CN106543221A - 烷基亚膦酸二酯化合物或烷基次膦酸酯化合物的合成方法 - Google Patents
烷基亚膦酸二酯化合物或烷基次膦酸酯化合物的合成方法 Download PDFInfo
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- -1 diester compound Chemical class 0.000 title claims abstract description 56
- 239000002253 acid Substances 0.000 title claims abstract description 22
- 238000010189 synthetic method Methods 0.000 title claims abstract description 9
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- 239000002904 solvent Substances 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 16
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 12
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052740 iodine Inorganic materials 0.000 claims abstract description 11
- 239000011630 iodine Substances 0.000 claims abstract description 11
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 10
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- 150000003839 salts Chemical class 0.000 claims abstract description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 150000005690 diesters Chemical class 0.000 claims abstract 2
- 125000000217 alkyl group Chemical group 0.000 claims description 13
- 125000000524 functional group Chemical group 0.000 claims description 10
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 125000001072 heteroaryl group Chemical group 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
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- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 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
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- 125000001743 benzylic group Chemical group 0.000 abstract 1
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 40
- 238000000926 separation method Methods 0.000 description 37
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- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 20
- 238000005160 1H NMR spectroscopy Methods 0.000 description 20
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- DPKBAXPHAYBPRL-UHFFFAOYSA-M tetrabutylazanium;iodide Chemical compound [I-].CCCC[N+](CCCC)(CCCC)CCCC DPKBAXPHAYBPRL-UHFFFAOYSA-M 0.000 description 20
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
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- IAUSZEXXGVYYQH-UHFFFAOYSA-N benzylphosphonous acid Chemical compound OP(O)CC1=CC=CC=C1 IAUSZEXXGVYYQH-UHFFFAOYSA-N 0.000 description 5
