CN1150796A - 芳香族或杂芳族磺酰卤类的制备方法 - Google Patents
芳香族或杂芳族磺酰卤类的制备方法 Download PDFInfo
- Publication number
- CN1150796A CN1150796A CN95193639A CN95193639A CN1150796A CN 1150796 A CN1150796 A CN 1150796A CN 95193639 A CN95193639 A CN 95193639A CN 95193639 A CN95193639 A CN 95193639A CN 1150796 A CN1150796 A CN 1150796A
- Authority
- CN
- China
- Prior art keywords
- general formula
- ring
- aromatic
- described method
- heteroaromatic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D275/00—Heterocyclic compounds containing 1,2-thiazole or hydrogenated 1,2-thiazole rings
- C07D275/02—Heterocyclic compounds containing 1,2-thiazole or hydrogenated 1,2-thiazole rings not condensed with other rings
- C07D275/03—Heterocyclic compounds containing 1,2-thiazole or hydrogenated 1,2-thiazole rings not condensed with other rings 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/02—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/02—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof
- C07C303/16—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof by oxidation of thiols, sulfides, hydropolysulfides, or polysulfides with formation of sulfo or halosulfonyl groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C315/00—Preparation of sulfones; Preparation of sulfoxides
- C07C315/04—Preparation of sulfones; Preparation of sulfoxides by reactions not involving the formation of sulfone or sulfoxide groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
- C07C319/20—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides by reactions not involving the formation of sulfide groups
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D241/00—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings
- C07D241/02—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings
- C07D241/10—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
- C07D241/14—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members 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
- C07D241/18—Oxygen or sulfur atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
- C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
- C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
- C07D251/14—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom
