氯乙醛
氯乙醛 | |
---|---|
IUPAC名 Chloroacetaldehyde | |
系统名 Chloroethanal | |
别名 | 一氯代乙醛,一氯乙醛,2-氯乙醛 |
识别 | |
CAS号 | 107-20-0 34789-09-8(水合物) |
PubChem | 33 |
ChemSpider | 32 |
SMILES |
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InChI |
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InChIKey | QSKPIOLLBIHNAC-UHFFFAOYSA-N |
EINECS | 203-472-8 |
性质 | |
化学式 | C2H3ClO |
摩尔质量 | 78.50 g·mol⁻¹ |
外观 | 无色液体[1] |
氣味 | 辛辣,有穿透性[2] |
密度 | 1.19 g/cm3[1] |
熔点 | -16.3 °C(257 K)([1]) |
沸点 | 85-86 °C(358-359 K)([1][3][5]) |
溶解性(水) | 443 g/L[1][3] |
溶解性 | 可溶于有机溶剂[3] |
折光度n D |
() 1.397[4] |
危险性 | |
警示术语 | R:R24/25-R26-R34-R40-R50[6] |
安全术语 | S:S26-S28-S36/37/39-S45-S61[6] |
欧盟分类 | [6] |
主要危害 | 烷化剂 |
闪点 | 87.78 °C[4] |
PEL | C 1 ppm(3 mg/m3)[7] |
致死量或浓度: | |
LD50(中位剂量)
|
89 mg/kg(大鼠,口服) 82 mg/kg(小鼠,口服)[8] |
LC50(中位浓度)
|
200 ppm(大鼠,1小时)[9] |
相关物质 | |
相关化学品 | 氯乙醇 氯乙酸 二氯乙醛 三氯乙醛 |
若非注明,所有数据均出自标准状态(25 ℃,100 kPa)下。 |
氯乙醛是一种有机化合物,结构式ClCH2CHO。它是无色具刺鼻辛辣气味的液体,也是强亲电试剂和危险的烷基化试剂。氯乙醛通常不以无水物存在,而是以半缩水合醛(ClCH2CH(OH))2O形式存在。它可用于有机合成。
氯乙醛是抗肿瘤药异环磷酰胺的代谢产物,被认为是异环磷酰胺某些毒性的来源。[10]氯乙醛也是氯乙烯和1,2-二氯乙烷的代谢产物。[11]它会腐蚀粘膜及刺激眼睛、皮肤和呼吸道。[2]
制备
[编辑]把乙醛或三聚乙醛氯化能得到氯乙醛[2]。反应也会产生二氯乙醛和三氯乙醛[12],而这三者都是乙烯通过瓦克尔法转化成乙醛时产生的副产物。[12]无水氯乙醛可由高碘酸盐氧化3-氯-1,2-丙二醇而成。[5][13]氯乙醛还能通过氯乙烯和氯水的反应产生:[12]
- ClCH=CH2 + Cl2 + H2O → ClCH2CHO + 2 HCl
除此之外,氯乙醛还可以通过一氯代碳酸乙烯酯的分解产生。[12][14]
反应
[编辑]无水氯乙醛在室温下容易聚合成三聚体、四聚体或多聚体。[12]氯乙醛也会和水反应,生成缩醛半水合物1,1'-二羟基-2,2'-二氯乙醚。[12]这种化合物是无色晶体,熔点43-50 °C,沸点84 °C,并分解成氯乙醛和水。[12]
这种半水合物可被浓硫酸脱水,生成三聚氯乙醛(2,4,6-三(氯甲基)-1,3,5-三𫫇烷)。[12][15]它是无色晶体,熔点88–89 °C。[12]
半水合物通过共沸蒸馏脱水得到的是四聚氯乙醛(2,4,6,8-四(氯甲基)-1,3,5,7-四氧杂环辛烷)。[16][12]和三聚体一样,它也是无色晶体,熔点65–67 °C。[12]
用途
[编辑]氯乙醛是有机合成原料[5],可以合成吡咯[17]、呋喃[18][19]、噻吩[20][21]、咪唑[22][23]、𫫇唑啉[24]、噻唑啉[25]、噻唑[26][27]和吲哚[28]。此外,氯乙醛也是生产药品、杀虫剂、杀真菌剂、消毒剂、染料、环氧树脂硬化剂和抗静电剂的原料。[3]它也用于去除树皮。[2]
参考资料
[编辑]- ^ 1.0 1.1 1.2 1.3 1.4 Record of Chloracetaldehyd in the GESTIS Substance Database from the IFA
- ^ 2.0 2.1 2.2 2.3 The Merck index. S Budavari, M O'Neil, A Smith 12. Merck. 1996: 2108. ISBN 9780911910124.
