CN113387880B - 2-巯基吡啶和2,2’-吡啶硫醚的集成制备方法 - Google Patents
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- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000003054 catalyst Substances 0.000 claims abstract description 21
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000002131 composite material Substances 0.000 claims abstract description 20
- 229910052979 sodium sulfide Inorganic materials 0.000 claims abstract description 19
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000011593 sulfur Substances 0.000 claims abstract description 19
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 19
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- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
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- 238000005406 washing Methods 0.000 claims description 11
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
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- 238000000605 extraction Methods 0.000 claims description 7
- 150000005749 2-halopyridines Chemical class 0.000 claims description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- IMRWILPUOVGIMU-UHFFFAOYSA-N 2-bromopyridine Chemical compound BrC1=CC=CC=N1 IMRWILPUOVGIMU-UHFFFAOYSA-N 0.000 claims description 4
- 230000003472 neutralizing effect Effects 0.000 claims description 4
- OKDGRDCXVWSXDC-UHFFFAOYSA-N 2-chloropyridine Chemical group ClC1=CC=CC=N1 OKDGRDCXVWSXDC-UHFFFAOYSA-N 0.000 claims description 3
- ONIBWKKTOPOVIA-BYPYZUCNSA-N L-Proline Chemical compound OC(=O)[C@@H]1CCCN1 ONIBWKKTOPOVIA-BYPYZUCNSA-N 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 3
- 239000000047 product Substances 0.000 abstract description 8
- 238000000034 method Methods 0.000 abstract description 6
- 239000006227 byproduct Substances 0.000 abstract description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 7
- 230000006872 improvement Effects 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000012074 organic phase Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 4
- UBQKCCHYAOITMY-UHFFFAOYSA-N pyridin-2-ol Chemical compound OC1=CC=CC=N1 UBQKCCHYAOITMY-UHFFFAOYSA-N 0.000 description 4