- C07D251/22—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom to two ring carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
- C07D263/02—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings
- C07D263/30—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D263/34—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members 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
- C07D263/46—Sulfur atoms
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Pyridine Compounds (AREA)
Abstract
本发明是通式(3)所示芳香族或杂芳族磺酰卤类的制备方法,其特征在于通式(1)所示芳香族或杂芳族甲硫醚类或者通式(2)所示芳香族或杂芳族亚砜类在水的存在下用卤化剂卤化,
ArSCH3-mXm)n (1)
ArSOCH3-mXm)n (2)
ArSO2Y)n (3)式中Ar表示无取代或有任意取代基的芳香环或杂芳环,X和Y表示卤原子,m表示0~3的整数,n表示1或2。按照本发明,可在工业上廉价且容易地得到芳香族或杂芳族磺酰卤类。
Description
技术领域
本发明涉及芳香族或杂芳族磺酰卤类的新型制备方法。芳香族或杂芳族磺酰卤类是可用于医药、农药、功能性材料等各种用途的有用化合物。
背景技术
以前,关于芳香族磺酰卤类的制备方法,已知有许多方法,这些制备方法可按如下所述分类。
(A)经由磺化的方法
磺酸盐的卤素置换反应
用氯磺酸等进行磺化
M.S.Morgan,L.H.Cretcher,J.Am.Chem.Soc.(美国化学会志),70.375(1948)
(B)经由重氮盐的方法
H.Meerwein,E.Buchner,K.van Emster,J.Prakt,Chem.(化学),[2]152.251(1939)(C)利用金属化反应的方法T.Hamada和O.Yonemitsu,Synthesis(合成),852
(D)用硫醇衍生物氯化进行的方法
I.B.Douglass,T.B.Johnson,J.Am.Chem.Soc.(美国化学会志),60,1486(1938)
Y.J.Park,H.Hyun,Y.H.Kim,Chem.Lett.(化学快报),1483,1992
然而,这些众所周知的方法在工业上实施时有如下缺点。
(A)的方法在芳香环上带有硝基、氰基、羧基等的情况下或有吡啶环等时反应难以进行。而且,这种方法要在一个芳香环上引进2个或2个以上卤化磺酰基一般是不容易的。
(B)的方法易于使工艺拖长,或由于大量使用铜盐而有废水处理问题,在经济性或环境保护方面都不好。而且,重氮盐本身也决定了难以谈论其稳定性,在进行安全操作方面也是有问题的。
(C)的方法收率低,要使用昂贵的试剂等,在工业上实施时经济性不相称的情况居多。
(D)的方法,作为原料使用的芳香族取代硫醇衍生物在工业规模上难以廉价获得的情况居多。
如上所述,先有的芳香族磺酰卤类的制备方法在多数情况下经济性欠缺、工业上制备不容易,需要寻找能在工业上廉价地制备各种各样的芳香族磺酰卤衍生物的方法。
发明公开
本发明的目的是提供在工业上廉价且容易地制备芳香族或杂芳族磺酰卤类的方法。
本发明者等人进行了深入研究,以期排除上述己知方法的缺点,并提供在工业上廉价且容易地制备芳香族或杂芳族磺酰卤类的方法。
其结果,发现了用芳香族或杂芳族硫醚类或者芳香族或杂芳族亚砜类作为原料,通过在水的存在下使该化合物卤化,能高收率地得到作为目标的芳香族或杂芳族磺酰卤类,终于完成了本申请的发明。
其反应机理虽然不详,但可以推测,作为原料的芳香族或杂芳族甲硫醚或者芳香族或杂芳族甲基亚砜的硫原子与甲基碳原子之间的键选择性地且容易地发生断裂,并几乎同时发生硫原子的氧化·卤化。
这就是说,本申请的第一项发明是,下述通式(1)所示的芳香族或杂芳族甲硫醚类在水的存在下用卤化剂进行卤化,制备通式(3)所示的芳香族或杂芳族磺酰卤类的新型制备方法: 式中Ar表示无取代或有任意取代基的芳香环或杂芳环,X和Y表示卤原子,m表示0~3的整数,n表示1或2。
此外,本申请的第二项发明是,下述通式(2)所示的芳香族或杂芳族甲基亚砜类在水的存在下用卤化剂进行卤化,制备通式(3)所示的芳香族或杂芳族磺酰卤类的新型制备方法: 式中Ar表示无取代或有任意取代基的芳香环或杂芳环,X和Y表示卤原子,m表示0~3的整数,n表示1或2。
按照本发明,迄今为止难以合成或需要多阶段步骤的、在有氰基等取代的芳香环或吡啶环等上引进卤化磺酰基,或在一个芳香环上引进1个或2个卤化磺酰基,均可容易地进行。
以下依次具体地说明本发明。
本申请的发明中使用的通式(1)、(2)所示的原料硫醚类、亚砜类、无论用何种制备法得到的均可使用,但按照本发明者等人业已阐明的2,5-二氯烷硫基苯的制备法(特开平6-56760号)等,可以更容易地制备。
