Acetoacetic acid (no longer recommended[1]) Diacetic acid
Identifiers
CAS Number
541-50-4Y
3D model (JSmol)
Interactive image
ChEBI
CHEBI:15344Y
ChEMBL
ChEMBL1230762N
ChemSpider
94Y
DrugBank
DB01762N
KEGG
C00164Y
PubChem CID
96
InChI
InChI=1S/C4H6O3/c1-3(5)2-4(6)7/h2H2,1H3,(H,6,7)Y
Key: WDJHALXBUFZDSR-UHFFFAOYSA-NY
InChI=1/C4H6O3/c1-3(5)2-4(6)7/h2H2,1H3,(H,6,7)
Key: WDJHALXBUFZDSR-UHFFFAOYAH
SMILES
O=C(C)CC(=O)O
Properties
Chemical formula
C4H6O3
Molar mass
102.088 g/mol
Appearance
colorless, oily liquid
Melting point
36.5 °C (97.7 °F; 309.6 K)
Boiling point
Decomposes
Solubility in water
soluble
Solubility
soluble in ethanol, ether
Acidity (pKa)
3.58 [2]
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
Nverify (what is YN ?)
Infobox references
Acetoacetic acid (also diacetic acid) is the organic compound with the formula CH3COCH2COOH. It is the simplest beta-keto acid group, and like other members of this class, it is unstable. The methyl and ethyl esters, which are quite stable, are produced on a large scale industrially as precursors to dyes. Acetoacetic acid is a weak acid.[3]
Contents
1Biochemistry
2Synthesis and properties
3Applications
4Detection
5See also
6References
Biochemistry
Under typical physiological conditions, acetoacetic acid exists as its conjugate base, acetoacetate.
Acetoacetate is produced in mitochondria of the liver from acetoacetyl coenzyme A (CoA). First another acetyl group is added from acetyl CoA to form 3-hydroxy-3-methylgluteryl CoA, and then an acetyl CoA is lost from this yielding acetoacetate. The initial acetoacetate can come from the last cycle in the beta oxidation of a fatty acid, or it can be synthesized from two acetyl CoA molecules, catalyzed by thiolase.[4]
In mammals acetoacetate produced in the liver (along with the other two "ketone bodies") is released into the bloodstream as an energy source during periods of fasting, exercise, or as a result of type 1 diabetes mellitus.[5] First a CoA group is enzymatically transferred to it from succinyl CoA, converting it back to acetoacetyl CoA. This is then broken into two acetyl CoA molecules by thiolase, and these then enter the citric acid cycle. Heart muscle and renal cortex prefer acetoacetate over glucose. The brain uses acetoacetate when glucose levels are low due to fasting or diabetes.[6]
Synthesis and properties
Acetoacetic acid may be prepared by the hydrolysis of diketene. Its esters are produced analogously via an reaction between diketene and alcohols,[3] and acetoacetic acid can be prepared by the hydrolysis of these species.[7]
In general, acetoacetic acid is generated at 0 °C and used in situ immediately.[8] It decomposes at a moderate rate to acetone and carbon dioxide:
CH3C(O)CH2CO2H → CH3C(O)CH3 + CO2
The acid form has a half-life of 140 minutes at 37 °C in water, whereas the basic form (the anion) has a half-life of 130 hours. That is, it reacts about 55 times more slowly.[9]
It is a weak acid (like most alkyl carboxylic acids), with a pKa of 3.58.
