CN112010897B - 一种铜催化二芳基磷氧与硫醇氧化脱氢偶联制备硫代膦酸酯的新方法 - Google Patents
一种铜催化二芳基磷氧与硫醇氧化脱氢偶联制备硫代膦酸酯的新方法 Download PDFInfo
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- -1 diaryl phosphorus oxide Chemical compound 0.000 title claims abstract description 39
- 238000000034 method Methods 0.000 title claims abstract description 23
- 229910001392 phosphorus oxide Inorganic materials 0.000 title claims abstract description 11
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 title claims description 8
- 238000005839 oxidative dehydrogenation reaction Methods 0.000 title claims description 5
- 238000005859 coupling reaction Methods 0.000 title claims description 4
- 230000008878 coupling Effects 0.000 title description 2
- 238000010168 coupling process Methods 0.000 title description 2
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000003054 catalyst Substances 0.000 claims abstract description 14
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910021595 Copper(I) iodide Inorganic materials 0.000 claims abstract description 10
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 claims abstract description 10
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000003446 ligand Substances 0.000 claims abstract description 8
- 239000003513 alkali Substances 0.000 claims abstract description 6
- 125000000524 functional group Chemical group 0.000 claims abstract description 6
- 239000003960 organic solvent Substances 0.000 claims abstract description 5
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical group CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 27
- 150000001875 compounds Chemical class 0.000 claims description 11
- WQAQPCDUOCURKW-UHFFFAOYSA-N butanethiol Chemical compound CCCCS WQAQPCDUOCURKW-UHFFFAOYSA-N 0.000 claims description 7
- YFPJFKYCVYXDJK-UHFFFAOYSA-N Diphenylphosphine oxide Chemical compound C=1C=CC=CC=1[P+](=O)C1=CC=CC=C1 YFPJFKYCVYXDJK-UHFFFAOYSA-N 0.000 claims description 6
- BDFAOUQQXJIZDG-UHFFFAOYSA-N 2-methylpropane-1-thiol Chemical compound CC(C)CS BDFAOUQQXJIZDG-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- PMBXCGGQNSVESQ-UHFFFAOYSA-N 1-Hexanethiol Chemical compound CCCCCCS PMBXCGGQNSVESQ-UHFFFAOYSA-N 0.000 claims description 3
- JNNKFUNOEOWVSD-UHFFFAOYSA-N 1-fluoro-3-(3-fluorophenyl)phosphonoylbenzene Chemical compound FC1=CC=CC(P(=O)C=2C=C(F)C=CC=2)=C1 JNNKFUNOEOWVSD-UHFFFAOYSA-N 0.000 claims description 3
- WVDYBOADDMMFIY-UHFFFAOYSA-N Cyclopentanethiol Chemical compound SC1CCCC1 WVDYBOADDMMFIY-UHFFFAOYSA-N 0.000 claims description 3
- UENWRTRMUIOCKN-UHFFFAOYSA-N benzyl thiol Chemical compound SCC1=CC=CC=C1 UENWRTRMUIOCKN-UHFFFAOYSA-N 0.000 claims description 3
- LMXRTXPFJNGAAX-UHFFFAOYSA-N bis(3,5-dimethylphenyl)-oxophosphanium Chemical compound CC1=CC(C)=CC([P+](=O)C=2C=C(C)C=C(C)C=2)=C1 LMXRTXPFJNGAAX-UHFFFAOYSA-N 0.000 claims description 3
- ZHIPXAFNKGZMSC-UHFFFAOYSA-N bis(4-methylphenyl)-oxophosphanium Chemical compound C1=CC(C)=CC=C1[P+](=O)C1=CC=C(C)C=C1 ZHIPXAFNKGZMSC-UHFFFAOYSA-N 0.000 claims description 3