这就是说,无取代或有任意取代基的芳香族或杂芳族化合物和烷硫醇在碱和季铵盐催化剂的存在下,在水或水-非水溶性有机溶剂中,进行非均相体系反应,可以容易地得到原料硫醚类。而且,通过使这种硫醚氧化或卤化,可以得到亚砜类、卤甲基硫醚类等。
通式中Ar所代表的芳香环或杂芳环没有特别限定,系指无取代或有任意取代基的、范围广泛的芳香环或杂芳环。作为这种芳香环或杂芳环,可以列举诸如苯环、萘环、吡啶环、吡唑环、吡嗪环、三嗪环、***环、噁唑环、异噁唑环、噻唑环、异噻唑环、噻吩环、苯并噻吩环、呋喃环、苯并呋喃环、吡咯环、吲哚环等,但较好可以列举苯环、吡啶环、噻吩环、噻唑环、异噻唑环。
此外,作为任意取代基,可以列举卤素、氰基、硝基、甲酰基、烷基碳酰基、羧酯基、氨基甲酰基、烷基、烷氧基、有取代的苯硫基等。
通式(1)所示的硫醚类或通式(2)所示的亚砜类中的X表示氯原子或溴原子,但从经济上说较好的是氯原子。此外, m表示0~3的整数,但m为0者一般容易获得。然而,在要提高目的物收率的情况下,m为1,即卤甲基硫醚类或卤甲基亚砜类,或m为2,即二卤甲基硫醚类或二卤甲基亚砜类,可以给出较好的结果。
在本申请的发明中,是在水的存在下,通过添加卤化剂,高收率地进行从硫醚类或亚砜类向磺酰卤类转化的反应的。本申请发明中水的用量因原料是硫醚类还是亚砜类而异,不能一概而论,但相对于原料硫醚类或亚砜类而言,通常是1~100倍摩尔量,较好的是3~50倍摩尔量。
作为反应中使用的卤化剂,可以列举氯、溴、硫 酰 氯、硫 酰溴等,但从经济观点来看,较好的是氯。卤化剂的用量因所使用的原料而异,不能一概而论,但相对于原料硫醚类或亚砜类而言,通常是2~50倍摩尔量、较好的是3~20倍摩尔量。
溶剂,只要对所生成的磺酰卤类没有活性就没有特别限定,即使是水溶剂也是可以的,但可以列举诸如已烷、环已烷、庚烷等烃类,二氯乙烷、二氯甲烷、氯仿等卤代烃,氯苯、二氯苯、三氯苯等芳香族烃。在使用溶剂的情况下,其使用量没有特别限定,通常相对于硫醚或亚砜类而言是0.1~10倍重量。
反应温度范围通常是-10~100℃,较好的是0~50℃。反应温度若太低则反应速度慢,反之,若太高则会发生副反应而成为收率低下的原因。反应时间范围通常是约0.5~10小时。
这样生成的芳香族或杂芳族磺酰卤类,用通常的蒸馏、结晶就能容易地进行分离。
作为本申请发明得到的芳香族或杂芳族磺酰卤类,虽说有多种化合物,但可以列举诸如4-氯苯磺酰氯,4-溴苯磺酰溴,2,5-二氯苯磺酰氯,1,2-苯二磺酰氯,4-硝基苯磺酰氯,2-硝基苯磺酰氯,4-氰基苯磺酰氯,2-氰基苯磺酰氯,4-甲基苯磺酰氯,(4-氯磺酰苯基)乙基酮,4-氯磺酰苯甲酰胺,4-氯磺酰苯甲酸甲酯,2-氰基-3-氯苯磺酰氯,(4-氯磺酰苯基)苯基硫醚,2-氯磺酰吡啶,2,6-二氯磺酰吡啶,2-氯磺酰噻吩,2,5-二氯磺酰噻吩,2-氯磺酰吡嗪,4-氯磺酰***,2-氯磺酰噁唑,4-氯磺酰异噁唑,2-氯磺酰噻唑,4-氯磺酰异噻唑等。较好的是2-氰基苯磺酰氯,4-氰基苯磺酰氯,2-硝基苯磺酰氯和4-硝基苯磺酰氯。
此外,本申请发明所得到的化合物完全不受上述实例限制。
本申请发明提供了可用于医药、农药、功能性材料等各种各样用途的芳香族或杂芳族磺酰卤类的新型制备方法。按照本申请发明的方法,可以使工业上有可能得到的芳香族或杂芳族甲基硫醚类或者芳香族或杂芳族甲基亚砜类在水的存在下进行卤化,以简单的工艺高收率地得到目的物。因而,其经济价值和工业价值是极大的。
发明的最佳实施形态
以下用实施例更详细地说明本申请发明,但本申请发明完全不受这些实施例限制。
实施例1
作为原料使用的4-氰基苯基甲硫醚是参照特开平6-56760号所述的方法制备的,即,向配备了搅拌器、温度计、冷凝管的21四口烧瓶中添加165.1g(1.2摩尔)1-氯-4-氰基苯,和17.8g(0.055摩尔)作为相转移催化剂的溴化四正丁铵,然后加入616.0g(1.3摩尔)调整至15%(重量)浓度的甲硫醇钠盐水溶液,在80℃搅拌3小时。冷却至室温后,将析出的结晶滤出,再用甲醇使其重结晶,得到170.4g 4-氰基苯基甲硫醚。
这样得到的4-氰基苯基甲硫醚149.0g(1.00摩尔)加入配备了搅拌器、温度计、冷凝管和气体导入管的21四口烧瓶中,加水80g、-氯苯800g,在25℃用约5小时时间通入氯气497g(7.00摩尔),使反应终止。反应终止后,将油层分离,添加约50g无水硫酸钠、静置约1小时、除去水分后,蒸出溶剂,得到粗结晶。将这种粗结晶溶解在-氯苯中,添加不良溶剂进行重结晶,得到183.5g 4-氰基苯磺酰氯白色结晶。根据4-氰基苯基甲硫醚计算的收率为91%。
实施例2~26
除作为起始原料使用的芳香族或杂芳族甲硫醚类改变成表1、表2和表3中所示的化合物外,进行与实施例1第二段同样的操作,得到对应的芳香族或杂芳族磺酰氯。
表1
起始原料 | 生成物 | 收率(%) | ||
实施例 | 234567891011 | 4-氯苯基甲硫醚2-氯苯基三氯甲基硫醚2-氯苯基甲硫醚2,4-二氯苯基甲硫醚2,5-二氯苯基二氯甲基硫醚2,6-二溴苯基氯甲基硫醚3,5-二溴苯基甲基亚砜4-溴苯基氯甲基硫醚4-溴苯基二氯甲基硫醚1,4-二(二氯甲硫基)苯 | 4-氯苯磺酰氯2-氯苯磺酰氯2-氯苯磺酰氯2,4-二氯苯磺酰氯2,5-二氯苯磺酰氯2,6-二溴苯磺酰氯3,5-二溴苯磺酰氯4-溴苯磺酰氯4-溴苯磺酰氯1,4-苯二磺酰氯 | 90.292.190.294.192.594.593.089.091.285.2 |
