CN1138043A - 在硫存在下由烷基硫醇与三氯化磷反应制备二硫代磷酸酯酰二氯的方法 - Google Patents
在硫存在下由烷基硫醇与三氯化磷反应制备二硫代磷酸酯酰二氯的方法 Download PDFInfo
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- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
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- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
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Abstract
本发明公开了一种制备二硫代磷酸酯酰二氯的方法,它包括在胺催化剂存在下使硫醇与三氯化磷和硫反应。
Description
本发明涉及改进的制备二硫代磷酸酯酰二氯的方法,二硫代磷酸酯酰二氯可用作合成杀虫活性化合物的中间体。
先有技术中公开了通过将相应的磷酸烷基酯酰二氯与硫化磷(V)加热到140-150℃制备二硫代磷酸酯酰二氯的方法(参见:Houben-Weyl:“Die Methoden Der Organischen Chemie”(The Methodsof Organic Chemitry),Volume 12/2,Page 682[1964],George ThiemeVerlag Stuttgart)。或者,可以使O-烷基酯酰二氯直接与硫化磷(V)反应,得到二硫代磷酸烷基酯酰二氯。
在工业上进行这些方法时,人们发现存在着分离和除去五氧化二磷副产物的问题。分离所产生的二硫代磷酸烷基酯酰二氯后,剩下了固态五氧化二磷和含硫的、恶臭的化合物,通过在碱性介质中氧化将它们除去而留下无味的产物只是部分可行的,并且需要长时间和高成本。
另一种制备二硫代磷酸酯酰二氯的方法包括使元素硫与硫代磷酸酯酰二氯反应,后者由硫醇与三氯化磷反应得到。硫与硫代磷酸酯酰二氯的反应只在100℃以上温度下发生。硫代磷酸酯酰二氯的硫化伴随着显著的歧化成二硫代磷酸二酯酰氯和三氯化磷的反应。为了抑制歧化反应,硫化反应必须在高压下进行(参见Houben-Weyl,loc.cit.)。
美国专利3,879,500和Russian专利187,785公开了一种似乎简单的制备二硫代磷酸酯酰二氯的方法。该方法包括使相应的硫醇化合物与硫代磷酰氯反应。然而,如果在该反应中使用太大量的硫醇化合物,那么作为反应产物几乎排外地是三硫代磷酸二酯酰氯和四硫代磷酸酯,即使在酸结合剂存在下也是如此(也参见:Houben-Weyl,loc.cit.)。
美国专利4,082,822公开了一种在催化剂存在下通过硫醇化合物与硫代磷酰卤反应制备二硫代磷酸酯酰二氯的方法。截然不同地,所述催化剂选自金属、无水金属卤化物、路易斯酸、N-烷基化的内酰胺或在大约0-170℃温度下的N,N-二取代的羧酸酰胺或磷酸酰胺。
本发明提供了有利于环境的和高产率的制备二硫代磷酸酯酰二氯的方法。
现在,本发明提供了高效的制备下述通式的二硫代磷酸酯酰二氯的方法,式中R代表最多8个碳原子的直链或支链烷基(它可任选地被烷氧基或烷硫基取代)、5或6元的环脂基、具有6-8个碳原子的芳烷基,所述方法包括使下述物质反应:(i)式R-SH的硫醇,其中R具有上述意义;(ii)式PCl3的三氯化磷;及(iii)硫;其中反应在叔胺催化剂存在下进行。
与已知的制备二硫代磷酸酯酰二氯的方法相比,本发明方法有许多优点。它需要的起始原料易得,该原料可以按易于调节的一釜法反应,得到高产率的所期望的产物。该方法可以用来制备具有各种可能的取代基的二硫代磷酸酯酰二氯。按照本发明方法得到的二硫代磷酸酯酰二氯可以通过简单的操作诸如蒸镏或结晶从反应混合物中离。有利的是,本发明方法不污环境。副产物氯化氢易于除去,催化剂可以反复循环。因此,催化剂用后不必要从反应容器中弃去。
所述硫醇是一种选自下列硫醇的烷基硫醇:甲硫醇、乙硫醇、正丙硫醇、异丙硫醇、正丁硫醇、仲丁硫醇、叔丁硫醇和异丁硫醇。较优选地,所述硫醇是丙硫醇。
进行本发明的方法时,各反应物以生产二硫代磷酸酯酰二氯的有效比率使用。就每摩尔硫醇而言,可以使用1.0-1.5、优选1.0-1.1摩尔的三氯化磷。就每摩尔PCl3而言,可以使用1.0摩尔的硫(M=32)。
本发明所用的催化剂是叔胺类碱催化剂,它们可选自吡啶类如5-乙基-2-甲基吡啶、2-甲基吡啶、2,4-二甲基吡啶、2,6-二甲基吡啶或2,4,6-三甲基吡啶;三烷基胺类如三正丙基胺和三正丁基胺。作为催化剂,优选的是5-乙基-2-甲基吡啶和三正丁基胺。就每摩尔硫醇而言,可以以0.005-0.05摩尔的量使用催化剂。
当进行本发明的方法时不必要使用溶剂或稀释剂,但可以使用卤代烃类如单氯代苯或二氯代苯。
反应完成并蒸掉过量的硫代磷酰卤和二硫代磷酸酯酰二氯后,再使含有催化剂的蒸馏残渣与三氯化磷、硫和硫醇反应,而不用加入大量的新鲜催化剂。因此,制备二硫代磷酸酯酰二氯(它们通过蒸馏纯化)的方法可以通过循环含催化剂的残渣进行。通常,二硫代磷酸酯酰二氯是液体,可以通过减压蒸馏分离。
如可以从前述看出的,本发明的方法可以由下述优点而特征化:使用工业上易得的起始原料三氯化磷、硫和硫醇;使用叔胺催化剂,对反应混合物蒸馏后它产生液体残渣。按照本发明,二硫代磷酸酯酰二氯可以在环境有利的和成本有效(适中)的条件下以高产率制备。在本发明的实践中,所述的二硫代磷酸酯酰二氯可用作合成杀虫硫代磷酸酯的中间体。