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- SJHCUXCOGGKFAI-UHFFFAOYSA-N tripropan-2-yl phosphite Chemical compound CC(C)OP(OC(C)C)OC(C)C SJHCUXCOGGKFAI-UHFFFAOYSA-N 0.000 description 3
- GEZMEIHVFSWOCA-UHFFFAOYSA-N (4-fluorophenyl)methanol Chemical class OCC1=CC=C(F)C=C1 GEZMEIHVFSWOCA-UHFFFAOYSA-N 0.000 description 2
- 125000002927 2-methoxybenzyl group Chemical group [H]C1=C([H])C([H])=C(C(OC([H])([H])[H])=C1[H])C([H])([H])* 0.000 description 2
- WRMNZCZEMHIOCP-UHFFFAOYSA-N 2-phenylethanol Chemical compound OCCC1=CC=CC=C1 WRMNZCZEMHIOCP-UHFFFAOYSA-N 0.000 description 2
- 125000006497 3-methoxybenzyl group Chemical group [H]C1=C([H])C(=C([H])C(OC([H])([H])[H])=C1[H])C([H])([H])* 0.000 description 2
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 2
- 239000012190 activator Substances 0.000 description 2
- OOCCDEMITAIZTP-UHFFFAOYSA-N allylic benzylic alcohol Natural products OCC=CC1=CC=CC=C1 OOCCDEMITAIZTP-UHFFFAOYSA-N 0.000 description 2
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical class BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 2
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- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical class [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
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- XTTGYFREQJCEML-UHFFFAOYSA-N tributyl phosphite Chemical compound CCCCOP(OCCCC)OCCCC XTTGYFREQJCEML-UHFFFAOYSA-N 0.000 description 2
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- MLOUGLNUGXYJFP-UHFFFAOYSA-N (4-bromophenyl)methyl-diethoxyphosphane Chemical class CCOP(OCC)CC1=CC=C(Br)C=C1 MLOUGLNUGXYJFP-UHFFFAOYSA-N 0.000 description 1
- NSWQJASYEPJGJA-UHFFFAOYSA-N CCOP(C)(O)OCC.CNC(S)=N Chemical compound CCOP(C)(O)OCC.CNC(S)=N NSWQJASYEPJGJA-UHFFFAOYSA-N 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- IJMWOMHMDSDKGK-UHFFFAOYSA-N Isopropyl propionate Chemical compound CCC(=O)OC(C)C IJMWOMHMDSDKGK-UHFFFAOYSA-N 0.000 description 1
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- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
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- YOJPYCBLLSSTBL-UHFFFAOYSA-N benzyl(diethoxy)phosphane Chemical compound CCOP(OCC)CC1=CC=CC=C1 YOJPYCBLLSSTBL-UHFFFAOYSA-N 0.000 description 1
