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{{Use dmy dates|date=March 2020}} |
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{{for|chloroacetic acids in general|Chloroacetic acids}} |
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{{chembox |
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| verifiedrevid = 407461882 |
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|verifiedrevid = 464362551 |
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| Name = '''Chloroacetic acid''' |
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|Name = Chloroacetic acid |
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| ImageFile1 = Chloroacetic-acid-2D-skeletal.png |
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|ImageFile1 = 2-chloroacetic acid 200.svg |
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| ImageSize1 = |
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|ImageSize1 = 150px |
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| ImageName1 = Chloroacetic acid |
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|ImageName1 = Chloroacetic acid |
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| ImageFile2 = Chloroacetic-acid-3D-vdW.png |
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|ImageClass1 = skin-invert |
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|ImageFile2 = Chloroacetic-acid-3D-vdW.png |
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| ImageSize2 = 150px |
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|ImageSize2 = 200px |
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| ImageName2 = Chloroacetic acid |
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|ImageName2 = Chloroacetic acid |
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|PIN = Chloroacetic acid <!-- the locant ‘2’ for acetic acid is not cited, see P-14.3.4.3 of Nomenclature of Organic Chemistry – IUPAC Recommendations and Preferred Names 2013 (Blue Book) --> |
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| IUPACName = Chloroacetic acid |
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| SystematicName = Chloroethanoic acid |
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|SystematicName = Chloroethanoic acid |
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|OtherNames = 2-Chloroacetic acid<br />2-Chloroethanoic acid |
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| Section1 = {{Chembox Identifiers |
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|Section1={{Chembox Identifiers |
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| ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}} |
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|ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}} |
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| ChemSpiderID = 10772140 |
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| UNII_Ref = {{fdacite|correct|FDA}} |
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|ChemSpiderID = 10772140 |
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|UNII_Ref = {{fdacite|correct|FDA}} |
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| UNII = 5GD84Y125G |
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|UNII = 5GD84Y125G |
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| KEGG_Ref = {{keggcite|changed|kegg}} |
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|KEGG_Ref = {{keggcite|correct|kegg}} |
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| KEGG = D07677 |
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|KEGG = D07677 |
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|KEGG1 = C06755 |
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| InChI = 1/C2H3ClO2/c3-1-2(4)5/h1H2,(H,4,5) |
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|PubChem = 300 |
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| ChEBI_Ref = {{ebicite|changed|EBI}} |
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|InChI = 1/C2H3ClO2/c3-1-2(4)5/h1H2,(H,4,5) |
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| ChEBI = 27869 |
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|ChEBI_Ref = {{ebicite|correct|EBI}} |
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| SMILES = ClCC(O)=O |
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|ChEBI = 27869 |
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| InChIKey = FOCAUTSVDIKZOP-UHFFFAOYAR |
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|3DMet = B02139 |
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| ChEMBL_Ref = {{ebicite|correct|EBI}} |
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|SMILES = ClCC(O)=O |
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| ChEMBL = 14090 |
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|InChIKey = FOCAUTSVDIKZOP-UHFFFAOYAR |
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| StdInChI_Ref = {{stdinchicite|correct|chemspider}} |
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|ChEMBL_Ref = {{ebicite|correct|EBI}} |
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| StdInChI = 1S/C2H3ClO2/c3-1-2(4)5/h1H2,(H,4,5) |
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|ChEMBL = 14090 |
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| StdInChIKey_Ref = {{stdinchicite|correct|chemspider}} |
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|StdInChI_Ref = {{stdinchicite|correct|chemspider}} |
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| StdInChIKey = FOCAUTSVDIKZOP-UHFFFAOYSA-N |
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|StdInChI = 1S/C2H3ClO2/c3-1-2(4)5/h1H2,(H,4,5) |
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| CASNo = 79-11-8 |
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| CASNo_Ref = {{cascite|correct|CAS}} |
