CN116273160A - 一种用于五价磷化合物制备三价磷化合物的催化剂 - Google Patents
一种用于五价磷化合物制备三价磷化合物的催化剂 Download PDFInfo
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- CN116273160A CN116273160A CN202310134908.0A CN202310134908A CN116273160A CN 116273160 A CN116273160 A CN 116273160A CN 202310134908 A CN202310134908 A CN 202310134908A CN 116273160 A CN116273160 A CN 116273160A
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- phosphorus compound
- catalyst
- cdcl
- nmr
- pentavalent
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- -1 phosphorus compound Chemical class 0.000 title claims abstract description 145
- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 113
- 239000011574 phosphorus Substances 0.000 title claims abstract description 113
- 239000003054 catalyst Substances 0.000 title claims abstract description 69
- 238000006243 chemical reaction Methods 0.000 claims abstract description 101
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 88
- 238000000034 method Methods 0.000 claims abstract description 38
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 36
- 229910052742 iron Inorganic materials 0.000 claims abstract description 31
- 150000003018 phosphorus compounds Chemical class 0.000 claims abstract description 26
- 239000007769 metal material Substances 0.000 claims abstract description 5
- 239000002904 solvent Substances 0.000 claims description 25
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 19
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- 239000012190 activator Substances 0.000 claims description 14
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 12
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 12
- 238000002360 preparation method Methods 0.000 claims description 11
- 239000001257 hydrogen Substances 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 8
- 150000002431 hydrogen Chemical class 0.000 claims description 8
- 239000000460 chlorine Substances 0.000 claims description 7
- 125000003118 aryl group Chemical group 0.000 claims description 6
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- 239000000126 substance Substances 0.000 claims description 5
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- 238000004519 manufacturing process Methods 0.000 claims description 4
- CTSLXHKWHWQRSH-UHFFFAOYSA-N oxalyl chloride Chemical compound ClC(=O)C(Cl)=O CTSLXHKWHWQRSH-UHFFFAOYSA-N 0.000 claims description 4
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- DPKBAXPHAYBPRL-UHFFFAOYSA-M tetrabutylazanium;iodide Chemical class [I-].CCCC[N+](CCCC)(CCCC)CCCC DPKBAXPHAYBPRL-UHFFFAOYSA-M 0.000 claims description 3
- UCPYLLCMEDAXFR-UHFFFAOYSA-N triphosgene Chemical compound ClC(Cl)(Cl)OC(=O)OC(Cl)(Cl)Cl UCPYLLCMEDAXFR-UHFFFAOYSA-N 0.000 claims description 3
- 125000004400 (C1-C12) alkyl group Chemical group 0.000 claims description 2
- JNVXRQOSRUDXDY-UHFFFAOYSA-N 1,1-diiodoethane Chemical compound CC(I)I JNVXRQOSRUDXDY-UHFFFAOYSA-N 0.000 claims description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
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- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 2
- 229910052788 barium Inorganic materials 0.000 claims description 2
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- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 2
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 claims description 2
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 2
- YWWZCHLUQSHMCL-UHFFFAOYSA-N diphenyl diselenide Chemical compound C=1C=CC=CC=1[Se][Se]C1=CC=CC=C1 YWWZCHLUQSHMCL-UHFFFAOYSA-N 0.000 claims description 2
- VRLFOXMNTSYGMX-UHFFFAOYSA-N diphenyl ditelluride Chemical compound C=1C=CC=CC=1[Te][Te]C1=CC=CC=C1 VRLFOXMNTSYGMX-UHFFFAOYSA-N 0.000 claims description 2
- 229940076136 ferrous iodide Drugs 0.000 claims description 2
- 150000002391 heterocyclic compounds Chemical class 0.000 claims description 2
- BQZGVMWPHXIKEQ-UHFFFAOYSA-L iron(ii) iodide Chemical compound [Fe+2].[I-].[I-] BQZGVMWPHXIKEQ-UHFFFAOYSA-L 0.000 claims description 2
- 150000002825 nitriles Chemical class 0.000 claims description 2
- 235000007715 potassium iodide Nutrition 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 229910052711 selenium Inorganic materials 0.000 claims description 2
- 239000011669 selenium Substances 0.000 claims description 2
- 235000009518 sodium iodide Nutrition 0.000 claims description 2
- 229910052712 strontium Inorganic materials 0.000 claims description 2
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 2
- 239000011593 sulfur Substances 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 229910052714 tellurium Inorganic materials 0.000 claims description 2
- 239000007858 starting material Substances 0.000 claims 2
