1-丙氧基-2,2,6,6-四甲基哌啶醇的合成
|
摘要
以4-羟基-2,2,6,6-四甲基哌啶氮氧自由基(ZJ-701)和正丁醛为原料,质量分数30%的H_2O_2为氧化剂,CuCl为还原剂,通过O-烷基化反应合成了1-丙氧基-2,2,6,6-四甲基哌啶醇,并通过红外光谱、核磁共振氢谱、核磁共振碳谱和质谱表征了其结构。结果表明,其较佳工艺条件为n(ZJ-701)∶n(正丁醛)∶n(H_2O_2)∶n(CuCl)=1∶3.56∶2.80∶0.045,烷基化反应温度20℃,烷基化反应时间12h。在上述条件下合成的产品通过重结晶,产品的质量分数可达96.6%,熔点为61～62℃,分离产率超过69%。
1-Propoxy-2,2,6,6-tetramethylpiperidine-4-ol was synthesized through O-alkylation by using 4-hydroxy-2,2,6,6-tetramethyl-piperidinooxy(ZJ-701)and n-butyraldehyde as raw materials,30% H_2O_2 as oxidant,CuCl as reducing agent,and its structure was characterized by IR,~1H NMR,~(13)C NMR and MS.The results revealed that its optimal conditions were as follows:n(ZJ-701)∶n(nbutylaldehyde)∶n(H_2O_2)∶n(CuCl)=1∶3.56∶2.80∶0.045,the alkylation time being 12 h,and the alkylation temperature being 20℃.The weight fraction of the product was 96.6%,the melting point was 61～62℃ and the separation yield was over 69% by recrystallization of the crude products obtained under the optimal conditions.
1-Propoxy-2,2,6,6-tetramethylpiperidine-4-ol was synthesized through O-alkylation by using 4-hydroxy-2,2,6,6-tetramethyl-piperidinooxy(ZJ-701)and n-butyraldehyde as raw materials,30% H_2O_2 as oxidant,CuCl as reducing agent,and its structure was characterized by IR,~1H NMR,~(13)C NMR and MS.The results revealed that its optimal conditions were as follows:n(ZJ-701)∶n(nbutylaldehyde)∶n(H_2O_2)∶n(CuCl)=1∶3.56∶2.80∶0.045,the alkylation time being 12 h,and the alkylation temperature being 20℃.The weight fraction of the product was 96.6%,the melting point was 61～62℃ and the separation yield was over 69% by recrystallization of the crude products obtained under the optimal conditions.
引文
[1]WILEN C,PFAENDNER R.Polymer Green Flame Retardants[M].Amsterdam Netherland:Elsevier,2014:267-288.
[2]杨晶巍,吴鸿志,侯小敏,等.1-环己氧基-4-羟基-2,2,6,6-四甲基哌啶醇的合成[J].青岛科技大学学报(自然科学版),2018,39(4):23-27.
[3]DICHTL A,SEYFRIDE M,SCHOENING K U,et al.A novel method for the synthesis of N-alkoxyamines starting from nitroxide radicals and ketones[J].Synlett,2008,12:1877-1881.
[4]KIPKE A,SCHNING K,YUSUBOV M,et al.TEMPO-mediated oxidative deformylation of aldehydes:Applications in the synthesis of polyketide fragments[J].European Journal of Organic Chemistry,2017,46:6906-6913.
[5]NESVADBA P.N-alkoxyamines:synthesis,properties,and applications in polymer chemistry,organic synthesis,and materials science[J].Chimia International Journal for Chemistry,2006,60(12):832-840.
[6]杨晶巍,杜玉莹,朱鑫,等.1-乙氧基-4-羟基-2,2,6,6-四甲基哌啶醇的合成[J].化工科技,2018,26(1):19-23.
[7]GALBO J P,SELTZER R.N-hydrocarbyloxy hindered amine light stabilizers substituted with phosphorus moieties:EP0389430[P].1990-03-13.