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethanethiol Chemical compound CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 claims description 3
- SUVIGLJNEAMWEG-UHFFFAOYSA-N propane-1-thiol Chemical compound CCCS SUVIGLJNEAMWEG-UHFFFAOYSA-N 0.000 claims description 3
- GGIQQYHOHRKDNO-UHFFFAOYSA-N 1-methyl-3-(3-methylphenyl)phosphonoylbenzene Chemical compound CC1=CC=CC(P(=O)C=2C=C(C)C=CC=2)=C1 GGIQQYHOHRKDNO-UHFFFAOYSA-N 0.000 claims description 2
- 125000001637 1-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C(*)=C([H])C([H])=C([H])C2=C1[H] 0.000 claims description 2
- 125000001622 2-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C(*)C([H])=C([H])C2=C1[H] 0.000 claims description 2
- 125000004180 3-fluorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C(F)=C1[H] 0.000 claims description 2
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 claims description 2
- KKBXIQVJXZVRHH-UHFFFAOYSA-N C1=CC=C2C(P(C=3C4=CC=CC=C4C=CC=3)=O)=CC=CC2=C1 Chemical compound C1=CC=C2C(P(C=3C4=CC=CC=C4C=CC=3)=O)=CC=CC2=C1 KKBXIQVJXZVRHH-UHFFFAOYSA-N 0.000 claims description 2
- 239000002585 base Substances 0.000 claims description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 2
- RREGWFNURZJKNB-UHFFFAOYSA-N bis(4-methoxyphenyl)-oxophosphanium Chemical compound C1=CC(OC)=CC=C1[P+](=O)C1=CC=C(OC)C=C1 RREGWFNURZJKNB-UHFFFAOYSA-N 0.000 claims description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims description 2
- UJBHOFPPZWFQKO-UHFFFAOYSA-N dinaphthalen-2-yl(oxo)phosphanium Chemical compound C1=CC=CC2=CC([P+](C=3C=C4C=CC=CC4=CC=3)=O)=CC=C21 UJBHOFPPZWFQKO-UHFFFAOYSA-N 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 2
- 125000000040 m-tolyl group Chemical group [H]C1=C([H])C(*)=C([H])C(=C1[H])C([H])([H])[H] 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
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- 230000002194 synthesizing effect Effects 0.000 abstract description 8
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- 239000007800 oxidant agent Substances 0.000 abstract description 3
- 230000001590 oxidative effect Effects 0.000 abstract description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract 1
- 229910052760 oxygen Inorganic materials 0.000 abstract 1
- 239000001301 oxygen Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 description 17
- 238000004440 column chromatography Methods 0.000 description 7
- 239000012299 nitrogen atmosphere Substances 0.000 description 7
- 229910052698 phosphorus Inorganic materials 0.000 description 6
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 6
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 6
- 239000011574 phosphorus Substances 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 238000006880 cross-coupling reaction Methods 0.000 description 3
- 239000000543 intermediate Substances 0.000 description 3
- 150000002903 organophosphorus compounds Chemical class 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