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|StdInChIKey_Ref = {{stdinchicite|correct|chemspider}} |
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|StdInChIKey = FOCAUTSVDIKZOP-UHFFFAOYSA-N |
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| RTECS = AF8575000 |
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|CASNo = 79-11-8 |
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}} |
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|CASNo_Ref = {{cascite|correct|CAS}} |
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| Section2 = {{Chembox Properties |
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|RTECS = AF8575000 |
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| C = 2 | H = 3 | Cl = 1 | O = 2 |
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|EINECS = 201-178-4 |
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| Appearance = Colorless or white ]s |
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| Density = 1.58 g cm<sup>−3</sup>, solid |
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| Solubility = 85.8 g/100mL (25 °C) |
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| MeltingPtC = 63 |
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| BoilingPt = 189.3 °C, 462.5 K, 372.7 °F |
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| pKa = 2.86<ref>Dippy, J.F.J., Hughes, S.R.C., Rozanski, A., ''J. Chem Soc.'', '''1959''', 2492.</ref> |
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}} |
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| Section7 = {{Chembox Hazards |
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| ExternalMSDS = |
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| MainHazards = alkylating agent |
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| NFPA-H = 3 |
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| NFPA-F = 1 | Reactivity=0 |
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| NFPA-R = |
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| FlashPt = 126 °C |
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| RPhrases = {{R25}} {{R34}} {{R50}} |
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| SPhrases = {{S23}} {{S37}} {{S45}} {{S61}} |
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}} |
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| Section8 = {{Chembox Related |
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| OtherCpds = ]<br />] |
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|Section2={{Chembox Properties |
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|Formula = {{chem2|ClCH2CO2H}} |
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'''Chloroacetic acid''', industrially known as '''monochloroacetic acid (MCA)''' is the ] with the formula ClCH<sub>2</sub>CO<sub>2</sub>H. This ] is a useful building-block in ]. |
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|C=2 | H=3 | Cl=1 | O=2 |
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|Appearance = Colorless or white ]s |
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|Density = 1.58 g/cm<sup>3</sup> |
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|Solubility = 85.8 g/(100 mL) (25 °C) |
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|SolubleOther = Soluble in ], ], ], ], ], ] |
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|MeltingPtC = 63 |
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|BoilingPtC = 189.3 |
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|pKa = 2.86<ref>{{cite journal |author1=Dippy, J. F. J. |author2=Hughes, S. R. C. |author3=Rozanski, A. |title = 498. The dissociation constants of some symmetrically disubstituted succinic acids |journal = Journal of the Chemical Society |year = 1959 |volume = 1959 |pages = 2492–2498 |doi = 10.1039/JR9590002492}}</ref> |
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|LogP = 0.22 |
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|RefractIndex = 1.4351 (55 °C) |
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|VaporPressure = 0.22 hPa |
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|MagSus = −48.1{{e|−6}} cm<sup>3</sup>/mol |
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}} |
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|Section3={{Chembox Structure |
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|CrystalStruct = Monoclinic |
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}} |
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|Section4={{Chembox Thermochemistry |
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|DeltaHf = −490.1 kJ/mol |
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|HeatCapacity = 144.02 J/(K·mol) |
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}} |
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|Section7={{Chembox Hazards |
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|ExternalSDS = |
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|MainHazards = alkylating agent |
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|NFPA-H = 3 |
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|NFPA-F = 1 |
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|NFPA-R = 0 |
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|FlashPtC = 126 |
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|AutoignitionPtC = 470 |
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|GHSPictograms = {{GHS05}}{{GHS06}}{{GHS09}} |
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|GHSSignalWord = Danger |
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|HPhrases = {{H-phrases|301|311|314|331|400}} |
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|PPhrases = {{P-phrases|260|261|264|270|271|273|280|301+310|301+330+331|302+352|303+361+353|304+340|305+351+338|310|311|312|321|322|330|361|363|391|403+233|405|501}} |
