CN1138044A - 由烷基硫醇与三氯化磷、硫代磷酰氯和硫反应制备二硫代磷酸酯酰二氯的方法 - Google Patents
由烷基硫醇与三氯化磷、硫代磷酰氯和硫反应制备二硫代磷酸酯酰二氯的方法 Download PDFInfo
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- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
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- 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
- C07C303/24—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of esters of sulfuric acids
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- C—CHEMISTRY; METALLURGY
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- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- 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,它包括在碱催化剂存在下使硫醇、三氯化磷、硫代磷酰氯和硫反应。
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)三氯化磷(PCl3);(iii)硫代磷酰氯(PSCl3);及(vi)硫;其中反应在碱性催化剂存在下进行。
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,各反应物按本发明以生产二硫代磷酸酯酰二氯的有效比率使用。就每摩尔硫代磷酰氯而言,可以使用0.5-1.0、优选0.5-0.75摩尔的三氯化磷。就每摩尔硫醇而言,可以使用0.75-1.5、优选0.9-1.0摩尔的硫代磷酰氯。本发明的区别特征是可以用含三氯化磷的硫代磷酰氯粗品作为所要求保护的本发明的反应物(ii)和(iii)的来源。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化合物,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0.005-0.1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。
在下述说明性而非限制性的本发明的具体实施方案中,所述方法包括在硫存在下使正丙硫醇与粗制的含三氯化磷的硫代磷酰氯反应。该反应在大约50℃至80℃、优选55℃至60℃的初始温度下进行。
反应完成并蒸掉过量的硫代磷酰氯和二硫代磷酸酯酰二氯后,再使含有催化剂的蒸馏残渣与硫代磷酰氯和硫醇反应,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使用叔胺催化剂的优点而特征化,对反应混合物蒸馏之后,它产生液体残渣,可通过本发明方法制备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。该新的制备二硫代磷酸酯酰二氯的方法允许使用粗制的、通常含0.5摩尔当量至1摩尔当量的PCl3的PSCl3,而不影响二硫代磷酸酯酰二氯的纯度和产率。
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PSCl3、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 68.5g(0.5mol)
硫 16.0(0.5mol)
PSCl3 169.4(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169.4g PSCl3、68.5g PCl3和16g硫。充分搅拌得到的混合物。向充分搅拌过的混合物中加入来自前面产生的各批的酯酰二氯的“残渣”的混合物(100g)。(所述残渣通过PCl3、硫和硫醇在90°-110℃反应制备)。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。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(大约100g)用于循环到下一批反应中。
蒸馏过的产物分析结果含97.4%活性成分(气相色谱分析),含0.4% PSCl3、0.2%二丙基二硫化物和0.5%(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20批。整个20批中,蒸馏过的产物的产率基于丙硫醇进料高达97.0%。
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。
2,6-二甲基吡啶 | 1 | 47.3 | 0.4 | 83.6 | A.I.97.2% |
2 | 56.8 | 0.3 | 93.9 | ||
3 | 62.3 | 0.3 | 97.1 | ||
4 | 63.0 | 0.3 | 97.1 | ||
三丁胺 | 1 | 48.5 | 0.2 | 86.2 | A.I.97.4% |
2 | 57.1 | 0.3 | 94.3 | ||
3 | 62.8 | 0.3 | 96.2 | ||
4 | 63.5 | 0.3 | 97.5 | ||
N,N-二甲基苄胺 | 1 | 47.8 | 0.3 | 85.4 | A.I.97.2 |
2 | 56.3 | 0.2 | 93.9 | ||
3 | 61.8 | 0.3 | 95.8 | ||
4 | 62.9 | 0.3 | 96.5 |
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 (10)
2.根据权利要求1的方法,其中三氯化磷和硫代磷酰氯存在在粗制的硫代磷酰氯中。
3.根据权利要求1的方法,其中所述的碱性催化剂是叔胺。
4.根据要求要求3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。
5.根据权利要求4的方法,其中所述胺是5-乙基-2-甲基吡啶。
6.根据权利要求4的方法,其中所述胺是三正丁基胺。
7.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。
8.根据权利要求7的方法,其中所述硫醇是正丙硫醇。
9.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液态蒸馏残渣,它含有催化剂。
10.根据权利要求9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以及硫反应,而基本上不加入新鲜催化剂。
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Application Number | Priority Date | Filing Date | Title |
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US442623 | 1982-11-18 | ||
US08/442,623 US5543543A (en) | 1995-05-17 | 1995-05-17 | Process for preparing phosphorodichloridodithioates by reacting alkyl mercaptans with PCI3 PSCI3 and sulfur |
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CN1138044A true CN1138044A (zh) | 1996-12-18 |
CN1065247C CN1065247C (zh) | 2001-05-02 |
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CN96105676A Expired - Fee Related CN1065247C (zh) | 1995-05-17 | 1996-05-17 | 一种制备二硫代磷酸酯酰二氯的方法 |
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Country | Link |
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US (1) | US5543543A (zh) |
JP (1) | JPH08311087A (zh) |
KR (1) | KR960041155A (zh) |
CN (1) | CN1065247C (zh) |
CA (1) | CA2172572A1 (zh) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101486729B (zh) * | 2008-12-12 | 2012-09-12 | 荆州市沙市东方有机化工研究所 | 一种o,o-二烷基硫代磷酰氯的生产方法 |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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 US08/442,623 patent/US5543543A/en not_active Expired - Lifetime
-
1996
- 1996-03-25 CA CA002172572A patent/CA2172572A1/en not_active Abandoned
- 1996-05-10 JP JP8139753A patent/JPH08311087A/ja active Pending
- 1996-05-13 KR KR1019960015764A patent/KR960041155A/ko not_active Application Discontinuation
- 1996-05-17 CN CN96105676A patent/CN1065247C/zh not_active Expired - Fee Related
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
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CN101486729B (zh) * | 2008-12-12 | 2012-09-12 | 荆州市沙市东方有机化工研究所 | 一种o,o-二烷基硫代磷酰氯的生产方法 |
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Publication number | Publication date |
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CA2172572A1 (en) | 1996-11-18 |
JPH08311087A (ja) | 1996-11-26 |
CN1065247C (zh) | 2001-05-02 |
US5543543A (en) | 1996-08-06 |
KR960041155A (ko) | 1996-12-19 |
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