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- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- 238000003383 Atherton-Todd reaction Methods 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000007036 catalytic synthesis reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
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- 230000000536 complexating effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
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- 238000005516 engineering process Methods 0.000 description 1
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- 239000003063 flame retardant Substances 0.000 description 1
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- 230000002140 halogenating effect Effects 0.000 description 1
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- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 230000026731 phosphorylation Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000012916 structural analysis Methods 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
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- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/30—Phosphinic acids [R2P(=O)(OH)]; Thiophosphinic acids ; [R2P(=X1)(X2H) (X1, X2 are each independently O, S or Se)]
- C07F9/32—Esters thereof
- C07F9/3258—Esters thereof the ester moiety containing a substituent or a structure which is considered as characteristic
- C07F9/3264—Esters with hydroxyalkyl compounds
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- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
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Abstract
本发明提供了一种高效、高选择性合成含不同取代官能团的硫代膦酸酯类衍生物的方法,其采用碘化亚铜作为催化剂,2,2’‑联吡啶作为配体,吡啶作为碱,氧气作为氧化剂,以二芳基磷氧与硫醇类化合物作为反应底物,反应体系加入了有机溶剂。该方法的优点:催化剂与氧化剂廉价易得;底物适用性高;反应条件温和,安全可靠;所得目标产物的选择性接近100%,产率高达90%以上。该方法解决了传统合成硫代膦酸酯类衍生物的反应选择性差、反应步骤繁琐、产率低以及需要用到对环境有害试剂等不足,具有良好的工业应用前景。本发明同时还提供了对应的含不同取代官能团的硫代膦酸酯类衍生物。
Description
技术领域
本发明涉及硫代膦酸酯类化合物的应用催化合成领域,具体地说涉及一种铜催化二芳基磷氧与硫醇类化合物通过氧化脱氢偶联反应高效制备硫代膦酸酯类衍生物的制备方法。
背景技术
硫代膦酸酯类衍生物是一类重要的有机合成中间体。它们在医药中间体、光电材料、阻燃材料以及催化剂配体的制备等方面有着广泛应用。在各种不同配位的有机磷化合物中,三价及五价有机磷化合物是磷化学领域研究的重点。
四配位磷试剂在磷酰化反应过程中最终都转化成三价的有机磷化合物,由于磷原子中心存在孤电子对,上述三价磷化合物在氧化剂存在下极易被氧化为有机磷酸类化合物。在过渡金属及有机配体的存在下,该类三价磷化合物会与过渡金属及有机配体发生氧化加成反应形成中间体或过渡态,正是由于这种不同配位数化合物之间的相互转化,才使有机磷试剂在有机合成中得以广泛应用,成为有机磷化学,特别是有机合成化学的重要组成部分。
目前文献已报道的合成有机硫代膦酸酯类衍生物的方法主要包括:(1)Atherton-Todd反应:利用四氯化碳直接卤化P-H键,进而与硫醇类化合物进行交叉偶联反应;(2) 交叉偶联反应:利用贵金属催化剂(钯、银、镍)催化P-H键与硫醇类化合物的氧化脱氢交叉偶联反应;(3) 亲核取代反应:利用磷酰氯与硫醇类化合物在碱的促进下发生亲核取代反应。但是,上述方法一般都采用对空气敏感的试剂(磷酰氯、四氯化碳等),而且还存在着实验步骤繁琐、催化剂昂贵且难以回收利用、反应条件苛刻、底物适用性差、产率较低以及对环境的污染较大等缺陷。
迄今为止,有机硫代膦酸酯类衍生物的高效合成存在着原料质量、生产的安全性(四氯化碳、磷酰氯具有较强的腐蚀性)以及产品的稳定性及纯度等几个方面的难题,合成技术难度较大,目前只有美、日等国的几家公司在生产,而我国高端有机硫代膦酸酯产品目前的情况主要是依靠于进口。
针对现有的有机硫代膦酸酯合成工艺的不足,业界正着力于利用廉价催化剂高效催化研制由稳定、廉价易得的二芳基磷氧作为磷酰化试剂制备对应的有机硫代膦酸酯类化合物的新方法。
发明内容
本发明的目的是提供一种由廉价易得的二芳基磷氧与硫醇类化合物作为原料的高效、高选择性合成对应的有机硫代膦酸酯类化合物的新方法,以克服现有技术中的上述缺陷。
本发明包含下述步骤:取反应量的二芳基磷氧、硫醇、催化剂、配体、碱和有机溶剂在空气条件下置于反应容器中进行混合,于室温条件下搅拌反应12小时,即制得相应的含不同取代官能团的有机硫代膦酸酯类衍生物。具体反应式如下:
