CN108821955B - 一种通过脱除邻香兰素的甲基制备2,3-二羟基苯甲醛的方法 - Google Patents
一种通过脱除邻香兰素的甲基制备2,3-二羟基苯甲醛的方法 Download PDFInfo
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- IXWOUPGDGMCKGT-UHFFFAOYSA-N 2,3-dihydroxybenzaldehyde Chemical compound OC1=CC=CC(C=O)=C1O IXWOUPGDGMCKGT-UHFFFAOYSA-N 0.000 title claims abstract description 32
- JJVNINGBHGBWJH-UHFFFAOYSA-N ortho-vanillin Chemical compound COC1=CC=CC(C=O)=C1O JJVNINGBHGBWJH-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 238000000034 method Methods 0.000 title claims abstract description 17
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 title claims abstract description 15
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 17
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims abstract description 9
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000010504 bond cleavage reaction Methods 0.000 claims abstract description 6
- 239000003960 organic solvent Substances 0.000 claims abstract description 5
- 238000010992 reflux Methods 0.000 claims abstract description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 15
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 claims description 15
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 claims description 9
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 claims description 9
- SUSQOBVLVYHIEX-UHFFFAOYSA-N phenylacetonitrile Chemical compound N#CCC1=CC=CC=C1 SUSQOBVLVYHIEX-UHFFFAOYSA-N 0.000 claims description 6
- 235000009518 sodium iodide Nutrition 0.000 claims description 5
- 125000005207 tetraalkylammonium group Chemical group 0.000 claims description 5
- 229940107816 ammonium iodide Drugs 0.000 claims description 4
- BTGRAWJCKBQKAO-UHFFFAOYSA-N adiponitrile Chemical compound N#CCCCCC#N BTGRAWJCKBQKAO-UHFFFAOYSA-N 0.000 claims description 3
- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 claims description 3
- ZTOMUSMDRMJOTH-UHFFFAOYSA-N glutaronitrile Chemical compound N#CCCCC#N ZTOMUSMDRMJOTH-UHFFFAOYSA-N 0.000 claims description 3
- LRDFRRGEGBBSRN-UHFFFAOYSA-N isobutyronitrile Chemical compound CC(C)C#N LRDFRRGEGBBSRN-UHFFFAOYSA-N 0.000 claims description 3
- CUONGYYJJVDODC-UHFFFAOYSA-N malononitrile Chemical compound N#CCC#N CUONGYYJJVDODC-UHFFFAOYSA-N 0.000 claims description 3
- -1 n-dodecyl Chemical group 0.000 claims description 3
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 claims description 3
- IAHFWCOBPZCAEA-UHFFFAOYSA-N succinonitrile Chemical compound N#CCCC#N IAHFWCOBPZCAEA-UHFFFAOYSA-N 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 15
- JIVGSHFYXPRRSZ-UHFFFAOYSA-N 2,3-dimethoxybenzaldehyde Chemical compound COC1=CC=CC(C=O)=C1OC JIVGSHFYXPRRSZ-UHFFFAOYSA-N 0.000 description 4
- ILAHWRKJUDSMFH-UHFFFAOYSA-N boron tribromide Chemical compound BrB(Br)Br ILAHWRKJUDSMFH-UHFFFAOYSA-N 0.000 description 4
