CN109651123A - 一种负载型碳化钨催化柑青醛选择环化制环柑青醛的方法 - Google Patents
一种负载型碳化钨催化柑青醛选择环化制环柑青醛的方法 Download PDFInfo
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- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 title claims abstract description 36
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- RRQHXKQSKXLECT-UHFFFAOYSA-N 8,8-dimethyl-7H-naphthalene-2-carbaldehyde Chemical class CC1(CC=CC=2C=CC(=CC1=2)C=O)C RRQHXKQSKXLECT-UHFFFAOYSA-N 0.000 claims abstract description 12
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- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
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- B01J29/00—Catalysts comprising molecular sieves
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Abstract
本发明涉及碳化钨催化柑青醛的环化反应,具体地说是一种负载型碳化钨催化柑青醛选择环化制环柑青醛的方法。该方法以对位/间位柑青醛为原料,在有机溶剂中于50℃‑150℃,实现高选择性环化反应生成环柑青醛1,2,3,4,5,6,7,8‑八氢‑,8,8‑二甲基‑2‑萘醛和1,2,3,4,5,6,7,8‑八氢‑5,5‑二甲基‑2‑萘醛。底物转化率最高达100%,目标产物收率最高达99%。与传统催化路线相比,本发明使用负载型非贵金属碳化钨为催化剂,无需使用无机酸、碱,避免了传统催化大量酸液的产生;具有反应条件温和、催化剂廉价且可循环使用、活性和选择性高、反应过程环境友好等特征。
Description
技术领域
本发明涉及从柑青醛高效催化反应制备环柑青醛香料,具体地说是一种利用负载型非贵金属碳化钨替代传统液体酸催化剂催化柑青醛高效转化制备环柑青醛香料的方法。
背景技术
环柑青醛又名美乐馥,包括两种异构体(式1),全称分别为 1,2,3,4,5,6,7,8-八氢-,8,8-二甲基-2-萘醛和1,2,3,4,5,6,7,8-八氢-5,5-二甲基-2- 萘醛。这两种异构体分别具有令人愉快的木质馥郁馨香气味和一种复杂的药草香韵,是合成多种名贵香料的必需中间体,在香料和化妆品等领域有广泛的应用(参见文献:a)Ohloff,G.RiechstoffeAromen 1957,38-40. b)Ohloff,G.DE 1057108,1957,Dragoco Spezialfabrikkonz.Riech-und Aromastoffe Gerberding&Co.,G.m.b.H.[Chem.Abstr.55,48611].)。环柑青醛的传统生产工艺采用质子酸如硫酸、磷酸、对甲苯磺酸、Amberlite H+等为催化剂(Bull.Chem.Soc.Chim.Fr.1959,601-606;EP 0743297, priority 16.5.1995 toGivaudan[Chem.Abstr.126,103856h]),存在催化剂用量大、反应条件相对苛刻,产物不易分离、对环境污染严重和不能重复使用等缺点。
式1环柑青醛两种异构体的结构式
发明内容
本发明的目的在于提供一种替代液体酸催化的环柑青醛制备方法。利用负载型碳化钨催化剂(多相催化剂)实现了在不同溶剂中催化对位/间位柑青醛高收率、高选择性地转化为1,2,3,4,5,6,7,8-八氢-,8,8-二甲基-2-萘醛和 1,2,3,4,5,6,7,8-八氢-5,5-二甲基-2-萘醛。
为实现上述目的,本发明采取的技术方案为:
一种负载型碳化钨催化柑青醛选择环化制备环柑青醛的方法,其特征在于:在负载型碳化钨作用下,4-和3-(4-甲基-3-戊烯基)-3-环己烯醛(对位柑青醛和/或间位柑青醛)在非极性有机溶剂中于密闭反应釜中在惰性气氛和/ 或空气氛条件下反应,高选择性环化生成环柑青醛(1,2,3,4,5,6,7,8-八氢-,8,8- 二甲基-2-萘醛和1,2,3,4,5,6,7,8-八氢-5,5-二甲基-2-萘醛);
所述负载型碳化钨催化剂由活性组分和载体两部分构成;所述活性组分为碳化钨;所述载体为活性炭、氧化铝、氧化硅、氧化锆、二氧化钛、硅铝分子筛、磷铝分子筛中的一种或二种以上;碳化钨于载体中的担载量为 5-80wt%。
所述反应底物与催化剂的质量比为2:1-100:1,室温下反应釜中填充空气和/或惰性气氛(如:氮气)的初始压力为0.1MPa-20MPa;反应温度为 50-200℃;反应时间为0.5–24h。
所述碳化钨于载体中的担载量优选担载量为10-50wt%,更优选担载量为15-40wt%。
所述非极性有机溶剂为正己烷、环己烷、甲苯、二甲苯中的一种或二种以上。
为加快反应,所述反应底物与催化剂的质量比优选为2:1-20:1;室温下反应釜中填充空气和/或惰性气氛的初始压力优选为0.1MPa-5MPa;反应温度优选为100℃-150℃。
与现有技术相比,本发明有如下优点:
本发明催化剂为负载型碳化钨,催化剂以廉价碳化钨为主要活性组分、成本低廉、催化剂可循环使用、反应条件温和、活性和选择性高;反应过程中不使用无机酸、碱,避免了传统环柑青醛生产工艺中液体酸难以回收使用,环境污染等问题,符合可持续发展的要求。
下面通过具体实施例予以进一步的详细说明。
具体实施方式
实施例1
W2C/AC(W2C为碳化钨,AC为活性炭)具体制备方法如下:
将偏钨酸氨溶于水使偏钨酸氨的质量浓度为0.4g/ml。而后,以等体积浸渍的方法将溶液浸渍活性炭载体(AC)。经120℃烘箱干燥12h后,将催化剂前体置于H2气氛中进行程序升温碳热反应,具体反应过程为:1.0g 前体在石英反应管中由室温1h升温至400℃,而后以1℃/min升温至700 ℃并保持1h进行碳化,氢气流速为60ml/min。得到碳化钨担载量为30wt%的W2C/AC催化剂。
其它条件不变,仅改变浸渍液中偏钨酸氨的浓度得到碳化钨担载量不同的催化剂;碳化钨担载量分别为5wt%,10wt%,15wt%,40wt%,50wt%, 60wt%,80wt%。
实施例2
碳化钨分别担载于氧化铝、氧化硅、氧化钛、氧化锆、二氧化钛、硅铝分子筛、磷铝分子筛上制备负载型碳化钨催化剂WxC/B(WxC为碳化钨, 1≤x≤2;B为多孔载体,为活性炭、氧化铝、氧化硅、氧化锆、二氧化钛、硅铝分子筛、磷铝分子筛)。:制备过程类似于实施例1,不同之处在于载体分别使用的是氧化铝、氧化硅、氧化锆、二氧化钛、硅铝分子筛、磷铝分子筛而非活性炭,同时,碳化气体由氢气换为CH4/H2(体积比1:4),催化剂中碳化钨担载量为30wt%,由此得到碳化钨担载于氧化铝、氧化硅、氧化锆、二氧化钛、硅铝分子筛、磷铝分子筛上共六种催化剂。
实施例3-18
W2C/AC催化对位柑青醛选择环化制备环柑青醛:在反应釜中将0.5g的柑青醛与一定质量的W2C/AC催化剂分别溶于50ml甲苯中,用氮气置换五次后使氮气初始压力为0.1MPa-20MPa,升温至50-200℃,以1000转/min 的速度进行搅拌反应0.5–24h。反应结束后,降至室温,上层清液过滤后取样分析。产物定性分析通过GC-MS联用技术及标样对照,定量分析通过气相色谱内标法实现。反应结果见表1。
表1不同条件下W2C/AC催化4-(4-甲基-3-戊烯基)-3-环己烯醛(对位柑青醛) 环化反应生成环柑青醛1,2,3,4,5,6,7,8-八氢-,8,8-二甲基-2-萘醛的反应结果
从表中可以看出,所合成的碳化钨催化剂能催化4-(4-甲基-3-戊烯基)-3-环己烯醛(对位柑青醛)环化反应生成环柑青醛1,2,3,4,5,6,7,8-八氢-,8,8-二甲基 -2-萘醛,不同负载量的催化剂活性有所差别。
实施例19-24
不同载体负载的W2C催化剂催化对位柑青醛选择环化制备环柑青醛:在反应釜中将0.5g的柑青醛与100mg碳化钨催化剂分别溶于50ml甲苯中,用氮气置换五次后使氮气初始压力为0.1MPa,升温至120℃,以1000转 /min的速度进行搅拌反应10h。反应结束后,降至室温,上层清液过滤后取样分析。产物定性分析通过GC-MS联用技术及标样对照,定量分析通过气相色谱内标法实现。反应结果见表2。