Acetoacetic acid displays keto-enol tautomerisation, with the enol form being partially stabilised by extended conjugation and intramolecular H-bonding. The equilibrium is strongly solvent depended; with the keto form dominating in polar solvents (98% in water) and the enol form accounting for 25-49% of material in non-polar solvents.[10]
Applications
Acetoacetic esters are used for the acetoacetylation reaction, which is widely used in the production of arylide yellows and diarylide dyes.[3] Although the esters can be used in this reaction, diketene also reacts with alcohols and amines to the corresponding acetoacetic acid derivatives in a process called acetoacetylation. An example is the reaction with 2-aminoindane:[11]
Pigment Yellow 16 is a typical dye containing the acetoacetyl group
Detection
Acetoacetic acid is measured in the urine of people with diabetes to test for ketoacidosis[12] and for monitoring people on a ketogenic or low-carbohydrate diet,[13][14] This is done using dipsticks coated in nitroprusside or similar reagents. Nitroprusside changes from pink to purple in the presence of acetoacetate, the conjugate base of acetoacetic acid, and the colour change is graded by eye. The test does not measure β-hydroxybutyrate, the most abundant ketone in the body; during treatment of ketoacidosis β-hydroxybutyrate is converted to acetoacetate so the test is not useful after treatment begins[12] and may be falsely low at diagnosis.[15]
Similar tests are used in dairy cows to test for ketosis.[16]
See also
3-Hydroxybutyrate dehydrogenase
References
^ abNomenclature of Organic Chemistry : IUPAC Recommendations and Preferred Names 2013 (Blue Book). Cambridge: The Royal Society of Chemistry. 2014. p. 748. doi:10.1039/9781849733069-FP001. ISBN 978-0-85404-182-4.
^Dawson, R. M. C., et al., Data for Biochemical Research, Oxford, Clarendon Press, 1959.
^ abcFranz Dietrich Klingler; Wolfgang Ebertz (2005). "Oxocarboxylic Acids". Ullmann's Encyclopedia of Industrial Chemistry. Weinheim: Wiley-VCH. doi:10.1002/14356007.a18_313.
^Lubert Stryer (1981). Biochemistry (2nd ed.). p. 393.
^Stryer, Lubert (1995). Biochemistry (Fourth ed.). New York: W.H. Freeman and Company. pp. 510–515, 581–613, 775–778. ISBN 0 7167 2009 4.
^Stryer 1981, p. 394.
^Robert C. Krueger (1952). "Crystalline Acetoacetic Acid". Journal of the American Chemical Society. 74 (21): 5536–5536. doi:10.1021/ja01141a521.
^Reynolds, George A.; VanAllan, J. A. (1952). "Methylglyoxal-ω-Phenylhydrazone". Organic Syntheses. 32: 84. doi:10.15227/orgsyn.032.0084.; Collective Volume, 4, p. 633
^Hay, R. W.; Bond, M. A. (1967). "Kinetics of decarboxilation of acetoacetic acid". Aust. J. Chem. 20 (9): 1823–8. doi:10.1071/CH9671823.
^Grande, Karen D.; Rosenfeld, Stuart M. (1980). "Tautomeric equilibriums in acetoacetic acid". The Journal of Organic Chemistry. 45 (9): 1626–1628. doi:10.1021/jo01297a017. ISSN 0022-3263.
^Kiran Kumar Solingapuram Sai; Thomas M. Gilbert; Douglas A. Klumpp (2007). "Knorr Cyclizations and Distonic Superelectrophiles". J. Org. Chem.72 (25): 9761–9764. doi:10.1021/jo7013092. PMID 17999519.
^ abNyenwe, EA; Kitabchi, AE (April 2016). "The evolution of diabetic ketoacidosis: An update of its etiology, pathogenesis and management". Metabolism: clinical and experimental. 65 (4): 507–21. doi:10.1016/j.metabol.2015.12.007. PMID 26975543.
^Hartman, AL; Vining, EP (January 2007). "Clinical aspects of the ketogenic diet". Epilepsia. 48 (1): 31–42. doi:10.1111/j.1528-1167.2007.00914.x. PMID 17241206.
^Sumithran, Priya; Proietto, Joseph (2008). "Ketogenic diets for weight loss: A review of their principles, safety and efficacy". Obesity Research & Clinical Practice. 2: 1–13. doi:10.1016/j.orcp.2007.11.003.
^Misra, S; Oliver, NS (28 October 2015). "Diabetic ketoacidosis in adults" (PDF). BMJ (Clinical research ed.). 351: h5660. doi:10.1136/bmj.h5660. PMID 26510442.