其中,
所述催化剂选自碘化亚铜,配体选自2,2’-联吡啶,碱选自吡啶,有机溶剂选自乙腈;
Ar是选自苯基、4-甲基苯基、3-甲基苯基、4-甲氧基苯基、3,5-二甲基苯基、3-氟苯基、1-萘基、2-萘基;
R是甲基、乙基、丙基、丁基、异丁基、苄基、环戊基、己基。
上述由二芳基磷氧与硫醇类化合物合成硫代膦酸酯类化合物的方法中,二芳基磷氧是选自二苯基磷氧、二(4-甲基苯基)磷氧、二(3-甲基苯基)磷氧、二(4-甲氧基苯基)磷氧、二(3,5-二甲基苯基)磷氧、二(3-氟苯基)磷氧、二(1-萘基)磷氧、二(2-萘基)磷氧。
上述由二芳基磷氧与硫醇类化合物合成硫代膦酸酯类化合物的方法中,硫醇是选自甲硫醇、乙硫醇、丙硫醇、丁硫醇、异丁硫醇、苄硫醇、环戊硫醇、正己硫醇。
上述由二芳基磷氧与硫醇类化合物合成硫代膦酸酯类化合物的方法中,所述二芳基磷氧与硫醇类化合物的摩尔比为1:[1.0~3.0];二芳基磷氧与催化剂的摩尔比为1:[0.05-0.2];二芳基磷氧与配体的摩尔比为1:[0.05-0.2];二芳基磷氧与碱的摩尔比为1:[0.2-2.0]。
本发明所提供由二芳基磷氧和硫醇类化合物高效、高选择性的合成有机硫代膦酸酯类化合物的方法,反应过程温和易控制。在获得较高产率和100%选择性的同时,该方法简单易行,而且所用催化剂廉价易得,制备简单、具有良好的工业应用前景。
【具体实施方式】
下面结合本发明的实施例对本发明做进一步说明:
一、测试与分析
本发明下述实施例中反应产物的结构分析采用Agilent公司生产的配置HP-5MS毛细管色谱柱(30m×0.45mm×0.8μm)的气相-质谱仪联用仪GC/MS (6890N/5973N)以及Bruker公司生产的Bruker Avance-III 500核磁共振分析仪。目标产物选择性和产率则采用由Bruker公司生产的Bruker Avance-III 500核磁共振分析仪进行分析 。
二、实施例
实施例1
将101 mg (0.5 mmol) 的二苯基磷氧、90 mg (1.0 mmol) 的丁硫醇、9.5 mg(0.05 mmol) 碘化亚铜、7.8 mg (0.05 mmol) 2,2’-联吡啶、79 mg (0.5 mmol) 吡啶,在氮气环境下加入Schlenk管里,在空气条件下加入1.0 mL 乙腈,于室温搅拌反应12小时。待反应结束后,经过柱层析色谱分离提纯,目标产物的产率为95%。
实施例2
将101 mg (0.5 mmol) 的二苯基磷氧、90 mg (1.0 mmol) 的异丁硫醇、9.5 mg(0.05 mmol) 碘化亚铜、7.8 mg (0.05 mmol) 2,2’-联吡啶、79 mg (0.5 mmol) 吡啶,在氮气环境下加入Schlenk管里,在空气条件下加入1.0 mL 乙腈,于室温搅拌反应12小时。待反应结束后,经过柱层析色谱分离提纯,目标产物的产率为92%。
实施例3
将101 mg (0.5 mmol) 的二苯基磷氧、124 mg (1.0 mmol) 的苄硫醇、9.5 mg(0.05 mmol) 碘化亚铜、7.8 mg (0.05 mmol) 2,2’-联吡啶、79 mg (0.5 mmol) 吡啶,在氮气环境下加入Schlenk管里,在空气条件下加入1.0 mL 乙腈,于室温搅拌反应12小时。待反应结束后,经过柱层析色谱分离提纯,目标产物的产率为86%。
实施例4
将101 mg (0.5 mmol) 的二苯基磷氧、102 mg (1.0 mmol) 的环戊硫醇、9.5 mg(0.05 mmol) 碘化亚铜、7.8 mg (0.05 mmol) 2,2’-联吡啶、79 mg (0.5 mmol) 吡啶,在氮气环境下加入Schlenk管里,在空气条件下加入1.0 mL 乙腈,于室温搅拌反应12小时。待反应结束后,经过柱层析色谱分离提纯,目标产物的产率为81%。
实施例5
将115 mg (0.5 mmol) 的二(4-甲基苯基)磷氧、90 mg (1.0 mmol) 的丁硫醇、9.5 mg (0.05 mmol) 碘化亚铜、7.8 mg (0.05 mmol) 2,2’-联吡啶、79 mg (0.5 mmol)吡啶,在氮气环境下加入Schlenk管里,在空气条件下加入1.0 mL 乙腈,于室温搅拌反应12小时。待反应结束后,经过柱层析色谱分离提纯,目标产物的产率为93%。
实施例6
将129 mg (0.5 mmol) 的二(3,5-二甲基苯基)磷氧、90 mg (1.0 mmol) 的丁硫醇、9.5 mg (0.05 mmol) 碘化亚铜、7.8 mg (0.05 mmol) 2,2’-联吡啶、79 mg (0.5mmol) 吡啶,在氮气环境下加入Schlenk管里,在空气条件下加入1.0 mL 乙腈,于室温搅拌反应12小时。待反应结束后,经过柱层析色谱分离提纯,目标产物的产率为89%。
实施例7
将119 mg (0.5 mmol) 的二(3-氟苯基)磷氧、90 mg (1.0 mmol) 的丁硫醇、9.5mg (0.05 mmol) 碘化亚铜、7.8 mg (0.05 mmol) 2,2’-联吡啶、79 mg (0.5 mmol) 吡啶,在氮气环境下加入Schlenk管里,在空气条件下加入1.0 mL 乙腈,于室温搅拌反应12小时。待反应结束后,经过柱层析色谱分离提纯,目标产物的产率为85%。
由上述实施例可以看出,本发明所采用的利用二芳基磷氧与硫醇类化合物高效反应制备相应的含不同取代官能团的有机硫代膦酸酯类化合物的方法具有反应条件温和、催化剂廉价易得以及制备简单等优点。此外,该方法还具有底物适用性广、高产率等优点,提供了一种高效合成含不同取代官能团的有机硫代膦酸酯类化合物的方法。
以上所述实施例仅表达了本发明的几种实施方式,其描述较为具体和详细,但并不能因此而理解为对本发明专利范围的限制。应当指出的是,对于本领域的普通技术人员来说,在不脱离本发明构思的前提下,还可以做出若干变形和改进,这些都属于本发明的保护范围。因此,本发明专利的保护范围应以所附权利要求为准。
Claims (4)
2.根据权利要求1所述的制备方法,其特征在于,所述二芳基磷氧是选自二苯基磷氧、二(4-甲基苯基)磷氧、二(3-甲基苯基)磷氧、二(4-甲氧基苯基)磷氧、二(3,5-二甲基苯基)磷氧、二(3-氟苯基)磷氧、二(1-萘基)磷氧、二(2-萘基)磷氧。
3.根据权利要求1所述的制备方法,其特征在于,所述硫醇是选自甲硫醇、乙硫醇、丙硫醇、丁硫醇、异丁硫醇、苄硫醇、环戊硫醇、正己硫醇。
4.根据权利要求1所述的制备方法,其特征在于,所述二芳基磷氧与硫醇类化合物的摩尔比为1:[1.0~3.0]; 二芳基磷氧与催化剂的摩尔比为1:[0.05-0.2];二芳基磷氧与配体的摩尔比为1:[0.05-0.2];二芳基磷氧与碱的摩尔比为1:[0.2-2.0]。
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