- ^ 3.0 3.1 3.2 3.3 Entry on Chloracetaldehyd. at: Römpp Online. Georg Thieme Verlag, retrieved 2015-04-17.
- ^ 4.0 4.1 中国化工产品大全 上卷,Da137 (一)氯乙醛,页511
- ^ 5.0 5.1 5.2 e-EROS Encyclopedia of Reagents for Organic Synthesis, 1999–2013, John Wiley and Sons, Inc., Eintrag für Chloroacetaldehyde, abgerufen am 4. November 2015.
- ^ 6.0 6.1 6.2 氯乙醛. www.chemicalbook.com.
- ^ NIOSH Pocket Guide to Chemical Hazards. #0118. NIOSH.
- ^ Chloroacetaldehyde. National Institute for Occupational Safety and Health. 2014-12-04 [2015-02-20]. (原始内容存档于2023-03-30).
- ^ Chloroacetaldehyde. Immediately Dangerous to Life and Health Concentrations (IDLH). National Institute for Occupational Safety and Health (NIOSH).
- ^ Springate, James E. Ifosfamide Metabolite Chloroacetaldehyde Causes Renal Dysfunctionin vivo. Journal of Applied Toxicology (Wiley). 1997, 17 (1): 75–79. ISSN 0260-437X. doi:10.1002/(sici)1099-1263(199701)17:1<75::aid-jat397>3.0.co;2-c.
- ^ Proctor, Nick H.; Hughes, James P.; Hathaway, Gloria J. Proctor and Hughes' Chemical hazards of the workplace.. Hoboken, N.J.: Wiley-Interscience. 2004. ISBN 0-471-26883-6. OCLC 53369421.
- ^ 12.00 12.01 12.02 12.03 12.04 12.05 12.06 12.07 12.08 12.09 12.10 12.11 Jira, Reinhard; Kopp, Erwin; McKusick, Blaine C.; Röderer, Gerhard; Bosch, Axel; Fleischmann, Gerald, Chloroacetaldehydes, Wiley, 2007-07-15, ISBN 978-3-527-30385-4, doi:10.1002/14356007.a06_527.pub2
- ^ Hatch, Lewis F.; Alexander, Harold E. Preparation of Chloroacetaldehyde Hydrate. Journal of the American Chemical Society (American Chemical Society (ACS)). 1945, 67 (4): 688–688. ISSN 0002-7863. doi:10.1021/ja01220a504.
- ^ Gross, Hans. Über ?-Halogenäther. XVI. Monochloracetaldehyd bzw. Derivate des Glykolaldehyds und Glyoxals aus ?-Halogenäthern. Journal für Praktische Chemie (Wiley). 1963, 21 (1-2): 99–102. ISSN 0021-8383. doi:10.1002/prac.19630210115 (德语).
- ^ Natterer, Konrad. Über Monochloraldehyd. Monatshefte für Chemie (Springer Science and Business Media LLC). 1882, 3 (1): 442–464. ISSN 0026-9247. doi:10.1007/bf01516819 (德语).
- ^ Kopp, Erwin; Smidt, Jürgen. Reaktionen mit Chloracetaldehyd und 2.4-Dichlor-crotonaldehyd. Justus Liebigs Annalen der Chemie (Wiley). 1966-05-31, 693 (1): 117–127. ISSN 0075-4617. doi:10.1002/jlac.19666930110 (德语).
- ^ Quijano, M. Luisa; Nogueras, Manuel; Sánchez, Aldolfo; De Cienfuegos, Gerardo Alvarez; Melgarejo, Miguel. Synthesis, anticancer and antimicrobiological activities of pyrrolo[2,3-d]pyrimidines. Journal of Heterocyclic Chemistry (Wiley). 1990, 27 (4): 1079–1083. ISSN 0022-152X. doi:10.1002/jhet.5570270449.