表2
起始原料 | 生成物 | 收率(%) | ||
实施例 | 121314151617181920 | 1,4-二(甲磺酰)苯1,2-二甲硫基苯1,2-二甲硫基-4-丁基苯4-氰基苯基氯甲基硫醚2-氰基苯基二氯甲基硫醚4-硝基苯基氯甲基亚砜2-硝基苯基甲硫醚4-甲硫基苯甲酸甲酯2-氰基-3-氯苯基甲硫醚 | 1,4-苯二磺酰氯1,2-苯二磺酰氯4-丁基-1,2-苯二磺酰氯4-氰基苯磺酰氯2-氰基苯磺酰氯4-硝基苯磺酰氯2-硝基苯磺酰氯4-氯磺酰苯酸甲酯2-氰基-3-氯苯磺酰氯 | 86.482.382.695.085.095.095.090.193.1 |
表3
起始原料 | 生成物 收率(%) | ||
实施例 | 212223242526 | 4,4′-二(甲硫基)二苯基硫醚4,4′-二(甲硫基)-2,2′-二氰基二苯基硫醚4-(苯磺酰)苯基甲硫醚1-萘基甲硫醚1-氰基-4-甲硫基萘3-甲硫基-2,5-噻吩二羧酸甲酯 | 4,4′-二(氯磺酰) 94.5二苯基硫醚2,2′-二氰基 95.6-4,4′-二(氯磺酰)二苯基硫醚4-(苯磺酰)苯磺酰氯 92.11-萘基磺酰氯 92.81-氰基-4-氯磺酰萘 92.83-氯磺酰-2,5-噻吩 85.2二羧酸甲酯 |
实施例27
向配备了搅拌器、温度计、冷凝管和带侧管滴液漏斗的21四口烧瓶中添加4-硝基苯基甲硫醚20.4g(0.10摩尔)、水1 0g、-氯苯200g,在1 0℃用约2小时时间滴加硫酰氯94.5g(0.70摩尔), 此后在10℃继续搅拌6小时,使反应终止。反应终止后,将油层分离,加10g水进行水洗。再将油层分离,添加约5g无水硫酸钠静置约1小时,除去水分后,蒸出溶剂,得到粗结晶。将这种粗结晶溶解于-氯苯中,添加不良溶剂进行重结晶,得到21.1g 4-硝基苯磺酰氯白色结晶。根据4-硝基苯基甲硫醚计算的收率为95%。
实施例28~52
除作为起始原料使用的芳香族或杂芳族甲硫醚类与卤化剂的组合改变成表4、表5、表中所示的化合物外,进行与实施例27同样的操作,得到对应的芳香族或杂芳族磺酰卤类。
表4
起始原料 | 卤化剂 生成物 | 收率(%) | ||
实施例 | 2829303132333334353637 | 2-吡啶基甲硫醚4-吡啶基甲硫醚2,6-二(甲硫基)吡啶2-吡嗪基甲硫醚4-三嗪基氯甲基硫醚2-噁唑基二氯甲基硫醚4-异噻唑基二氯甲基硫醚3,5-二氯苯基二氯甲基硫醚4-溴苯基二氯甲基硫醚4-溴苯基三氯甲基硫醚 | 硫酰氯2-氯磺酰吡啶硫酰氯4-氯磺酰吡啶硫酰氯2,6-二(氯磺酰)吡啶硫酰氯2-氯磺酰吡嗪硫酰氯4-氯磺酰三嗪硫酰氯2-氯磺酰噁唑硫酰氯4-氯磺酰异噻唑溴 3,5-二氯苯磺酰溴溴 4-溴苯磺酰溴溴 4-溴苯磺酰溴 | 93.194.595.694.392.192.894.590.295.492.1 |
表5
起始原料 | 卤化剂 | 生成剂 | 收率(%) | ||
实施例 | 383940414243444546 | 1,4-二(二氯甲硫基)苯1,4-二(三氯甲硫基)苯1,2-二(二氯甲硫基)苯1,2-二(二氯甲硫基)-4-丁基苯4-氰基苯基二氯甲基硫醚2-氰基苯基二氯甲基硫醚4-硝基苯基二氯甲基硫醚4-(二氯甲硫基)苯甲酸甲酯2-氰基-3-氯苯基二氯甲基硫醚 | 溴溴溴溴溴溴溴溴溴 | 1,4-苯二磺酰溴1,4-苯二磺酰溴1,2-苯二磺酰溴4-丁基-1,2-苯二磺酰溴4-氰基苯磺酰溴2-氰基苯磺酰溴4-硝基苯磺酰溴4-溴磺酰苯甲酸甲酯2-氰基-3-氯苯磺酰溴 | 90.294.192.594.593.089.091.285.286.4 |
表6
起始原料 | 卤化剂 | 生成物 收率(%) | ||
实施例 | 474849505152 | 4,4′-二(二氯甲硫基)二苯基硫醚4,4′-二(二氯甲硫基)-2,2′-二氰基-二苯基硫醚4-(苯硫基)苯基二氯甲基硫醚4-(苯磺酰)苯基二氯甲基硫醚l-萘基二氯甲基硫醚2-萘基二氯甲基硫醚 | 溴溴溴溴溴溴 | 4,4′-二(溴磺酰) 82.3二苯基硫醚2,2′-二氰基 82.6-4,4′-二(溴磺酰)二苯基硫醚4-(苯硫基)苯磺酰溴 95.04-(苯磺酰)苯磺酰溴 85.01-萘磺酰溴 95.02-萘磺酰溴 90.1 |
Claims (16)
2.权利要求1所述的方法,其特征在于通式(1)的X是氯原子。
3.权利要求1所述的方法,其特征在于通式(1)的m是0。
4.权利要求1所述的方法,其特征在于通式(1)的m是1或2。
5.权利要求1所述的方法,其特征在于卤化剂是氯。
6权利要求1所述的方法,其特征在于通式(1)和通式(3)的Ar是无取代或有任意取代基的苯环、吡啶环、噻吩环、噻唑环或异噻唑环。
7.权利要求1所述的方法,其特征在于通式(1)和通式(3)的Ar是在任意位置上有卤素、氰基、硝基、甲酰基、烷基碳酰基、羧酯基、氨基甲酰基、烷基、烷氧基或有取代苯硫基的芳香环或杂芳环。
8.权利要求1所述的方法,其特征在于通式(3)所示的化合物是2-氰基苯磺酰氯,4-氰基苯磺酰氯,2-硝基苯磺酰氯或4-硝基苯磺酰氯。