- 150000001768 cations Chemical class 0.000 claims 1
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 11
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- 229910052751 metal Inorganic materials 0.000 abstract description 10
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- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 abstract description 8
- 239000002994 raw material Substances 0.000 abstract description 6
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- 229910000085 borane Inorganic materials 0.000 abstract description 5
- 229910052990 silicon hydride Inorganic materials 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- DPTATFGPDCLUTF-UHFFFAOYSA-N phosphanylidyneiron Chemical compound [Fe]#P DPTATFGPDCLUTF-UHFFFAOYSA-N 0.000 abstract 1
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Abstract
本发明涉及一种用于五价磷化合物制备三价磷化合物的催化剂,属于有机合成技术领域。本发明将所述催化剂用于五价磷化合物制备三价磷化合物的反应中,并将金属铁或含铁的金属材料作为还原剂,可实现在不高于100℃下将五价磷化合物还原,并制备出产率较高的三价磷化合物或三价磷的铁配合物;本发明中五价磷化合物的底物兼容性广泛,克服了现有技术在还原五价磷化合物时由于反应温度较高从而限制五价磷化合物底物适用范围的问题;同时,本发明采用的原料廉价易得,未采用价格高昂的硅氢、硼烷等试剂,具有显著的成本优势,更适合大规模工业化应用。
Description
技术领域
本发明涉及有机合成技术领域,尤其涉及一种用于五价磷化合物制备三价磷化合物的催化剂。
背景技术
三价磷化合物中有孤对电子和空轨道,因此具有较强的亲核性和配位性,在有机合成中有着非常重要的作用;如:作为反应底物参与反应、作为催化剂或者配体催化反应等。但是由于三价磷具有强亲核性,导致其不稳定,很容易被氧化成磷氧化合物;因此,关于磷氧化合物还原制备三级磷化合物的研究备受关注。然而,由于磷氧化合物的P=O键具有非常高的键能(546kJ/mol),而高键能代表磷氧化合物具有极强的稳定性,因此还原磷氧化合物具有较大的挑战性。
目前关于磷氧化合物的还原方法可以分为两大类:直接还原和间接还原。直接还原即采用还原试剂直接还原磷氧键,常用的试剂有PhSiH3,HSiCl3和TMDS等,其中,硅烷还原剂是目前应用较为普遍的磷氧还原剂,这类试剂具有底物兼容性广、转化率高等优点,但是硅烷试剂价格昂贵,在反应时会产生有毒的化合物,如SiCl4;LiAlH4,AlH3等铝氢化物试剂的反应活性高,一般温和条件下就可以实现还原的效果,但是金属氢化物底物官能团兼容性较差,另外氢气还原条件较为苛刻,通常需要高温,高压条件才能还原,如Angew.Chem.Int.Ed.2018,57,15253–15256;BH3,NaBH4,LiBH4等硼氢化合物在还原富电子磷氧时也具有非常大的优势;磷交换法通常通过高反应活性的磷来合成低反应活性的磷,但该方法会引入新的磷氧,并不可取。
间接还原即将磷氧化合物转换成活性中间体,常见的是转化成磷氯中间体CPS,然后再用还原试剂还原该活性中间体,常用的试剂有活泼金属单质,比如Mg,Al,Fe,其中金属Mg和Al具有较高的氧化电势,在还原CPS时比较有优势,主要体现在反应快,反应温和,转化率高等方面,但是这些金属价格昂贵,并且存在粉尘,容易爆炸,造成安全隐患;而金属Fe具有相对较弱的氧化电势,还原CPS时并不理想,一般需要100℃以上的高温才能实现还原,并不利于实验操作;同时,在已知文献报道中,金属Fe还原的五价磷化合物的底物范围也非常有限,即使在较高的温度条件下,也无法实现富电子磷的有效还原,且此类反应通常需要使用还原性铁粉,具有局限性。
针对上述现有技术中存在的问题,开发一种可用于五价磷化合物制备三价磷化合物反应,且可使反应条件温和、五价磷化合物中底物适用范围广的催化剂是目前研究的重点。
发明内容
本发明的目的在于克服上述现有技术的不足之处而提供一种用于五价磷化合物制备三价磷化合物的催化剂。
为实现上述目的,本发明采取的技术方案为:
第一方面,本发明提供了一种用于五价磷化合物制备三价磷化合物的催化剂,所述催化剂的结构为XCR1R2CR3R4X或MXn;其中,R1-R4独立地选自氢、卤素、C1-C4的烷基或苯基,M选自季铵正离子(R5R6R7R8N)、季鏻正离子(R5R6R7R8P)、铁、铜、钠、锂、钾、锌、镁、钙、锶、钡、铝或铯,其中,R5-R8选自氢、C1-C12的烷基、苯基、苄基中的至少一种,X选自氯、溴、碘、硫芳基、硒芳基或碲芳基,所述X中的芳基选自一个或多个C1-C4烷基取代或未取代的苯基。
本发明将上述催化剂用于五价磷化合物制备三价磷化合物的反应中,克服了现有技术在还原五价磷化合物时由于反应温度较高,从而限制了五价磷化合物底物的适用范围等问题;发明人通过大量实验探究,使本发明实现了在较低温度(≤100℃)的温和条件下将五价磷化合物还原,并制备出产率较高的三价磷化合物。
作为本发明用于五价磷化合物制备三价磷化合物的催化剂的优选实施方式,所述催化剂的结构为XCR1R2CR3R4X或MXn;其中,R1-R4选自氢、卤素、C1-C4的烷基或苯基,M选自季铵正离子(R5R6R7R8N)、季鏻正离子(R5R6R7R8P)、铁、钠、锂、钾、镁、钙、铝、锌或铜,其中,R5-R8选自氢、C1-C4的烷基、苯基、苄基中的至少一种,X选自溴、碘、硒芳基或碲芳基,所述X中的芳基选自一个或多个C1-C4烷基取代或未取代的苯基。
作为本发明用于五价磷化合物制备三价磷化合物的催化剂的更优选实施方式,所述催化剂包含四正丁铵碘盐、四正丁铵溴盐、碘单质、碘化锂、碘化钠、碘化钾、联苯二碲、碘化亚铁、碘化亚铜、二碘乙烷、二苯基二硒醚、二苯基二硫醚中的至少一种;发明人通过大量创造性实验发现,采用上述催化剂不仅具有优异的催化效果,使本发明制备得到的三价磷化合物的产率较高,且上述催化剂成本较低,具有较好的工业应用价值。
第二方面,本发明提供了一种三价磷化合物,所述三价磷化合物的制备原料包含如第一方面所述的催化剂。
作为本发明三价磷化合物的优选实施方式,所述三价磷化合物的制备原料还包含五价磷化合物、还原剂、活化剂和溶剂。
作为本发明三价磷化合物的更优选实施方式,所述五价磷化合物的结构式如下式所示:
其中,R1,R2,R3选自烷基、环烷基、芳基或杂环化合物。
作为本发明三价磷化合物的更优选实施方式,所述还原剂为金属铁或包含铁的金属材料,如铁粉、不锈钢、铁丝、铁箔、铁片等,发明人通过大量实验发现,金属铁或包含铁的金属材料具有较低的氧化还原电势,且可使本发明反应在温和的条件下进行,且所述还原剂成本更低,具有较好的实用价值。
需要说明的是,本发明的发明人通过无数次实验发现,铁丝、铁箔、铁片和不锈钢等材料,存放时间过久易导致表面存在杂质,但在本发明催化剂存在的条件下,依然可使最终三价磷化合物的产率达到较好的效果。
作为本发明三价磷化合物的更优选实施方式,所述活化剂包含草酰氯(C2Cl2O2)、二(三氯甲基)碳酸酯((CCl3CO)2O)、光气(CCl2O)和二光气(C2Cl4O2)。
作为本发明三价磷化合物的最优选实施方式,所述活化剂为C2Cl2O2,发明人通过大量实验发现,采用C2Cl2O2作为活化剂,可使最终得到的三价磷化合物的产率较高。
作为本发明三价磷化合物的更优选实施方式,所述溶剂包含C1-C4烷基取代或卤代的芳香烃、多卤代乙烷和腈类。
作为本发明三价磷化合物的最优选实施方式,所述溶剂包含甲苯、氯苯、1,2-二氯乙烷和乙腈。
作为本发明三价磷化合物的最最优选实施方式,所述溶剂包含1,2-二氯乙烷和乙腈,发明人通过大量创造性实验发现,采用上述溶剂,可使本发明所述反应的反应速率加快,节省时间成本。
作为本发明三价磷化合物的最优选实施方式,所述催化剂中五价磷化合物中磷的个数与催化剂中X的物质的量之比≥1:0.3mol,发明人通过大量实验发现,在该条件下,可使最终得到的三价磷化合物的产率最高,同时可节约实验成本。
作为本发明三价磷化合物的最优选实施方式,所述五价磷化合物中磷的个数与活化剂的物质的量之比为1:1-1.5mol,发明人通过实验发现,在该条件下,可使最终得到的三价磷化合物的产率较高,若活化剂添加量较少,导致五价磷化合物无法完全被还原,而活化剂加入量过多,则会导致生成的三价磷化合物又重新发生氧化,影响实验结果。
作为本发明三价磷化合物的最优选实施方式,所述五价磷化合物中磷的个数与还原剂的物质的量之比为1:1-3mol。
作为本发明三价磷化合物的最优选实施方式,所述五价磷化合物中磷的个数与溶剂的体积之比为1:0.5-10mL。
本发明还提供了所述三价磷化合物的制备方法,包含以下步骤:将五价磷化合物、活化剂、催化剂和还原剂在干燥的气氛下加入溶剂中进行反应,待冷却至室温后进行萃取、干燥、提纯,即得所述三价磷化合物;
其中,也可将五价磷化合物在干燥的气氛下先溶解于溶剂中,再滴加活化剂进行反应,反应后再向其中加入催化剂和还原剂再次反应;发明人经过大量实验发现,采用上述方法可使所述反应的速率有所提升;
所述方法的具体合成路线如下:
作为本发明三价磷化合物的制备方法的优选实施方式,所述干燥气体包含干燥空气、氮气、氩气和氦气。
在上述反应中,催化剂与五价磷化合物先进行反应,此过程中催化剂失去电子被氧化,随后,催化剂再与还原剂进行反应从而得到电子,再生催化剂,完成催化循环。
发明人通过大量探索性实验发现,本发明所述催化剂需要同时满足以下几点:1.催化剂需要具有一定的氧化还原性,但其氧化性和还原性都不能过强,否则将无法实现催化循环,否则催化剂将在反应过程中和CPS或者金属Fe反应而永久性失活;2.催化剂和CPS中间体作用的速率要快于和金属Fe的反应,否则也不能够催化反应;3.催化剂不容易和金属及其表面氧化物之间发生作用而失活。
作为本发明三价磷化合物的制备方法的优选实施方式,反应温度为0-100℃,反应时间为0.5-72h。