- 230000000975 bioactive effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- QSVDSCBXEHUUEH-UHFFFAOYSA-N diethoxy(2-phenylethyl)phosphane Chemical class CCOP(OCC)CCC1=CC=CC=C1 QSVDSCBXEHUUEH-UHFFFAOYSA-N 0.000 description 1
- NSSMTQDEWVTEKN-UHFFFAOYSA-N diethoxy(methyl)phosphane Chemical compound CCOP(C)OCC NSSMTQDEWVTEKN-UHFFFAOYSA-N 0.000 description 1
- PRJQMGXSQGBMNW-UHFFFAOYSA-N diethoxy(thiophen-2-ylmethyl)phosphane Chemical class CCOP(OCC)CC1=CC=CS1 PRJQMGXSQGBMNW-UHFFFAOYSA-N 0.000 description 1
- JJPBKCZJVYSKGV-UHFFFAOYSA-N diethoxyphosphane Chemical class CCOPOCC JJPBKCZJVYSKGV-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
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- 238000012986 modification Methods 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
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- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 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
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/40—Esters thereof
- C07F9/4003—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
- C07F9/4056—Esters of arylalkanephosphonic acids
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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
- C07F9/3205—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
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- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/40—Esters thereof
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Abstract
本发明公开了烷基亚膦酸二酯化合物或烷基次膦酸酯化合物的合成方法，该方法使用廉价易得、来源广泛、稳定低毒的醇类为烷基化试剂，使用廉价易得的碘盐为催化剂，无需溶剂，经反应可选择性地直接得到烷基亚膦酸二酯化合物。该反应方法简单，条件温和、无需有机溶剂、易于操作。本方法对反应条件的要求较低，可利用苄基型、烯丙基型和脂肪型等各种类型的醇为烷基化试剂，实现不同类型取代的烷基亚膦酸二酯的合成，还可以进一步扩展到取代亚膦酸二酯与醇的反应合成烷基次膦酸酯化合物。
Description
技术领域
本发明属于化学合成领域，具体涉及一种碘盐催化下烷基亚膦酸二酯化合物或烷基次膦酸酯化合物的合成方法。
背景技术
烷基亚膦酸酯和烷基次膦酸酯结构及其衍生物大量存在于天然产物和药理活性化合物中。它们还可作为中间产物还可以进一步转化为烷基亚膦酸和烷基次膦酸化合物、以及烯烃等具有较好抗癌能力、抗氧化能力的生物活性分子。因此，烷基亚膦酸酯和烷基次膦酸酯化合物的合成引起了越来越多有机化学家们的重视。
以烷基亚膦酸酯的合成为例，传统方法一般通过卤代烃和亚磷酸酯在高温下的阿尔布佐夫反应来合成，反应温度通常≥150℃，而且需采用毒性大、稳定性差的卤代烃作为烷基化试剂，且反应会产生活性高、沸点低的小分子卤代烃为副产物，产生污染。目前也有通过使用醇为烷基化试剂直接和亚磷酸酯反应制备烷基亚膦酸酯化合物的方法，但是需要使用过量的活化剂（如碘化锌）来促进反应，同样存在反应副产物多，纯化困难等问题。综上所述，已知的烷基亚膦酸酯的合成方法仍有不少缺点，阻碍了其在合成和工业上进一步的应用。
因此，寻找一种新的合成方法、可利用稳定低毒的原料一步得到烷基亚膦酸酯化合物，对有机合成、生化和药物化学家而言都是非常有意义的研究。
发明内容
本发明的目的是为了克服现有技术存在的缺点和不足，而提供一种烷基亚膦酸二酯化合物或烷基次膦酸酯化合物的合成方法。该方法使用原料来源广泛，廉价易得、稳定低毒，且反应高效。
为实现上述目的，本发明的技术方案是一种烷基亚膦酸二酯化合物或烷基次膦酸酯化合物的合成方法，