10.权利要求9所述的方法,其特征在于通式(2)的X是氯原子。
11.权利要求9所述的方法,其特征在于通式(2)的m是0。
12.权利要求9所述的方法,其特征在于通式(2)的m是1或2。
13.权利要求9所述的方法,其特征在于卤化剂是氯。
14.权利要求9所述的方法,其特征在于通式(2)和通式(3)的Ar是无取代或有任意取代基的苯环、吡啶环、噻吩环、噻唑环或异噻唑环。
15.权利要求9所述的方法,其特征在于通式(2)和通式(3)的Ar是在任意位置上有卤素、氰基、硝基、甲酰基、烷基碳酰基、羧酯基、氨基甲酰基、烷基、烷氧基或有取代苯硫基的芳香环或杂芳环。
16.权利要求9所述的方法,其特征在于通式(3)所示的化合物是2-氰基苯磺酰氯,4-氰基苯磺酰氯,2-硝基苯磺酰氯和4-硝基苯磺酰氯。
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP09099395A JP3814696B2 (ja) | 1995-04-17 | 1995-04-17 | 芳香族またはヘテロ芳香族スルホニルハライド類の製造方法 |
JP90993/95 | 1995-04-17 | ||
JP90993/1995 | 1995-04-17 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN1150796A true CN1150796A (zh) | 1997-05-28 |
CN1075058C CN1075058C (zh) | 2001-11-21 |
Family
ID=14014044
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN95193639A Expired - Fee Related CN1075058C (zh) | 1995-04-17 | 1995-12-25 | 芳香族磺酰卤类的制备方法 |
Country Status (10)
Country | Link |
---|---|
US (1) | US5811571A (zh) |
EP (1) | EP0770599B1 (zh) |
JP (1) | JP3814696B2 (zh) |
KR (1) | KR100445930B1 (zh) |
CN (1) | CN1075058C (zh) |
CA (1) | CA2190256C (zh) |
DE (1) | DE69527716T2 (zh) |
ES (1) | ES2179894T3 (zh) |
TW (1) | TW367319B (zh) |
WO (1) | WO1996033167A1 (zh) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101228118B (zh) * | 2005-07-21 | 2013-09-18 | 惠氏公司 | 由磺酸盐合成磺酰卤和磺酰胺的方法 |
CN106831502A (zh) * | 2017-03-13 | 2017-06-13 | 苏州市泽宸贸易有限公司 | 邻硝基苯磺酰氯、其合成方法及应用 |
CN110105251A (zh) * | 2019-05-20 | 2019-08-09 | 苏州市泽宸贸易有限公司 | 一种邻硝基苯磺酰氯的工业化生产方法 |
CN113666848A (zh) * | 2021-08-18 | 2021-11-19 | 山东同成医药股份有限公司 | 邻硝基苯磺酰氯制备方法 |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7847179B2 (en) * | 2005-06-06 | 2010-12-07 | Board Of Trustees Of Michigan State University | Thermoelectric compositions and process |
US20080289677A1 (en) * | 2007-05-25 | 2008-11-27 | Bsst Llc | Composite thermoelectric materials and method of manufacture |
US20090269584A1 (en) * | 2008-04-24 | 2009-10-29 | Bsst, Llc | Thermoelectric materials combining increased power factor and reduced thermal conductivity |
WO2010085968A1 (en) | 2008-12-30 | 2010-08-05 | European Molecular Biology Laboratory (Embl) | Toluidine sulfonamides and their use as hif-inhibitors |
WO2010075869A1 (en) | 2008-12-30 | 2010-07-08 | European Molecular Biology Laboratory (Embl) | Toluidine sulfonamides and their use |