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- 238000002425 crystallisation Methods 0.000 description 3
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- 230000008569 process Effects 0.000 description 2
- 229960002429 proline Drugs 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
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- 239000008346 aqueous phase Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 1
- 229910000024 caesium carbonate Inorganic materials 0.000 description 1
- AIYUHDOJVYHVIT-UHFFFAOYSA-M caesium chloride Chemical compound [Cl-].[Cs+] AIYUHDOJVYHVIT-UHFFFAOYSA-M 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
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- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
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- 229910001385 heavy metal Inorganic materials 0.000 description 1
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- 230000004048 modification Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000003444 phase transfer catalyst Substances 0.000 description 1
- CYQAYERJWZKYML-UHFFFAOYSA-N phosphorus pentasulfide Chemical compound S1P(S2)(=S)SP3(=S)SP1(=S)SP2(=S)S3 CYQAYERJWZKYML-UHFFFAOYSA-N 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- 239000012217 radiopharmaceutical Substances 0.000 description 1
- 229940121896 radiopharmaceutical Drugs 0.000 description 1
- 230000002799 radiopharmaceutical effect Effects 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- HYHCSLBZRBJJCH-UHFFFAOYSA-M sodium hydrosulfide Chemical compound [Na+].[SH-] HYHCSLBZRBJJCH-UHFFFAOYSA-M 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000000446 sulfanediyl group Chemical group *S* 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Pyridine Compounds (AREA)
Abstract
本发明公开了一种2‑巯基吡啶和2,2’‑吡啶硫醚的集成制备方法,包括如下步骤:在作为溶剂的水中加入硫磺、硫化钠和复合催化剂,于加热条件下均匀搅拌至硫磺、硫化钠和复合催化剂均溶解;再加入2‑卤代吡啶于回流温度下反应20~30小时;所述复合催化体系是由醋酸铯中添加等重量的助催化剂制备而成;反应结束后,反应液冷却到室温后进行萃取,分别得萃取液和萃余反应液,萃取液、萃余反应液各自经过后处理,分别对应得到2,2’‑吡啶硫醚、2‑巯基吡啶。本发明的方法能同时得到两种主产品,减少了副产物的生成。
Description
技术领域
本发明涉及一种2-巯基吡啶和2,2’-吡啶硫醚的集成制备方法。
背景技术
