CN110183396A - 一种苯并噻唑类离子液体、制备方法及其在尼泊金酯和肉桂酸酯的合成中的应用 - Google Patents
一种苯并噻唑类离子液体、制备方法及其在尼泊金酯和肉桂酸酯的合成中的应用 Download PDFInfo
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- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical class C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 239000002608 ionic liquid Substances 0.000 title claims abstract description 32
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical class OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 title claims abstract description 18
- WBYWAXJHAXSJNI-VOTSOKGWSA-M trans-cinnamate Chemical compound [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 title claims abstract description 13
- 229940114081 cinnamate Drugs 0.000 title claims abstract description 12
- 230000015572 biosynthetic process Effects 0.000 title abstract description 9
- 238000003786 synthesis reaction Methods 0.000 title abstract description 9
- 238000002360 preparation method Methods 0.000 title abstract description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims abstract description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 150000003839 salts Chemical class 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 13
- 239000012065 filter cake Substances 0.000 claims abstract description 9
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 claims abstract description 8
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 claims abstract description 8
- 235000019441 ethanol Nutrition 0.000 claims abstract description 7
- 239000005457 ice water Substances 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims abstract description 3
- 239000011964 heteropoly acid Substances 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims 3
- 229910052698 phosphorus Inorganic materials 0.000 claims 3
- 239000011574 phosphorus Substances 0.000 claims 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 2
- 239000003208 petroleum Substances 0.000 claims 1
- 230000035484 reaction time Effects 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- 239000003054 catalyst Substances 0.000 abstract description 5
- 230000032050 esterification Effects 0.000 abstract description 4
- 238000005886 esterification reaction Methods 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 8
- 230000009102 absorption Effects 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 7
- LXCFILQKKLGQFO-UHFFFAOYSA-N methylparaben Chemical compound COC(=O)C1=CC=C(O)C=C1 LXCFILQKKLGQFO-UHFFFAOYSA-N 0.000 description 5
- 229960004756 ethanol Drugs 0.000 description 4
- -1 hydrogen salt Chemical class 0.000 description 4
- 238000012544 monitoring process Methods 0.000 description 4