以碘盐为催化剂，亚磷酸三酯或亚膦酸二酯与醇在直接反应得到烷基亚膦酸二酯，反应温度为80～160℃，反应时间为1～60小时，分别制备烷基亚膦酸二酯化合物或烷基次膦酸酯化合物，其具体反应式为：
其中：
R1为各种官能团取代在2-、3-、4-、5-或6-位的苯基或其他取代芳基、稠环，或各种官能团取代的杂芳基，还可以是各种碳链长度和支链官能团取代的烷基；
R2是各种直链或支链取代的烷基，或各类官能团取代的芳基；
R3是各种直链或支链取代的烷基、或各类官能团取代的芳基、稠环以及各类官能团取代杂芳基。
进一步设置是所述的催化剂无机碘盐、有机碘盐、以及碘单质或碘代烷烃通过反应原位生成的碘盐。
进一步设置是催化剂的用量为0.1～100mol%。
进一步设置是所述反应在无溶剂条件下进行。
进一步设置是所述反应在在惰性气体保护下进行。
进一步设置是反应温度为100～150℃，反应时间为12～48小时。
本发明旨在开发一种碘盐为非过渡金属催化剂，以绿色的醇为烷基化试剂，与亚磷酸三酯化合物在无溶剂下进行高选择性反应合成烷基亚膦酸二酯化合物的新方法。本发明还将该方法进一步扩展到烷基次膦酸酯化合物的合成。
本发明的优点是：与文献方法相比，本方法可使用廉价易得、来源广泛、稳定低毒、绿色的醇类化合物为烷基化试剂，不使用过渡金属催化剂和配体，反应无需活化剂，不使用有机溶剂，副产物为小分子醇，绿色环保污染小。因此，本方法对反应条件的要求较低、适用范围较广，与已知方法相比优势明显，具有潜在广泛的应用前景。
下面结合具体实施方式对本发明做进一步介绍。
具体实施方式
下面通过实施例对本发明进行具体的描述，只用于对本发明进行进一步说明，不能理解为对本发明保护范围的限定，该领域的技术工程师可根据上述发明的内容对本发明作出一些非本质的改进和调整。
实施例1
亚磷酸三乙酯和苯甲醇制备苄基亚膦酸二乙酯
20mL管形反应器中依次加入苯甲醇（54.0mg,0.50mmol)，亚磷酸三乙酯（166.0mg,1.0mmol,2.0equiv.）和四丁基碘化铵（3.7mg,0.01mmol,2mol%），抽真空氮气保护，然后在无溶剂条件下加热到120℃反应24h。TLC监测反应完全后，产物用柱色谱分离提纯，分离收率90%。1H NMR(500MHz,CDCl3)δ7.44–6.87(m,5H),3.99–3.84(m,4H),3.08(d,J=21.5Hz,2H),1.17(t,J=7.0Hz,6H).13C NMR(125MHz,CDCl3)δ131.62(d,J=9.0Hz),129.77(d,J=6.5Hz),128.50(d,J=3.0Hz),126.84(d,J=3.6Hz),62.09(d,J=6.8Hz),33.79(d,J=138.2Hz),16.34(d,J=6.0Hz).31P NMR(202MHz,CDCl3)δ26.48(s)。
实施例2
亚磷酸三乙酯和4-氟苯甲醇制备4-氟苄基亚膦酸二乙酯
20mL管形反应器中依次加入4-氟苯甲醇（63.0mg,0.50mmol)，亚磷酸三乙酯（166.0mg,1.0mmol,2.0equiv.）和四丁基碘化铵（3.7mg,0.01mmol,2mol%），抽真空氮气保护，然后在无溶剂条件下加热到120℃反应24h。TLC监测反应完全后，产物用柱色谱分离提纯，分离收率81%。1H NMR(500MHz,CDCl3)δ7.29–7.24(m,2H),7.00(t,J=8.5Hz,2H),4.07–3.90(m,4H),3.12(d,J=21.5Hz,2H),1.25(t,J=7.0Hz,6H).13C NMR(126MHz,CDCl3)δ161.93(dd,J=245.3,3.9Hz),131.24(dd,J=7.9,6.7Hz),127.31(dd,J=9.2,3.3Hz),115.41(dd,J=21.5,3.0Hz),62.18(d,J=6.8Hz),32.90(d,J=139.2Hz),16.35(d,J=6.0Hz).31P NMR(202MHz,CDCl3)δ26.15(d,J=5.7Hz)。
实施例3
亚磷酸三乙酯和4-溴苯甲醇制备4-溴苄基亚膦酸二乙酯
20mL管形反应器中依次加入4-溴苯甲醇（93.0mg,0.50mmol)，亚磷酸三乙酯（166.0mg,1.0mmol,2.0equiv.）和四丁基碘化铵（3.7mg,0.01mmol,2mol%），抽真空氮气保护，然后在无溶剂条件下加热到120℃反应24h。TLC监测反应完全后，产物用柱色谱分离提纯，分离收率90%。1H NMR(500MHz,CDCl3)δ7.44(d,J=8.0Hz,2H),7.17(dd,J=8.0,2.0Hz,2H),4.10–3.94(m,4H),3.09(d,J=21.5Hz,2H),1.25(t,J=7.0Hz,6H).13C NMR(126MHz,CDCl3)δ131.64(d,J=3.0Hz),131.43(d,J=6.6Hz),130.78(d,J=9.1Hz),120.93(d,J=4.6Hz),62.22(d,J=6.8Hz),33.28(d,J=138.7Hz),16.37(d,J=5.9Hz).31P NMR(202MHz,CDCl3)δ25.51(s)。
实施例4
亚磷酸三乙酯和4-氰基苯甲醇制备4-（氰基）苄基亚膦酸二乙酯