作为本发明三价磷化合物的制备方法的优选实施方式,所述后处理的具体步骤为:向冷却至室温后的溶液中加入氢氧化钠水溶液,随后过滤,并用乙酸乙酯萃取出有机相,再用无水硫酸钠进行干燥,最后利用柱层析法提纯,脱溶后即得所述三价磷化合物。
与现有技术相比,本发明的有益效果为:本发明提供了一种用于五价磷化合物制备三价磷化合物的催化剂,将所述催化剂用于五价磷化合物制备三价磷化合物的反应中,并将金属铁或含铁的金属材料作为还原剂,可实现在不高于100℃下将五价磷化合物还原,并制备出产率较高的三价磷化合物或三价磷的铁配合物;本发明中五价磷化合物的底物兼容性广泛,克服了现有技术在还原五价磷化合物时由于反应温度较高,从而限制五价磷化合物底物适用范围的问题;同时,本发明采用的原料廉价易得,未采用价格高昂的硅氢、硼烷等试剂,具有显著的成本优势,更适合大规模工业化应用。
附图说明
图1为本发明所述五价磷化合物制备三价磷化合物的流程图。
具体实施方式
为更好地说明本发明的目的、技术方案和优点,下面将结合具体实施例对本发明作进一步说明。
本发明所用试剂或仪器未注明生产厂商者,均为可以通过市购获得的常规产品;所述实验方法,如无特殊说明,均为常规方法。
本发明所用还原剂的参数如下:
铁丝(diam:0.5mm,99.9%),铁丝(diam:1.0mm,99.9%),铁箔(thickness:0.1mm,99.9%),铁片(thickness:1.0mm,99.9%),不锈钢粉(100mesh,Type:304-L),铁粉(100-200mesh,99%)。
本发明实施例中所述还原剂或催化剂的摩尔比百分比为占1当量磷的摩尔百分比。
实施例1
本发明所述用于五价磷化合物制备三价磷化合物的催化剂的一种实施例,本实施例所述三价磷化合物的制备过程和反应式如下:
在氮气氛围下将上式所述磷氧化合物(1.0mmol,1eq)溶于2.0mL的乙腈中,随后缓慢滴加(COCl)2(1.05eq),滴加完毕后反应30min,随后加入TBAI(10mol%),1.25eq铁粉(100mesh,99%),在60℃下反应24h,待反应完成后,冷却至室温,然后用6M的氢氧化钠溶液淬灭反应,并用硅藻土过滤得到滤饼,再用乙酸乙酯洗涤滤饼,合并有机相后,用无水硫酸钠进行干燥,浓缩后进行层析得到白色固体,转化率96%,产率为83%,所得产物的结构表征数据如下:Rf=0.65(PE:EA=10:1,v/v),1H NMR(400MHz,CDCl3,7.27ppm)δ:7.57–7.55(m,1H),7.37–7.32(m,2H),7.25–7.14(m,4H),7.06(d,J=7.43Hz,1H),2.06(s,3H),2.02–1.94(m,1H),1.76–1.53(m,11H),1.37–0.92(m,10H);13C NMR(101MHz,CDCl3,77.16ppm)δ:149.82(d,J=30.91Hz),142.47(d,J=6.44Hz),135.60(d,J=1.72Hz),134.50(d,J=19.57Hz),132.57(d,J=3.16Hz),130.83(d,J=2.61Hz),130.02(d,J=5.85Hz),129.36(s),128.22(s),127.20(s),126.32(s),124.50(s),35.40(d,J=15.40Hz),33.23(d,J=13.02Hz),30.74(d,J=15.09Hz),30.03(s),29.85(s),29.73(s),28.89(d,J=5.13Hz),27.61(s),27.49(s),27.44(s),27.18(s),27.08(d,J=2.43Hz),26.42(d,J=8.53Hz),20.66(d,J=5.01Hz);31P NMR(162MHz,CDCl3,7.27ppm)δ:-11.54;HRMS-ESI(m/z)forC25H33P[M+H]+,计算值365.2398,实验值365.2388。
实施例2-7
实施例2-7与实施例1的区别仅在于:还原剂和反应温度不同,其余步骤均与实施例1一致;实施例2-7所用还原剂、反应温度和产物的转化率如下表1所示。
表1
还原剂 | 温度 | 转化率 | |
实施例2 | 铁丝(diam:0.5mm,99.9%) | 80℃ | 97% |
实施例3 | 铁丝(diam:1.0mm,99.9%) | 80℃ | 92% |
实施例4 | 铁箔(thickness:0.1mm,99.9%) | 80℃ | 94% |
实施例5 | 铁片(thickness:1.0mm,99.9%) | 80℃ | 91% |
实施例6 | 不锈钢粉(100mesh,Type:304-L) | 80℃ | 98% |
实施例7 | 铁粉(200mesh,99%) | 60℃ | 98% |
实施例8-20
实施例8-20与实施例1的区别仅在于:催化剂的种类及物质的量不同,其余步骤均与实施例1一致;实施例8-20所用还原剂、反应温度和产物的转化率如下表1所示。
表2
实施例21
本实施例与实施例1的区别仅在于:所述磷氧化合物的结构式如下式所示,5mol%Bu4NI,60℃下反应2h,其余步骤均与实施例1一致,得到白色固体,产率为93%,所述产物的结构表征数据如下:Rf=0.46(PE),1H NMR(400MHz,CDCl3,7.27ppm)δ:7.57(d,J=7.88Hz,2H),7.41–7.31(m,12H);13C NMR(101MHz,CDCl3,77.16ppm)δ:142.83(d,J=14.30Hz),135.99(d,J=10.40Hz),133.90(d,J=19.97Hz),133.54(d,J=18.90Hz),130.93(s),130.61(s),130.29(s),129.97(s),129.20(s),128.72(d,J=6.92Hz),128.12(s),125.41(s),125.07(q,J=7.53Hz,3.82Hz),122.71(s),120.00(s);31P NMR(162MHz,CDCl3,7.27ppm)δ:-5.39;19FNMR(300MHz,CDCl3)δ:-62.75;HRMS-ESI(m/z)for C19H14F3P[M+H]+,计算值331.0863,实验值331.0852。
实施例22
本实施例与实施例1的区别仅在于:所述磷氧化合物的结构式如下式所示,5mol%Bu4NI,60℃下反应2h,其余步骤均与实施例1一致,得到白色固体的产率为87%,所述产物的结构表征数据如下:Rf=0.17(PE),1H NMR(400MHz,CDCl3,7.27ppm)δ:7.92(dd,J=8.49,1.42Hz,2H),7.50–7.30(m,12H);13C NMR(101MHz,CDCl3,77.16ppm)δ:149.26(d,J=18.68Hz),134.82(d,J=10.22Hz),134.12(d,J=20.58Hz),133.66(d,J=18.20Hz),132.29(d,J=24.58Hz),129.71(s),128.95(d,J=7.61Hz),127.79(d,J=5.88Hz);31P NMR(162MHz,CDCl3)δ:-3.99;19F NMR(300MHz)δ:66.12;HRMS-ESI(m/z)for C18H14FO2PS[M+H]+:计算值345.0514,实验值345.0505。
实施例23
本实施例与实施例1的区别仅在于:所述磷氧化合物的结构式如下式所示,5mol%Bu4NI,30℃下反应6h,其余步骤均与实施例1一致,得到白色固体的产率为83%,所述产物的结构表征数据为如下:Rf=0.52(PE:EA=10:1),1H NMR(400MHz,CDCl3,7.27ppm)δ:8.00(t,J=2.45Hz,1H),7.40–7.33(m,7H),7.27–7.13(m,4H),7.14(dd,J=7.88,2.96Hz,1H),2.44(s,3H);13C NMR(101MHz,CDCl3,77.16ppm)δ:140.43(s),138.38(s),138.14(d,J=4.84Hz),137.90(s),137.00(s),136.68(s),136.36(s),135.85(d,J=11.43Hz),135.63(s),133.88(d,J=20.60Hz),131.39(d,J=4.10Hz),129.28(s),128.82(d,J=7.02Hz),21.15(s);31PNMR(162MHz,CDCl3)δ:-9.84(d);19F NMR(300MHz,CDCl3,77.16ppm)δ:64.69;HRMS-ESI(m/z)for C19H16FO2PS[M+H]+:计算值358.0593,实验值358.0583。
实施例24
本实施例与实施例1的区别仅在于:所述磷氧化合物的结构式如下式所示,5mol%Bu4NI,60℃下反应2h,其余步骤均与实施例1一致,得到白色固体的产率为83%,所述产物的结构表征数据如下:Rf=0.12(PE:EA=10:1,v/v),1H NMR(400MHz,CDCl3,7.27ppm)δ:7.74(d,J=7.40Hz,2H),7.37–7.30(m,17H),6.37(br,1H),4.66(d,J=5.32Hz,2H);13C NMR(101MHz,CDCl3,7.27ppm)δ:167.03(s),142.21(d,J=13.64Hz),138.05(s),136.27(d,J=10.59Hz),134.33(s),133.85(d,J=19.77Hz),133.55(d,J=18.96Hz),129.06(s),128.78(s),128.64(d,J=7.21Hz),127.87(s),127.65(s),126.82(d,J=6.57Hz),44.14(s);31PNMR(162MHz,CDCl3,7.27ppm)δ:-5.53;HRMS-ESI(m/z)for C26H22NOP[M+H]+:计算值396.1517,实验值396.1508。
实施例25
本实施例与实施例1的区别仅在于:所述磷氧化合物的结构式如下式所示,5mol%Bu4NI,60℃下反应2h,其余步骤均与实施例1一致,得到白色固体的产率为86%,所述产物的结构表征数据为:Rf=0.38(PE:EA=10:1,v/v),1H NMR(400MHz,CDCl3,7.27ppm)δ:7.86(dd,J=8.24,1.62Hz,2H),7.37–7.30(m,12H),2.55(s,3H);13C NMR(101MHz,CDCl3,77.16ppm)δ:197.56(s),144.26(d,J=14.56Hz),136.63(s),135.94(d,J=10.67Hz),133.81(d,J=20.03Hz),133.17(d,J=18.60Hz),129.04(s),128.57(d,J=7.30Hz),127.88(d,J=6.35Hz),26.48(s);31P NMR(162MHz,CDCl3,7.27ppm)δ:-5.07;HRMS-ESI(m/z)for C20H17O2P[M+H]+:计算值305.1095,实验值305.087。
