CN116143715A - 一种2-(4,6-二苯基-1,3,5-三嗪-2-基)-5-正己烷氧基苯酚合成方法 - Google Patents
一种2-(4,6-二苯基-1,3,5-三嗪-2-基)-5-正己烷氧基苯酚合成方法 Download PDFInfo
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- LEVFXWNQQSSNAC-UHFFFAOYSA-N 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-hexoxyphenol Chemical compound OC1=CC(OCCCCCC)=CC=C1C1=NC(C=2C=CC=CC=2)=NC(C=2C=CC=CC=2)=N1 LEVFXWNQQSSNAC-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 238000001308 synthesis method Methods 0.000 title claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 18
- -1 4, 6-diphenyl-1, 3, 5-triazin-2-yl Chemical group 0.000 claims abstract description 15
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 11
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- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 42
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 24
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 24
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 21
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 claims description 16
- MGNCLNQXLYJVJD-UHFFFAOYSA-N cyanuric chloride Chemical compound ClC1=NC(Cl)=NC(Cl)=N1 MGNCLNQXLYJVJD-UHFFFAOYSA-N 0.000 claims description 15
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- YCNFNXPUWNPXMG-UHFFFAOYSA-N 4-(4,6-diphenyl-1,3,5-triazin-2-yl)benzene-1,3-diol Chemical compound OC1=CC(O)=CC=C1C1=NC(C=2C=CC=CC=2)=NC(C=2C=CC=CC=2)=N1 YCNFNXPUWNPXMG-UHFFFAOYSA-N 0.000 claims description 9
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- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 3
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- HJIAMFHSAAEUKR-UHFFFAOYSA-N (2-hydroxyphenyl)-phenylmethanone Chemical class OC1=CC=CC=C1C(=O)C1=CC=CC=C1 HJIAMFHSAAEUKR-UHFFFAOYSA-N 0.000 description 1
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
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- 238000007796 conventional method Methods 0.000 description 1