- 239000000543 intermediate Substances 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000017858 demethylation Effects 0.000 description 3
- 238000010520 demethylation reaction Methods 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000003818 flash chromatography Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 2
- 235000019345 sodium thiosulphate Nutrition 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- NIBFJPXGNVPNHK-UHFFFAOYSA-N 2,2-difluoro-1,3-benzodioxole-4-carbaldehyde Chemical compound C1=CC(C=O)=C2OC(F)(F)OC2=C1 NIBFJPXGNVPNHK-UHFFFAOYSA-N 0.000 description 1
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 1
- 239000005781 Fludioxonil Substances 0.000 description 1
- 239000002879 Lewis base Substances 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- CECABOMBVQNBEC-UHFFFAOYSA-K aluminium iodide Chemical compound I[Al](I)I CECABOMBVQNBEC-UHFFFAOYSA-K 0.000 description 1
- ANJZXLNYANULQR-UHFFFAOYSA-K aluminum pyridine triiodide Chemical compound N1=CC=CC=C1.[I-].[I-].[I-].[Al+3] ANJZXLNYANULQR-UHFFFAOYSA-K 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000012649 demethylating agent Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- MUJOIMFVNIBMKC-UHFFFAOYSA-N fludioxonil Chemical compound C=12OC(F)(F)OC2=CC=CC=1C1=CNC=C1C#N MUJOIMFVNIBMKC-UHFFFAOYSA-N 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- LHGVFZTZFXWLCP-UHFFFAOYSA-N guaiacol Chemical compound COC1=CC=CC=C1O LHGVFZTZFXWLCP-UHFFFAOYSA-N 0.000 description 1
- 229910000042 hydrogen bromide Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 150000007527 lewis bases Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- OLHYBANWJHBMLO-UHFFFAOYSA-K pyridine;trichloroalumane Chemical compound [Al+3].[Cl-].[Cl-].[Cl-].C1=CC=NC=C1 OLHYBANWJHBMLO-UHFFFAOYSA-K 0.000 description 1
- FGQOOHJZONJGDT-UHFFFAOYSA-N vanillin Natural products COC1=CC(O)=CC(C=O)=C1 FGQOOHJZONJGDT-UHFFFAOYSA-N 0.000 description 1
- 235000012141 vanillin Nutrition 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- 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
- C07C45/64—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 by introduction of functional groups containing oxygen only in singly bound form
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- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明公开了一种通过脱除邻香兰素的甲基制备2,3‑二羟基苯甲醛的方法，包括如下步骤：在有机溶剂中，在三氯化铝和碘化物存在的条件下，邻香兰素在‑20℃至回流的温度下发生醚键断裂反应，生成2,3‑二羟基苯甲醛。该方法条件温和，操作简便，而且收率高。
Description
背景技术
本发明涉及药物和化工原料的中间体合成技术领域，具体涉及一种通过脱除邻香兰素的甲基制备2,3-二羟基苯甲醛的方法。
背景技术
2,3-二羟基苯甲醛是一种重要的化工中间体，比如可以用于制备杀虫剂咯菌腈的一种关键中间体2,2-二氟-1,3-苯并二恶茂-4-甲醛(CN106699722)，以及合成3’-取代的苯并冠醚衍生物的中间体3’-甲酰基苯并冠醚的重要原料(郑州轻工业学院学报1995,10,61-62)。
2,3-二羟基苯甲醛可以用邻香兰素脱甲基得到，比如Potisek等人报道了一种用三溴化硼在二氯甲烷中脱除邻香兰素的甲基制备2,3-二羟基苯甲醛的方法(Journal ofthe American Chemical Society 2007,129,13808-13809)；Hoyng报道了用氢溴酸在冰乙酸中脱除这个甲基的方法(Organic Preparations and Procedures International,1981,17,175-178)。首先，三溴化硼价格昂贵，制备成本高，难以实现工业化生产；其次，溴化氢脱甲基的收率比较低，操作也不方便。
