CN117417305A - 一种高纯度2-（4-甲氧基苯基）-4,6-二(2,4-二羟基苯基)-1,3,5-三嗪的合成方法 - Google Patents

一种高纯度2-（4-甲氧基苯基）-4,6-二(2,4-二羟基苯基)-1,3,5-三嗪的合成方法 Download PDF

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CN117417305A
CN117417305A CN202311382253.5A CN202311382253A CN117417305A CN 117417305 A CN117417305 A CN 117417305A CN 202311382253 A CN202311382253 A CN 202311382253A CN 117417305 A CN117417305 A CN 117417305A
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methoxyphenyl
dihydroxyphenyl
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triazine
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王荣
刘启发
***
廉云
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Anqing Kesi Chemical Co ltd
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    • C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
    • C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
    • C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D251/14—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom
    • C07D251/24—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom to three ring carbon atoms
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    • B01J27/125—Halogens; Compounds thereof with scandium, yttrium, aluminium, gallium, indium or thallium
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    • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
    • B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
    • B01J31/2442—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising condensed ring systems
    • B01J31/2447—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising condensed ring systems and phosphine-P atoms as substituents on a ring of the condensed system or on a further attached ring
    • B01J31/2452—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising condensed ring systems and phosphine-P atoms as substituents on a ring of the condensed system or on a further attached ring with more than one complexing phosphine-P atom
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Abstract

本发明涉及防晒剂领域，尤其涉及一种高纯度2‑(4‑甲氧基苯基)‑4,6‑二(2,4‑二羟基苯基)‑1,3,5‑三嗪的合成方法，以DCT、间苯二酚为原料，加入溶剂、主催化剂、助催化剂，在40‑50℃的条件下进行反应，反应结束后，经过后处理，得到高纯度2‑(4‑甲氧基苯基)‑4,6‑二(2,4‑二羟基苯基)‑1,3,5‑三嗪，与现有技术相比，本发明的有益效果是：本发明采用主催化剂和助催化剂相配合，有效增加了DCT选择性，收率明显增加，所得RET成品杂质大大减少，纯度明显增加，对以此中间体进行的下一步反应得到有效提升。