本发明进一步通过下述实施例来说明,但并不是企图用这些实施例限制本发明。实施例中所有份数和百分率都是按重量计,除非另有说明。
实施例1
通过正丙硫醇与PCl3和硫反应合成二硫代磷酸正丙酯酰二氯。
用5-乙基-2-甲基吡啶催化
进料:
PCl3 137.0g(1.0mol)
硫 32.06(1.0mol)
5-乙基-2-甲基吡啶 1g
正丙硫醇 76.16g(1.0mol)
步骤:
向装配有高架搅拌器、温度计、加液漏斗、盐水冷却的冷凝器(-5℃)、NaOH涤气系统和氮气入口的1000ml四颈圆底烧瓶中装入137.0g(1.0mol)PCl3和32.06g硫。充分搅拌得到的混合物。然后向混合物中加入1.0g 5-乙基-2-甲基吡啶催化剂,将混合物的温度逐渐升到55°-60℃,在1小时内用轻轻的氮气流向反应混合物中加入76.16g(1.0mol)正丙硫醇。PCl3与正丙硫醇的最终摩尔比是1.52;另外的PCl3由上批循环的“残渣”提供。(所述残渣可在90-110℃温度下在催化剂存在下由PCl3、S和硫醇反应制备)。将反应温度逐渐升至145℃,并在该温度下蒸煮反应混合物4小时。
对反应混合物进行真空蒸镏(10mmHg),在25°-79℃温度范围内收集头馏分(大部分是PSCl3)。在95°-110℃温度范围内收集主馏分,分析结果含90%酯酰二氯。将含(PrS)2P(=S)Cl和(PrS)3P=S作为主要组分的残渣残余物留下用于下一批反应。通过在10mm Hg下真空蒸馏进一步精制粗产物。收集PSCl3和二丙基二硫化物(DPDS)作为头馏分。作为主要馏分收集酯酰二氯,同时将较高沸点的组分馏在“残渣”中,合并所有的头馏分和“残渣”残余物用于循环到下一批反应中。
蒸馏过的产物分析结果含96.5%活性成分(气/液色谱分析),含0.5% PSCl3、0.3%二丙基二硫化物和0.7%(PrS)2P(=S)Cl作为主要杂质。
在随后的各批中不另加5-乙基-2-甲基吡啶重复上述方法30批。整个30批中,蒸馏过的产物的产率基于丙硫醇进料高达96.0%。
实施例2-5
在下述实施例中,基本上使用实施例1中所述的同样的方法步骤和评估。结果列在以下各表中。
* 每摩尔n-PrSH用1g叔胺作为催化剂。** 数次循环后蒸馏残留物(残渣)在室温下为液体
虽然为了具体说明目的在上面已详述了本发明,但是应该理解,这样详述只是为了说明的目的,而本领域技术人员在不离开本发明的精神和范围的情况下可以进行各种变化,除非它可以被所述权利要求限定。
Claims (9)
2.根据权利要求1的方法,其中所述的碱催化剂是叔胺。
3.根据要求要求2的方法,其中所述胺选自5-乙基-2-甲基吡啶、2-甲基吡啶、2,4-二甲基吡啶、2,6-二甲基吡啶、2,4,6-三甲基吡啶、三正丙基胺和三正丁基胺。
4.根据权利要求3的方法,其中所述胺是5-乙基-2-甲基吡啶。
5.根据权利要求3的方法,其中所述胺是三正丁基胺。
6.根据权利要求1的方法,其中所述硫醇是选自下列硫醇的烷基硫醇:甲硫醇、乙硫醇、正丙硫醇、异丙硫醇、正丁硫醇、仲丁硫醇、叔丁硫醇和异丁硫醇。
7.根据权利要求6的方法,其中所述硫醇是正丙硫醇。
8.根据权利要求1的方法,它还包括蒸馏二硫代磷酸酯酰二氯和副产物硫代磷酰氯提供含有催化剂的液态蒸馏残渣。
9.根据权利要求8的方法,还包括使所述的蒸馏残渣与硫醇、硫代磷酰氯和三氯化磷反应,而基本上不加入新鲜催化剂。
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US442621 | 1982-11-17 | ||
US442,621 | 1982-11-17 | ||
US08/442,621 US5523449A (en) | 1995-05-17 | 1995-05-17 | Process for preparing phosphorodichlorido-dithioates by reacting alkylmercaptans with phosphorus trichloride in the presence of sulfur |
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CN1138043A true CN1138043A (zh) | 1996-12-18 |
CN1064689C CN1064689C (zh) | 2001-04-18 |
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US (1) | US5523449A (zh) |
JP (1) | JP3726248B2 (zh) |
KR (1) | KR960041156A (zh) |
CN (1) | CN1064689C (zh) |
CA (1) | CA2172573A1 (zh) |
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CA2797133C (en) | 2010-04-27 | 2019-08-06 | Zealand Pharma A/S | Peptide conjugates of glp-1 receptor agonists and gastrin and their use |
TW201326194A (zh) | 2011-11-03 | 2013-07-01 | Zealand Pharma As | Glp-1胃泌素受體促效劑肽結合物 |
