CN106905368B - 氨基酸促进的10-芳硫基-9-氧杂-10-膦杂菲-10-氧化物的制备方法 - Google Patents

氨基酸促进的10-芳硫基-9-氧杂-10-膦杂菲-10-氧化物的制备方法 Download PDF

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CN106905368B
CN106905368B CN201710075386.6A CN201710075386A CN106905368B CN 106905368 B CN106905368 B CN 106905368B CN 201710075386 A CN201710075386 A CN 201710075386A CN 106905368 B CN106905368 B CN 106905368B
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oxide
oxa
phosphine
sulfonyl chloride
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CN106905368A (zh
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张兴华
王敦盖
潘安健
宋翔
王紫豪
张高奇
李亮
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Shanghai Institute of Technology
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
    • C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
    • C07F9/6574—Esters of oxyacids of phosphorus
    • C07F9/65744—Esters of oxyacids of phosphorus condensed with carbocyclic or heterocyclic rings or ring systems
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
    • B01J31/2208—Oxygen, e.g. acetylacetonates
    • B01J31/2217—At least one oxygen and one nitrogen atom present as complexing atoms in an at least bidentate or bridging ligand
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
    • B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
    • B01J31/30—Halides

Abstract

本发明公开了一种氨基酸促进的10‑芳硫基‑9‑氧杂‑10‑膦杂菲‑10‑氧化物的制备方法。该方法使用绿色无毒的氨基酸作为反应促进剂，在温和条件下，芳基磺酰氯与9,10‑二氢‑9‑氧杂‑10‑磷杂菲‑10‑氧化物在催化剂作用下发生偶联反应制备得到相应的10‑芳硫基‑9‑氧杂‑10‑膦杂菲‑10‑氧化物。和现有技术相比，本发明的方法简单易行，具有时间短、产率高等特点。合成产物在阻燃材料方面有较多应用。

Description

氨基酸促进的10-芳硫基-9-氧杂-10-膦杂菲-10-氧化物的制 备方法
技术领域
本发明属于有机合成技术领域，涉及一种氨基酸促进的10-芳硫基-9-氧杂-10-膦杂菲-10-氧化物的制备方法。
背景技术
众所周知，含有P-S-C键的化合物具有优异的性能，尤其在阻燃材料领域，磷系和硫系阻燃剂一直是研究热点。但目前制备含硫有机磷化合物的方法多需要强碱等苛刻条件，因此，采用温和高效的制备方法制备含有P-S-C键的化合物就显得尤为重要。
发明内容
本发明的目的在于提供一种操作简单，绿色的方法高效制备10-芳硫基-9-氧杂-10-膦杂菲-10-氧化物。
为实现上述之目的，本发明采用如下技术方案。
本发明提供一种氨基酸促进的10-芳硫基-9-氧杂-10-膦杂菲-10-氧化物的制备方法，具体步骤如下：将芳基磺酰氯和9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物置于有机溶剂中，加入催化剂和配体，在0～80℃的温度下反应1～12h，反应结束后浓缩、分离纯化即得相应的10-芳硫基-9-氧杂-10-膦杂菲-10-氧化物；其中：所述配体为氨基酸。
本发明中，所述芳基磺酰氯为未取代、单取代或多取代的苯基磺酰氯；取代时，取代基为烷基、烷氧基或卤素中的任意一种或多种。
本发明中，烷基和烷氧基的C原子个数均在1～20之间。
本发明中，芳基磺酰氯和9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物的摩尔比是1:3-1:5。
本发明中，有机溶剂选自四氢呋喃；有机溶剂的用量如下：每摩尔芳基磺酰氯用1-6L有机溶剂。
本发明中，所用催化剂为二水合氯化铜；所用配体为L-脯氨酸。
本发明中，催化剂用量为芳基磺酰氯的物质的量(摩尔数)的5-10％；配体用量为芳基磺酰氯的物质的量(摩尔数)的10-20％。
本发明中，反应温度为50～80℃，反应温度为1～3h。
本发明中，分离纯化时，将浓缩后的反应物以乙酸乙酯/石油醚＝2/1-1/10(V/V)为展开剂，进行柱层析分离。
本发明涉及的反应通式如下：
其中，R为未取代、单取代或者多取代的苯基，所述取代基为烷氧基、烷基或卤素中的任意一种或多种。
本发明的氨基酸促进的10-芳硫基-9-氧杂-10-膦杂菲-10-氧化物的制备方法，采用价廉易得的芳基磺酰氯和9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物为原料，采用廉价的金属铜盐为催化剂，反应中加入适量氨基酸，无需加碱，无需氮气保护；本发明的制备方法工艺简单，操作方便，底物范围广，具有较优秀的产率，适合推广应用。
具体实施方式
为了使本领域技术人员更好地理解本发明，以下通过实施例对本发明做进一步说明，但这些实施例并不限制本发明的范围。
实施例1
10-(2,4,6-甲基苯基硫基)-9-氧杂-10-膦杂菲-10-氧化物的制备方法，包括下列步骤：
称取2.0mmol的9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物与0.5mmol2,4,6-三甲基苯磺酰氯于反应瓶中，加入0.025mmol二水合氯化铜和0.05mmol的L-脯氨酸，加入1.0mL四氢呋喃，80℃下反应3h。反应液减压浓缩，以乙酸乙酯/石油醚＝1:5(v/v)为展开剂柱层析分离，得163mg目标化合物。
本实施例的目标产品收率为89﹪。
对目标产品进行核磁表征，如下：1H NMR(500MHz,CDCl3):δ7.84-7.80(m,2H),7.73-7.71(m,1H),7.67-7.64(m,1H),7.46-7.42(m,1H),7.30-7.26(m,1H),7.16-7.11(m,2H),6.64(s,2H),2.14(s,6H),2.11(s,3H)。