Description

一种高纯度2-(4-甲氧基苯基)-4,6-二(2,4-二羟基苯基)-1, 3,5-三嗪的合成方法
技术领域
本发明涉及防晒剂领域，尤其涉及一种高纯度2-(4-甲氧基苯基)-4,6-二(2,4-二羟基苯基)-1,3,5-三嗪的合成方法。
背景技术
天来施S是一种油溶性的有机化合物，添加于防晒乳中吸收紫外线。BASF与Ashland Inc分别以商品名Tinosorb S及Escalol S推出上市。天来施S是广域性(宽频)的紫外线吸收剂，能吸收UVB以至UVA，它的吸收顶峰有两个，分别位于波长310及340nm处。其光稳定性极高，即使施予50MEDs之紫外线，仍能保有98.4％的量不被分解，与其他防晒剂例如阿伏苯宗混合还能抑制它们产生光分解反应。化学结构式如下：
2-(4-甲氧基苯基)-4,6-二(2,4-二羟基苯基)-1,3,5-三嗪(RET)做为天来施S的关键中间体，其结构式如下：
RET的合成，目前主要以2,4-二氯-6-(4-甲氧基苯基)-1,3,5-三嗪(DCT)为起始物，与间苯二酚进行F-C反应得到。根据现有工艺制备方法，F-C反应主要以Lewi s酸，特别为氯化铝做为催化体系，以环丁砜等可分散卤化铝的溶剂进行反应，氯化铝用量大，在反应结束后，直接水解过滤，需要用大量的水将体系内的Lewi s酸洗除至中性，将产生大量废酸水，且在反应及洗涤过程中，产生大量具有腐蚀性的气体，对人体、现场环境、安全及环保产生较大影响，并对大生产设备需求较严格，最终所得RET纯度及含量较低，存在较多杂质且含量不稳定，不利于下一步的天来施S的合成。以上种种不利于工业化要求，且不符合现在绿色化学生产要求。
发明内容
为了解决上述背景技术中提到的问题，本发明提供一种高纯度2-(4-甲氧基苯基)-4,6-二(2,4-二羟基苯基)-1,3,5-三嗪的合成方法，以DCT、间苯二酚为原料，加入溶剂、主催化剂、助催化剂，在40-50℃的条件下进行反应，反应结束后，经过后处理，得到高纯度2-(4-甲氧基苯基)-4,6-二(2,4-二羟基苯基)-1,3,5-三嗪。
优选的，所述主催化剂为三氯化铝。
优选的，所述助催化剂为氯化钯、S-(-)-1,1'-联萘-2,2'-双二苯膦按照摩尔比1:1组成。
优选的，所述溶剂体积用量以DCT摩尔用量计为1-5L/mo l。
优选的，所述DCT、间苯二酚、主催化剂、助催化剂的摩尔比为1:1.05：(0.1-0.2):(0.01-0.05)。
优选的，所述溶剂选自甲苯、环丁砜、DMF中的任意一种。
与现有技术相比，本发明的有益效果是：
1.本发明采用主催化剂和助催化剂相配合，有效增加了DCT选择性，收率明显增加，所得RET成品杂质大大减少，纯度明显增加，对以此中间体进行的下一步反应得到有效提升；
2.由于采用了微量的助催化剂，使得主催化剂三氯化铝的用量大大降低，有效的减少后处理废水的产生，对环保及现场环境得到有效改善；
3.浓缩溶解结晶进行纯化，有效提升了RET成品的品质，减少了RET的杂质产生，对天来施S的最终产品的合成产生较积极作用，对最终成品的合成及品质控制更加方便，使产品更具市场竞争性；
4.本发明从根本上解决了现有工艺中存在的废水多、难处理及现场环境差的不足，达到了反应稳定，易于操作，成品品质更加稳定，增加相应经济效益，并大大减少环保压力及现场环境，使产品更具竞争性。
具体实施方式
除非另有说明，本发明中的份数均为质量份；
除非另有说明，以下实施例中使用的原料和试剂均为市售商品，或者可以通过已知方法制备。
实施例1
一种高纯度2-(4-甲氧基苯基)-4,6-二(2,4-二羟基苯基)-1,3,5-三嗪的合成方法，氮气保护下，将1mol DCT、1.05mol间苯二酚、0.15mol三氯化铝、0.03mol氯化钯、0.03molS-(-)-1,1'-联萘-2,2'-双二苯膦和2L甲苯混合均匀，在40℃的条件下进行反应，取样检测，待反应结束后，分3次，每次加入1L水搅拌均匀后分液，合并有机相，有机相蒸馏采出甲苯，馏底中加入1L 2-甲基四氢呋喃，升温至60℃，乘热过滤，滤液缓慢降温至5℃，加入晶种1g，搅拌1h，抽滤，滤饼经烘干后，得到高纯度2-(4-甲氧基苯基)-4,6-二(2,4-二羟基苯基)-1,3,5-三嗪，经过计算，纯度99.6％，收率94.2％。
实施例2
本实施例与实施例1的不同之处在于：0.15mol三氯化铝，其余部分与实施例1完全相同，经过计算，纯度99.2％，收率93.2％。
实施例3
本实施例与实施例1的不同之处在于：0.2ol三氯化铝，其余部分与实施例1完全相同，经过计算，纯度99.3％，收率93.7％。
实施例4
本实施例与实施例1的不同之处在于：0.01mol氯化钯、0.01molS-(-)-1,1'-联萘-2,2'-双二苯膦，其余部分与实施例1完全相同，经过计算，纯度98.7％，收率90.3％。
实施例5
本实施例与实施例1的不同之处在于：0.05mol氯化钯、0.05molS-(-)-1,1'-联萘-2,2'-双二苯膦铝，其余部分与实施例1完全相同，经过计算，纯度99.1％，收率91.8％。
对比例1
一种2-(4-甲氧基苯基)-4,6-二(2,4-二羟基苯基)-1,3,5-三嗪的合成方法，氮气保护下，将1mol DCT、1.05mol间苯二酚、1mol三氯化铝和2L甲苯混合均匀，在70℃的条件下进行反应，取样检测，待反应结束后，分3次，每次加入1L水搅拌均匀后分液，合并有机相，有机相蒸馏采出甲苯，馏底中加入1L2-甲基四氢呋喃，升温至60℃，乘热过滤，滤液缓慢降温至5℃，加入晶种1g，搅拌1h，抽滤，滤饼经烘干后，得到2-(4-甲氧基苯基)-4,6-二(2,4-二羟基苯基)-1,3,5-三嗪，经过计算，纯度90.2％，收率88.3％。
以上所述，仅为本发明较佳的具体实施方式，但本发明的保护范围并不局限于此，任何熟悉本技术领域的技术人员在本发明揭露的技术范围内，根据本发明的技术方案及其发明构思加以等同替换或改变，都应涵盖在本发明的保护范围之内。

Claims (6)

1.一种高纯度2-(4-甲氧基苯基)-4,6-二(2,4-二羟基苯基)-1,3,5-三嗪的合成方法，其特征在于：以DCT、间苯二酚为原料，加入溶剂、主催化剂、助催化剂，在40-50℃的条件下进行反应，反应结束后，经过后处理，得到高纯度2-(4-甲氧基苯基)-4,6-二(2,4-二羟基苯基)-1,3,5-三嗪。
2.根据权利要求1所述的一种高纯度2-(4-甲氧基苯基)-4,6-二(2,4-二羟基苯基)-1,3,5-三嗪的合成方法，其特征在于，所述主催化剂为三氯化铝。
3.根据权利要求1所述的一种高纯度2-(4-甲氧基苯基)-4,6-二(2,4-二羟基苯基)-1,3,5-三嗪的合成方法，其特征在于，所述助催化剂为氯化钯、S-(-)-1,1'-联萘-2,2'-双二苯膦按照摩尔比1:1组成。
4.根据权利要求1所述的一种高纯度2-(4-甲氧基苯基)-4,6-二(2,4-二羟基苯基)-1,3,5-三嗪的合成方法，其特征在于，所述溶剂体积用量以DCT摩尔用量计为1-5L/mol。
5.根据权利要求1所述的一种高纯度2-(4-甲氧基苯基)-4,6-二(2,4-二羟基苯基)-1,3,5-三嗪的合成方法，其特征在于，所述DCT、间苯二酚、主催化剂、助催化剂的摩尔比为1:1.05：(0.1-0.2):(0.01-0.05)。
6.根据权利要求1所述的一种高纯度2-(4-甲氧基苯基)-4,6-二(2,4-二羟基苯基)-1,3,5-三嗪的合成方法，其特征在于，所述溶剂选自甲苯、环丁砜、DMF中的任意一种。
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