2-巯基吡啶和2,2’-吡啶硫醚均是重要的有机硫化物,广泛应用于医药、染料、农用化学品的生产中。目前制备它们的主要方法有:
2-巯基吡啶的合成方法有:由2-羟基吡啶为起始原料,与硫氢化钠反应(陈煦,李永强,天津化工,第5期26-27,2000);与五硫化二磷反应(Pettersson,Birgitta et al,PCTInt.Appl.,2012104415,2012;Bergman,Jan et al,Journal of Organic Chemistry,76(6),1546-1553,2011;Noel,J.P.and Pichat,L.Journal of Labelled Compounds andRadiopharmaceuticals,20(11),1243-56,1983;Kandror,I.I.and Bragina,I.O.Izvestiya Akademii Nauk SSSR,Seriya Khimicheskaya,(9),2121-5,1982;Pilipenko,V.S.et al,Zhurnal Organicheskoi Khimii,15(12),2586-90,1979);与有机硫代试剂反应(Renault,J.,Bulletin de la Societe Chimique de France,1001-6,1953);与硫脲反应(Xiantao Ma,et al,Adv.Synth.Catal.,359,1649-1655,2017)。
有研究者(Rostami,Abed et al.,Synthesis,49(22),5025-5038,2017)以2-羟基吡啶和升华硫为原料,在溶剂、三氟甲磺酸和铜催化剂等作用下,得到目标产物2,2’-吡啶硫醚。
发明内容
本发明要解决的问题是提供一种2-巯基吡啶和2,2’-吡啶硫醚的集成制备方法,本发明的2-巯基吡啶和2,2’-吡啶硫醚集成制备方法,具有生产成本低、原料易得等特点。
为了解决上述技术问题,本发明提供一种2-巯基吡啶和2,2’-吡啶硫醚的集成制备方法,包括如下步骤:
1)、在作为溶剂的水中加入硫磺、硫化钠和复合催化剂,于加热条件下均匀搅拌至硫磺、硫化钠和复合催化剂均溶解;再加入2-卤代吡啶于回流温度下反应20~30小时;
所述复合催化体系是由醋酸铯中添加等重量的助催化剂制备而成,所述助催化剂为以下任一:四丁基溴化铵(TBAB)、或乙二胺四乙酸(EDTA)、或L-脯氨酸(L-Pro);
2-卤代吡啶:醋酸铯=1:0.02~0.05的摩尔比;
每1mol的2-卤代吡啶配用80~120g的硫化钠以及20~50g(优选30~50g)的硫磺;
2)、反应结束后,反应液冷却到室温后进行萃取,分别得萃取液(位于上层)和萃余反应液(位于下层);
萃取液、萃余反应液各自经过后处理,分别对应得到2,2’-吡啶硫醚、2-巯基吡啶。
作为本发明的2-巯基吡啶和2,2’-吡啶硫醚的集成制备方法的改进:所述2-卤代吡啶为2-氯吡啶、2-溴吡啶。
作为本发明的2-巯基吡啶和2,2’-吡啶硫醚的集成制备方法的进一步改进:步骤2)萃取所用的萃取剂为酯类、醚类或卤代烷类;
酯类为乙酸乙酯;醚类为乙醚;卤代烷类为二氯甲烷。
作为本发明的2-巯基吡啶和2,2’-吡啶硫醚的集成制备方法的进一步改进:
萃取液的后处理为:将萃取液经过滤、洗涤、浓缩、冷却结晶、干燥,得到2,2’-吡啶硫醚;
萃余反应液的后处理为:将萃余反应液经中和(中和至pH约为2)、过滤、冷却结晶、干燥,得到2-巯基吡啶。
作为本发明的2-巯基吡啶和2,2’-吡啶硫醚的集成制备方法的进一步改进:
萃取液经洗涤所得的洗涤液与萃余反应液合并后一起进行后处理。
作为本发明的2-巯基吡啶和2,2’-吡啶硫醚的集成制备方法的进一步改进:所述步骤1)中,每1mol的2-卤代吡啶配用300~500g的水。
作为本发明的2-巯基吡啶和2,2’-吡啶硫醚的集成制备方法的进一步改进:所述步骤1)中,在水中加入硫磺、硫化钠和复合催化剂,于90±5℃的加热条件下均匀搅拌1~2小时。
作为本发明的2-巯基吡啶和2,2’-吡啶硫醚的集成制备方法的进一步改进:
所述步骤1):在430±50ml水中加入35g硫磺、110g硫化钠和复合催化剂,所述复合催化剂由8g醋酸铯和8g EDTA组成,于加热条件下均匀搅拌至硫磺、硫化钠和复合催化剂均溶解;再加入158g的2-溴吡啶于回流温度下反应30小时;
所述步骤2)所用的萃取剂为乙醚。
本发明的集成制备2-巯基吡啶和2,2’-吡啶硫醚的方法,在水溶剂中加入硫磺、硫化钠,复合催化剂,加热搅拌后,加入2-卤代吡啶,再回流反应,化学反应式如下:
反应结束后,反应液经先冷却、萃取。萃取液经过滤、洗涤、浓缩、冷却结晶、干燥,
得到2,2’-吡啶硫醚;萃余液经中和、过滤、冷却结晶、干燥,得到2-巯基吡啶。
本发明具有以下技术优势:
1、本发明使用廉价的原料2-卤代吡啶为主原料,并使用便宜易得的复合催化剂,因此能降低成本;
2、使用硫磺、硫化钠、复合催化剂和卤代吡啶反应,同时得到两种主产品,减少了副产的生成;