Claims (7)

1.一种氨基酸促进的10-芳硫基-9-氧杂-10-膦杂菲-10-氧化物的制备方法，其特征在于：将芳基磺酰氯和9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物置于有机溶剂中，加入催化剂和配体，在0～80℃的温度下反应1～12h，反应结束后浓缩、分离纯化即得相应的10-芳硫基-9-氧杂-10-膦杂菲-10-氧化物；其中：所用催化剂为二水合氯化铜；所用配体为L-脯氨酸。
2.根据权利要求1所述的制备方法，所述芳基磺酰氯为未取代、单取代或多取代的苯基磺酰氯；取代时，取代基为烷基、烷氧基或卤素中的任意一种或多种。
3.根据权利要求2所述的制备方法，其特征在于，烷基和烷氧基的C原子个数均在1～20之间。
4.根据权利要求1所述的制备方法，其特征在于：芳基磺酰氯和9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物的摩尔比是1:3-1:5。
5.根据权利要求1所述的制备方法，其特征在于：有机溶剂选自四氢呋喃；有机溶剂的用量如下：每摩尔芳基磺酰氯用1-6L有机溶剂。
6.根据权利要求1所述的制备方法，其特征在于：催化剂用量为芳基磺酰氯的物质的量的5-10％；配体用量为芳基磺酰氯的物质的量的10-20％。
7.根据权利要求1所述的制备方法，其特征在于，反应温度为50～80℃，反应温度为1～3h。
CN201710075386.6A 2017-02-13 2017-02-13 氨基酸促进的10-芳硫基-9-氧杂-10-膦杂菲-10-氧化物的制备方法 Expired - Fee Related CN106905368B (zh)

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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104292255A (zh) * 2014-01-06 2015-01-21 郑州大学 一种s-芳基硫代磷酸酯的制备方法

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104292255A (zh) * 2014-01-06 2015-01-21 郑州大学 一种s-芳基硫代磷酸酯的制备方法

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
Direct synthesis of thiophosphates by reaction of diphenylphosphine oxide with sulfonyl chlorides;He, Wei et al;《Tetrahedron》;20161011;第72卷;第7594-7598页
Metal and base-free reductive coupling reaction of P(O)–H with aryl/alkyl sulfonyl chlorides: a novel protocol for the construction of P–S–Cbonds;Dungai Wang et al;《Org. Biomol. Chem.》;20161129;第15卷;第545-549页
铜催化芳基磺酰氯与亚磷酸酯还原偶联反应合成S_芳基硫代磷酸酯;白洁;《中国优秀硕士学位论文全文数据库》;20150215(第2期);第1-2章

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