CN112094210A - 一种取代的亚磺酸盐的制备方法 - Google Patents
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- DOUHZFSGSXMPIE-UHFFFAOYSA-N hydroxidooxidosulfur(.) Chemical class [O]SO DOUHZFSGSXMPIE-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical class ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 15
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 10
- 239000002253 acid Substances 0.000 claims abstract description 9
- 239000011230 binding agent Substances 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 7
- 230000007062 hydrolysis Effects 0.000 claims abstract description 5
- 238000004519 manufacturing process Methods 0.000 claims abstract description 4
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 230000008569 process Effects 0.000 claims abstract description 3
- 238000006722 reduction reaction Methods 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 11
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 6
- -1 sulfone compound Chemical class 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 4
- OAKJQQAXSVQMHS-UHFFFAOYSA-N hydrazine group Chemical group NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 4
- 125000001624 naphthyl group Chemical group 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- 125000004076 pyridyl group Chemical group 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- 125000003107 substituted aryl group Chemical group 0.000 claims description 4
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical group OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 3
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 3
- JJXWKXZOHOUFCX-UHFFFAOYSA-N methylhydrazine;hydrate Chemical compound O.CNN JJXWKXZOHOUFCX-UHFFFAOYSA-N 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- 230000009471 action Effects 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011736 potassium bicarbonate Substances 0.000 claims description 2
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 2
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 235000011181 potassium carbonates Nutrition 0.000 claims description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 2
- 235000011118 potassium hydroxide Nutrition 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 239000002699 waste material Substances 0.000 abstract description 2
- BUUPQKDIAURBJP-UHFFFAOYSA-N sulfinic acid Chemical compound OS=O BUUPQKDIAURBJP-UHFFFAOYSA-N 0.000 description 6
- CSKNSYBAZOQPLR-UHFFFAOYSA-N benzenesulfonyl chloride Chemical compound ClS(=O)(=O)C1=CC=CC=C1 CSKNSYBAZOQPLR-UHFFFAOYSA-N 0.000 description 4
