770-12-7 二氯化磷酸苯酯

危险品运输编号UN 3265 8/PG 2，危险等级8，包装类别II，海关编码29209085，存储类别8A（可燃，腐蚀性物质），危险性类别皮肤腐蚀类别1B。非危险化学品（常温运输）。

二氯化磷酸苯酯用作有机合成的中间体，亦可用作二甲亚砜氧化反应的脱水剂，在生物农药甲氨基阿维菌素与兽药乙酰氨基阿维菌素的氧化物中间体合成中广泛应用；用于甲氨基阿维菌素苯甲酸盐的合成、磷酸二酯的制备，也用作亚磺酸与乙醇、氨、三醇等的偶联剂。

医药; 农药; 化学合成

合成路线 1（1. 合成：770-12-7）

产率：98% 合成条件：With triethylamine; trichlorophosphate In tert-butyl methyl ether at -55 - 20℃; for 4 h; 实验步骤：将L-丙氨酸（25g，280.6mmol，1当量）悬浮于甲苯（700mL），对甲苯磺酸（58.7g，308.7mmol，1.1当量）和HDP-OH（169g，561.2mmol，2）中。 加入等量的混合物，将得到的混合物加热回流，用Dean-Stark分离器过夜。 将反应混合物真空蒸发。 将粗固体在己烷中研磨，过滤并干燥，得到130g（85％收率）略微不纯的N，为甲苯磺酸盐。 该物质无需进一步纯化即可使用。 参考文献：[1] Patent: WO2010/135520, 2010, A1. Location in patent: Page/Page column 88 [2] Tetrahedron, 2004, vol. 60, # 46 SPEC. ISS., p. 10505 - 10513 [3] Synthetic Communications, 2000, vol. 30, # 18, p. 3473 - 3479 [4] Phosphorus, Sulfur and Silicon and Related Elements, 1997, vol. 127, p. 59 - 66 [5] Zhurnal Obshchei Khimii, 1956, vol. 26, p. 3060,3062 [6] J. Gen. Chem. USSR (Engl. Transl.), 1956, vol. 26, p. 3407,3409, 3410 [7] Journal of the American Chemical Society, 1958, vol. 80, p. 727,729 [8] Justus Liebigs Annalen der Chemie, 1947, vol. 558, p. 234,237 [9] Patent: US2397928, 1940, [10] Chemische Berichte, 1939, vol. 72, p. 2121,2127 [11] Recueil des Travaux Chimiques des Pays-Bas, 1917, vol. 36, p. 30 [12] Journal of the American Chemical Society, 1938, vol. 60, p. 750 [13] Journal of the Chemical Society, 1939, p. 907,915 [14] Journal of Medicinal Chemistry, 1993, vol. 36, # 8, p. 1048 - 1052 [15] Journal of Chemical Research, Miniprint, 1987, # 3, p. 815 - 830 [16] Arzneimittel-Forschung/Drug Research, 2005, vol. 55, # 2, p. 114 - 122 [17] Indian Journal of Chemistry - Section B Organic and Medicinal Chemistry, 2005, vol. 44, # 6, p. 1248 - 1251 [18] Journal of Medicinal Chemistry, 2006, vol. 49, # 24, p. 7215 - 7226 [19] Patent: US6350736, 2002, B1. Location in patent: Page column 14 [20] Patent: WO2006/50161, 2006, A2. Location in patent: Page/Page column 125 [21] Nucleosides, Nucleotides and Nucleic Acids, 2008, vol. 27, # 1, p. 37 - 42 [22] Journal of Agricultural and Food Chemistry, 2008, vol. 56, # 10, p. 3721 - 3731 [23] Journal of Medicinal Chemistry, 2008, vol. 51, # 23, p. 7593 - 7601 [24] Journal of the Chinese Chemical Society (Taipei, Taiwan), 2009, vol. 56, # 1, p. 51 - 58 [25] Phosphorus, Sulfur and Silicon and the Related Elements, 2010, vol. 185, # 2, p. 274 - 278 [26] Patent: WO2010/81082, 2010, A2. Location in patent: Page/Page column 88-89 [27] Asian Journal of Chemistry, 2012, vol. 24, # 3, p. 1097 - 1100 [28] Journal of the Indian Chemical Society, 2012, vol. 89, # 5, p. 701 - 703 [29] Bioorganic and Medicinal Chemistry Letters, 2013, vol. 23, # 2, p. 503 - 506 [30] Chemical Communications, 2013, vol. 49, # 41, p. 4619 - 4621 [31] Chemical Communications, 2013, vol. 49, # 41, p. 4682 - 4684 [32] Organic Letters, 2013, vol. 15, # 9, p. 2186 - 2189 [33] Asian Journal of Chemistry, 2013, vol. 25, # 11, p. 5985 - 5988 [34] Patent: US2014/179627, 2014, A1. Location in patent: Paragraph 0504 [35] Patent: US2015/105341, 2015, A1. Location in patent: Paragraph 0979 [36] Journal of Medicinal Chemistry, 2015, vol. 58, # 8, p. 3445 - 3458 [37] Patent: US2015/366888, 2015, A1. Location in patent: Paragraph 0883; 0900 [38] Patent: US2015/366887, 2015, A1. Location in patent: Paragraph 0833; 0850 [39] Patent: TW2016/5885, 2016, A. Location in patent: Page/Page column 111; 112 [40] Patent: CN106554382, 2017, A. Location in patent: Paragraph 1059; 1060; 1061 [41] Journal of Medicinal Chemistry, 2017, vol. 60, # 8, p. 3518 - 3524 [42] Journal of Organic Chemistry, 2017, vol. 82, # 6, p. 3102 - 3124 [43] Patent: WO2017/79195, 2017, A1. Location in patent: Page/Page column 34 [44] Tetrahedron Letters, 2018, vol. 59, # 14, p. 1404 - 1408 [45] DRP/DRBP Org.Chem., [46] Patent: GB651656, 1948, [47] Patent: US4016223, 1977, A 通过三氯氧磷与无水苯酚钠反应制备而来 (式1)。 通过三氯氧磷与无水苯酚钠反应制备而来 ( 式1)。