实施例26
本实施例与实施例1的区别仅在于:所述磷氧化合物的结构式如下式所示,5mol%Bu4NI,60℃下反应2h,其余步骤均与实施例1一致,得到白色固体的产率为96%,所述产物的结构表征数据为Rf=0.37(PE),1H NMR(400MHz,CDCl3,7.27ppm)δ:7.45–7.41(m,4H),7.36–7.31(m,6H),2.08–2.04(m,2H),1.46–1.42(m,4H),0.90(t,J=7.20Hz,3H);13C NMR(101MHz,CDCl3,77.16ppm)δ:132.71(d,J=18.17Hz),128.40(d,J=16.50Hz),128.39(s),28.11(d,J=15.57Hz),27.70(d,J=10.45Hz),24.30(d,J=13.18Hz),13.76(s);31P NMR(162MHz,CDCl3,7.27ppm)δ:-15.83;HRMS-ESI(m/z)for C16H19P[M+H]+:计算值243.1303,实验值243.1294。
实施例27
本实施例与实施例1的区别仅在于:所述磷氧化合物的结构式如下式所示,5mol%Bu4NI,60℃下反应2h,其余步骤均与实施例1一致,其余步骤均与实施例1一致,得到白色固体的产率为94%,所述产物的结构表征数据为Rf=0.3(PE),1H NMR(400MHz,CDCl3,7.27ppm)δ:7.54–7.50(m,4H),7.36–7.33(m,6H),2.46(m,1H),1.09(dd,J=15.41,6.90Hz,6H);13C NMR(101MHz,CDCl3,77.16ppm)δ:137.65(d,J=13.98Hz),133.65(d,J=18.91Hz),128.76(s),128.39(d,J=6.96Hz),25.15(d,J=8.14Hz),19.80(d,J=18.05Hz);31P NMR(162MHz,CDCl3,7.27ppm)δ:1.24;HRMS-ESI(m/z)for C15H17P[M+H]+:计算值229.1146,实验值229.1137。
实施例28
本实施例与实施例1的区别仅在于:所述磷氧化合物的结构式如下式所示,5mol%Bu4NI,60℃下反应2h,其余步骤均与实施例1一致,得到白色固体的产率为86%,所述产物的结构表征数据为Rf=0.57(PE:EA=10:1,v/v),1H NMR(400MHz,CDCl3,7.27ppm)δ:1H NMR(400MHz,CDCl3,7.27ppm)δ:7.34–7.23(m,11H),6.90–6.83(m,3H),3.71(s,3H);13C NMR(101MHz,CDCl3,77.16ppm)δ:159.47(d,J=8.36Hz),138.70(d,J=11.33Hz),136.99(d,J=10.88Hz),133.69(d,J=19.38Hz),129.44(d,J=7.75Hz),128.69(s),128.43(d,J=6.89Hz),125.96(d,J=18.71Hz),118.93(d,J=21.17Hz),114.23(s),55.04(s);31P NMR(162MHz,CDCl3,7.27ppm)δ:-4.58;HRMS-ESI(m/z)for C19H17OP[M+H]+:计算值293.1095,实验值293.1086。
实施例29
本实施例与实施例1的区别仅在于:所述磷氧化合物的结构式如下式所示,5mol%Bu4NI,60℃下反应2h,其余步骤均与实施例1一致,得到白色固体的产率为92%,所述产物的结构表征数据为Rf=0.21(PE:EA=1:1,v/v),1H NMR(400MHz,CDCl3,7.27ppm)δ:7.29(d,J=3.88Hz,8H),7.27–7.23(m,2H),6.69(d,J=8.37Hz,2H),2.96(s,6H);13C NMR(101MHz,CDCl3,77.16ppm)δ:150.83(s),138.64(d,J=10.48Hz),135.54(d,J=21.67Hz),133.27(d,J=18.70Hz),128.26(d,J=6.57Hz),128.14(s),112.31(d,J=8.38Hz),40.19(s);31PNMR(162MHz,CDCl3,7.27ppm)δ:-7.20;HRMS-ESI(m/z)for C20H20NP[M+H]+:计算值306.1412,实验值306.1398。
实施例30
本实施例与实施例1的区别仅在于:所述磷氧化合物的结构式如下式所示,5mol%Bu4NI,60℃下反应2h,其余步骤均与实施例1一致,得到白色固体的产率为81%,所述产物的结构表征数据为Rf=0.32(PE),1H NMR(400MHz,CDCl3,7.27ppm)δ:7.38–7.32(m,6H),7.31–7.22(m,6H),7.1–7.08(m,1H),6.80–6.77(m,1H),2.41(s,3H);13C NMR(101MHz,CDCl3,77.16ppm)δ:143.41(d,J=8.03Hz),133.59(d,J=12.86Hz),133.31(s),132.28(s),132.22(d,J=2.76Hz),132.06(s),131.96(s),131.90(d,J=2.69Hz),131.34(s),130.32(s),128.68(d,J=12.08Hz),125.30(d,J=12.87Hz),21.78(d,J=4.65Hz);31P NMR(162MHz,CDCl3,7.27ppm)δ:-13.32;HRMS-ESI(m/z)for C19H17P[M+H]+:计算值277.1146,实验值277.1137。
实施例31
本实施例与实施例1的区别仅在于:所述磷氧化合物的结构式如下式所示,5mol%Bu4NI,60℃下反应2h,其余步骤均与实施例1一致,得到白色固体的产率为89%,所述产物的结构表征数据为Rf=0.25(PE),1H NMR(400MHz,CDCl3,7.27ppm)δ:7.55-7.50(m,4H),7.38–7.32(m,6H),2.25–2.23(m,1H),1.78–1.72(m,5H),1.32-1.20(m,5H);13C NMR(101MHz,CDCl3,77.16ppm)δ:137.13(d,J=13.69Hz),133.70(d,J=19.05Hz),128.70(s),128.38(d,J=6.91Hz),35.53(d,J=8.68Hz),29.69(d,J=15.23Hz),26.91(d,J=11.29Hz),26.47(s);31P NMR(162MHz,CDCl3,7.27ppm)δ-3.60;HRMS-ESI(m/z)for C18H21P[M+H]+:计算值269.1459,实验值269.1452。
实施例32
本实施例与实施例1的区别仅在于:所述磷氧化合物的结构式如下式所示,5mol%Bu4NI,60℃下反应2h,其余步骤均与实施例1一致,得到白色固体的产率为81%,所述产物的结构表征数据为Rf=0.3(PE),1H NMR(400MHz,CDCl3,7.27ppm)δ:7.31–7.28(m,10H),7.24–7.20(m,2H),7.16–7.14(m,2H),2.34(s,3H);13C NMR(101MHz,CDCl3,77.16ppm)δ138.81(s),137.51(d,J=10.69Hz),133.89(d,J=19.96Hz),133.57(d,J=19.24Hz),133.39(s),129.33(d,J=7.26Hz),128.54(s),128.41(d,J=6.88Hz),21.29(s);31P NMR(162MHz,CDCl3,7.27ppm)δ:-6.24,HRMS-ESI(m/z)for C19H18P[M+H]+:计算值277.1146,实验值277.1137。
实施例33
本实施例与实施例1的区别仅在于:所述磷氧化合物的结构式如下式所示,5mol%Bu4NI,60℃下反应2h,其余步骤均与实施例1一致,得到白色固体的产率为81%,所述产物的结构表征数据为Rf=0.4(PE:EA=10:1,v/v),1H NMR(400MHz,CDCl3,7.27ppm)δ:7.33–7.24(m,12H),6.89(d,J=8.27Hz,2H),3.80(s,3H);13C NMR(101MHz,CDCl3,77.16ppm)δ:160.38(s),137.82(d,J=10.41Hz),135.60(d,J=21.26Hz),133.40(d,J=19.04Hz),128.48(s),128.40(d,J=6.77Hz),127.55(d,J=7.79Hz),114.23(d,J=8.05Hz),55.17(s);31P NMR(162MHz,CDCl3,7.27ppm)δ:-7.02;HRMS-ESI(m/z)for C26H24NO3PS[M+H]+:计算值293.1095,实验值293.1085。
实施例34
本实施例与实施例1的区别仅在于:所述磷氧化合物的结构式如下式(Ⅱ)所示,其余步骤均与实施例1一致,得到白色固体的产率为85%,所述产物的结构表征数据为Rf=0.68(PE:EA=10:1,v/v),1H NMR(400MHz,CDCl3,7.27ppm)δ:7.60–7.57(m,1H),7.38–7.25(m,8H),1.85–1.79(m,2H),1.71–1.55(m,10H),1.28–0.99(m,10H);13C NMR(101MHz,CDCl3,77.16ppm)δ:150.57(d,J=28.30Hz),142.86(d,J=6.10Hz),134.05(d,J=21.40Hz),132.80(d,J=2.95Hz),130.59(d,J=4.13Hz),130.17(d,J=5.27Hz),128.11(s),127.25(s),126.51(d,J=22.35Hz),34.70(d,J=14.51Hz),30.38(d,J=17.28Hz),29.25(d,J=8.96Hz),27.24(d,J=5.82Hz),27.15(s),26.38(s);31P NMR(162MHz,CDCl3,7.27ppm)δ:-13.13;HRMS-ESI(m/z)for C24H31P[M+H]+:计算值351.2242,实验值351.2234。
实施例35