MY170671A (en) | 2012-07-23 | 2019-08-26 | Zealand Pharma As | Glucagon analogues |
TWI608013B (zh) | 2012-09-17 | 2017-12-11 | 西蘭製藥公司 | 升糖素類似物 |
US9988429B2 (en) | 2013-10-17 | 2018-06-05 | Zealand Pharma A/S | Glucagon analogues |
HUE039616T2 (hu) | 2013-10-17 | 2019-01-28 | Zealand Pharma As | Acilezett glükagon analógok |
JP2017503474A (ja) | 2013-11-06 | 2017-02-02 | ジーランド ファーマ アクティーゼルスカブ | グルカゴン−glp−1−gipトリプルアゴニスト化合物 |
US10093713B2 (en) | 2013-11-06 | 2018-10-09 | Zealand Pharma A/S | GIP-GLP-1 dual agonist compounds and methods |
BR112017008659A2 (pt) | 2014-10-29 | 2018-01-30 | Zealand Pharma As | ?métodos e compostos de agonista de gip? |
US10336802B2 (en) | 2015-04-16 | 2019-07-02 | Zealand Pharma A/S | Acylated glucagon analogue |
JP6563614B1 (ja) | 2016-12-09 | 2019-08-21 | ジーランド・ファーマ・ア/エス | アシル化glp−1/glp−2二重アゴニスト |
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US3879500A (en) * | 1973-10-15 | 1975-04-22 | Stauffer Chemical Co | Process for Preparing mono- and di-alkylmercaptophosphorothionochloridates |
DE2532396C3 (de) * | 1975-07-19 | 1978-09-14 | Bayer Ag, 5090 Leverkusen | Verfahren zur Herstellung von Dithiophosphorsäureesterdichloriden |
US4035449A (en) * | 1975-10-23 | 1977-07-12 | Mobay Chemical Corporation | Process for the production of S-alkyl phosphoro dihalogenidodithioate |
US4197209A (en) * | 1977-03-10 | 1980-04-08 | Ciba-Geigy Corporation | Lubricant compositions containing sulfur-containing esters of phosphoric acid |
US4120917A (en) * | 1977-03-28 | 1978-10-17 | Mobil Oil Corporation | Process for preparing tertiary alkylphosphorodichloridites |
US5081272A (en) * | 1990-08-20 | 1992-01-14 | Imperial Chemical Industries Plc | Process for preparation of phosphorodichlorothioates |
-
1995
- 1995-05-17 US US08/442,621 patent/US5523449A/en not_active Expired - Lifetime
-
1996
- 1996-03-25 CA CA002172573A patent/CA2172573A1/en not_active Abandoned
- 1996-05-10 JP JP13975696A patent/JP3726248B2/ja not_active Expired - Fee Related
- 1996-05-13 KR KR1019960015765A patent/KR960041156A/ko not_active Application Discontinuation
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JPH08311088A (ja) | 1996-11-26 |
CN1064689C (zh) | 2001-04-18 |
JP3726248B2 (ja) | 2005-12-14 |
US5523449A (en) | 1996-06-04 |
CA2172573A1 (en) | 1996-11-18 |
KR960041156A (ko) | 1996-12-19 |
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