国产的马尾松松节油的主要成分是α-蒎烯, 其中左 旋 α-蒎烯 36

The main component is made of turpentine massoniana α- pinene, wherein L-α- pinene ee values ​​between 40 and 36% to 50%, optical purity is not high, the conventional method has poor resolution, back to purified difficult. It has been reported by catalytic hydrogenation of 36, 100% conversion, 38-cis-pinane selectivity of 98.3%. in 37 L-β- pinene turpentine Pinus elliottii higher levels can reach 20% to 35%, and after distillation of commercially ee of 37 may be up to 92.1% have been reported in diethylene glycol dimethyl ether with sodium borohydride, boron trifluoride reduction of L-β- pinene, 98 can % obtained in a yield of cis-pinane 38. the pyrolysis step 38, has been reported at a cracking temperature of 580 ℃, dihydromyrcenyl 39 content in the product can reach 71.2%. step preparation of dextrose citronella alcohol 40, has been reported with malonic acid and sodium borohydride malonyloxyborohydride generated by the reaction of sodium borohydride, reaction at 60 deg.] C in THF with 39 in 6 h, the reaction occurs in 100% of the terminal double bond, oxidation 40 mass fraction of 90%, and did not find one generation. the fourth step selectively oxidized with oxygen to give dextrorotatory hydroxy at catalytic tetrapropylammonium perruthenate 4 Mao aldehyde, yield 91% following step process consistent with Takasago (Scheme 10). This route convenient source of starting material, the yield of each step are high, industrial prospects clear [4].

国产的马尾松松节油的主要成分是α-蒎烯, 其中左 旋 α-蒎烯 36 的 ee 值在 40%～50%之间, 光学纯度不高, 普通方法又不好拆分, 给后面的纯化带来困难. 有报道 对36用镍催化加氢, 转化率100%, 顺式蒎烷38选择性 达98.3%. 左旋β-蒎烯37在湿地松的松节油中含量较 高, 可以达到 20%～35%, 且精馏后商业化的 37 的 ee 值可以高达 92.1%. 有报道在二乙二醇二甲醚中用硼 氢化钠、三氟化硼还原左旋 β-蒎烯, 能以 98%的产率得到顺式蒎烷38. 第二步高温裂解38, 有报道显示在裂 解温度580 ℃下, 产物中的二氢月桂烯39含量可以达到 71.2%. 第三步制备右旋香茅醇 40, 有报道用丙二酸 与硼氢化钠反应生成的丙二酰氧基硼氢化钠在 THF 中 与39反应, 60 ℃下反应6 h, 反应100%发生在末端双键 上, 氧化生成 40 的质量分数为 90% , 且没有发现酮生 成. 第四步在四丙基高钌酸铵催化下用氧气选择性氧 化羟基得到右旋香茅醛 4, 产率 91%. 后面的步骤跟 高砂工艺一致(Scheme 10). 这条路线的原料来源方便, 每一步产率都较高, 工业化前景明晰[4]。

The main component of the domestic turpentine is α - pinene, in which the EE value of l-α-pinen36 is between 40% and 50%, the optical purity is not high, and the common method is not easy to separate, which makes the subsequent purification difficult. It has been reported that for the hydrogenation of 36 with nickel catalyst, the conversion rate is 100%, and the selectivity of CIS pina38 is 98.3%. The content of l-β-pinen37 is high in turpentine of Pinus elliottii, It has been reported that the reduction of l-β - pinene with sodium borohydride and boron trifluoride in diethylene glycol dimethyl ether can yield CIS pinane with 98% yield. In the second step, high temperature cracking 38, it is reported that the cracking temperature is 580 ℃, The content of dihydrolaurene 39 in the product can reach 71.2%. The third step is to prepare d-citronellol 40. It has been reported that the reaction of malonic acid and sodium borohydride to produce malonyloxyborohydride in THF with 39, at 60 ℃ for 6 hours, 100% of the reaction takes place on the end double bond, and the mass fraction of oxidation to produce 40 is 90%, In the fourth step, under the catalysis of tetrapropyl high ruthenium acid ammonium, the hydroxyl is oxidized selectively with oxygen to get citronellal 4, with the yield of 91%. The following steps are consistent with scheme 10. This route has convenient raw material source, high yield in each step, and clear industrialization prospect [4].