原碳酸四乙酯

原碳酸四乙酯
	IUPAC名; (Triethoxymethoxy)ethane
别名	四乙氧基甲烷
识别
CAS号	78-09-1
PubChem	66213
ChemSpider	59598
SMILES	CCOC(OCC)(OCC)OCC;
InChI	1S/C9H20O4/c1-5-10-9(11-6-2,12-7-3)13-8-4/h5-8H2,1-4H3;
InChIKey	CWLNAJYDRSIKJS-UHFFFAOYSA-N
EINECS	201-082-2
性质
化学式	C9H20O4
摩尔质量	192.25 g·mol⁻¹
外观	液体
密度	0.919
沸点	159.5 °C（433 K）
危险性
	GHS危险性符号;
H-术语	H226, H315, H319, H335
相关物质
其他阳离子	原硅酸四乙酯
相关化学品	原碳酸四甲酯
	若非注明，所有数据均出自标准状态（25 ℃，100 kPa）下。

原碳酸四乙酯是一种有机化合物，是假想化合物原碳酸C(OH)₄的四乙酯。

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历史

原碳酸四乙酯于1864年首次被报道。^[1]

制备

原碳酸四乙酯可以由剧毒的三氯硝基甲烷开始合成，^[1]^[2]^[3]^[4]产率只有46-49^[3]至58%：^[4]

类似原碳酸四甲酯，从四氯甲烷开始的合成路线没有得到四乙氧基甲烷。^[5]

相较三氯硝基甲烷，毒性较低的三氯乙腈合成原碳酸四乙酯可以得到更高的产率（85%）。^[6]另一种绕过有问题的反应物的替代反应是二烷基锡二醇盐与二硫化碳在高温高压下的反应：^[7]

最近的合成直接从乙醇钠、四氯化锡和二硫化碳开始合成原碳酸四乙酯。^[8]

性质

原碳酸四乙酯是一种清澈、芳香或水果味的液体，^[9]粘度低，对强酸和强碱不稳定。^[10]

用处

原碳酸四乙酯可用作溶剂或是CH酸性化合物（例如酚和羧酸）的烷基化试剂。它和胺、烯醇醚和磺酰胺反应，^[11] 形成螺环化合物。螺环原碳酸盐（SOCs）^[12]具有一定的工业意义，因为它们可用作添加剂，以减少环氧化物聚合过程中的收缩（它们用于膨胀单体（英语：Expanding Monomers））。^[13]

参考资料

[1]
Bassett, Henry. Ueber das vierfach-basische kohlensaure Aethyl.. Annalen der Chemie und Pharmacie (Wiley). 1864, 132 (1): 54–61. ISSN 0075-4617. doi:10.1002/jlac.18641320106 （德语）.
[2]
TIECKELMANN, HOWARD; POST, HOWARD W. THE PREPARATION OF METHYL, ETHYL, PROPYL, AND BUTYL ORTHOCARBONATES1. The Journal of Organic Chemistry (American Chemical Society (ACS)). 1948, 13 (2): 265–267. ISSN 0022-3263. doi:10.1021/jo01160a014.
[3]
J.D. Roberts, R.E. McMahon (1952). "Ethyl Orthocarbonate". Org. Synth.; Coll. Vol. 4: 457.
[4]
Europäische Patentschrift EP 0881212 B1, Production method of aminobenzene compound （页面存档备份，存于互联网档案馆）, Erfinder: H. Hashimoto et al., Anmelder: Takeda Chemical Industries, Ltd., veröffentlicht am 30. Oktober 2001.
[5]
DeWolfe, Robert H. Carboxylic ortho acid derivatives; preparation and synthetic applications. New York,: Academic Press. 1970. ISBN 0-12-214550-X. OCLC 73498.
[6]
US-Patent US 6825385, Process for the preparation of orthocarbonates （页面存档备份，存于互联网档案馆）, Erfinder: G. Fries, J. Kirchhoff, Anmelder: Degussa AG, erteilt am 30. November 2004.
[7]
Sakai, Shizuyoshi; Kobayashi, Yoshihiro; Ishii, Yoshio. Reaction of dialkyltin dialkoxides with carbon disulfide at higher temperature. Preparation of orthocarbonates. The Journal of Organic Chemistry (American Chemical Society (ACS)). 1971, 36 (9): 1176–1180. ISSN 0022-3263. doi:10.1021/jo00808a002.
[8]
Sakai, Shizuyoshi; Kominami, Mitsuhiro; Chonan, Kohzo; Enomoto, Takayasu; Fujinami, Tatsuo. A New Method for Preparation of Tetraalkyl Orthocarbonates from Sodium Alkoxides, Tetrachlorostannane, and Carbon Disulfide. Synthesis (Georg Thieme Verlag KG). 1984, 1984 (03): 233–234. ISSN 0039-7881. doi:10.1055/s-1984-30785.
[9]
J. H. Ruth, Odor Thresholds and Irritation Levels of Several Chemical Substances: A Review, Am. Ind. Hyg. Assoc. J. 47, A-142 – A-151, (1986).
[10]
来源：Sigma-Aldrich Co., product no. 163627 .
[11]
W. Kantlehner et al., Die präparative Chemie der O- und N-funktionellen Orthokohlensäure-Derivate, Synthesis, 1977, 73–90.
[12]
Vodak, David T.; Braun, Matthew; Iordanidis, Lykourgos; Plévert, Jacques; Stevens, Michael; Beck, Larry; Spence, John C. H.; O'Keeffe, Michael; Yaghi, Omar M. One-Step Synthesis and Structure of an Oligo(spiro-orthocarbonate). Journal of the American Chemical Society (American Chemical Society (ACS)). 2002-04-11, 124 (18): 4942–4943. ISSN 0002-7863. doi:10.1021/ja017683i.
[13]
Acosta Ortiz, Ricardo; Duarte, María Lydia Berlanga; Gómez, Amy Grace Savage; Sangermano, Marco; García Valdez, Aída E. Novel diol spiro orthocarbonates derived from glycerol as anti-shrinkage additives for the cationic photopolymerization of epoxy monomers. Polymer International (Wiley). 2010-01-08, 59 (5): 680–685. ISSN 0959-8103. doi:10.1002/pi.2755.

