–Lam coupling is catalyzed by copper complexes. It can be conducted in air at room temperature. The more popular Buchwald–Hartwig coupling relies on the use of palladium.

<i>N</i>-Hydroxyphthalimide Chemical compound

N-Hydroxyphthalimide is the N-hydroxy derivative of phthalimide. The compound can be utilized as a catalyst for oxidation reactions, in particular for the selective oxidation with molecular oxygen under mild conditions.

<i>tert</i>-Butyl peroxybenzoate Chemical compound

tert-Butyl peroxybenzoate (TBPB) an organic compound with the formula C6H5CO3CMe3 (Me = CH3). It is the most widely produced perester; it is an ester of peroxybenzoic acid (C6H5CO3H). It is often used as a radical initiator in polymerization reactions, such as the production of LDPE from ethylene, and for crosslinking, such as for unsaturated polyester resins.

2-Methylbutanoic acid, also known as 2-methylbutyric acid is a branched-chain alkyl carboxylic acid with the chemical formula CH3CH2CH(CH3)CO2H, classified as a short-chain fatty acid. It exists in two enantiomeric forms, (R)- and (S)-2-methylbutanoic acid. (R)-2-methylbutanoic acid occurs naturally in cocoa beans and (S)-2-methylbutanoic occurs in many fruits such as apples and apricots, as well as in the scent of the orchid Luisia curtisii.

<i>tert</i>-Butyldimethylsilyl chloride Chemical compound

tert-Butyldimethylsilyl chloride is an organosilicon compound with the formula (Me3C)Me2SiCl (Me = CH3). It is commonly abbreviated as TBSCl or TBDMSCl. It is a chlorosilane containing two methyl groups and a tert-butyl group. As such it is more bulky that trimethylsilyl chloride. It is a colorless or white solid that is soluble in many organic solvents but reacts with water and alcohols. The compound is used to protect alcohols in organic synthesis.

<i>tert</i>-Butyl nitrite Chemical compound

tert-Butyl nitrite is an organic compound with the formula (CH3)3CONO. A colorless liquid, it is the tert-butyl ester of nitrous acid. It is typically employed as a solution with tert-butyl alcohol.

References

  1. ↑ 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. ↑ "A. Henninger, aus Paris 10. Februar 1873". Berichte der Deutschen Chemischen Gesellschaft. 6: 144–147. 1873. doi:10.1002/cber.18730060154.
  3. ↑ Butlerow, Ann. 165, 322 (1873).[ full citation needed ]
  4. ↑ 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.; Collective Volume, vol. 1, p. 524
  5. ↑ L. T. Sandborn; E. W. Bousquet (1941). "Trimethylacetic acid from Pinacolone". Organic Syntheses . doi:10.15227/orgsyn.008.0104.; Collective Volume, vol. 1, p. 524
  6. ↑ 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. ↑ 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. ↑ 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. ↑ 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. ↑ 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. ↑ 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. ↑ 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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