- 238000004128 high performance liquid chromatography Methods 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- SRJQTHAZUNRMPR-UYQKXTDMSA-N spinosyn A Chemical compound O([C@H]1CCC[C@@H](OC(=O)C[C@H]2[C@@H]3C=C[C@@H]4C[C@H](C[C@H]4[C@@H]3C=C2C(=O)[C@@H]1C)O[C@H]1[C@@H]([C@H](OC)[C@@H](OC)[C@H](C)O1)OC)CC)[C@H]1CC[C@H](N(C)C)[C@@H](C)O1 SRJQTHAZUNRMPR-UYQKXTDMSA-N 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000002168 alkylating agent Substances 0.000 description 1
- 229940100198 alkylating agent Drugs 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000000269 nucleophilic effect Effects 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- CHLCPTJLUJHDBO-UHFFFAOYSA-M sodium;benzenesulfinate Chemical compound [Na+].[O-]S(=O)C1=CC=CC=C1 CHLCPTJLUJHDBO-UHFFFAOYSA-M 0.000 description 1
- MZSDGDXXBZSFTG-UHFFFAOYSA-M sodium;benzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=CC=C1 MZSDGDXXBZSFTG-UHFFFAOYSA-M 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- NVBFHJWHLNUMCV-UHFFFAOYSA-N sulfamide Chemical compound NS(N)(=O)=O NVBFHJWHLNUMCV-UHFFFAOYSA-N 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C313/00—Sulfinic acids; Sulfenic acids; Halides, esters or anhydrides thereof; Amides of sulfinic or sulfenic acids, i.e. compounds having singly-bound oxygen atoms of sulfinic or sulfenic groups replaced by nitrogen atoms, not being part of nitro or nitroso groups
- C07C313/02—Sulfinic acids; Derivatives thereof
- C07C313/04—Sulfinic acids; Esters thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C315/00—Preparation of sulfones; Preparation of sulfoxides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/62—Oxygen or sulfur atoms
- C07D213/70—Sulfur atoms
- C07D213/71—Sulfur atoms to which a second hetero atom is attached
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明公开了一种取代的亚磺酸盐的制备方法,以取代的磺酰氯作为原料,在还原剂和缚酸剂存在的条件下,取代的磺酰氯在水中进行水解还原反应,生成相应的取代的亚磺酸盐。本发明是一种易于实施且适合工业规模生产的制备亚磺酸盐及其衍生物的新方法,该方法工艺过程简单,产物纯度高,三废易于处理,安全环保。
Description
技术领域
本发明涉及一种亚磺酸盐及其衍生物的制备新方法,可以其钠盐的形式得到,并进一步反应生成类似物,属于有机合成技术领域。
背景技术
亚磺酸及其盐类广泛地应用于医药、印染、农药等领域,不仅可以作为偶联试剂用来制备各种异构和杂环化合物,也可作为亲核或亲电试剂用于各种反应,是制备砜、亚砜、磺酰胺、磺酰氯等含有磺酰基(-SO_2-)的有机化合物的重要中间体。近些年来,基于亚磺酸及其盐参与的偶联反应发展迅速,可以在不同的反应条件下构筑碳-碳键、碳-杂键、硫-杂键等化学键,从而制备出拥有各式各样官能团的有机化合物,这使得亚磺酸及其盐化合物的重要性日益增长。
然而,目前报道的关于亚磺酸的合成方法都或多或少的存在一些缺点,例如需要用到昂贵的过渡金属催化剂与配体,反应底物需要具有特定的官能团,反应条件苛刻,反应时间长,实验操作复杂,反应成本高等。因此,开发出一条简单高效、反应条件温和、原料廉价易得的亚磺酸制备路线是很有必要性和意义的。
发明内容
本发明所要解决的技术问题是针对现有技术中存在的不足,而提供一种取代的亚磺酸盐的制备方法,是一种易于实施且适合工业规模生产的制备亚磺酸盐及其衍生物的新方法,该方法工艺过程简单,产物纯度高,三废易于处理,安全环保。
为了实现上述目的,本发明采用如下技术方案:
一种取代的亚磺酸盐的制备方法,以式I所示的取代的磺酰氯作为原料,在还原剂和缚酸剂存在的条件下,取代的磺酰氯在水中进行水解还原反应,生成式II所示的取代的亚磺酸盐;
其中:R为烷基、环烷基、芳基或取代芳基;R'为Na或K。