- 238000006467 substitution reaction Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 229960000935 dehydrated alcohol Drugs 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 235000010270 methyl p-hydroxybenzoate Nutrition 0.000 description 2
- 239000004292 methyl p-hydroxybenzoate Substances 0.000 description 2
- 229960002216 methylparaben Drugs 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- WBYWAXJHAXSJNI-SREVYHEPSA-N Cinnamic acid Chemical compound OC(=O)\C=C/C1=CC=CC=C1 WBYWAXJHAXSJNI-SREVYHEPSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 125000005605 benzo group Chemical group 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229930016911 cinnamic acid Natural products 0.000 description 1
- 235000013985 cinnamic acid Nutrition 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- BEFDCLMNVWHSGT-UHFFFAOYSA-N ethenylcyclopentane Chemical compound C=CC1CCCC1 BEFDCLMNVWHSGT-UHFFFAOYSA-N 0.000 description 1
- 229960001617 ethyl hydroxybenzoate Drugs 0.000 description 1
- 235000010228 ethyl p-hydroxybenzoate Nutrition 0.000 description 1
- 239000004403 ethyl p-hydroxybenzoate Substances 0.000 description 1
- NUVBSKCKDOMJSU-UHFFFAOYSA-N ethylparaben Chemical compound CCOC(=O)C1=CC=C(O)C=C1 NUVBSKCKDOMJSU-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 235000010199 sorbic acid Nutrition 0.000 description 1
- 239000004334 sorbic acid Substances 0.000 description 1
- 229940075582 sorbic acid Drugs 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
- B01J27/19—Molybdenum
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
- B01J31/0285—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre also containing elements or functional groups covered by B01J31/0201 - B01J31/0274
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- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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Abstract
本发明公开了一种制备苯并噻唑类离子液体的制备方法及其在尼泊金酯和肉桂酸酯的合成中的应用:以苯并噻唑及磷钨酸、磷钼酸为原料,合成了2种苯并噻唑离子液体:[HBth]H4O41PMo12,[HBth]H2O40PW12。向反应容器中加入A mmol苯并噻唑、B mL乙醇,在冰水浴及搅拌下分批次加入C mmol磷钨酸或磷钼酸,TLC监测至反应结束;抽滤,用乙酸乙酯洗涤(滤饼即苯并噻唑离子液体盐)平均产率高于80%。并且其催化剂活性较高、易分离、可循环使用。此类离子液体催化剂具有过程清洁、使用周期长等优点,完全可以替代传统催化剂催化酯化反应。
Description
技术领域
本发明属于化学合成技术领域,特别涉及一种制备尼泊金酯的方法。
背景技术
所设计的新型杂多酸-苯并噻唑离子液体在尼泊金酯及肉桂酸酯的中酯化反应中,催化效果佳。因其杂多酸阴离子所具备的Keggin构型可以将反应分子吸附至其内表面,形成“假液相”体系,极大增加了其催化活性。而对于杂多酸-苯并噻唑离子液体而言,不仅保持了杂多酸阴离子的高催化活性,而且将自身转变为了非均相固体催化剂,绿色环保、易于回收,是一种兼备高效与绿色的新型离子液体型催化剂。
尼泊金酯、肉桂酸酯及其衍生物具有很高的实用性,并且绿色无毒。其中尼泊金酯类化合物因具备羟基结构,其抗菌的活性与广谱性明显高于如山梨酸等其他传统添加剂。肉桂酸脂类化合物因其具备独特的芳香性,在香料添加剂中也具备不可替代的作用。并且由于两者具有无毒易降解的特点,在食品工业中是不可或缺的一员。
发明内容
本发明的目的是提供一种制备苯并噻唑类离子液体的方法,并且该离子液体能绿色、高效的催化尼泊金酯及肉桂酸酯的合成。
为了实现上述目的,本发明采用如下技术方案:
一种制备苯并噻唑类离子液体的方法,其包括以下步骤:
向反应容器中加入A mmol苯并噻唑,B mL乙醇,在冰水浴中及搅拌下分批次加入Cmmol磷钨酸或磷钼酸,可观察有固体析出,TLC监测至反应结束;抽滤,用乙酸乙酯洗涤;回收滤饼,滤饼即苯并噻唑离子液体。
所述苯并噻唑离子液体盐的结构式为:
X-:H4O41PMo12 -,H2O40PW12 -
所述步骤中,A:B:C为1.2:4:1。
与现有技术相比,本发明具有以下优点:
第一:杂多酸-苯并噻唑离子液体具有更好的催化活性;
第二:杂多酸-苯并噻唑离子液体作为催化剂可回收再利用;
第三:通过本发明的方法能高效率、高产率、高纯度的制备尼泊金酯。后处理简单,绿色,环保和经济。
附图说明
图1为苯并噻唑磷钼酸四氢盐的FT-IR谱图;
图2为苯并噻唑磷钨酸二氢盐的FT-IR谱图;
图3为苯并噻唑磷钨酸二氢盐粉末XRD谱图;
图4为苯并噻唑磷钼酸四氢盐粉末XRD谱图。
具体实施方式
本发明为一种制备苯并噻唑类离子液体的方法,其反应式如下:
X=H4Mo12O41P,H2W12O40P
将其应用于催化酯化反应,其反应式如下:
1、催化合成尼泊金酯
其中,R为CH3,C2H5,C3H7,(CH3)2CH,C4H9,(CH3)2C2H3,(CH3)2C3H5, (CH3)2C6H11,C10H21,C12H25,C16H33。
2、催化合成肉桂酸酯
其中,R为CH3,C2H5,C3H7,(CH3)2CH,C4H9,(CH3)2C2H3,(CH3)2C3H5, (CH3)2C6H11,C10H21,C12H25,C16H33。
下面结合本发明的具体实例对本发明作进一步详细说明,但本发明的实施方式不限于此。
实施例1[HBth]H2O40PW12的制备:
在250mL三口瓶中加入5.0g(0.0017mol)磷钨酸以及20ml无水乙醇,在0- 5℃下搅拌至完全溶解,在搅拌下缓慢滴加0.234g(0.0017mol)苯并噻唑的乙醇溶液,在室温下反应12h,至反应完全(TLC监测)。用布氏漏斗抽滤,并用乙酸乙酯洗涤,干燥得淡黄色固体,产率71.2%。m.p.>250℃。IR(KBr,ν/cm-1): 3502cm(N-H伸缩振动吸收峰);3065(苯环C-H伸缩振动吸收峰);1697(C=N 伸缩振动吸收峰);1431(苯环骨架振动);1262(C-S伸缩振动吸收峰);809(苯环邻位二取代)。
实施例2[HBth]H4O41PMo12的制备:
在250mL三口瓶中加入5.0g(0.0027mol)磷钼酸以及20ml无水乙醇,在0- 5℃下搅拌至完全溶解,在搅拌下缓慢滴加0.366g(0.0027mol)苯并噻唑的乙醇溶液,在室温下反应12h,至反应完全(TLC监测)。用布氏漏斗抽滤,并用乙酸乙酯洗涤,干燥得鲜黄色固体,产率70.4%。m.p.>250℃。IR(KBr,ν/cm-1): 3516(N-H伸缩振动吸收峰);3086(苯环C-H伸缩振动吸收峰);1698(C=N伸缩振动吸收峰);1430(苯环骨架振动);1216(C-S伸缩振动吸收峰);795(苯环邻位二取代)。
实施例3[HBth]H2O40PW12催化尼泊金甲酯的制备:
在250mL三口瓶中加入10mL甲醇,2.00g(0.0145mol)对羟基苯甲酸搅拌至完全溶解,在搅拌下加入5.25g(0.0017mol)苯并噻唑离子液体。升温至回流反应 8h,至反应完全(TLC监测),将反应液自然冷却至室温,抽滤并回收滤饼(滤饼即苯并噻唑离子液体)。旋蒸滤液除去大部分溶剂,冷却至室温,将反应液倒入10ml冰水中,待产物充分析出,抽滤,干燥得白色粉末(尼泊金甲酯),产率87.4%。m.p.126℃-128℃。IR(KBr,cm-1)ν:3292(-OH伸缩振动吸收峰),3037(苯环C-H伸缩振动吸收峰),2958(饱和C-H伸缩振动吸收峰),1679(C=O伸缩振动吸收峰),1593,1514,1438(苯环骨架振动),1278(C-O-C伸缩振动吸收峰),850(苯环1,4取代)。
实施例4[HBth]H4O41PMo12催化尼泊金甲酯的制备:
在250mL三口瓶中加入10mL乙醇,2.00g(0.0145mol)对羟基苯甲酸搅拌至完全溶解,在搅拌下加入一定质量3.41g(0.0017mol)苯并噻唑离子液体。升温至回流反应8h,至反应完全(TLC监测)。将反应液自然冷却至室温,抽滤并回收滤饼(滤饼即苯并噻唑离子液体)。旋蒸滤液除去大部分溶剂,冷却至室温,将反应液倒入10ml冰水中,待产物充分析出,抽滤,干燥得白色粉末(尼泊金乙酯),产率88.7%。m.p.126℃-128℃。IR(KBr,cm-1)ν:3292(-OH伸缩振动吸收峰),3037(苯环C-H伸缩振动吸收峰),2958(饱和C-H伸缩振动吸收峰),1679(C=O伸缩振动吸收峰),1593,1514,1438(苯环骨架振动),1278(C-O-C伸缩振动吸收峰),850(苯环1,4取代)。
实施例5为了拓宽苯并噻唑类离子液体的应用范围,使用[HBth]H2O40PW12及[HBth]H2PO4·Mo12O3,通过相同方法合成其他尼泊金酯和肉桂酸酯。结果如表1、表2、表3、表4所示:
表1:[HBth]H2O40PW12催化尼泊金酯的合成
表2:[HBth]H2O40PW12催化肉桂酸酯的合成
表3:[HBth]H4O41PMo12催化尼泊金酯的合成
表4:[HBth]H4O41PMo12催化肉桂酸酯的合成
表1-4结果显示,[HBth]H2O40PW12及[HBth]H4O41PMo12具有高催化活性和广泛的应用,合成系列尼泊金酯及肉桂酸酯的平均酯化率高于85%。反应后,通过简单分离得到苯并噻唑离子液体可再循环使用。因此,苯并噻唑类离子液体对于尼泊金酯及肉桂酸酯的合成具有广泛性。
上述实例为本发明较佳的实验方式,但本发明的实施方式并不受上述实施例的限制,其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化,均应为等效的置换方式,都包含在本发明的保护范围之内。
Claims (8)
1.一种苯并噻唑类离子液体盐,其特征在于,结构式为:
式中,x-为H4O41PMo12 -或H2O40PW12 -。
2.一种制备苯并噻唑类离子液体盐的方法,其特征在于,包括以下步骤:
磷的杂多酸与苯并噻唑在醇液中反应,得到一种苯并噻唑类离子液体盐;所述磷的杂多酸为磷钨酸或磷钼酸。