- NLCKLZIHJQEMCU-UHFFFAOYSA-N cyano prop-2-enoate Chemical class C=CC(=O)OC#N NLCKLZIHJQEMCU-UHFFFAOYSA-N 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
- B01J2231/4205—C-C cross-coupling, e.g. metal catalyzed or Friedel-Crafts type
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
本发明提供了一种2‑(4,6‑二苯基‑1,3,5‑三嗪‑2‑基)‑5‑正己烷氧基苯酚合成方法。本发明的合成方法在4‑(4,6‑二苯基‑1,3,5‑三嗪‑2‑基)苯‑1,3‑二酚的合成中采用“一锅法”并以AlCl3/Ln(OTf)3作为催化剂,在减少步骤的同时提高了反应收率。本发明方法的步骤简化、三废少,产品收率和纯度高,具有广阔的应用前景。
Description
技术领域
本发明涉及化工领域,具体来说,本发明涉及一种2-(4,6-二苯基-1,3,5-三嗪-2-基)-5-正己烷氧基苯酚合成方法。
背景技术
聚合物材料如塑料、合成纤维、合成橡胶等在贮存和使用过程中易受到环境因素特别是紫外光的影响而发生物理或化学性质的改变,造成了材料老化、变脆、变色等,从而丧失使用价值。为了解决紫外光对聚合物材料的危害,一般会向其中添加光稳定剂、光屏蔽剂、猝灭剂、自由基捕获剂、紫外线吸收剂等助剂。
其中,紫外线吸收剂是能利用自身的结构特点,将光能转化为热能或无害的低辐射能释放出去,以避免聚合物材料发生光氧化反应的一类助剂。紫外线吸收剂有一个共同的特点,就是苯环上均有邻羟基的存在,通过氢键发生分子内重排的可逆变化,将激发能消耗掉,从而起到保护聚合物的作用。紫外线吸收剂按照化学结构可分为:邻羟基二苯酮类、苯并三唑类、水杨酸酯类、氰基丙烯酸酯类及三嗪类等。
2-(4,6-二苯基-1,3,5-三嗪-2-基)-5-正己烷氧基苯酚是一种典型的三嗪类紫外线吸收剂,商品名UV-1577,可应用于PET、PBT、PC、PMMA、PA、PS、SAN、ASA等聚合物中,具有良好的紫外线吸收效果。
2-(4,6-二苯基-1,3,5-三嗪-2-基)-5-正己烷氧基苯酚的主要合成方法包括:
路线1:
三聚氯氰与苯或溴苯反应生成2-氯-4,6-二苯基-1,3,5-均三嗪,其与间苯二酚反应得到4-(4,6-二苯基-1,3,5-三嗪-2-基)苯-1,3-二酚,在碳酸钾/DMF的条件下醚化得到目标产物。
路线2:
苯甲腈与尿素环合生成2-羟基-4,6-二苯基-1,3,5-均三嗪,再氯化得到2-氯-4,6-二苯基-1,3,5-均三嗪,后续步骤与路线1相同。
路线3:
直接由2-氯-4,6-二苯基-1,3,5-均三嗪与间正己氧基苯酚反应得到目标产物。
但是,上述方法大多存在步骤多、操作复杂、总收率低、经济性差等问题,路线3原料的制备也存在上述问题,因此有必要开发更为高效的2-(4,6-二苯基-1,3,5-三嗪-2-基)-5-正己烷氧基苯酚合成方法。
发明内容
为了解决现有技术中存在的问题,本发明提供了一种2-(4,6-二苯基-1,3,5-三嗪-2-基)-5-正己烷氧基苯酚合成方法,所述方法可“一锅法”地由三聚氯氰合成4-(4,6-二苯基-1,3,5-三嗪-2-基)苯-1,3-二酚,然后醚化得到目标产物。
在一个实施方案中,本发明所述2-(4,6-二苯基-1,3,5-三嗪-2-基)-5-正己烷氧基苯酚的合成方法包括:
其中,X为氯或溴
步骤a.三聚氯氰在A l C l 3/Ln(OTf)3催化下,先后与苯、间苯二酚反应生成4-(4,6-二苯基-1,3,5-三嗪-2-基)苯-1,3-二酚;
步骤b.4-(4,6-二苯基-1,3,5-三嗪-2-基)苯-1,3-二酚与溴己烷或氯己烷反应生成2-(4,6-二苯基-1,3,5-三嗪-2-基)-5-正己烷氧基苯酚。
在一个优选的实施方案中,步骤a包括:将有机溶剂加入到反应器中,向其中加入三聚氯氰、A l C l 3、Ln(OTf)3,搅拌均匀后缓慢滴加苯;滴毕后于30-50℃的温度下搅拌反应1-4h;然后补加A l C l 3,升温至60-90℃后分批加入间苯二酚,反应1-6h;将反应混合物缓慢倒入剧烈搅拌的酸与冰水混合物的混合液中,分出有机层,洗涤后减压蒸馏回收有机溶剂,抽滤、干燥,重结晶得到4-(4,6-二苯基-1,3,5-三嗪-2-基)苯-1,3-二酚。
优选的,所述有机溶剂选自氯苯、邻二氯苯、间二氯苯、对二氯苯、硝基苯中的至少一种。
Ln(OTf)3为三氟甲磺酸稀土,优选的,其选自YB(OTf)3、Sm(OTf)3、Nd(OTf)3、Er(OTf)3中的至少一种,更优选为YB(OTf)3。