- ^ Padwa, Albert; Gasdaska, John R. Generation of sulfur ylides by the desilylation of α-trimethylsilylbenzyl sulfonium salts. Tetrahedron (Elsevier BV). 1988, 44 (13): 4147–4156. ISSN 0040-4020. doi:10.1016/s0040-4020(01)86662-x.
- ^ Matsumoto, Masakatsu; Watanabe, Nobuko. A Facile Synthesis of 4-Oxo-4,5,6,7-tetrahydroindoles. HETEROCYCLES (The Japan Institute of Heterocyclic Chemistry). 1984, 22 (10): 2313. ISSN 0385-5414. doi:10.3987/r-1984-10-2313.
- ^ Hirota, Kosaku; Shirahashi, Mitsuomi; Senda, Shigeo; Yogo, Motoi. Pyrimidines. 65. Synthesis of 6-substituted thieno[2,3-d]pyrimidine-2,4(1H,3H)-diones. Journal of Heterocyclic Chemistry (Wiley). 1990, 27 (3): 717–721. ISSN 0022-152X. doi:10.1002/jhet.5570270345.
- ^ Aldvogel, Erwin. Synthese von 2-substituierten und 2,3-disubstituierten Alkyl- und Aryl-thiophenen und 2,3-anellierten Thiophen-Derivaten aus Ketonen als C2-Bausteine und Carbonodithiosäure-O-ethyl-S-(2-oxoethyl)ester als C2S-Baustein. Helvetica Chimica Acta (Wiley). 1992-05-06, 75 (3): 907–912. ISSN 0018-019X. doi:10.1002/hlca.19920750325.
- ^ Kluge, Arthur F. Synthesis of an imidazo[1,2-c]pyrimidine analog of a thiamine antagonist coccidiostat and a comparison of several methods for the preparation of imidazo[1,2-c]pyrimidines. Journal of Heterocyclic Chemistry (Wiley). 1978, 15 (1): 119–121. ISSN 0022-152X. doi:10.1002/jhet.5570150125.
- ^ Senga, Keitaro; Robins, Roland K.; O'Brien, Darrell E. Synthesis of certain imidazo[2,1-f] pyrazolo[3,4-d] pyrimidines. Journal of Heterocyclic Chemistry (Wiley). 1975, 12 (5): 1043–1044. ISSN 0022-152X. doi:10.1002/jhet.5570120547.
- ^ Weber, Maya; Jakobxht, Jürgen; Martens, Jürgen. Synthese und Reaktivität von 3-Oxazolinen. Liebigs Annalen der Chemie (Wiley). 1992-01-13, 1992 (1): 1–6. ISSN 0170-2041. doi:10.1002/jlac.199219920102 (德语).
- ^ Martens, Jürgen; Offermanns, Heribert; Scherberich, Paul. Einfache Synthese von racemischem Cystein. Angewandte Chemie (Wiley). 1981, 93 (8): 680–683. ISSN 0044-8249. doi:10.1002/ange.19810930808 (德语).
- ^ Begtrup, Mikael; Hansen, Lars Bo L.; Grundvig, S.; Stenstrøm, Yngve; Khan, Agha Zul-Quarnain; Sandström, Jan; Krogsgaard-Larsen, Povl. New Methods for the Introduction of Substituents into Thiazoles.. Acta Chemica Scandinavica (Danish Chemical Society). 1992, 46: 372–383. ISSN 0904-213X. doi:10.3891/acta.chem.scand.46-0372.
- ^ Brandsma, L.; De Jong, R. L. P.; Verkruijsse, H. D. An Efficient Synthesis of 1,3-Thiazole. Synthesis (Georg Thieme Verlag KG). 1985, 1985 (10): 948–949. ISSN 0039-7881. doi:10.1055/s-1985-31396.
- ^ Wender, Paul A.; White, Alan W. Methodology for the facile and regio-controlled synthesis of indoles. Tetrahedron (Elsevier BV). 1983, 39 (22): 3767–3776. ISSN 0040-4020. doi:10.1016/s0040-4020(01)88618-x.