本实施例与实施例1的区别仅在于:所述磷氧化合物的结构式如下式(Ⅱ)所示,其余步骤均与实施例1一致,得到白色固体的产率为75%,所述产物的结构表征数据为Rf=0.68(PE:EA=10:1,v/v),1H NMR(400MHz,CDCl3,7.27ppm)δ:7.56(d,J=7.31Hz,1H),7.41–7.34(m,1H),7.32–7.28(m,3H),7.06–6.96(m,3H),2.46(s,6H),2.06–2.00(m,1H),1.80–0.77(m,21H);13C NMR(101MHz,CDCl3,77.16ppm)δ:151.44(d,J=2.02Hz),149.63(d,J=30.86Hz),135.83(d,J=5.72Hz),135.28(d,J=20.06Hz),132.71(d,J=3.88Hz),132.35(d,J=1.65Hz),130.49(d,J=6.18Hz),128.51(s),128.08(s),125.81(s),120.64(s),117.28(s),43.28(s),36.66(d,J=15.97Hz),33.36(d,J=14.31Hz),30.76(d,J=15.77Hz),30.46(d,J=19.80Hz),29.66(d,J=12.80Hz),28.44(d,J=4.96Hz),27.56(d,J=16.60Hz),27.47(d,J=9.71Hz),27.22(d,J=11.51Hz),26.67(s),26.39(s);31P NMR(162MHz,CDCl3,7.27ppm)δ:-9.65;HRMS-ESI(m/z)for C26H36NP[M+H]+:计算值394.2664,实验值394.2650。
实施例36
本实施例与实施例1的区别仅在于:所述磷氧化合物的结构式如下式(Ⅱ)所示,其余步骤均与实施例1一致,得到白色固体的产率为80%,所述产物的结构表征数据为Rf=0.46(PE:EA=10:1,v/v),1H NMR(400MHz,CDCl3,7.27ppm)δ:7.59–7.56(m,1H),7.42–7.38(m,1H),7.36–7.30(m,2H),7.20–7.17(m,1H),6.60(d,J=8.36Hz,1H),3.69(s,6H),1.82–1.61(m,12H),1.29–0.99(m,10H);13C NMR(101MHz,CDCl3,77.16ppm)δ:157.40(s),142.86(d,J=31.95Hz),135.90(d,J=17.75Hz),132.32(d,J=3.68Hz),130.89(d,J=6.17Hz),128.76(s),128.18(s),126.13(s),119.89(d,J=7.26Hz),103.05(s),55.19(s),33.92(d,J=13.81Hz),29.93(d,J=16.93Hz),29.05(d,J=9.15Hz),27.51(s),27.37(d,J=3.64Hz),27.28(s),26.51(s);31P NMR(162MHz,CDCl3,7.27ppm)δ:-9.09;HRMS-ESI(m/z)for C26H35O2P[M+H]+:计算值411.2453,实验值411.2440。
实施例37
本实施例与实施例1的区别仅在于:所述磷氧化合物的结构式如下式(Ⅱ)所示,其余步骤均与实施例1一致,得到白色固体的产率为89%,所述产物的结构表征数据为Rf=0.62(PE:EA=10:1,v/v),1H NMR(400MHz,CDCl3,7.27ppm)δ:7.62–7.59(m,1H),7.37–7.29(m,2H),7.19–7.13(m,1H),7.01(s,2H),2.99–2.88(m,1H),2.47–2.37(m,2H),1.87–1.58(m,12H),1.31(d,J=6.91Hz,6H),1.24–1.10(m,16H),0.97(d,J=6.75Hz,6H);13C NMR(101MHz,CDCl3,77.16ppm)δ:147.87(s),147.56(s),145.94(s),136.56(d,J=4.63Hz),136.44(d,J=7.27Hz),132.29(d,J=2.9Hz),131.58(d,J=5.89Hz),127.56(s),126.06(s),120.30(s),34.58(d,J=15.59Hz),34.02(s),30.76(d,J=15.50Hz),30.53(s),29.38(s),27.57(d,J=11.01Hz),27.35(d,J=8.81Hz),26.45(s),25.84(s),24.02(s),22.86(s);31P NMR(162MHz,CDCl3,7.27ppm)δ:-12.30;HRMS-ESI(m/z)for C33H49P[M+H]+:计算值477.3650,实验值477.3636。
实施例38
本实施例与实施例1的区别仅在于:所述磷氧化合物的结构式如下式(II)所示,反应条件为10mol%Bu4NI、100℃、24h,加入水淬灭后,核磁产率为85%,产物用BH3保护后分离,其余步骤均与实施例1一致,得到的产率为71%,所述产物的结构表征数据为Rf=0.32(PE∶EA=8∶1,v/v),1H NMR(400MHz,CDCl3,7.27ppm)δ:1.89-1.70(m,18H),1.42-1.33(m,6H),1.25-1.21(m,8H);13C NMR(101MHz,CDCl3,77.16ppm)δ:31.07(s),30.77(s),27.88(s),27.30(d,J=10.40Hz),26.20(s);31P NMR(162MHz,CDCl3,7.27ppm)δ:27.80(br);HRMS-ESI(m/z)for C18H36BP[M+Na]+:计算值317.2545,实验值317.2535。
PCy3·BH3
实施例39
本实施例与实施例1的区别仅在于:所述磷氧化合物的结构式如下式(II)所示,反应条件为10mol%Bu4NI、100℃、24h,加入水淬灭后,核磁产率为92%,产物用BH3保护后分离,其余步骤均与实施例1一致,得到的产率为76%,所述产物的结构表征数据为Rf=0.30(PE∶EA=8∶1,v/v),1H NMR(400MHz,CDCl3,7.27ppm)δ:1.58-1.52(m,6H),1.48-1.38(m,12H),0.94-0.92(m,9H);13C NMR(101MHz,CDCl3,77.16ppm)δ:24.83(d,J=2.14Hz),24.50(d,J=12.59Hz),23.12(s),22.78(s),13.72(s);31P NMR(162MHz,CDCl3,7.27ppm)δ:14.40(br);HRMS-ESI(m/z)for C12H30BP[M+Na]+:计算值239.2076,实验值239.2073。
P(n-Bu)3·BH3
实施例40
本实施例与实施例1的区别仅在于:所述磷氧化合物的结构式如下式所示,60℃下反应2h,其余步骤均与实施例1一致,得到白色固体的产率为94%,Rf=0.36(PE:EA=10:1,V/V),1H NMR(400MHz,CDCl3,7.27ppm)δ:7.25–7.19(m,6H),6.89–6.85(m,6H),3.79(s,9H);13C NMR(101MHz,CDCl3,77.16ppm)δ:160.01(s),134.87(d,J=20.68Hz),128.92(d,J=7.96Hz),114.06(d,J=7.64Hz),55.09(s);31P NMR(162MHz,CDCl3,7.27ppm)δ:-10.10;HRMS-ESI(m/z)for C21H21O3P[M+H]+:计算值353.1307,实验值353.1295。
实施例41
本实施例与实施例1的区别仅在于:所述磷氧化合物的结构式如下式所示,60℃下反应2h,其余步骤均与实施例1一致,得到白色固体的产率为81%,所述产物的结构表征数据如下:Rf=0.2(PE:EA=10:1,v/v),1H NMR(400MHz,CDCl3,7.27ppm)δ:7.36–7.32(m,3H),6.92–6.89(m,3H),6.85(t,J=7.39Hz,3H),6.74–6.72(m,3H),3.76(s,9H);13C NMR(101MHz,CDCl3,77.16ppm)δ:161.72(d,J=16.54Hz),133.98(s),130.07(s),124.77(s),121.00(s),110.36(s),55.86(s);31P NMR(162MHz,CDCl3,7.27ppm)δ:-39.49;HRMS-ESI(m/z)for C21H21O3P[M+H]+:计算值353.1307,实验值352.1297。
实施例42
本实施例与实施例1的区别仅在于:所述磷氧化合物的结构式如下式所示,60℃下反应3h,其余步骤均与实施例1一致,得到白色固体的产率为84%,所述产物的结构表征数据如下:Rf=0.42(PE),1H NMR(400MHz,CDCl3,7.27ppm)δ:7.24–7.20(m,6H),7.16–7.14(m,6H),2.36(s,9H);13C NMR(101MHz,CDCl3,77.16ppm)δ:138.47(s),134.11(d,J=9.20Hz),133.60(d,J=19.51Hz),129.22(d,J=7.00Hz),21.26(s);31P NMR(162MHz,CDCl3,7.27ppm)δ:-7.87;HRMS-ESI(m/z)for C21H21P[M+H]+:计算值305.1459,实验值305.1448。
实施例43
本实施例与实施例1的区别仅在于:所述磷氧化合物的结构式如下式所示,60℃下反应2h,其余步骤均与实施例1一致,得到白色固体的产率为84%,所述产物的结构表征数据如下:Rf=0.48(PE),1H NMR(400MHz,CDCl3,7.27ppm)δ:7.27–7.20(m,6H),7.06(t,J=7.24Hz,3H),6.74–6.70(m,3H),2.39(s,9H);13C NMR(101MHz,CDCl3,77.16ppm)δ:142.88(d,J=26.05Hz),134.46(d,J=9.92Hz),133.21(s),130.22(d,J=4.77Hz),128.85(s),126.30(s),21.38(d,J=21.51Hz);31P NMR(162MHz,CDCl3,7.27ppm)δ:-29.38;HRMS-ESI(m/z)for C21H21P[M+H]+:计算值304.1381实验值304.1450。
实施例44
本实施例与实施例1的区别仅在于:所述磷氧化合物的结构式如下式所示,60℃下反应2h,其余步骤均与实施例1一致,得到白色固体的产率为84%,所述产物的结构表征数据如下:Rf=0.53(PE),1H NMR(400MHz,CDCl3,7.27ppm)δ:7.36–7.33(m,6H),7.24–7.18(m,6H);13C NMR(101MHz,CDCl3,77.16ppm)δ:135.54(s),134.92(s),134.79(s),134.72(s),128.98(d,J=7.09Hz);31PNMR(162MHz,CDCl3,7.27ppm)δ:-8.48;HRMS-ESI(m/z)forC18H12Cl3P[M+H]+:计算值364.9820,实验值364.9813。
实施例45
