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长链脂肪醇氯甲酸酯的合成
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Abstract:
在5℃~10℃下，以石油醚为溶剂、吡啶为缚酸剂，通过长链脂肪醇与三光气反应，制备得到长链脂肪醇氯甲酸酯，收率达到80%以上，含量超过95%。以氯甲酸十二醇酯为例，正十二醇投料放大到41.1 g，氯甲酸十二醇酯收率和含量分别达到89.5%和98.5%，吡啶回收率达到88.1%，该工艺操作简单、安全，具有良好的应用前景。
With petroleum ether as solvent and pyridine as acid binding agent, a series of chloroformic esters of long-chain fatty alcohols were synthesized by the reaction of long chain fatty alcohol with triphosgene at 5？C~10？C. The yields of chloroformates were over 80% and the content was over 95%. Taking dodecanol chloroformate as an example, the yield and content of dodecanol chloroformate were up to 89.5% and 98.5% respectively when the dosage of n-dodecanol is 41.1g, and the recovery of pyridine reaches 88.1%. The process is simple, safe and has a good application prospect.
| [1] | 孙逊, 林国强, 陆洪福, 等. 紫杉烷类衍生物及其制备方法和药用用途[P]. 中国专利, 101012210. 2007. |
| [2] | 赵毓, 周莎, 边强, 等. 一类烯啶胺酰基衍生物的合成及其应用[P]. 中国专利, 111978244. 2020. |
| [3] | 穆慧敏, 韩志惠, 张铁柱, 等. 高纯氯甲酸苄酯无溶剂生产工艺的研究[J]. 天津化工, 2009, 23(5): 34-36. |
| [4] | Jeong, Y., Jwa, D.G., You, A., et al. (2019) Photochemical Control of Polydopamine Coating in an Aprotic Organic Solvent. Asian Journal of Organic Chemistry, 8, 1610-1612. https://doi.org/10.1002/ajoc.201900246 |
| [5] | Paolo, F., Ivan, M., Elisabetta, R., et al. (2003) Polycaprolactone-Poly(Ethylene Glycol) Multiblock Copolymers as Potential Substitutes for Di(Ethylhexyl) Phthalate in Flexible Poly(Vinyl Chloride) Formulations. Biomacromolecules, 4, 181-188. https://doi.org/10.1021/bm020115q |
| [6] | 周祖新, 顾建生. 双光气法合成氯甲酸-9-芴甲酯[J]. 精细石油化工, 2004, 1(1): 37-39. |
| [7] | Venkatesh, Y., Nandi, S., Shee, M., et al. (2017) Bis-Acetyl Carbazole: A Photoremovable Protecting Group for Sequential Release of Two Different Functional Groups and Its Application in Therapeutic Release. European Journal of Organic Chemistry, 2017, 6121-6130. https://doi.org/10.1002/ejoc.201701253 |
| [8] | Gagnard, V., Leydet, A., Morère, A., et al. (2004) Synthesis and in vitro Evaluation of S-Acyl-3-Thiopropyl Prodrugs of Foscarnet. Bioorganic & Medicinal Chemistry, 12, 1393-1402. https://doi.org/10.1016/j.bmc.2004.01.017 |
| [9] | Figlus, M., Wellaway, N., Cooper, A.W.J., et al. (2011) Synthesis of Arrays Using Low Molecular Weight MPEG-Assisted Mitsunobu Reaction. ACS Combinatorial Science, 13, 280-285. https://doi.org/10.1021/co100091n |
| [10] | Pasquato, L., Modena, G., Cotarca, L., Delogu, P., Mantovani, S. (2000) Conversion of Bis(Trichloromethyl) Carbonate to Phosgene and Reactivity of Triphosgene, Diphosgene, and Phosgene with Methano. Journal of Organic Chemistry, 65, 8224-8228. https://doi.org/10.1021/jo000820u |
| [11] | Mannuthodikayil, J., Singh, S., Biswas, A., et al. (2019) Benzimidazolinone-Free Peptide o-Aminoanilides for Chemical Protein Synthesis. Organic Letters, 21, 9040-9044. https://doi.org/10.1021/acs.orglett.9b03440 |
| [12] | 李兴, 常宏宏, 魏文珑. 以固体光气为原料合成邻苯二甲酰氯的工艺研究[J]. 应用化工, 2010, 39(5): 716-719. |
| [13] | 童国通, 谢建武, 周小锋. 氯甲酸苄酯的非光气法合成研究[J]. 化学世界, 2007, 48(4): 226-227+231. |
| [14] | Wang, Q.M. and Huang, R.Q. (2001) Synthesis and Biological Activity of Novel N’-Tert-Butyl-N’-Substituted Benzoyl-N-(Substituted Phenyl) Aminocarbonylhydrazines and Their Derivatives. Tetrahedron Letters, 42, 8881-8883.
https://doi.org/10.1016/S0040-4039(01)01932-3 |
