烟草科技
煙草科技
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TOBACCO SCIENCE & TECHNOLOGY
2015年
6期
45-51
,共7页
李有桂%卢梦梦%朱成峰%徐迎波%陈开波
李有桂%盧夢夢%硃成峰%徐迎波%陳開波
리유계%로몽몽%주성봉%서영파%진개파
吡喃葡糖苷%甲基环戊烯醇酮%合成%热裂解%卷烟烟气
吡喃葡糖苷%甲基環戊烯醇酮%閤成%熱裂解%捲煙煙氣
필남포당감%갑기배무희순동%합성%열렬해%권연연기
Glucopyranoside%Methylcyclopentenolone%Synthesis%Pyrolysis%Cigarette smoke
以D-葡萄糖为原料,分别合成了2,3,4,6-四-O-乙酰基-α-D-溴代吡喃葡糖苷(2,溴代葡萄糖法)和2,3,4,6-四-O-乙酰基-α-D-葡萄糖基三氯乙酰亚胺酯(4,三氯乙腈法),2和4再分别与甲基环戊烯醇酮(MCP)进行偶联反应,然后脱乙酰基制备了结构不同的MCP-β-D-葡糖苷[3-甲基-1-氧代环戊-2-烯基-β-D-吡喃葡糖苷(1)和5-甲基-1-氧代环戊-2-烯基-β-D-吡喃葡糖苷(1′)];用1H NMR和HRMS技术对中间体和产物的结构进行了表征;并研究了糖苷1和1′的热裂解。结果表明:①两种合成方法所得到的产物都是目标产物,溴代葡萄糖法优于三氯乙腈法;②溴代葡萄糖法的最佳反应条件为甲基环戊烯醇酮与化合物2的摩尔比为1∶1.2,温度35℃,反应时间5 h,目标产物的产率82.0%,反应总产率59.6%;③卷烟燃吸过程中,糖苷1和1′热裂解为甲基环戊烯醇酮后,其在主流烟气中的转移率分别为16.13%和16.40%。
以D-葡萄糖為原料,分彆閤成瞭2,3,4,6-四-O-乙酰基-α-D-溴代吡喃葡糖苷(2,溴代葡萄糖法)和2,3,4,6-四-O-乙酰基-α-D-葡萄糖基三氯乙酰亞胺酯(4,三氯乙腈法),2和4再分彆與甲基環戊烯醇酮(MCP)進行偶聯反應,然後脫乙酰基製備瞭結構不同的MCP-β-D-葡糖苷[3-甲基-1-氧代環戊-2-烯基-β-D-吡喃葡糖苷(1)和5-甲基-1-氧代環戊-2-烯基-β-D-吡喃葡糖苷(1′)];用1H NMR和HRMS技術對中間體和產物的結構進行瞭錶徵;併研究瞭糖苷1和1′的熱裂解。結果錶明:①兩種閤成方法所得到的產物都是目標產物,溴代葡萄糖法優于三氯乙腈法;②溴代葡萄糖法的最佳反應條件為甲基環戊烯醇酮與化閤物2的摩爾比為1∶1.2,溫度35℃,反應時間5 h,目標產物的產率82.0%,反應總產率59.6%;③捲煙燃吸過程中,糖苷1和1′熱裂解為甲基環戊烯醇酮後,其在主流煙氣中的轉移率分彆為16.13%和16.40%。
이D-포도당위원료,분별합성료2,3,4,6-사-O-을선기-α-D-추대필남포당감(2,추대포도당법)화2,3,4,6-사-O-을선기-α-D-포도당기삼록을선아알지(4,삼록을정법),2화4재분별여갑기배무희순동(MCP)진행우련반응,연후탈을선기제비료결구불동적MCP-β-D-포당감[3-갑기-1-양대배무-2-희기-β-D-필남포당감(1)화5-갑기-1-양대배무-2-희기-β-D-필남포당감(1′)];용1H NMR화HRMS기술대중간체화산물적결구진행료표정;병연구료당감1화1′적열렬해。결과표명:①량충합성방법소득도적산물도시목표산물,추대포도당법우우삼록을정법;②추대포도당법적최가반응조건위갑기배무희순동여화합물2적마이비위1∶1.2,온도35℃,반응시간5 h,목표산물적산솔82.0%,반응총산솔59.6%;③권연연흡과정중,당감1화1′열렬해위갑기배무희순동후,기재주류연기중적전이솔분별위16.13%화16.40%。
Taking D-glucose as material, 2,3,4,6-Tetra-O-acetyl-α-D-glucopyranosyl bromide(Compound 2) and 2,3,4,6-Tetra-O-acetyl-α-D-glucopyranosyl trichloroacetimidate (Compound 4′) were synthesized byα-D-acetobromoglucose method (Method A) and trichloroacetonitrile method (Method B), respectively. Compounds 2 and 4′ were coupled with methylcyclopentenolone(MCP), then deacetylated to form MCP-β-D-glucopyranosides [3-methyl-1-oxocyclopenta-2-en-2-yl-β-D-glucopyranoside (Compound 1) and 5-methyl-1-oxocyclopenta-2-en-2-yl-β-D-glucopyranoside (Compound 1′), respectively. The molecular structures of intermediates and final products were characterized by 1H NMR and HRMS. The thermal pyrolysis of glucosides 1 and 1′ was also studied, and the results indicated that: 1) The compounds synthesized by the two methods were target products, Method A was better than Method B. 2)The optimal conditions of Method A were the molar ratio of MCP to compound 2 1∶1.2 and reacting at 35 ℃ for 5 hours, the yield of target product reached 82.0% and the total yield of reaction was 59.6%. 3)Glucosides 1 and 1′were added into cigarettes separately, the glucosides pyrolyzed into MCP during smoking, and their <br> transfer rates to mainstream cigarette smoke were 16.13% and 16.40%, respectively.