本实施例与实施例1的区别仅在于:所述磷氧化合物的结构式如下式所示,60℃下反应2h,其余步骤均与实施例1一致,得到白色固体的产率为89%,所述产物的结构表征数据如下:Rf=0.48(PE),1H NMR(400MHz,CDCl3,7.27ppm)δ:7.27–7.22(m,6H),7.05(t,J=8.53Hz,6H);13C NMR(101MHz,CDCl3,77.16ppm)δ:164.82(s),162.34(s),135.58(dd,J=21.16,8.09Hz),132.61(dd,J=10.87,3.51Hz),116.05(dd,J=20.95,7.39Hz);31P NMR(162MHz,CDCl3,7.27ppm)δ:-9.03;19F NMR(300MHz,CDCl3,7.27ppm)δ:111.91;HRMS-ESI(m/z)for C18H13F3P[M+H]+:计算值317.0707,实验值317.0699。
实施例46
本实施例与实施例1的区别仅在于:所述磷氧化合物的结构式如下式所示,60℃下反应2h,其余步骤均与实施例1一致,得到白色固体的产率为85%,所述产物的结构表征数据如下:Rf=0.36(PE),1H NMR(400MHz,CDCl3,7.27ppm)δ:7.60(dd,J=4.91,1.11Hz,4H),7.38-7.36(m,4H),7.12–7.09(m,4H);13CNMR(101MHz,CDCl3,77.16ppm)δ:138.97(d,J=21.51Hz),135.50(d,J=27.68Hz),132.02(s),128.03(d,J=8.58Hz);31P NMR(162MHz,CDCl3,7.27ppm)δ:-46.23;HRMS-ESI(m/z)for C12H9PS3[M+H]+:计算值280.9682,实验值280.9673。
实施例47
本实施例与实施例1的区别仅在于:所述磷氧化合物的结构式如下式所示,60℃下反应2h,其余步骤均与实施例1一致,得到白色固体的产率为80%,所述产物的结构表征数据如下:Rf=0.36(PE),1H NMR(400MHz,CDCl3,7.27ppm)δ:7.93(d,J=7.78Hz,2H),7.70–7.67(m,2H),7.44(dd,J=7.55,1.24Hz,2H),7.32–7.30(td,J=7.42,3.77Hz,4H),7.29–7.18(m,3H);13C NMR(101MHz,CDCl3,77.16ppm)δ:143.6(s),142.5(s),136.10(d,J=18.72Hz),132.62(d,J=19.75Hz),130.40(d,J=21.62Hz),129.22(s),128.62(s),128.61(d,J=7.21Hz),127.54(d,J=7.28Hz),121.34(s);31P NMR(162MHz,CDCl3,7.27ppm)δ:-10.08;HRMS-ESI(m/z)for C18H13P[M+H]+:计算值261.0833,实验值261.0825。
实施例48
本实施例与实施例1的区别仅在于:所述磷氧化合物的结构式如下式所示,60℃下反应2h,其余步骤均与实施例1一致,得到白色固体的产率为78%,所述产物的结构表征数据如下:Rf=0.44(PE:EA=10:1,v/v),1H NMR(400MHz,CDCl3,7.27ppm)δ:8.00–7.99(m,2H),7.39–7.27(m,12H),4.44(t,J=12.00Hz,2H),1.15(t,J=8.01Hz,2H),0.10(s,9H);13CNMR(101MHz,CDCl3,77.16ppm)δ:166.68(s),143.94(d,J=13.99Hz),136.44(d,J=10.92Hz),134.11(d,J=20.00Hz),133.32(d,J=18.77Hz),130.76(s),129.38(d,J=2.08Hz),129.26(s),128.82(d,J=7.65Hz),63.46(s),17.59(s),-1.25(s);31P NMR(162MHz,CDCl3,7.27ppm)δ:-5.07;HRMS-ESI(m/z)for C24H27O2PSi[M+H]+:计算值406.1518,实验值407.1593。
实施例49
本实施例与实施例1的区别仅在于:所述磷氧化合物的结构式如下式所示,60℃下反应2h,其余步骤均与实施例1一致,得到白色固体的产率为78%,所述产物的结构表征数据如下:Rf=0.30(PE:EA=2:1,v/v),1H NMR(400MHz,CDCl3,7.27ppm)δ:7.49(d,J=1.39Hz,2H),7.37–7.30(m,12H),3.65(t,J=6.95Hz,2H),3.42(t,J=6.60Hz,2H),1.95(q,J=6.67Hz,2H),1.88(q,J=6.50Hz,2H);13C NMR(101MHz,CDCl3,77.16ppm)δ:169.26(s),139.67(d,J=12.67Hz),137.20(s),136.46(d,J=10.55Hz),133.79(d,J=19.78Hz),133.30(d,J=19.13Hz),128.90(s),128.54(d,J=6.99Hz),127.02(d,J=6.68Hz),49.52(s),46.13(s),26.32(s),24.36(s);31P NMR(162MHz,CDCl3,7.27ppm)δ:-5.50;HRMS-ESI(m/z)for C23H22OP[M+H]+:计算值360.1517,实验值360.1508。
实施例50
本实施例与实施例1的区别仅在于:所述磷氧化合物的结构式如下式所示,60℃下反应3h,其余步骤均与实施例1一致,得到白色固体的产率为91%,所述产物的结构表征数据如下:Rf=0.37(PE),1H NMR(400MHz,CDCl3,7.27ppm)δ:7.38–7.29(m,12H),7.06(t,J=8.64Hz,2H);13C NMR(101MHz,CDCl3,77.16ppm)δ:164.59(s),162.11(s),137.09(d,J=10.72Hz),135.87(d,J=8.06Hz),135.66(d,J=8.05Hz),133.52(d,J=19.54Hz),132.64(d,J=3.49Hz),132.53(d,J=3.54Hz),128.78(s),128.55(d,J=6.84Hz),115.79(d,J=7.75Hz),115.59(d,J=7.69Hz);31P NMR(162MHz,CDCl3,7.27ppm)δ:-6.68;19F NMR(300MHz,CDCl3)δ-112.41;HRMS-ESI(m/z)for C18H14FP[M+H]+:计算值281.0895,实验值281.0887。
实施例51
本实施例与实施例1的区别仅在于:所述磷氧化合物的结构式如下式所示,60℃下反应2h,其余步骤均与实施例1一致,得到白色固体的产率为86%,所述产物的结构表征数据如下:Rf=0.47(PE:EA=10:1,v/v),1H NMR(400MHz,CDCl3,7.27ppm)δ:7.59(dd,J=8.30,1.47Hz,2H),7.41–7.31(m,12H);13C NMR(101MHz,CDCl3,77.16ppm)δ:145.09(d,J=16.72Hz),135.33(d,J=10.47Hz),134.00(d,J=20.30Hz),133.45(d,J=18.58Hz),131.67(d,J=6.05Hz),129.45(s),128.83(d,J=7.35Hz),118.69(s),111.86(s);31P NMR(162MHz,CDCl3,7.27ppm)δ:-4.31;HRMS-ESI(m/z)for C19H14NP[M+H]+:计算值288.0942,实验值288.0932。
实施例52
本实施例与实施例1的区别仅在于:所述磷氧化合物的结构式如下式所示,60℃下反应2h,其余步骤均与实施例1一致,得到白色固体的产率为78%,所述产物的结构表征数据如下:Rf=0.44(PE:EA=10:1,v/v),1H NMR(400MHz,CDCl3,7.27ppm)δ:7.47–7.45(m,2H),7.35–7.31(m,12H),5.81(s,1H),4.15–4.10(m,2H),4.09–4.05(m,2H);13C NMR(101MHz,CDCl3,77.16ppm)δ:138.69(d,J=11.39Hz),138.43(s),137.03(d,J=10.54Hz),133.89(d,J=19.49Hz),128.92(s),128.65(d,J=6.97Hz),126.69(d,J=6.94Hz),103.60(s),65.52(s);31P NMR(162MHz,CDCl3,7.27ppm)δ:-5.75;HRMS-ESI(m/z)for C21H19O2P[M+H]+:计算值335.1201,实验值335.1188。
实施例53
本实施例与实施例1的区别仅在于:所述磷氧化合物的结构式如下式所示,60℃下反应2h,其余步骤均与实施例1一致,得到白色固体的产率为86%,所述产物的结构表征数据如下:Rf=0.13(PE:EA=10:1,v/v),1H NMR(400MHz,CDCl3,7.27ppm)δ:8.53-8.51(m,2H),7.44–7.32(m,10H),7.13–7.10(m,2H);13C NMR(101MHz,CDCl3,77.16ppm)δ:149.24(d,J=4.36Hz),148.98(d,J=17.99Hz),134.86(d,J=9.92Hz),134.18(d,J=20.37Hz),129.53(s),128.82(d,J=7.51Hz),127.21(d,J=15.13Hz);31P NMR(162MHz,CDCl3,7.27ppm)δ:-6.98;HRMS-ESI(m/z)for C17H14NP[M+H]+:计算值264.0942,实验值264.0934。
实施例54
本实施例与实施例1的区别仅在于:所述磷氧化合物的结构式如下式所示,60℃下反应2h,其余步骤均与实施例1一致,得到白色固体的产率为76%,所述产物的结构表征数据如下:Rf=0.21(PE),1H NMR(400MHz,CDCl3,7.27ppm)δ:8.71(d,J=8.3Hz,1H),8.65(d,J=8.28Hz,1H),8.45(dd,J=8.24,4.72Hz,1H),7.61(q,J=7.2Hz,3H),7.53–7.46(m,2H),7.39–7.31(m,10H),7.24–7.22(m,2H);13C NMR(101MHz,CDCl3,77.16ppm)δ:135.98(d,J=9.39Hz),134.34(d,J=19.92Hz),133.76(s),133.39(d,J=3.53Hz),133.22(d,J=10.54Hz),131.36(d,J=2.42Hz),130.73(s),130.12(d,J=4.34Hz),128.96(s),128.90(s),128.61(d,J=7.17Hz),127.26(s),127.11(s),126.85(s),126.69(d,J=2.39Hz),126.63(s),122.94(d,J=1.83Hz),122.46(s);31P NMR(162MHz,CDCl3,7.27ppm)δ:-12.91;HRMS-ESI(m/z)for C26H19P[M+H]+:计算值363.1303,实验值363.1292。