3、使用便宜易得的相转移催化剂做助剂,少量醋酸铯为主催化剂;没有过渡金属的参与,可减少产品中重金属的残留;
4、用水做溶剂合成反应,避免使用有机溶剂可能发生的安全隐患。
综上,本发明的技术属于2-巯基吡啶和2,2’-吡啶硫醚的集成制备方法,具有生产工艺过程较简单,产物总收率较高,生产成本较低等特点。
具体实施方式
下面结合具体实施例对本发明进行进一步描述,但本发明的保护范围并不仅限于此:
实施例1:集成制备2-巯基吡啶和2,2’-吡啶硫醚,依次进行以下步骤:
1)、在1000毫升的三口烧瓶中,加入300毫升的水(作为溶剂)、85克硫化钠、35克硫磺、醋酸铯4克(0.021mol)和EDTA 4克,在90℃下搅拌混合2小时后,加入114克(约1mol)2-氯吡啶,回流反应24小时。
2)、所得的反应液冷却到室温,用300毫升乙酸乙酯均分三次萃取反应液,分别得位于上层的有机相和位于下层的水相,有机相合并作为萃取液;水相作为萃余反应液;
萃取液经过滤(过d 15cm的常规圆形滤纸),并用30毫升10%氢氧化钠溶液洗涤,分别得洗涤后有机相和洗涤液,洗涤后有机相减压脱去2/3体积的萃取剂,再静止降温到0-5℃结晶,过滤出晶体,干燥(80℃干燥3小时),得到2,2’-吡啶硫醚26.4克;
萃余反应液和上述洗涤液(氢氧化钠洗涤有机相所得的水相)合并搅拌,再用30%的盐酸溶液中和到pH约为2,再进行过滤,滤液在0-5℃下结晶、过滤出晶体,干燥(100℃干燥2小时),得到2-巯基吡啶60.5克。
实施例2~12的操作过程类同于实施例1,即,改变实施例1步骤1)的工艺参数及步骤2)所用萃取剂,具体如下表1所示,其余等同于实施例1。所得结果如表1所示。
表1、制备2-巯基吡啶和2,2’-吡啶硫醚的实施例
对比例1-1、取消EDTA的使用,即,EDTA的用量为0,其余等同于实施例12。
对比例1-2、将EDTA的用量由8g改成4g,其余等同于实施例12。
对比例1-3、将EDTA的用量由8g改成12g,其余等同于实施例12。
对比例2-1、将醋酸铯改成碳酸铯、氯化铯,摩尔用量保持不变;其余等同于实施例12。
对比例2-2、将醋酸铯改成醋酸钠、醋酸钾,摩尔用量保持不变;其余等同于实施例12。
上述对比例所得结果如下表2所示。
表2
对比例3、将“1.410mol(110克)硫化钠+1.094mol(35克)硫磺”,改成全部使用2.5mol的硫化钠或者改成全部使用2.5mol的硫磺,其余等同于实施例12。这均会导致:无法同时获得2-巯基吡啶和2,2’-吡啶硫醚这2种产物,且还导致产物收率的大大下降,仅仅约为本发明实施例12产物收率的50~60%。
最后,应指出,以上列举的仅是本发明的若干个具体实施例。显然,本发明不限于以上实施例,还可以有许多变形。本领域的普通技术人员能从本发明公开的内容直接导出或联想到的所有变形,均应认为是本发明的保护范围。
Claims (5)
1.2-巯基吡啶和2,2’-吡啶硫醚的集成制备方法,其特征是包括如下步骤:
1)、在作为溶剂的水中加入硫磺、硫化钠和复合催化剂,于加热条件下均匀搅拌至硫磺、硫化钠和复合催化剂均溶解;再加入2-卤代吡啶于回流温度下反应20~30小时;
所述复合催化剂是由醋酸铯中添加等重量的助催化剂制备而成,所述助催化剂为以下任一:四丁基溴化铵、乙二胺四乙酸、L-脯氨酸;
2-卤代吡啶:醋酸铯=1:0.02~0.05的摩尔比;
每1mol的2-卤代吡啶配用80~120g的硫化钠以及20~50g的硫磺;
2)、反应结束后,反应液冷却到室温后进行萃取,分别得萃取液和萃余反应液;
萃取液、萃余反应液各自经过后处理,分别对应得到2,2’-吡啶硫醚、2-巯基吡啶;
萃取所用的萃取剂为乙酸乙酯、乙醚或二氯甲烷;
萃取液的后处理为:将萃取液经过滤、洗涤、浓缩、冷却结晶、干燥,得到2,2’-吡啶硫醚;
萃余反应液的后处理为:将萃余反应液经中和、过滤、冷却结晶、干燥,得到2-巯基吡啶;
萃取液经洗涤所得的洗涤液与萃余反应液合并后一起进行后处理。
2.根据权利要求1所述的2-巯基吡啶和2,2’-吡啶硫醚的集成制备方法,其特征是:所述2-卤代吡啶为2-氯吡啶、2-溴吡啶。
3.根据权利要求2所述的2-巯基吡啶和2,2’-吡啶硫醚的集成制备方法,其特征是:
所述步骤1)中,每1mol的2-卤代吡啶配用300~500g的水。
4.根据权利要求2所述的2-巯基吡啶和2,2’-吡啶硫醚的集成制备方法,其特征是:
所述步骤1)中,在水中加入硫磺、硫化钠和复合催化剂,于90±5℃的加热条件下均匀搅拌1~2小时。
5.根据权利要求1~4任一所述的2-巯基吡啶和2,2’-吡啶硫醚的集成制备方法,其特征是:
所述步骤1):在430±50ml水中加入35g硫磺、110g硫化钠和复合催化剂,所述复合催化剂由8 g醋酸铯和8 g EDTA组成,于加热条件下均匀搅拌至硫磺、硫化钠和复合催化剂均溶解;再加入158 g的2-溴吡啶于回流温度下反应30小时;
所述步骤2)所用的萃取剂为乙醚。
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