^Tatone, EH; Gordon, JL; Hubbs, J; LeBlanc, SJ; DeVries, TJ; Duffield, TF (1 August 2016). "A systematic review and meta-analysis of the diagnostic accuracy of point-of-care tests for the detection of hyperketonemia in dairy cows". Preventive Veterinary Medicine. 130: 18–32. doi:10.1016/j.prevetmed.2016.06.002. PMID 27435643.
v
t
e
Cholesterol and steroid metabolic intermediates
Mevalonate pathway
to HMG-CoA
Acetyl-CoA
Acetoacetyl-CoA
HMB
HMB-CoA
HMG-CoA
Ketone bodies
Acetone
Acetoacetic acid
β-Hydroxybutyric acid
to DMAPP
Mevalonic acid
Phosphomevalonic acid
5-Diphosphomevalonic acid
Isopentenyl pyrophosphate
Dimethylallyl pyrophosphate
Geranyl-
Geranyl pyrophosphate
Geranylgeranyl pyrophosphate
Carotenoid
Prephytoene diphosphate
Phytoene
Non-mevalonate pathway
DOXP
MEP
CDP-ME
CDP-MEP
MEcPP
HMB-PP
IPP
DMAPP
To Cholesterol
Farnesyl pyrophosphate
Squalene
2,3-Oxidosqualene
Lanosterol
Lanosterol
Lathosterol
7-Dehydrocholesterol
Cholesterol
Lanosterol
Zymosterol
7-Dehydrodesmosterol
Desmosterol
Cholesterol
From Cholesterol (to steroids)
22R-Hydroxycholesterol
20α,22R-Dihydroxycholesterol
Steroid hormones
See here instead.
Nonhuman
Phytosterols
Stigmasterol
Brassicasterol
Ergosterols
Ergosterol
Ergocalciferol
v
t
e
Histone deacetylase inhibitors
3,3'-Diindolylmethane
β-Hydroxybutyric acid (β-hydroxybutyrate)
Abexinostat
Acetoacetic acid (acetoacetate)
Allyl mercaptan
Apicidin
Belinostat
Butyric acid (butyrate)
Capsaicin
Chidamide
Citarinostat
Curcumin
Diallyl disulfide
Entinostat
Fimepinostat
Givinostat
Indole-3-carbinol
Kevetrin
Martinostat
Mocetinostat
Nicotinamide
Panobinostat
Parthenolide
Phenylbutyrate
Pracinostat
Quisinostat
Resminostat
Romidepsin
Scriptaid
Sodium butyrate
Sodium oxybate (GHB sodium)
Sodium phenylbutyrate
Sodium valproate
Sulforaphane
Trapoxin B
Trichostatin A
Valnoctamide
Valproic acid (valproate)
Valproate pivoxil
Valproate semisodium
Valpromide
Vorinostat (SAHA)
See also: Receptor/signaling modulators
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5. 血清クレアチニン濃度を上昇させる剤 drugs that elevate the serum creatinine concentration
English Journal
1,25(OH)2D3 inhibits oxidative stress and monocyte adhesion by mediating the upregulation of GCLC and GSH in endothelial cells treated with acetoacetate (ketosis).
Kanikarla-Marie P1, Jain SK2.
The Journal of steroid biochemistry and molecular biology.J Steroid Biochem Mol Biol.2016 May;159:94-101. doi: 10.1016/j.jsbmb.2016.03.002. Epub 2016 Mar 3.
BACKGROUND: There is a significantly higher incidence of cardiovascular disease (CVD) among type 1 diabetic (T1D) patients than among non-diabetic subjects. T1D is associated with hyperketonemia, a condition with elevated blood levels of ketones, in addition to hyperglycemia. The biochemical mechani
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A series of novel 4-amino-6-(1,3,4-oxadiazolo/1,3,4-thiadiazolo)-pyrimidine derivatives of biological interest were prepared by sequential amination, hydrazide formation, and hydrazine carbothioamidination followed by cyclization. All the synthesized compounds (6a-6h and 7a-7f) were screened for ant
Biochemical and biophysical research communications.Biochem Biophys Res Commun.2016 Apr 29;473(2):537-44. doi: 10.1016/j.bbrc.2016.03.109. Epub 2016 Mar 25.
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New synthesis of a stereoisomeric mixture of methyl 12-trishomofarnesoate, a juvenile hormone mimic useful in sericulture by increasing silk production
ac·e·to·ac·e·tate (ăs′ĭ-tō-ăs′ĭ-tāt′, ə-sē′tō-) n. A salt of acetoacetic acid. acetoacetate A ketone body—salt of acetoacetic acid—which is increased in diabetic ketoacidosis. Ref range 0.02–0.20 mmol/L. Specimen Plasma; blood in ...
