CN108822055B - 一种2-丁基-1,2-苯并异噻唑啉-3-酮的方法 - Google Patents
一种2-丁基-1,2-苯并异噻唑啉-3-酮的方法 Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 17
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 title description 4
- -1 2- normal-butyl Chemical group 0.000 claims abstract description 9
- CSNDZKLCEPJMFZ-UHFFFAOYSA-N n-butyl-2-methylsulfanylbenzamide Chemical compound CCCCNC(=O)C1=CC=CC=C1SC CSNDZKLCEPJMFZ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000010189 synthetic method Methods 0.000 claims abstract 2
- 238000006243 chemical reaction Methods 0.000 claims description 14
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical class OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 5
- 239000000706 filtrate Substances 0.000 claims description 4
- 238000000605 extraction Methods 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- 150000001408 amides Chemical class 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims 3
- 238000005406 washing Methods 0.000 claims 1
- 239000000460 chlorine Substances 0.000 abstract description 3
- 229910052801 chlorine Inorganic materials 0.000 abstract description 3
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 231100000331 toxic Toxicity 0.000 abstract description 2
- 230000002588 toxic effect Effects 0.000 abstract description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 abstract 1
- 229910021645 metal ion Inorganic materials 0.000 abstract 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 abstract 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 18
- LUYIHWDYPAZCNN-UHFFFAOYSA-N 2-butyl-1,2-benzothiazol-3-one Chemical compound C1=CC=C2C(=O)N(CCCC)SC2=C1 LUYIHWDYPAZCNN-UHFFFAOYSA-N 0.000 description 3
- HDCGAHPPUWORDU-UHFFFAOYSA-N 2-butyl-3h-1,2-benzothiazole Chemical compound C1=CC=C2SN(CCCC)CC2=C1 HDCGAHPPUWORDU-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- DMSMPAJRVJJAGA-UHFFFAOYSA-N benzo[d]isothiazol-3-one Chemical compound C1=CC=C2C(=O)NSC2=C1 DMSMPAJRVJJAGA-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 3
- HHFALMJKJOCCKC-UHFFFAOYSA-N 2-fluoro-1,4-diazabicyclo[2.2.2]octane Chemical compound FC1N2CCN(C1)CC2 HHFALMJKJOCCKC-UHFFFAOYSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- LBEMXJWGHIEXRA-UHFFFAOYSA-N 2-[(2-carboxyphenyl)disulfanyl]benzoic acid Chemical compound OC(=O)C1=CC=CC=C1SSC1=CC=CC=C1C(O)=O LBEMXJWGHIEXRA-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 230000000855 fungicidal effect Effects 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N sec-butylidene Natural products CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D275/00—Heterocyclic compounds containing 1,2-thiazole or hydrogenated 1,2-thiazole rings