[8]SCHOENING K U,FISCHER W,HAUCK,et al.Synthetic studies on N-alkoxyamines:A mild and broadly applicable route starting from nitroxide radicals and aldehydes[J].JOrg Chem,2009(74):1567-1573.
[9]COTE E,CHAFIN L,DIFAZIO M,et al.Development of a scalable synthesis of oligomeric piperidine-n-o-alkyl ethers[J].Org Process Resdev,2014,18(12):1843-1849.
[10]WAGNER CHRISTINE B,STUDER ARMIDO.Oxidation of alkylcatecholboranes with functionalized nitroxides for chemical modification of cyclohexene,perallylated polyglycerol and of poly(butadiene)[J].Eur J Org Chem,2010:5782-5786.
[11]LI L Y,YU,et al.Copper-catalyzed aminoxylation of different types of hydrocarbons with TEMPO:A concise route to N-alkoxyaminederivatives[J].Advanced Synthesis&Catalysis,2015,357(16/17):3495-3500.
[12]FISCHER W,BASBAS A I,SCHOENING K U,et al.Synthesis of 3-substituted derivatives of 2,2,6,6-tetramethylpiperidine-N-alkoxyamine ethers:Novel alkoxyamine building blocks[J].Synthesis,2010(22):3873-3878.
[2]杨晶巍,吴鸿志,侯小敏,等.1-环己氧基-4-羟基-2,2,6,6-四甲基哌啶醇的合成[J].青岛科技大学学报(自然科学版),2018,39(4):23-27.
[3]DICHTL A,SEYFRIDE M,SCHOENING K U,et al.A novel method for the synthesis of N-alkoxyamines starting from nitroxide radicals and ketones[J].Synlett,2008,12:1877-1881.
[4]KIPKE A,SCHNING K,YUSUBOV M,et al.TEMPO-mediated oxidative deformylation of aldehydes:Applications in the synthesis of polyketide fragments[J].European Journal of Organic Chemistry,2017,46:6906-6913.
[5]NESVADBA P.N-alkoxyamines:synthesis,properties,and applications in polymer chemistry,organic synthesis,and materials science[J].Chimia International Journal for Chemistry,2006,60(12):832-840.
[6]杨晶巍,杜玉莹,朱鑫,等.1-乙氧基-4-羟基-2,2,6,6-四甲基哌啶醇的合成[J].化工科技,2018,26(1):19-23.
[7]GALBO J P,SELTZER R.N-hydrocarbyloxy hindered amine light stabilizers substituted with phosphorus moieties:EP0389430[P].1990-03-13.
[8]SCHOENING K U,FISCHER W,HAUCK,et al.Synthetic studies on N-alkoxyamines:A mild and broadly applicable route starting from nitroxide radicals and aldehydes[J].JOrg Chem,2009(74):1567-1573.
[9]COTE E,CHAFIN L,DIFAZIO M,et al.Development of a scalable synthesis of oligomeric piperidine-n-o-alkyl ethers[J].Org Process Resdev,2014,18(12):1843-1849.
[10]WAGNER CHRISTINE B,STUDER ARMIDO.Oxidation of alkylcatecholboranes with functionalized nitroxides for chemical modification of cyclohexene,perallylated polyglycerol and of poly(butadiene)[J].Eur J Org Chem,2010:5782-5786.
[11]LI L Y,YU,et al.Copper-catalyzed aminoxylation of different types of hydrocarbons with TEMPO:A concise route to N-alkoxyaminederivatives[J].Advanced Synthesis&Catalysis,2015,357(16/17):3495-3500.
[12]FISCHER W,BASBAS A I,SCHOENING K U,et al.Synthesis of 3-substituted derivatives of 2,2,6,6-tetramethylpiperidine-N-alkoxyamine ethers:Novel alkoxyamine building blocks[J].Synthesis,2010(22):3873-3878.