现代农药
現代農藥
현대농약
MODERN AGROCHEMICALS
2013年
5期
15-17
,共3页
S-2-氯丙酸甲酯%R-乳酸甲酯%Vilsmeier试剂%氯化
S-2-氯丙痠甲酯%R-乳痠甲酯%Vilsmeier試劑%氯化
S-2-록병산갑지%R-유산갑지%Vilsmeier시제%록화
methyl S-2-chloropropionate%methyl R-2-hydroxy propionate%Vilsmeier reagent%chlorination
以R-乳酸甲酯为原料，以氯化亚砜和DMF形成的Vilsmeier试剂为氯化剂，以DMF为催化剂兼溶剂，经亲核取代反应合成S-2-氯丙酸甲酯。主要考查R-乳酸甲酯和Vilsmeier试剂物质的量之比、反应温度、反应时间、溶剂种类等因素对收率的影响，优化了工艺条件。结果表明：当Vilsmeier试剂与R-乳酸甲酯物质的量之比为1.15∶1，反应温度为50～60℃，反应时间为5 h时，较传统的氯化亚砜/吡啶/PCl5/POCl3氯化体系，收率从72%提高到89%，光学纯度(e.e%)达98.2%。并用FT-IR，1H NMR，GC-MS表征了其分子结构。
以R-乳痠甲酯為原料，以氯化亞砜和DMF形成的Vilsmeier試劑為氯化劑，以DMF為催化劑兼溶劑，經親覈取代反應閤成S-2-氯丙痠甲酯。主要攷查R-乳痠甲酯和Vilsmeier試劑物質的量之比、反應溫度、反應時間、溶劑種類等因素對收率的影響，優化瞭工藝條件。結果錶明：噹Vilsmeier試劑與R-乳痠甲酯物質的量之比為1.15∶1，反應溫度為50～60℃，反應時間為5 h時，較傳統的氯化亞砜/吡啶/PCl5/POCl3氯化體繫，收率從72%提高到89%，光學純度(e.e%)達98.2%。併用FT-IR，1H NMR，GC-MS錶徵瞭其分子結構。
이R-유산갑지위원료，이록화아풍화DMF형성적Vilsmeier시제위록화제，이DMF위최화제겸용제，경친핵취대반응합성S-2-록병산갑지。주요고사R-유산갑지화Vilsmeier시제물질적량지비、반응온도、반응시간、용제충류등인소대수솔적영향，우화료공예조건。결과표명：당Vilsmeier시제여R-유산갑지물질적량지비위1.15∶1，반응온도위50～60℃，반응시간위5 h시，교전통적록화아풍/필정/PCl5/POCl3록화체계，수솔종72%제고도89%，광학순도(e.e%)체98.2%。병용FT-IR，1H NMR，GC-MS표정료기분자결구。
Optically pure methyl S-2-chloropropionate was prepared starting from methyl R-2-hydroxy propionate, by using Vilsmeier reagent from thionyl chloride and dimethyl formamide (DMF) as chlorinating reagent, DMF also as solvent and catalyst. The effects of some reaction conditions on the yield were researched, for instance, the molar ratio of raw materials, solvents, reaction temperature and time. The optimum conditions of nucleophilic chlorination were as follows: the reaction temperature of 50-60℃, time of 5 h and n(R-2-hydroxy propionate)∶n(Vilsmeier reagent)=1∶1.15. The yield was improved from 72% to 89%, compared to the traditional methods which used SOCl2/pyridine/PCl5/POCl3 as chlorinating reagents, and the optical purity (e.e%) was 98.2%. The product structure was characterized by FT-IR ,1H NMR and GC-MS.