- C07D275/04—Heterocyclic compounds containing 1,2-thiazole or hydrogenated 1,2-thiazole rings condensed with carbocyclic rings or ring systems
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- Organic Chemistry (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
本发明涉及精细化工技术领域,公开一种2‑正丁基苯并异噻唑啉‑3‑酮的合成方法。具体步骤:N‑丁基‑2‑甲硫基苯甲酰胺与1‑氯甲基‑4‑氟‑1,4‑重氮双环[2.2.2]辛烷双(四氟硼酸盐)在N,N‑二甲基甲酰胺中60摄氏度反应6小时,即可得到2‑正丁基苯并异噻唑啉‑3‑酮。同现有的技术相比,此方法无需引入金属离子或者含氯有毒试剂,产率高,操作简单,对环境影响较小,具有潜在的工业价值,值得推广应用。
Description
技术领域
本发明属于精细化工领域,涉及一种2-丁基-1,2-苯并异噻唑啉-3-酮合成的方法。
背景技术
2-丁基-1,2-苯并异噻唑啉-3-酮(BBIT)是一种重要的工农业杀菌剂,广泛用于塑料等高分子以及木质家具等防腐与杀菌,因此其研究一直受到广泛关注。目前合成2-丁基-1,2-苯并异噻唑啉-3-酮的常用方法有二种:第一种方法,以二硫代二苯甲酸为原料,通过二氯亚砜酰氯化后与正丁胺反应生成相应的酰胺,再通过二硫键断裂环合得到2-丁基-1,2-苯并异噻唑啉-3-酮。该方法不足之处在于需要使用有毒的二氯亚砜试剂,同时反应产生的大量氯化氢和二氧化硫废气需要处理,而且目标产物的总收率不高于65%,收率较低,三废量较大。第二种方法由1,2-苯并异噻唑啉-3-酮(BIT)与碱反应,得到1,2-苯并异噻唑啉-3-酮碱金属盐,将所得的碱金属盐与卤代正丁烷反应,得到2-丁基-1,2-苯并异噻唑啉-3-酮。该方法不足之处在于选择性差,并且有大量副产物产生,从而导致目标产物难以提纯分离,总收率在65%左右。
发明内容
本发明的目的在于克服现有技术的不足,提供一种选择性高、产率高、易于分离提纯、环境危害小的合成2-丁基-1,2-苯并异噻唑啉-3-酮的方法。
本发明所涉及的合成2-丁基-1,2-苯并异噻唑啉-3-酮反应步骤如下:将N-丁基-2-甲硫基苯甲酰胺和1-氯甲基-4-氟-1,4-二氮杂双环[2.2.2]辛烷二(四氟硼酸)盐,依次加入反应溶剂N,N-二甲基甲酰胺中,40-80℃剧烈搅拌5-7h,反应结束后,进行水洗,萃取,减压蒸馏滤液,即可获得2-丁基-1,2-苯并异噻唑啉-3-酮。
本发明中溶剂可以为N,N-二甲基甲酰胺,也可以为乙腈或N,N-二甲基甲酰胺与乙腈的混合有机溶剂,优选N,N-二甲基甲酰胺。
发明中N-丁基-2-甲硫基苯甲酰胺与-氯甲基-4-氟-1,4-二氮杂双环[2.2.2]辛烷二(四氟硼酸)盐的用量摩尔比1:1。
本发明中所述的反应温度为40-80℃,优选60℃。
本发明中所述的反应时间为5-7h,优选60h。
具体实施方式
下面的实施例将有助于说明本发明,但是不局限其范围。
具体实施例1:
在100mL的圆底烧瓶中依次加入N-丁基-2-甲硫基苯甲酰胺(20mmol,2.23g)、1-氯甲基-4-氟-1,4-二氮杂双环[2.2.2]辛烷二(四氟硼酸)盐(20mmol,3.55g)以及20mL的N,N-二甲基甲酰胺,反温度控制在60℃,并且剧烈搅拌反应6h。反应结束后,冷却至室温,对反应体系进行水洗,萃取,减压蒸馏滤液,收集主馏分,即可获得2-丁基-1,2-苯并异噻唑啉-3-酮(3.80g,92%)。
反应涉及的方程式如下:
具体实施例2:
在100mL的圆底烧瓶中依次加入N-丁基-2-甲硫基苯甲酰胺(20mmol,4.46g)、1-氯甲基-4-氟-1,4-二氮杂双环[2.2.2]辛烷二(四氟硼酸)盐(20mmol,7.10g)以及20mL的N,N-二甲基甲酰胺,反温度控制在40℃,并且剧烈搅拌反应6h。反应结束后,冷却至室温,对反应体系进行水洗,萃取,减压蒸馏滤液,收集主馏分,即可获得2-丁基-1,2-苯并异噻唑啉-3-酮(3.40g,82%)。
以上描述了本发明的可选实施方案,以教导本领域技术人员如何实施和再现本发明。为了教导本发明方案,已经对一些常规技术方面进行了简化和省去。本领域技术人员应该理解源自这方面的变型,均在本发明的保护范围之内。
Claims (6)
1.2-正丁基苯并异噻唑啉-3-酮合成的方法:在有机溶剂中加入N-丁基-2-甲硫基苯甲酰胺和氟盐并加热,即可得到2-正丁基苯并异噻唑啉-3-酮,反应所使用的氟盐为1-氯甲基-4-氟-1,4-二氮杂双环[2.2.2]辛烷二(四氟硼酸)盐。
2.根据权利要求1所述的方法,其特征在于,所述方法还包括反应之后进行的水洗,萃取,减压蒸馏滤液,收集主馏分。
3.如权利要求1所述的方法,其特征在于:反应温度在60℃。
4.如权利要求1所述的方法,其特征在于:反应时间为6h。
5.如权利要求1所述的方法,其特征在于:N-丁基-2-甲硫基苯甲酰胺与氟盐的加入量按照摩尔比为1:1的标准加入。
6.如权利要求1所述的方法,其特征在于:反应所使用的有机溶剂为N,N-二甲基甲酰胺。
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