实施例55
本实施例与实施例1的区别仅在于:所述磷氧化合物的结构式如下式所示,60℃下反应2h,其余步骤均与实施例1一致,得到白色固体的产率为82%,所述产物的结构表征数据如下:Rf=0.42(PE),1H NMR(400MHz,CDCl3,7.27ppm)δ:7.60(dd,J=4.99,1.12Hz,1H),7.42–7.31(m,10H),7.17–7.09(m,1H);13CNMR(101MHz,CDCl3,77.16ppm)δ:137.91(d,J=8.65Hz),13.43(s),136.17(s),133.06(d,J=19.60Hz),133.98(s),128.82(s),128.41(d,J=6.99Hz),128.00(d,J=8.01Hz);31P NMR(162MHz,CDCl3,7.27ppm)δ:-19.91;HRMS-ESI(m/z)for C16H13PS[M+H]+:计算值269.0554,实验值269.0544。
实施例56
本实施例与实施例1的区别仅在于:所述磷氧化合物的结构式如下式所示,80℃下反应24h,其余步骤均与实施例1一致,得到白色固体的产率为87%,所述产物的结构表征数据如下:Rf=0.48(PE),1H NMR(400MHz,CDCl3,7.27ppm)δ:7.40–7.35(m,8H),7.32–7.30(m,12H),2.21(t,J=7.77Hz,4H),1.68–1.55(m,2H);13C NMR(101MHz,CDCl3,77.16ppm)δ:138.62(d,J=12.58Hz),132.82(d,J=18.46Hz),128.65(s),128.52(d,J=6.64Hz),29.74(t,J=12.31Hz),22.49(t,J=16.95Hz);31P NMR(162MHz,CDCl3,7.27ppm)δ:-17.55;HRMS-ESI(m/z)for C27H26P2[M+H]+:计算值413.1588,实验值413.1574。
实施例57
本实施例与实施例1的区别仅在于:所述磷氧化合物的结构式如下式所示,80℃下反应24h,其余步骤均与实施例1一致,得到白色固体的产率为89%,所述产物的结构表征数据如下:Rf=0.40(PE:EA=10:1,v/v),1H NMR(400MHz,CDCl3,7.27ppm)δ:7.44–7.41(m,8H),7.38–7.34(m,12H),2.03(t,J=7.32Hz,4H),1.57–1.55(m,4H);13C NMR(101MHz,CDCl3,7.27ppm)δ:138.76(d,J=12.19Hz),132.66(d,J=18.03Hz),128.44(s),128.32(d,J=4.36Hz),27.76–27.39(m);31P NMR(162MHz,CDCl3,7.27ppm)δ:-16.10;HRMS-ESI(m/z)for C28H28P2[M+H]+:计算值427.1744,实验值427.1730。
实施例58
本实施例与实施例1的区别仅在于:所述磷氧化合物的结构式如下式所示,80℃下反应24h,其余步骤均与实施例1一致,得到白色固体的产率为89%,所述产物的结构表征数据如下:Rf=0.84(PE:EA=10:1,v/v),1H NMR(400MHz,CDCl3,7.27ppm)δ:7.43–7.38(m,8H),7.35–7.31(m,12H),2.03–1.98(m,4H),1.62–1.54(m,2H),1.50–1.42(m,2H);13C NMR(101MHz,CDCl3,77.16ppm)δ:138.93(d,J=12.75Hz),132.79(d,J=18.26Hz),128.58(s),128.48(d,J=6.60Hz),32.71(t,J=12.93Hz),27.89(d,J=11.08Hz),25.61(d,J=16.07Hz);31P NMR(162MHz,CDCl3,7.27ppm)δ:-16.17;HRMS-ESI(m/z)for C29H30P2[M+H]+:计算值441.1901,实验值441.1887。
实施例59
本实施例与实施例1的区别仅在于:所述磷氧化合物的结构式如下式所示,80℃下反应24h,其余步骤均与实施例1一致,得到白色固体的产率为89%,所述产物的结构表征数据如下:Rf=0.76(PE:EA=10:1,v/v),1H NMR(400MHz,CDCl3,7.27ppm)δ:7.42–7.38(m,8H),7.35–7.30(m,12H),2.01(t,J=7.13Hz,3H);13C NMR(101MHz,CDCl3,77.16ppm)δ:138.98(d,J=12.59Hz),132.81(d,J=18.27Hz),128.59(s),128.50(d,J=6.58Hz),30.94(d,J=12.84Hz),28.07(d,J=10.92Hz),25.95(d,J=15.93Hz);31P NMR(162MHz,CDCl3,7.27ppm)δ:-16.17;HRMS-ESI(m/z)for C30H32P2[M+H]+:计算值455.2057,实验值455.2045。
实施例60
本实施例与实施例1的区别仅在于:所述磷氧化合物的结构式如下式所示,80℃下反应24h,其余步骤均与实施例1一致,得到白色固体的产率为77%,所述产物的结构表征数据如下:Rf=0.19(PE:EA=2:1,v/v),1H NMR(400MHz,CDCl3,7.27ppm)δ:7.72-7.67(m,3H),7.57–7.53(m,1H),7.43–7.30(m,8H),7.24–7.17(m,5H),7.07–7.03(m,3H);13C NMR(101MHz,CDCl3,77.16ppm)δ:142.52(dd,J=23.36,10.87Hz),139.52(s),139.20(s),138.50(s),138.18(s),137.16(m),134.08(m),133.31(d,J=19.44Hz),132.87(s),132.13(dd,J=9.67,2.41Hz),131.80(d,J=2.67Hz),131.46(d,J=2.75Hz),128.64(d,J=12.07Hz),128.25(d,J=2.09Hz),128.14(m);31P NMR(162MHz,CDCl3,7.27ppm)δ:30.53(d),-14.02(d);HRMS-ESI(m/z)for C30H24OP2[M+H]+:计算值463.1381,实验值463.1364。
实施例61
本实施例与实施例1的区别仅在于:所述磷氧化合物的结构式如下式所示,80℃下反应24h,其余步骤均与实施例1一致,得到白色固体的产率为73%,所述产物的结构表征数据如下:Rf=0.37(PE:EA=2:1,v/v),1H NMR(400MHz,CDCl3,7.27ppm)δ:7.86–7.80(m,4H),7.73–7.67(m,4H),7.47–7.34(m,11H),7.30–7.20(m,9H),6.83–6.78(m,4H);13C NMR(101MHz,CDCl3,77.16ppm)δ:144.99(m),142.97(s),142.67(s),138.83(d,J=12.82Hz),137.25(d,J=13.47Hz),136.91(d,J=11.37Hz),134.80(d,J=22.37Hz),134.61(s),134.15(s),133.75(d,J=11.59Hz),133.57(s),133.39(s),133.19(m),132.36(s),132.23(d,J=9.59Hz),131.69(d,J=9.46Hz),131.30(d,J=2.87Hz),130.86(d,J=2.87Hz),130.06(s),129.26(s),128.92(s),128.79(s),128.49(d,J=8.65Hz),128.11(m),127.87(d,J=7.22Hz),17.72(s),127.59(d,J=4.37Hz),127.45(d,J=2.43Hz),127.09(d,J=2.81Hz),126.13(d,J=10.28Hz),125.63(s);31P NMR(162MHz,CDCl3,7.27ppm)δ:27.25,-15.14;HRMS-ESI(m/z)for C44H32OP[M+H]+:计算值639.2007,实验值639.1989。
实施例62
本实施例与实施例1的区别仅在于:所述磷氧化合物的结构式如下式所示,80℃下反应24h,其余步骤均与实施例1一致,得到白色固体的产率为88%,所述产物的结构表征数据如下:Rf=0.56(PE:EA=10:1,v/v),1H NMR(400MHz,CDCl3,7.27ppm)δ:7.74–7.07(m,26H),6.07–6.04(m,2H);13C NMR(101MHz,CDCl3,77.16ppm)δ:159.32(d,J=17.73Hz),136.73(d,J=12.07Hz),133.98(d,J=20.65Hz),130.24(s),129.10(d,J=16.68Hz),128.48(s),128.33(m),123.65(s),118.11(s);31P NMR(162MHz,CDCl3,7.27ppm)δ:-16.66;HRMS-ESI(m/z)for C36H28OP2[M+H]+:计算值539.1694,实验值539.1683。
实施例63
本实施例所述通过五价磷化合物制备三价磷化合物的方法包含以下步骤:在氮气保护下将55.6g的下式所述磷氧化合物溶于乙腈(——400.0mL)中,在室温下缓慢滴加210mmol的(COCl)2,滴加完毕后反应30min,随后向上述溶液中加入n-Bu4NI 5%和250mmol的铁粉,在60℃下反应8h;待反应完成后,冷却至室温,然后向反应体系中加入500mL 3.0M的NaOH溶液,再加入硅藻土过滤,再用乙酸乙酯洗涤滤饼,合并有机相后,用无水硫酸钠进行干燥——。并浓缩,得到的粗产品在惰性气体保护下,用MeOH/H2O 3:1的混合液60℃下打浆纯化,最终得到无色固体49.2g,收率为93.5%,纯度为>99.5%。
实施例64