3.根据权利要求2所述的一种制备苯并噻唑类离子液体盐的方法,其特征在于,所述配方中,苯并噻唑与磷的杂多酸的摩尔比为1.2:1。
4.根据权利要求2所述的一种制备苯并噻唑类离子液体盐的方法,其特征在于,具体步骤包括:
向反应容器中加入A mmol苯并噻唑,B mL乙醇,在冰水浴中及搅拌下分批次加入Cmmol磷钨酸或磷钼酸,可观察有固体析出,TLC监测至反应结束;抽滤,用乙酸乙酯洗涤;回收滤饼,滤饼即苯并噻唑离子液体。
5.根据权利要求2所述的一种制备苯并噻唑类离子液体盐的方法,其特征在于,反应温度为0-5℃,反应时间为24h。
6.根据权利要求2所述的一种制备苯并噻唑类离子液体盐的方法,其特征在于,TLC所用展开剂为:乙酸乙酯、石油醚中的一种或多种。
7.权利要求1所述的一种苯并噻唑类离子液体盐用于催化合成尼泊金酯的应用。
8.权利要求1所述的一种苯并噻唑类离子液体盐用于催化合成肉桂酸酯的应用。
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN111170960A (zh) * | 2020-01-17 | 2020-05-19 | 东莞波顿香料有限公司 | 肉香味化合物及其制备方法和香料添加剂 |
CN111269115A (zh) * | 2020-02-26 | 2020-06-12 | 陕西科技大学 | 一种低共熔溶剂中肉桂酸酯的制备方法 |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101863855A (zh) * | 2010-06-29 | 2010-10-20 | 四川大学 | 温敏型酸性离子液体的制备及其催化醇酸酯化的方法 |
CN101982453A (zh) * | 2010-09-10 | 2011-03-02 | 周峰岩 | 一种磺酸型离子液体促进下尼泊金酯类化合物的制备方法 |
CN102295603A (zh) * | 2011-06-08 | 2011-12-28 | 东南大学 | 基于过氧杂多酸的离子液体及其制备方法 |
US20120231972A1 (en) * | 2009-03-19 | 2012-09-13 | Golyshin Peter N | Probe Compound for Detecting and Isolating Enzymes and Means and Methods Using the Same |
CN103506156A (zh) * | 2013-09-18 | 2014-01-15 | 南京工业大学 | 一种非均相酸性催化剂及其制备方法与应用 |
CN107805199A (zh) * | 2017-11-14 | 2018-03-16 | 润泰化学(泰兴)有限公司 | 一种2,2,4‑三甲基戊二醇双酯的合成方法 |
CN108587737A (zh) * | 2018-02-06 | 2018-09-28 | 周文辽 | 一种润滑防锈油的制备方法 |
-
2019
- 2019-05-17 CN CN201910411736.0A patent/CN110183396A/zh active Pending
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20120231972A1 (en) * | 2009-03-19 | 2012-09-13 | Golyshin Peter N | Probe Compound for Detecting and Isolating Enzymes and Means and Methods Using the Same |
CN101863855A (zh) * | 2010-06-29 | 2010-10-20 | 四川大学 | 温敏型酸性离子液体的制备及其催化醇酸酯化的方法 |
CN101982453A (zh) * | 2010-09-10 | 2011-03-02 | 周峰岩 | 一种磺酸型离子液体促进下尼泊金酯类化合物的制备方法 |
CN102295603A (zh) * | 2011-06-08 | 2011-12-28 | 东南大学 | 基于过氧杂多酸的离子液体及其制备方法 |
CN103506156A (zh) * | 2013-09-18 | 2014-01-15 | 南京工业大学 | 一种非均相酸性催化剂及其制备方法与应用 |
CN107805199A (zh) * | 2017-11-14 | 2018-03-16 | 润泰化学(泰兴)有限公司 | 一种2,2,4‑三甲基戊二醇双酯的合成方法 |
CN108587737A (zh) * | 2018-02-06 | 2018-09-28 | 周文辽 | 一种润滑防锈油的制备方法 |
Non-Patent Citations (4)
Title |
---|
D. YIN ET AL.: ""Novel Benzothiazole Ionic Liquids as Catalysts for the Synthesis of Parabens"", 《RUSSIAN JOURNAL OF ORGANIC CHEMISTRY》 * |
孟晓宇 等: ""咪唑类酸性离子液体修饰磷钨酸盐催化剂在酯化反应中的应用"", 《聊城大学学报(自然科学版)》 * |
江春涛 等: ""杂多酸离子液体在催化有机合成反应中的研究进展"", 《精细石油化工进展》 * |
陈卓 等: ""室温离子液体催化肉桂酸甲酯的合成"", 《贵州科学》 * |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN111170960A (zh) * | 2020-01-17 | 2020-05-19 | 东莞波顿香料有限公司 | 肉香味化合物及其制备方法和香料添加剂 |
CN111269115A (zh) * | 2020-02-26 | 2020-06-12 | 陕西科技大学 | 一种低共熔溶剂中肉桂酸酯的制备方法 |
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