表2不同载体负载的碳化钨(负载量30wt%)催化4-(4-甲基-3-戊烯基)-3- 环己烯醛(对位柑青醛)环化反应生成环柑青醛1,2,3,4,5,6,7,8-八氢-,8,8-二甲基-2-萘醛的反应结果
从表中可以看出,所合成的不同载体负载型碳化钨催化剂能催化4-(4-甲基-3-戊烯基)-3-环己烯醛(对位柑青醛)环化反应生成环柑青醛1,2,3,4,5,6,7,8- 八氢-,8,8-二甲基-2-萘醛,根据载体不同,催化剂活性有所差别。
实施例25-31
不同W2C催化剂催化间位柑青醛选择环化制备环柑青醛:在反应釜中将 0.5g的间位柑青醛与100mg碳化钨催化剂分别溶于50ml甲苯中,用氮气置换五次后使氮气初始压力为0.1MPa,升温至120℃,以1000转/min的速度进行搅拌反应10h。反应结束后,降至室温,上层清液过滤后取样分析。产物定性分析通过GC-MS联用技术及标样对照,定量分析通过气相色谱内标法实现。反应结果见表3。
表3不同碳化钨催化剂(碳化钨负载量30wt%)催化3-(4-甲基-3-戊烯基)-3-环己烯醛(间位柑青醛)环化反应生成环柑青醛1,2,3,4,5,6,7,8-八氢 -,5,5-二甲基-2-萘醛的反应结果
实施例32-42
不同溶剂中W2C/AC催化剂(W2C负载量为30wt%)催化对位柑青醛选择环化制备环柑青醛:在反应釜中将0.5g的对位柑青醛与100mg碳化钨催化剂分别溶于50ml溶剂中,分别在氮气氛或空气氛中升温至120℃,以 1000转/min的速度进行搅拌反应10h。反应结束后,降至室温,上层清液过滤后取样分析。产物定性分析通过GC-MS联用技术及标样对照,定量分析通过气相色谱内标法实现。反应结果见表4。
表4不同溶剂中碳化钨催化剂(碳化钨负载量30wt%)催化4-(4-甲基 -3-戊烯基)-3-环己烯醛(对位柑青醛)环化反应生成环柑青醛1,2,3,4,5,6,7,8- 八氢-,8,8-二甲基-2-萘醛的反应结果
实施例43-54
不同催化剂催化对位柑青醛选择环化制备环柑青醛:在反应釜中将0.5g 的对位柑青醛与100mg催化剂分别溶于50ml正己烷溶剂中,分别在空气氛中升温至120℃,以1000转/min的速度进行搅拌反应10h。反应结束后,降至室温,上层清液过滤后取样分析。产物定性分析通过GC-MS联用技术及标样对照,定量分析通过气相色谱内标法实现。反应结果见表4。
表4不同催化剂催化对位柑青醛选择环化制备环柑青醛1,2,3,4,5,6,7,8-八氢-,8,8-二甲基-2-萘醛的反应结果
实施例43-54所使用的各种催化剂都不能催化4-(4-甲基-3-戊烯基)-3-环己烯醛(对位柑青醛)环化反应生成环柑青醛1,2,3,4,5,6,7,8-八氢-,8,8-二甲基-2-萘醛,反应结果非常不理想,环柑青醛1,2,3,4,5,6,7,8-八氢-,8,8-二甲基 -2-萘醛收率低于12%。
Claims (5)
1.一种负载型碳化钨催化柑青醛选择环化制备环柑青醛的方法,其特征在于:在负载型碳化钨作用下,4-和3-(4-甲基-3-戊烯基)-3-环己烯醛(对位柑青醛和/或间位柑青醛)在非极性有机溶剂中于密闭反应釜中在惰性气氛和/或空气氛条件下反应,高选择性环化生成环柑青醛(1,2,3,4,5,6,7,8-八氢-,8,8-二甲基-2-萘醛和1,2,3,4,5,6,7,8-八氢-5,5-二甲基-2-萘醛);
所述负载型碳化钨催化剂由活性组分和载体两部分构成;所述活性组分为碳化钨;所述载体为活性炭、氧化铝、氧化硅、氧化锆、二氧化钛、硅铝分子筛、磷铝分子筛中的一种或二种以上;碳化钨于载体中的担载量为5-80wt%。
2.按照权利要求1所述的方法,其特征在于:所述反应底物与催化剂的质量比为2:1-100:1,室温下反应釜中填充空气和/或惰性气氛(如:氮气)的初始压力为0.1MPa-20MPa;反应温度为50-200℃;反应时间为0.5–24h。
3.按照权利要求1所述的方法,其特征在于:碳化钨于载体中的担载量优选担载量为10-50wt%,更优选担载量为15-40wt%。
4.按照权利要求1所述的方法,其特征在于:所述非极性有机溶剂为正己烷、环己烷、甲苯、二甲苯中的一种或二种以上。
5.按照权利要求1或2所述的方法,其特征在于:为加快反应,所述反应底物与催化剂的质量比优选为2:1-20:1;室温下反应釜中填充空气和/或惰性气氛的初始压力优选为0.1MPa-5MPa;反应温度优选为100℃-150℃。
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