CN104557800B (zh) * | 2014-12-31 | 2017-04-26 | 常州大学 | 2‑苯氧基四氢呋(吡)喃衍生物及其在五氟磺草胺合成中的应用 |
CN113194954A (zh) | 2018-10-04 | 2021-07-30 | 国家医疗保健研究所 | 用于治疗角皮病的egfr抑制剂 |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CA1216290A (en) * | 1982-05-17 | 1987-01-06 | Alden D. Josey | Process for the nucleophilic substitution of unactivated aromatic and heteroaromatic substrates |
JPS58208239A (ja) * | 1982-05-17 | 1983-12-03 | イ−・アイ・デユポン・デ・ニモアス・アンド・カンパニ− | 活性化されていない芳香族又はヘテロ芳香族物質の求核置換反応 |
-
1995
- 1995-04-17 JP JP09099395A patent/JP3814696B2/ja not_active Expired - Fee Related
- 1995-12-21 TW TW084113701A patent/TW367319B/zh not_active IP Right Cessation
- 1995-12-25 US US08/765,246 patent/US5811571A/en not_active Expired - Lifetime
- 1995-12-25 ES ES95941882T patent/ES2179894T3/es not_active Expired - Lifetime
- 1995-12-25 KR KR1019960707218A patent/KR100445930B1/ko not_active IP Right Cessation
- 1995-12-25 CA CA002190256A patent/CA2190256C/en not_active Expired - Fee Related
- 1995-12-25 CN CN95193639A patent/CN1075058C/zh not_active Expired - Fee Related
- 1995-12-25 EP EP95941882A patent/EP0770599B1/en not_active Expired - Lifetime
- 1995-12-25 DE DE69527716T patent/DE69527716T2/de not_active Expired - Lifetime
- 1995-12-25 WO PCT/JP1995/002675 patent/WO1996033167A1/ja active IP Right Grant
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101228118B (zh) * | 2005-07-21 | 2013-09-18 | 惠氏公司 | 由磺酸盐合成磺酰卤和磺酰胺的方法 |
CN106831502A (zh) * | 2017-03-13 | 2017-06-13 | 苏州市泽宸贸易有限公司 | 邻硝基苯磺酰氯、其合成方法及应用 |
CN110105251A (zh) * | 2019-05-20 | 2019-08-09 | 苏州市泽宸贸易有限公司 | 一种邻硝基苯磺酰氯的工业化生产方法 |
CN113666848A (zh) * | 2021-08-18 | 2021-11-19 | 山东同成医药股份有限公司 | 邻硝基苯磺酰氯制备方法 |
Also Published As
Publication number | Publication date |
---|---|
JP3814696B2 (ja) | 2006-08-30 |
CN1075058C (zh) | 2001-11-21 |
DE69527716T2 (de) | 2003-04-03 |
DE69527716D1 (de) | 2002-09-12 |
EP0770599B1 (en) | 2002-08-07 |
KR100445930B1 (ko) | 2004-11-16 |
CA2190256C (en) | 2007-08-07 |
JPH08291133A (ja) | 1996-11-05 |
WO1996033167A1 (fr) | 1996-10-24 |
TW367319B (en) | 1999-08-21 |
EP0770599A1 (en) | 1997-05-02 |
EP0770599A4 (en) | 1999-12-08 |
CA2190256A1 (en) | 1996-10-24 |
ES2179894T3 (es) | 2003-02-01 |
US5811571A (en) | 1998-09-22 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN1075058C (zh) | 芳香族磺酰卤类的制备方法 | |