[Bassett-1] [1]
Bassett, Henry. Ueber das vierfach-basische kohlensaure Aethyl.. Annalen der Chemie und Pharmacie (Wiley). 1864, 132 (1): 54–61. ISSN 0075-4617. doi:10.1002/jlac.18641320106 （德语）.

[2] [2]
TIECKELMANN, HOWARD; POST, HOWARD W. THE PREPARATION OF METHYL, ETHYL, PROPYL, AND BUTYL ORTHOCARBONATES1. The Journal of Organic Chemistry (American Chemical Society (ACS)). 1948, 13 (2): 265–267. ISSN 0022-3263. doi:10.1021/jo01160a014.

[Organic_Syntheses-3] [3]
J.D. Roberts, R.E. McMahon (1952). "Ethyl Orthocarbonate". Org. Synth.; Coll. Vol. 4: 457.

[Hashimoto-4] [4]
Europäische Patentschrift EP 0881212 B1, Production method of aminobenzene compound （页面存档备份，存于互联网档案馆）, Erfinder: H. Hashimoto et al., Anmelder: Takeda Chemical Industries, Ltd., veröffentlicht am 30. Oktober 2001.

[De_Wolfe-5] [5]
DeWolfe, Robert H. Carboxylic ortho acid derivatives; preparation and synthetic applications. New York,: Academic Press. 1970. ISBN 0-12-214550-X. OCLC 73498.

[6] [6]
US-Patent US 6825385, Process for the preparation of orthocarbonates （页面存档备份，存于互联网档案馆）, Erfinder: G. Fries, J. Kirchhoff, Anmelder: Degussa AG, erteilt am 30. November 2004.

[7] [7]
Sakai, Shizuyoshi; Kobayashi, Yoshihiro; Ishii, Yoshio. Reaction of dialkyltin dialkoxides with carbon disulfide at higher temperature. Preparation of orthocarbonates. The Journal of Organic Chemistry (American Chemical Society (ACS)). 1971, 36 (9): 1176–1180. ISSN 0022-3263. doi:10.1021/jo00808a002.

[8] [8]
Sakai, Shizuyoshi; Kominami, Mitsuhiro; Chonan, Kohzo; Enomoto, Takayasu; Fujinami, Tatsuo. A New Method for Preparation of Tetraalkyl Orthocarbonates from Sodium Alkoxides, Tetrachlorostannane, and Carbon Disulfide. Synthesis (Georg Thieme Verlag KG). 1984, 1984 (03): 233–234. ISSN 0039-7881. doi:10.1055/s-1984-30785.

[9] [9]
J. H. Ruth, Odor Thresholds and Irritation Levels of Several Chemical Substances: A Review, Am. Ind. Hyg. Assoc. J. 47, A-142 – A-151, (1986).

[10] [10]
来源：Sigma-Aldrich Co., product no. 163627 .

[11] [11]
W. Kantlehner et al., Die präparative Chemie der O- und N-funktionellen Orthokohlensäure-Derivate, Synthesis, 1977, 73–90.

[12] [12]
Vodak, David T.; Braun, Matthew; Iordanidis, Lykourgos; Plévert, Jacques; Stevens, Michael; Beck, Larry; Spence, John C. H.; O'Keeffe, Michael; Yaghi, Omar M. One-Step Synthesis and Structure of an Oligo(spiro-orthocarbonate). Journal of the American Chemical Society (American Chemical Society (ACS)). 2002-04-11, 124 (18): 4942–4943. ISSN 0002-7863. doi:10.1021/ja017683i.

[13] [13]
Acosta Ortiz, Ricardo; Duarte, María Lydia Berlanga; Gómez, Amy Grace Savage; Sangermano, Marco; García Valdez, Aída E. Novel diol spiro orthocarbonates derived from glycerol as anti-shrinkage additives for the cationic photopolymerization of epoxy monomers. Polymer International (Wiley). 2010-01-08, 59 (5): 680–685. ISSN 0959-8103. doi:10.1002/pi.2755.

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