上述技术方案中,所述的R优选为C10以内的烷基或环烷基、苯基、取代苯基、萘基、取代萘基、吡啶基或取代吡啶基。
上述技术方案中,所述的还原剂为肼或其衍生物,优选为水合肼或水合甲基肼。
上述技术方案中,所述的缚酸剂为碳酸钠、碳酸钾、碳酸氢钠、碳酸氢钾、氢氧化钠、氢氧化钾中的任意一种、两种及以上以任意比例形成的混合物。
上述技术方案中,式I所示的取代的磺酰氯在缚酸剂和水形成的碱性水溶液中,在还原剂的作用下进行选择性水解反应生成对应的亚磺酸盐,反应温度为常温或者30-80℃(基于不同磺酰氯取代基团进行调整),反应时间为0.5-5h。
上述技术方案中,所述的还原剂与式I所示取代的磺酰氯的摩尔比为0.5-1:1。
上述技术方案中,所述的缚酸剂与式I所示取代的磺酰氯的摩尔比为0.5-2:1。
上述技术方案中,所述的水与式I所示取代的磺酰氯的质量比为0.5-2:1。
本发明还提供一种式II所示的取代的亚磺酸盐在制备式III所示的砜类化合物方面的应用。
上述技术方案中,式II所示的取代的亚磺酸盐在制备式III所示的砜类化合物时,式II所示的取代的亚磺酸盐与烷基化试剂反应得到式III所示的化合物,这些转化在本领域是众所周知的,且可通过基础有机化学等文献方法和条件进行:
其中,R为烷基、环烷基、芳基或取代芳基。
本发明方法工艺过程简单,产物纯度高,三废易于处理,安全环保。
具体实施方式
以下对本发明技术方案的具体实施方式详细描述,但本发明并不限于以下描述内容:
下面结合具体的实施例,对本发明进行阐述:
实施例1:
一种取代的亚磺酸盐的制备方法,以苯磺酰氯水解还原得苯亚磺酸钠盐为例:
在300g水中加入20.1g(0.402mol)水合肼,加入40.8g(0.385mol)碳酸钠后升温溶解,在60℃温度下,滴加111g(0.629mol)苯磺酰氯后,保温反应2h,合成液降温过滤,得到苯亚磺酸钠盐,HPLC进行纯度分析,结果总结于表1中。
实施例2-7:
实施例2-7的操作过程与实施例1相同,原料取代的磺酰氯如表1所示,水解温度如表1所示,得到相应的亚磺酸盐,HPLC进行纯度分析,结果总结于表1中:
表1:取代磺酰氯还原水解对比实施例
实施例8:
在300g水中加入40.3g(0.63mol)水合甲基肼,加入40.8g(0.385mol)碳酸钠后升温溶解,在60℃温度下,滴加111g(0.629mol)苯磺酰氯后,保温反应2.5h,合成液降温过滤,得到苯亚磺酸钠盐,HPLC进行纯度分析,混合物中亚磺酸盐占比95.2%,后处理后得含量98.1%的产物苯基亚磺酸钠,收率(以苯磺酰氯记)92.2%
上述实例只是为说明本发明的技术构思以及技术特点,并不能以此限制本发明的保护范围。凡根据本发明的实质所做的等效变换或修饰,都应该涵盖在本发明的保护范围之内。
Claims (10)
2.根据权利要求1所述的制备方法,其特征在于:所述的R为C10以内的烷基或环烷基、苯基、取代苯基、萘基、取代萘基、吡啶基或取代吡啶基。
3.根据权利要求1所述的制备方法,其特征在于:所述的还原剂为肼或其衍生物。
4.根据权利要求3所述的制备方法,其特征在于:所述的还原剂水合肼或水合甲基肼。
5.根据权利要求1所述的制备方法,其特征在于:所述的缚酸剂为碳酸钠、碳酸钾、碳酸氢钠、碳酸氢钾、氢氧化钠、氢氧化钾中的任意一种、两种及以上以任意比例形成的混合物。
6.根据权利要求1或5所述的制备方法,其特征在于:式I所示的取代的磺酰氯在缚酸剂和水形成的碱性水溶液中,在还原剂的作用下进行选择性水解反应生成对应的亚磺酸盐,反应温度为常温或者30-80℃,反应时间为0.5-5h。
7.根据权利要求1所述的制备方法,其特征在于:所述的还原剂与式I所示取代的磺酰氯的摩尔比为0.5-1:1。
8.根据权利要求1所述的制备方法,其特征在于:所述的缚酸剂与式I所示取代的磺酰氯的摩尔比为0.5-2:1。
9.根据权利要求1所述的制备方法,其特征在于:所述的水与式I所示取代的磺酰氯的质量比为0.5-2:1。
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CN1631909A (zh) * | 2004-11-25 | 2005-06-29 | 南开大学 | 聚苯乙烯亚磺酸盐型树脂及其制备方法 |
CN1639154A (zh) * | 2002-02-25 | 2005-07-13 | 库多斯药物有限公司 | 可用作atm抑制剂的吡喃酮 |
CN108440349A (zh) * | 2018-05-11 | 2018-08-24 | 上海晋鲁医药科技有限公司 | 一种手性光学纯对甲苯亚磺酰胺的制备方法 |
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Publication number | Priority date | Publication date | Assignee | Title |
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CN1639154A (zh) * | 2002-02-25 | 2005-07-13 | 库多斯药物有限公司 | 可用作atm抑制剂的吡喃酮 |
CN1631909A (zh) * | 2004-11-25 | 2005-06-29 | 南开大学 | 聚苯乙烯亚磺酸盐型树脂及其制备方法 |
CN108440349A (zh) * | 2018-05-11 | 2018-08-24 | 上海晋鲁医药科技有限公司 | 一种手性光学纯对甲苯亚磺酰胺的制备方法 |
Non-Patent Citations (1)
Title |
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CUSACK, N. J.等: "2,4,6-Tri-isopropylbenzenesulfonyl hydrazide: a convenient source of di-imide", 《TETRAHEDRON》 * |
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