优选的,三聚氯氰、首次加入的A l C l 3、Ln(OTf)3、苯的摩尔比为1:2-2.05:0.04-0.2:2-2.05,优选为1:2:0.08-0.15:2;补加的A l C l 3与三聚氯氰的摩尔比为1-1.1:1,优选为1-1.05:1。
优选的,滴加苯后的反应温度为35-40℃,加入间苯二酚后的反应温度为75-80℃。
优选的,所述酸与冰水混合物中的酸可以是盐酸、硫酸中的至少一种,更优选为10-20wt%的盐酸。
优选的,所述洗涤包括用5-15wt%的盐酸与水分别洗涤。
优选的,所述重结晶的溶剂为甲苯和石油醚混合溶剂,甲苯与石油醚的体积比为1-2:2-1。
在一个优选的实施方案中,步骤b可以采用本领域公知的醚化方法进行。例如可以用K2CO3、KOH等作为催化剂,在DMF中进行醚化反应。
优选的,所述步骤b包括:将碳酸钾和DMF加入到反应器中,加热搅拌溶解后加入4-(4,6-二苯基-1,3,5-三嗪-2-基)苯-1,3-二酚,升温至60-100℃,滴加溴代正己烷或氯代正己烷的DMF溶液,反应结束后冷却反应液,抽滤得到粗品,重结晶得到2-(4,6-二苯基-1,3,5-三嗪-2-基)-5-正己烷氧基苯酚。
优选的,4-(4,6-二苯基-1,3,5-三嗪-2-基)苯-1,3-二酚、碳酸钾、溴代正己烷/氯代正己烷的摩尔比为1:1-1.2:1-1.2。
有益效果
本发明提供了一种2-(4,6-二苯基-1,3,5-三嗪-2-基)-5-正己烷氧基苯酚合成方法。本发明所述合成方法采用“一锅法”,使三聚氯氰与苯、间苯二酚先后进行两次傅克烷基化反应,减少了反应步骤和后处理操作,并且在傅克烷基化反应中使用三氟甲磺酸稀土化合物作为助催化剂,其促进了烷基化反应的进行,大大提高了4-(4,6-二苯基-1,3,5-三嗪-2-基)苯-1,3-二酚的收率。本发明方法的步骤简化、三废少,产品收率和纯度高,具有广阔的应用前景。
具体实施方式
下面将结合本发明实施例的技术方案进行清楚、完整地描述,显然,所描述的实施例仅仅是本发明一部分实施例,而不是全部的实施例。基于本发明中的实施例,本领域技术人员在没有做出创造性劳动前提下所获得的所有其他实施例,都属于本发明的保护范围。
下面实施例中的实验方法,如无特殊说明,均为常规方法。实施例中未注明具体技术或条件者,按照本领域内的文献所描述的技术或条件,或者按照产品说明书进行。
实施例1:4-(4,6-二苯基-1,3,5-三嗪-2-基)苯-1,3-二酚的合成将150m l的邻二氯苯加入到装置有尾气吸收装置的反应器中,向其中加入18.4g(0.1mo l)三聚氯氰、26.6g(0.2mo l)A l C l 3、6.2g(0.01mo l)Yb(OTf)3,搅拌0.5h后,缓慢滴加15.6g(0.2mo l)苯,滴毕后于35-40℃的温度下搅拌反应3h;然后补加13.3g(0.1mo l)的A l C l 3,升温至75-80℃后分批加入1.1g(0.1mo l)间苯二酚,反应2h;将反应化合物缓慢倒入剧烈搅拌的100ml的15wt%盐酸水溶液与200m l冰水混合物的混合液中水解,分出有机层,用10wt%盐酸和水分别洗涤,减压蒸馏回收邻二氯苯,抽滤、干燥,用体积比为1:1的甲苯和石油醚重结晶得4-(4,6-二苯基-1,3,5-三嗪-2-基)苯-1,3-二酚31.2g,收率91.3%,纯度98.9%。熔点258~260℃,ES I-MS:342.2[M+H]+。
实施例2:4-(4,6-二苯基-1,3,5-三嗪-2-基)苯-1,3-二酚的合成将150m l的氯苯加入到装置有尾气吸收装置的反应器中,向其中加入18.4g(0.1mo l)三聚氯氰、26.6g(0.2mo l)A l C l 3、7.4g(0.012mo l)Yb(OTf)3,搅拌0.5h后,缓慢滴加15.6g(0.2mo l)苯,滴毕后于35-40℃的温度下搅拌反应3h;然后补加13.3g(0.1mo l)的A l C l 3,升温至75-80℃后分批加入1.1g(0.1mo l)间苯二酚,反应2h;将反应化合物缓慢倒入剧烈搅拌的100m l的15wt%盐酸水溶液与200m l冰水混合物的混合液中水解,分出有机层,用10wt%盐酸和水分别洗涤,减压蒸馏回收氯苯,抽滤、干燥,用体积比为1:1的甲苯和石油醚重结晶得4-(4,6-二苯基-1,3,5-三嗪-2-基)苯-1,3-二酚30.5g,收率89.4%,纯度98.8%。