Johnson et al. | Chemistry of sulfoxides and related compounds. XLIX. Synthesis of optically active sulfoximines from optically active sulfoxides | |
CN111116441B (zh) | 一种含有磺酸基的硫叶立德的合成方法及其应用 | |
Uchiro et al. | Non-aqueous reduction of aromatic sulfonyl chlorides to thiols using a dichlorodimethylsilane-zinc-dimethylacetamide system | |
Zarei et al. | Fast, efficient and convenient method for the preparation of arylazo sulfides using aryl diazonium silica sulfates under mild and solvent-free conditions | |
KR100424756B1 (ko) | 방향족또는헤테로방향족황화합물의제조방법 | |
JP4571374B2 (ja) | 7−置換3−アルキル−3h−イソベンゾフラン−1−オン誘導体の製造方法 | |
CN1332944C (zh) | 氨基酸促进的CuI催化的芳基卤化物和烃基亚磺酸盐的偶联反应 | |
CZ20031306A3 (cs) | Způsob přípravy thioxanthonů, tyto thioxanthony a farmaceutický prostředek, který je obsahuje | |
KR20120013961A (ko) | 이소티아졸 유도체의 제조 방법 | |
JP2590246B2 (ja) | 3‐トリフルオロメチルベンゼンスルホニルクロリド類の製造方法 | |
KR101244561B1 (ko) | 치환된 헤테로방향족의 제조 방법 | |
RU2001127642A (ru) | Способ получения полисульфидных полимеров | |
IE56017B1 (en) | Process for the nucleophilic substitution of unactivated aromatic and heteroaromatic substrates | |
WO2020072616A1 (en) | Process and intermediates for the preparation of certain nematicidal sulfonamides | |
US4990705A (en) | Preparation of 4-bromobiphenyl | |
JP4508377B2 (ja) | スルホニル化合物の製造方法 | |
RU2702653C1 (ru) | Способ получения триэтиламмониевой соли тозилметакриловой кислоты | |
JP2010260805A (ja) | イソチアゾール誘導体を製造する方法 | |
CN106187846A (zh) | 一种n‑芳硫基亚砜亚胺合成方法 | |
Nie et al. | Expedient Synthesis of Alkyl and Aryl Thioethers Using Xanthates as Thiol-Free Reagents | |
JP2620903B2 (ja) | 2−置換ベンゾ[b]チオフェンの製造方法 | |
JP2520246B2 (ja) | 5―(α―アルコキシイミノ)エチル―2―チオフェンスルホン酸及びその製造方法 | |
Arnswald et al. | Tin for organic synthesis. 10. Unconventional regiospecific syntheses of aromatic carbonamides and thiocarbonamides by means of tin-mediated Friedel-Crafts reactions | |
UA49813C2 (uk) | Спосіб одержання галогенметилбензоїлціанідів |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C14 | Grant of patent or utility model | ||
GR01 | Patent grant | ||
CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20011121 Termination date: 20141225 |
|
EXPY | Termination of patent right or utility model |