三氯化铝也是一种常用的脱甲基试剂，比如Lange发展了一种脱邻羟基苯甲醚的方法，用三氯化铝-吡啶体系在卤代烷烃或芳烃可以脱除香兰素的甲基(US3256336)，但是该方法不能用于邻香兰素的脱甲基反应(The Journal of Organic Chemistry 1962,27,2037-2039)。
此外，三碘化铝与各种路易斯碱组合的试剂体系也被用来脱除邻香兰素的甲基，比如CN106278825A公开了一种用三碘化铝-吡啶裂解醚键的方法，CN106866377A公开了用三碘化铝-碳二亚胺裂解醚键的方法，CN107473916公开了用三碘化铝-无机碱或者金属氧化物裂解醚键的方法，虽然这三种方法都可以用于脱除邻香兰素的甲基来制备2,3-二羟基苯甲醛，但这三种方法的收率都不高。
发明内容
为了解决上述现有技术存在的问题，本发明提供了一种通过脱除邻香兰素的甲基制备2,3-二羟基苯甲醛的方法，该方法条件温和，操作简便，而且收率高。
实现本发明上述目的所采用的技术方案为：
一种通过脱除邻香兰素的甲基制备2,3-二羟基苯甲醛的方法，包括如下步骤：
在有机溶剂中，在三氯化铝和碘化物存在的条件下，邻香兰素在-20℃至回流的温度下发生醚键断裂反应，生成2,3-二羟基苯甲醛。
进一步，所述的碘化物为碘化钠、碘化钾和四烷基碘化铵中一种，或者任意几种的组合。
进一步，所述的四烷基碘化铵中烷基为甲基、乙基、丙基、丁基、苄基或正十二烷基。
进一步，三氯化铝、碘化物和邻香兰素的摩尔比为0.5～5:0.5～10:1。
进一步，醚键断裂反应的反应时间为0.5～48小时。
进一步，所述的有机溶剂为乙腈、丙腈、丁腈、异丁腈、苯腈、苯乙腈、丙二腈、丁二腈、戊二腈和己二腈中的一种，或者任意几种的组合。
与现有技术相比，本发明的优点和有益效果在于：
1、本发明使用的三氯化铝和碘化物等原料来源广泛，价格低廉，存储方便。
2、本发明裂解醚键的反应提纯操作简单，而且收率高。
具体实施方式
下面结合具体实施例对本发明进行详细说明。
实施例1
向一个100ml茄形瓶中加入乙腈(40ml)、三氯化铝(0.804g,6.03mmol,1.1eq)、NaI(2.464g,16.44mmol，3.0eq)和邻香兰素(0.417g,2.74mmol)，加热至80℃，反应18小时后停止搅拌，冷至室温后向茄形瓶中加入2mol/L的稀盐酸(10ml)酸化，用乙酸乙酯(50ml×3)萃取，合并有机相，先用硫代硫酸钠饱和水溶液(10ml)洗涤，再用饱和食盐水(10ml)洗涤，无水硫酸镁干燥，过滤，滤液用旋转蒸发仪蒸干，残余物通过快速柱层析(淋洗剂为乙酸乙酯/石油醚＝1:4，体积比)纯化，得到0.322g 2,3-二甲氧基苯甲醛(黄色固体,收率85％)。
Rf＝0.58(石油醚/乙酸乙酯＝1:3)，mp106-108℃。
1H NMR(400MHz,DMSO-d6)δ10.22(s,1H),9.97(brs,2H),7.14(dd,J1＝7.8Hz,J2＝1.6Hz,1H),7.08(dd,J1＝7.8Hz,J2＝1.6Hz,1H),6.80(t,J＝7.8Hz,1H).
实施例2
向一个100ml茄形瓶中加入乙腈(40ml)、三氯化铝(0.752g,5.64mmol,1.1eq)、NaI(2.305g,15.38mmol,3.0eq)和邻香兰素(0.780g,5.13mmol)，加热至80℃，反应18小时后停止搅拌，冷至室温后向茄形瓶中加入2mol/L的稀盐酸(10ml)酸化，用乙酸乙酯(50ml×3)萃取，合并有机相，先用硫代硫酸钠饱和水溶液(10ml)洗涤，再用饱和食盐水(10ml)洗涤，无水硫酸镁干燥，过滤，滤液用旋转蒸发仪蒸干，残余物通过快速柱层析(淋洗剂为乙酸乙酯/石油醚＝1:4，体积比)纯化，得到0.620g 2,3-二甲氧基苯甲醛，(黄色固体，收率87％)。
Claims (3)
1.一种通过脱除邻香兰素的甲基制备2,3-二羟基苯甲醛的方法，其特征在于包括如下步骤：
在有机溶剂中，在三氯化铝和碘化物存在的条件下，邻香兰素在-20℃至回流的温度下发生醚键断裂反应，生成2,3-二羟基苯甲醛；
所述的碘化物为碘化钠、碘化钾和四烷基碘化铵中一种，或者任意几种的组合；
所述的四烷基碘化铵中烷基为甲基、乙基、丙基、丁基、苄基或正十二烷基；
所述的有机溶剂为乙腈、丙腈、丁腈、异丁腈、苯腈、苯乙腈、丙二腈、丁二腈、戊二腈和己二腈中的一种，或者任意几种的组合。
2.根据权利要求1所述的通过脱除邻香兰素的甲基制备2,3-二羟基苯甲醛的方法，其特征在于：三氯化铝、碘化物和邻香兰素的摩尔比为0.5～5:0.5～10:1。
3.根据权利要求1所述的通过脱除邻香兰素的甲基制备2,3-二羟基苯甲醛的方法，其特征在于：醚键断裂反应的反应时间为0.5～48小时。
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| US3256336A (en) * | 1961-06-21 | 1966-06-14 | Monsanto Co | Cleavage of alkyl o-hydroxyphenyl ethers |
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| CN106866377A (zh) * | 2017-02-13 | 2017-06-20 | 荆楚理工学院 | 一种苯基烷基醚的醚键断裂方法 |
| CN107473916A (zh) * | 2017-08-10 | 2017-12-15 | 荆楚理工学院 | 一种苯基烷基醚的醚键断裂方法 |
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- 2018-05-24 CN CN201810507815.7A patent/CN108821955B/zh active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3256336A (en) * | 1961-06-21 | 1966-06-14 | Monsanto Co | Cleavage of alkyl o-hydroxyphenyl ethers |
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