实施例3:4-(4,6-二苯基-1,3,5-三嗪-2-基)苯-1,3-二酚的合成将150m l的邻二氯苯加入到装置有尾气吸收装置的反应器中,向其中加入18.4g(0.1mo l)三聚氯氰、26.6g(0.2mo l)A l C l 3、6.0g(0.01mo l)Sm(OTf)3,搅拌0.5h后,缓慢滴加15.6g(0.2mo l)苯,滴毕后于35-40℃的温度下搅拌反应3h;然后补加13.3g(0.1mo l)的A l C l 3,升温至75-80℃后分批加入1.1g(0.1mo l)间苯二酚,反应2h;将反应化合物缓慢倒入剧烈搅拌的100ml的15wt%盐酸水溶液与200m l冰水混合物的混合液中水解,分出有机层,用10wt%盐酸和水分别洗涤,减压蒸馏回收邻二氯苯,抽滤、干燥,用体积比为1:1的甲苯和石油醚重结晶得4-(4,6-二苯基-1,3,5-三嗪-2-基)苯-1,3-二酚29.9g,收率87.6%,纯度98.9%。
对比例1:4-(4,6-二苯基-1,3,5-三嗪-2-基)苯-1,3-二酚的合成将150m l的邻二氯苯加入到装置有尾气吸收装置的反应器中,向其中加入18.4g(0.1mo l)三聚氯氰、26.6g(0.2mo l)A l C l 3,搅拌0.5h后,缓慢滴加15.6g(0.2mo l)苯,滴毕后于40-45℃的温度下搅拌反应4h;然后补加13.3g(0.1mo l)的A l C l 3,升温至85-90℃后分批加入1.1g(0.1mo l)间苯二酚,反应3h;将反应化合物缓慢倒入剧烈搅拌的100m l的15wt%盐酸水溶液与200ml冰水混合物的混合液中水解,分出有机层,用10wt%盐酸和水分别洗涤,减压蒸馏回收邻二氯苯,抽滤、干燥,用体积比为1:1的甲苯和石油醚重结晶得4-(4,6-二苯基-1,3,5-三嗪-2-基)苯-1,3-二酚23.5g,收率68.7%,纯度98.2%。
实施例4:2-(4,6-二苯基-1,3,5-三嗪-2-基)-5-正己烷氧基苯酚的合成将7.6g(0.055mo l)碳酸钾和75m l DMF加入到反应器中,加热搅拌溶解后加入17.1g(0.05mo l)4-(4,6-二苯基-1,3,5-三嗪-2-基)苯-1,3-二酚,升温至80℃,滴加9.1g(0.055mo l)溴代正己烷和10m l DMF的混合液,1h内滴完,恒温继续反应,用薄层色谱法对反应进行监控,反应到达终点后,冷却反应液,抽滤得到粗品,用DMF重结晶得淡黄色的产品17.3g,收率81.5%,纯度99.4%。熔点150~151℃,ES I-MS:426.2[M+H]+。
以上描述了本发明优选实施方式,然其并非用以限定本发明。本领域技术人员对在此公开的实施方案可进行并不偏离本发明范畴和精神的改进和变化。
Claims (10)
2.根据权利要求1所述的合成方法,其特征在于,步骤a包括:将有机溶剂加入到反应器中,向其中加入三聚氯氰、AlCl 3、Ln(OTf)3,搅拌均匀后缓慢滴加苯;滴毕后于30-50℃的温度下搅拌反应1-4h;然后补加AlCl 3,升温至60-90℃后分批加入间苯二酚,反应1-6h;将反应混合物缓慢倒入剧烈搅拌的酸与冰水混合物的混合液中,分出有机层,洗涤后减压蒸馏回收有机溶剂,抽滤、干燥,重结晶得到4-(4,6-二苯基-1,3,5-三嗪-2-基)苯-1,3-二酚。
3.根据权利要求2所述的合成方法,其特征在于,所述有机溶剂选自氯苯、邻二氯苯、间二氯苯、对二氯苯、硝基苯中的至少一种。
4.根据权利要求1或2所述的合成方法,其特征在于,Ln(OTf)3选自YB(OTf)3、Sm(OTf)3、Nd(OTf)3、Er(OTf)3中的至少一种。
5.根据权利要求2所述的合成方法,其特征在于,三聚氯氰、首次加入的AlCl 3、Ln(OTf)3、苯的摩尔比为1:2-2.05:0.04-0.2:2-2.05;补加的AlCl 3与三聚氯氰的摩尔比为1-1.1:1。
6.根据权利要求2所述的合成方法,其特征在于,滴加苯后的反应温度为35-40℃,加入间苯二酚后的反应温度为75-80℃。
7.根据权利要求2所述的合成方法,其特征在于,所述酸与冰水混合物中的酸是盐酸、硫酸中的至少一种。
8.根据权利要求2所述的合成方法,其特征在于,所述重结晶的溶剂为甲苯和石油醚混合溶剂,甲苯与石油醚的体积比为1-2:2-1。
9.根据权利要求1所述的合成方法,其特征在于,步骤b中用K2CO3或KOH作为催化剂,在DMF中进行醚化反应。
10.根据权利要求1所述的合成方法,其特征在于,步骤b包括:将碳酸钾和DMF加入到反应器中,加热搅拌溶解后加入4-(4,6-二苯基-1,3,5-三嗪-2-基)苯-1,3-二酚,升温至60-100℃,滴加溴代正己烷或氯代正己烷的DMF溶液,反应结束后冷却反应液,抽滤得到粗品,重结晶得到2-(4,6-二苯基-1,3,5-三嗪-2-基)-5-正己烷氧基苯酚。
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