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|LD50 = 76 mg/kg.<ref name=Ullmann/>}} |
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|Section8={{Chembox Related |
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|OtherCompounds = {{ubl|]|]|]|]|]|]|]|]|]|]}} |
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}} |
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}} |
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{{Distinguish|Acetyl chloride|Chloroacetyl chloride}} |
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'''Chloroacetic acid''', industrially known as '''monochloroacetic acid''' ('''MCA'''), is the ] with the formula {{chem2|ClCH2CO2H|auto=1}}. This ] is a useful building block in ]. It is a colorless solid. Related compounds are ] and ]. |
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==Production== |
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==Production== |
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Chloroacetic acid was first prepared (in impure form) by the French chemist ] (1813–1886) in 1843 by ] ] in the presence of sunlight,<ref>LeBlanc, Félix (1844) (in French), ''Annales de Chimie et de Physique'', 3rd series, '''10''' : 197–221 ; see especially p. 212.</ref> and in 1857 (in pure form) by the German chemist Reinhold Hoffmann (1831–1919) by refluxing ] in the presence of ] and ],<ref>Hoffmann, Reinhold (1857) (in German) (On mono-chloroacetic acid), ''Annalen der Chemie und Pharmacie'', '''102''' (1) : 1–20.</ref> and then by the French chemist ] by ] of ] ({{chem2|ClCH2COCl}}), also in 1857.<ref>Wurtz, Adolphe (1857) (in French) (Note on aldehyde and on acetyl chloride), ''Annales de chimie et de physique'', 3rd series, '''49''' : 58–62, see p. 61.</ref> |
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The production of chloroacetic acid was 706,000 tonnes/year in 2010<ref name=CEH>{{cite web|url=http://www.sriconsulting.com/CEH/Public/Reports/676.1000/|title=CEH Marketing Research Report: MONOCHLOROACETIC ACID|author=M.P. Malveda|work|date=july 2011|work=Chemical Economics Handbook|publisher=SRI consulting|accessdate=July 2011}}</ref>, of which over half is produced in China. Other countries with significant production capacity are Germany (105,000) the Netherlands (100,000), India (>65,000) and the United States (55,000). The largers producer is ].<ref name=CEH/> |
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Chloroacetic acid is prepared industrially by two routes. The predominant method involves ] of ], with ] as a ]: |
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===Processes=== |
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:{{chem2|H3C\sCOOH + Cl2 → ClH2C\sCOOH + HCl}} |
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Chloroacetic acid is prepared industrially via two routes. The predominant method involves ] of ]: |
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:CH<sub>3</sub>CO<sub>2</sub>H + Cl<sub>2</sub> → ClCH<sub>2</sub>CO<sub>2</sub>H + HCl |
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] serves as a ] for this reaction. |
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This route suffers from the production of ] and ] as impurities, which are difficult to separate by ]: |
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The other main industrial route to chloroacetic acid is ] of ] using ] as a catalyst. |
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:{{chem2|H3C\sCOOH + 2 Cl2 → Cl2HC\sCOOH + 2 HCl}} |
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:CCl<sub>2</sub>CHCl + 2 H<sub>2</sub>O → ClCH<sub>2</sub>CO<sub>2</sub>H + 2HCl |
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:{{chem2|H3C\sCOOH + 3 Cl2 → Cl3C\sCOOH + 3 HCl}} |
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The hydrolysis method produces a highly pure product, which can be important since mono-, di-, and trichloroacetic acids are difficult to separate by distillation. Approximately 420,000,000 kg/y are produced.<ref name=Ullmann>Günter Koenig, Elmar Lohmar, Norbert Rupprich "Chloroacetic Acids" in Ullmann's Encyclopedia of Industrial Chemistry 2002, Wiley-VCH, Weinheim. {{DOI|10.1002/14356007.a06_537}}</ref> |
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The second method entails hydrolysis of ]: |
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==Reactivity and uses== |
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: {{chem2|ClHC\dCCl2 + 2 H2O → ClH2C\sCOOH + 2 HCl}} |
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Illustrative of its usefulness in organic chemistry is the ''O''-alkylation of ] with chloroacetic acid, followed by ] of the resulting ], producing ].<ref>Burgstahler, A. W.; Worden, L. R. (1966). "." '']'' '''46''': 28.</ref> |
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The hydrolysis is conducted at 130–140 °C in a concentrated (at least 75%) solution of ]. This method produces a highly pure product, unlike the ] route. However, the significant quantities of ] released have led to the increased popularity of the halogenation route. Approximately 420,000 ] are produced globally per year.<ref name=Ullmann>{{Ullmann |author = Koenig, G. |author2 = Lohmar, E. |author3 = Rupprich, N. |title = Chloroacetic Acids |doi = 10.1002/14356007.a06_537 |year=2005}}</ref> |
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In industry, chloroacetic acid is used in the production of a wide variety of useful compounds, e.g., drugs, dyes, pesticides.<ref name=Ullmann/> Most reactions taking advantage of the high reactivity of the C-Cl bond. It is the precursor to the herbicide ]. The herbicides ] (2-methyl-4-chlorophenoxyacetic acid) and ] are prepared by alkylation with chloroacetic acid. Chloroacetic acid is converted to ], a precursor to ] (epinephrine). Displacement of chloride by sulfide gives ], which is used as a stabilizer in ] and a component in some ]s. |