本实施例所述通过五价磷化合物制备三价磷化合物的方法包含以下步骤:在氮气保护下将55.6g的下式所述磷氧化合物溶于乙腈(400.0mL)中,在室温下缓慢滴加210mmol的(COCl)2,滴加完毕后反应30min,随后向上述溶液中加入I2 2.5%和250mmol的铁粉,在60℃下反应8h;待反应完成后,冷却至室温,然后向反应体系中加入500mL 3.0M的NaOH溶液,再加入硅藻土过滤,再用乙酸乙酯洗涤滤饼,合并有机相后,用无水硫酸钠进行干燥并浓缩,得到的粗产品在惰性气体保护下,用MeOH/H2O 3:1的混合液60℃下打浆纯化,最终得到无色固体48.1g,收率为91.4%,纯度为≥99.5%。
实施例65
实施例65与实施例1的区别在于:所述三价磷化合物的制备反应如下式,所述还原剂为铁粉(100mesh,99%),反应温度为60℃,转化率为97%。
实施例66-71
实施例66-71与实施例65的区别仅在于:还原剂和反应温度不同,其余参数均与实施例65一致;实施例66-71所用还原剂、反应温度和产物的转化率如下表3所示。
表3
还原剂 | 温度 | 转化率 | |
实施例66 | 铁丝(diam:1.0mm,99.9%) | 80℃ | 90% |
实施例67 | 铁箔(thickness:0.1mm,99.9%) | 60℃ | 91% |
实施例68 | 铁片(thickness:1.0mm,99.9%) | 80℃ | 92% |
实施例69 | 不锈钢粉(100mesh,Type:304-L) | 80℃ | 86% |
实施例70 | 铁丝(diam:0.5mm,99.9%) | 60℃ | 90% |
实施例71 | 铁粉(200mesh,99%) | 60℃ | 95% |
实施例72
实施例72与实施例1的区别仅在于:所述催化剂为10mol%的Bu4NI,所述还原剂为铁粉,所述反应步骤为:先将催化剂与还原剂在溶剂中加热,随后与活化的五价磷化合物反应12h,最终产物的转化率94%。
实施例73
实施例73与实施例1的区别仅在于:所述催化剂为5mol%的I2,所述还原剂为铁粉,所述反应步骤为:先将催化剂与还原剂在溶剂中加热,随后与活化的五价磷化合物反应24h,最终产物的转化率96%。
实施例74
实施例74与实施例65的区别仅在于:催化剂加入量为1mol%,其余均与实施例65一致,最终反应产物的转化率为98%。
实施例75
实施例75与实施例65的区别仅在于后处理不同,具体为:反应后进行过滤,对粗产物进行重结晶,通过单晶结构分析,得到的产物为(PPh)2FeCl2,产率为63%。
实施例76
实施例76与实施例65的区别仅在于:反应时间为0.5h,其余均与实施例65相同,最终反应产物的转化率为88%。
实施例77
实施例77与实施例65的区别仅在于:催化剂加入量为0.1mol%,其余均与实施例65一致,最终反应产物的转化率为97%。
实施例78
实施例78与实施例65的区别仅在于:铁粉加入量为1eq,其余均与实施例65一致,最终反应产物的转化率为96%。
实施例79
实施例79与实施例65的区别仅在于:铁粉加入量为2eq,其余均与实施例65一致,最终反应产物的转化率为98%。
实施例80
实施例80与实施例65的区别仅在于:溶剂为1,2-二氯乙烷,其余均与实施例65一致,最终反应产物的转化率为90%。
实施例81
实施例81与实施例65的区别仅在于:催化剂为30mol%,其余均与实施例65一致,最终反应产物的转化率为97%。
实施例82
实施例82与实施例65的区别仅在于:溶剂为甲苯,100℃下反应72h,其余均与实施例65一致,最终反应产物的转化率为89%。
实施例83
实施例83与实施例65的区别仅在于:溶剂为氯苯,其余均与实施例65一致,最终反应产物的转化率为92%。
实施例84
实施例84与实施例36的区别仅在于:还原剂为3eq的铁粉,其余均与实施例36一致,最终反应产物的转化率为87%。
实施例85
实施例85与实施例65的区别仅在于:活化剂为二(三氯甲基)碳酸酯,其余均与实施例65一致,最终反应产物的转化率为94%。
实施例86
实施例86与实施例65的区别仅在于:活化剂为二光气,其余均与实施例65一致,最终反应产物的转化率为93%。
实施例87
实施例87与实施例65的区别仅在于:活化剂为光气溶液,其余均与实施例65一致,最终反应产物的转化率为97%。
实施例88
实施例88与实施例65的区别仅在于:反应浓度为2M,反应温度为0℃,反应时间为72h,其余均与实施例65一致,最终反应产物的转化率为92%。
实施例89
实施例89与实施例65的区别仅在于:反应温度为30℃,其余均与实施例65一致,最终反应产物的转化率为92%。
实施例90
实施例90与实施例65的区别仅在于:反应浓度为0.1M,其余均与实施例65一致,最终反应产物的转化率为92%。
实施例91
实施例91与实施例65的区别仅在于:反应浓度为2.0M,其余均与实施例65一致,最终反应产物的转化率为92%。
实施例92
实施例92与实施例65的区别仅在于:催化剂为5mol%1,2-二碘乙烷,其他均与实施例65一致,最终反应产物的转化率为98%。
实施例93
实施例93与实施例65的区别仅在于:催化剂为5% CuI,其他均与实施例65一致,最终反应产物的转化率为96%。
对比例1
对比例1与实施例1的区别仅在于:催化剂为10mol%NaOBz,其余步骤均与实施例1一致,转化率为0。
对比例2
对比例2与实施例1的区别仅在于:催化剂为10mol%NaOAc,其余步骤均与实施例1一致,转化率为0。
对比例3
对比例3与实施例36的区别仅在于:催化剂为5mol%LiAlH4,其余步骤均与实施例1一致,产率14%。
对比例4
对比例4与实施例36的区别仅在于:催化剂为5mol%镁粉,其余步骤均与实施例1一致,产率13%。
对比例5
对比例5与实施例36的区别仅在于:催化剂为5mol%锌粉,其余步骤均与实施例1一致,产率13%。
对比例6
对比例6与实施例36的区别仅在于:催化剂为5mol%HSiCl3,其余步骤均与实施例1一致,产率10%。
对比例7
对比例7与实施例1的区别仅在于:反应中溶剂为四氢呋喃,其余步骤均与实施例1一致,产率<5%。
对比例8
对比例8与实施例1的区别仅在于:反应中溶剂为1,4-二氧六环,其余步骤均与实施例1一致,产率<5%。
对比例9
对比例9与实施例1的区别仅在于:反应中溶剂为DMF,其余步骤均与实施例1一致,产率<5%。
对比例10
对比例10与实施例1的区别仅在于:反应中溶剂为DMSO,其余步骤均与实施例1一致,产率<5%。
对比例11
对比例11与实施例1的区别仅在于:反应中溶剂为乙醇,其余步骤均与实施例1一致,产率小于<5%。
对比例12
对比例12与实施例1的区别仅在于:不加铁粉,其余步骤均与实施例1一致,产率为0。
对比例13
对比例13与实施例1的区别仅在于:当量催化剂,不加铁粉,其余步骤均与实施例1一致,产率为0。
对比例14
对比例14与实施例1的区别仅在于:不加活化剂,其余步骤均与实施例1一致,产率为0。
对比例15
对比例15与实施例36的区别仅在于:不加催化剂,反应温度为120℃,反应溶剂为氯苯,其余步骤均与实施例1一致,产物核磁产率为15%,并伴有多种降解的未知含磷副产物。
根据本发明上述实施例所制备得到的三价磷化合物的结构表征数据可知,本发明成功制备出产率较高的三价磷化合物或三价磷的铁配合物,且在特定原料条件下,可实现在不高于100℃下将五价磷化合物还原;同时,将还原剂与催化剂先在溶剂中加热,然后在与被活化的五价磷化合物反应,反应速率也会大大提高。对比例3-6中虽然使用了还原性较强的原料作为催化剂,但是最终制得的产物产率均较低,且对比例3中催化剂为LiAlH4,一分子LiAlH4可以提供四个H-作为还原剂,因此对比例3中5mol%LiAlH4相当于20mol%的H-还原剂的量,即加入了过量的还原剂才使得反应产率高于10%;对比例4-6中采用的活泼金属催化剂在反应时均产生了MgCl2、ZnCl2和HCl等氯化物,氯化物将铁粉活化,才使得反应产率高于5%。
综上,本发明中五价磷化合物的底物兼容性广泛,能够高效地还原各种类型的五价磷,尤其对富电子磷的还原具有非常大的优势;本发明采用的原料廉价易得,未采用价格高昂的硅氢、硼烷等试剂,具有显著的成本优势,更适合大规模工业化应用。
最后所应当说明的是,以上实施例仅用以说明本发明的技术方案而非对本发明保护范围的限制,尽管参照较佳实施例对本发明作了详细说明,本领域的普通技术人员应当理解,可以对本发明的技术方案进行修改或者等同替换,而不脱离本发明技术方案的实质和范围。
Claims (10)
1.一种用于五价磷化合物制备三价磷化合物的催化剂,其特征在于,所述催化剂的结构为XCR1R2CR3R4X或MXn;其中,R1-R4独立地选自氢、卤素、C1-C4的烷基或苯基,M选自季铵正离子(R5R6R7R8N)、季鏻正离子(R5R6R7R8P)、铁、铜、钠、锂、钾、锌、镁、钙、锶、钡、铝或铯,其中,R5-R8选自氢、C1-C12的烷基、苯基、苄基中的至少一种,X选自氯、溴、碘、硫芳基、硒芳基或碲芳基,X中的芳基选自一个或多个C1-C4烷基取代或未取代的苯基。
2.如权利要求1所述用于五价磷化合物制备三价磷化合物的催化剂,其特征在于,所述催化剂的结构为XCR1R2CR3R4X或MXn;其中,R1-R4选自氢、卤素、C1-C4的烷基或苯基,M选自季铵正离子(R5R6R7R8N)、季鏻正离子(R5R6R7R8P)、铁、钠、锂、钾、镁、钙、铝、锌或铜,其中,R5-R8选自氢、C1-C4的烷基、苯基、苄基中的至少一种,X选自溴、碘、硒芳基或碲芳基,所述X中的芳基选自一个或多个C1-C4烷基取代或未取代的苯基。
3.如权利要求1所述用于五价磷化合物制备三价磷化合物的催化剂,其特征在于,所述催化剂包含四正丁铵碘盐、四正丁铵溴盐、碘单质、碘化锂、碘化钠、碘化钾、联苯二碲、碘化亚铁、碘化亚铜、二碘乙烷、二苯基二硒醚、二苯基二硫醚中的至少一种。
4.一种三价磷化合物,其特征在于,所述三价磷化合物的制备原料包含如权利要求1-3任一项所述的催化剂。
5.如权利要求4所述的三价磷化合物,其特征在于,所述三价磷化合物的制备原料还包含五价磷化合物、还原剂、活化剂和溶剂。
7.如权利要求5所述的三价磷化合物,其特征在于,所述还原剂为金属铁或包含铁的金属材料;
优选地,所述还原剂包含铁粉、不锈钢、铁丝、铁箔和铁片。
8.如权利要求1或5所述的三价磷化合物,其特征在于,采用如下(Ⅰ)-(Ⅵ)中的至少一种:
(Ⅰ)所述活化剂包含草酰氯、二(三氯甲基)碳酸酯、光气和二光气;
(Ⅱ)所述溶剂包含C1-C4烷基取代或卤代的芳香烃、多卤代乙烷和腈类,优选地,所述溶剂包含甲苯、氯苯、1,2-二氯乙烷和乙腈;
(Ⅲ)所述催化剂中五价磷化合物中磷的个数与催化剂中X的物质的量之比≥1:0.3mol;
(Ⅳ)所述五价磷化合物中磷的个数与活化剂的物质的量之比为1:1-1.5mol;
(Ⅴ)所述五价磷化合物中磷的个数与还原剂的物质的量之比为1:1-3mol;
(Ⅵ)所述五价磷化合物中磷的个数与溶剂的体积之比为1:0.5-10mL。
10.如权利要求9所述三价磷化合物的制备方法,其特征在于,所述反应温度为0-100℃,反应时间为0.5-72h。
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