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==Uses and reactions== |
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Most reactions take advantage of the high reactivity of the {{chem2|C\sCl}} bond. |
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In its largest-scale application, chloroacetic acid is used to prepare the thickening agent ] and ]. |
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In its largest-scale application, chloroacetic acid is used to prepare the thickening agent ] and ]. |
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Chloroacetic acid is also used in the production of ]s by etherification with chlorophenols. In this way ] (MCPA), ], and ] (2,4,5-T) are produced. It is the precursor to the herbicide ] and ]. Chloroacetic acid is converted to ], a precursor to ] (epinephrine). Displacement of chloride by sulfide gives ], which is used as a stabilizer in ] and a component in some ].<ref name=Ullmann/> |
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==Safety== |
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Like other ] and related halocarbons, chloroacetic acid is a potentially dangerous ]. The {{LD50}} for rats is 76 mg/kg.<ref name=Ullmann/> |
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Illustrative of its usefulness in organic chemistry is the ''O''-alkylation of ] with chloroacetic acid, followed by ] of the resulting ], producing ].<ref>{{OrgSynth |author = Burgstahler, A. W. |author2 = Worden, L. R. |title = Coumarone |year = 1966 |volume = 46 |pages = 28 |collvol = 5 |collvolpages = 251 |doi = 10.15227/orgsyn.046.0028}}.</ref><ref>{{cite journal |last1=Inglis |first1=J. K. H. |title=Ethyl Cyanoacetate |journal=Organic Syntheses |date=1928 |volume=8 |page=74 |doi=10.15227/orgsyn.008.0074}}</ref> |
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Chloroacetic acid easily penetrates skin and mucous membranes and interferes with cellular energy production. Initial dermal exposure to high concentrations (e.g., 80% solution) may not appear very damaging at first, however systemic poisoning may present within hours. Exposure can be fatal if greater than 6% body surface area is exposed to chloroacetic acid. The sodium salt does not penetrate the skin as well as the acid but can be as damaging given a longer duration and greater surface area of exposure. |
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==Safety== |
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Upon one's exposure to chloroacetic acid, immediate decontamination should be commenced by rinsing the affected area with water or bicarbonate solution in order to neutralize the acid and prevent further skin absorption. |
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] |
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Like other ] and related ], chloroacetic acid is a hazardous ]. The {{LD50}} for ] is 76 mg/kg.<ref name=Ullmann/> |
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It is classified as an ] in the United States as defined in Section 302 of the U.S. ] (42 U.S.C. 11002), and is subject to strict reporting requirements by facilities which produce, store, or use it in significant quantities.<ref name="gov-right-know">{{Citation | publisher = ] | title = 40 C.F.R.: Appendix A to Part 355—The List of Extremely Hazardous Substances and Their Threshold Planning Quantities | url = http://edocket.access.gpo.gov/cfr_2008/julqtr/pdf/40cfr355AppA.pdf | edition = 1 July 2008 | accessdate = 29 October 2011 | archive-url = https://web.archive.org/web/20120225051612/http://edocket.access.gpo.gov/cfr_2008/julqtr/pdf/40cfr355AppA.pdf | archive-date = 25 February 2012 | url-status = dead}}</ref> |
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The antidote of chloroacetic acid poisoning is ] (50 mg/kg IV over 10 mins, repeated in 2h; double dosage if hemodialysis is performed).{{Citation needed|date=March 2011}} |
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==See also== |
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==See also== |
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==References== |
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==References== |
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==External links== |
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==External links== |
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* {{cite web|url=http://www.dow.com/webapps/lit/litorder.asp?filepath=gco/pdfs/noreg/103-00133.pdf&pdf=true|title=Monochloroacetic Acid|publisher=Dow Chemical|accessdate=20 May 2007}} |
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*{{cite web|url=http://cabb-chemicals.com/en/chlorination.html|title=Monochloroacetic Acid|publisher=CABB|accessdate=6 February 2015|archive-url=https://web.archive.org/web/20150206132407/http://cabb-chemicals.com/en/chlorination.html|archive-date=6 February 2015|url-status=dead}} |
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* {{cite web|url=http://www.inchem.org/documents/pims/chemical/pim352.htm|title=Monochloroacetic Acid|publisher=IPCS Inchem|accessdate=20 May 2007}} |
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*{{cite web|url=http://www.inchem.org/documents/pims/chemical/pim352.htm|title=Monochloroacetic Acid|publisher=IPCS Inchem|accessdate=20 May 2007}} |
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{{Use dmy dates|date=March 2011}} |
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{{Authority control}} |
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{{DEFAULTSORT:Chloroacetic Acid}} |
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