20mL管形反应器中依次加入4-氰基苯甲醇（66.5mg,0.50mmol)，亚磷酸三乙酯（166.0mg,1.0mmol,2.0equiv.）和四丁基碘化铵（3.7mg,0.01mmol,2mol%），抽真空氮气保护，然后在无溶剂条件下加热到120℃反应24h。TLC监测反应完全后，产物用柱色谱分离提纯，分离收率80%。1H NMR(500MHz,CDCl3)δ7.62(d,J=8.0Hz,2H),7.43(dd,J=8.0,2.0Hz,2H),4.23–3.80(m,4H),3.21(d,J=22.5Hz,2H),1.26(t,J=7.0Hz,6H).13C NMR(125MHz,CDCl3)δ137.58(d,J=9.2Hz),132.25(d,J=3.1Hz),130.55(d,J=6.5Hz),118.70(d,J=2.2Hz),110.84(d,J=3.8Hz),62.40(d,J=6.8Hz),34.11(d,J=137.8Hz),16.34(d,J=6.0Hz).31P NMR(202MHz,CDCl3)δ24.42(s)。
实施例5
亚磷酸三乙酯和2-氯苯甲醇制备2-氯苄基亚膦酸二乙酯
20mL管形反应器中依次加入2-氯苯甲醇（71.0mg,0.50mmol)，亚磷酸三乙酯（166.0mg,1.0mmol,2.0equiv.）和四丁基碘化铵（3.7mg,0.01mmol,2mol%），抽真空氮气保护，然后在无溶剂条件下加热到120℃反应24h。TLC监测反应完全后，产物用柱色谱分离提纯，分离收率80%。1H NMR(500MHz,CDCl3)δ7.37(d,J=7.5Hz,1H),7.31(d,J=7.5Hz,1H),7.19–7.09(m,2H),4.01–3.95(m,4H),3.31(d,J=22.0Hz,2H),1.19(t,J=7.0Hz,6H).13C NMR(125MHz,CDCl3)δ134.29(d,J=8.3Hz),131.74(d,J=5.2Hz),130.08(d,J=9.0Hz),129.60(d,J=3.0Hz),128.29(d,J=3.6Hz),126.83(d,J=3.4Hz),62.24(d,J=6.7Hz),30.77(d,J=139.3Hz),16.32(d,J=6.1Hz).31P NMR(202MHz,CDCl3)δ25.23(s)。
实施例6
亚磷酸三乙酯和4-甲氧基苯甲醇制备4-（甲氧基）苄基亚膦酸二乙酯
20mL管形反应器中依次加入4-甲氧基苯甲醇（69.0mg,0.50mmol)，亚磷酸三乙酯（166.0mg,1.0mmol,2.0equiv.）和四丁基碘化铵（3.7mg,0.01mmol,2mol%），抽真空氮气保护，然后在无溶剂条件下加热到120℃反应24h。TLC监测反应完全后，产物用柱色谱分离提纯，分离收率85%。1H NMR(500MHz,CDCl3)δ7.14(dd,J=8.5,2.5Hz,2H),6.78(d,J=8.5Hz,2H),4.04–3.85(m,4H),3.72(s,3H),3.02(d,J=21.0Hz,2H),1.17(t,J=7.0Hz,6H).13C NMR(125MHz,CDCl3)δ158.60(d,J=3.4Hz),130.74(d,J=6.6Hz),123.45(d,J=9.2Hz),114.01(d,J=2.8Hz),62.06(d,J=6.8Hz),55.24(s),32.79(d,J=139.1Hz),16.38(d,J=6.0Hz).31PNMR(202MHz,CDCl3)δ26.88(s)。
实施例7
亚磷酸三乙酯和3-甲氧基苯甲醇制备3-（甲氧基）苄基亚膦酸二乙酯
20mL管形反应器中依次加入3-甲氧基苯甲醇（69.0mg,0.50mmol)，亚磷酸三乙酯（166.0mg,1.0mmol,2.0equiv.）和四丁基碘化铵（3.7mg,0.01mmol,2mol%），抽真空氮气保护，然后在无溶剂条件下加热到120℃反应24h。TLC监测反应完全后，产物用柱色谱分离提纯，分离收率84%。1H NMR(500MHz,CDCl3)δ7.22(t,J=8.0Hz,1H),6.96–6.84(m,2H),6.80(d,J=8.0Hz,1H),4.09–3.96(m,4H),3.80(s,3H),3.14(d,J=21.5Hz,2H),1.25(t,J=7.0Hz,6H).13C NMR(125MHz,CDCl3)δ159.63(d,J=3.1Hz),133.01(d,J=8.9Hz),129.44(d,J=3.0Hz),122.16(d,J=6.6Hz),115.30(d,J=6.5Hz),112.55(d,J=3.5Hz),62.12(d,J=6.8Hz),55.16(s),33.80(d,J=138.1Hz),16.36(d,J=6.0Hz).31P NMR(202MHz,CDCl3)δ26.35(s)。
实施例8
亚磷酸三乙酯和2-甲氧基苯甲醇制备2-（甲氧基）苄基亚膦酸二乙酯
20mL管形反应器中依次加入2-甲氧基苯甲醇（69.0mg,0.50mmol)，亚磷酸三乙酯（166.0mg,1.0mmol,2.0equiv.）和四丁基碘化铵（3.7mg,0.01mmol,2mol%），抽真空氮气保护，然后在无溶剂条件下加热到120℃反应24h。TLC监测反应完全后，产物用柱色谱分离提纯，分离收率85%。1H NMR(500MHz,CDCl3)δ7.35–7.17(m,2H),6.91–6.85(m,2H),4.15–3.91(m,4H),3.83(d,J=3.1Hz,3H),3.25(dd,J=21.5,3.0Hz,2H),1.23(td,J=7.0,3.5Hz,6H).13CNMR(125MHz,CDCl3)δ157.22(d,J=5.1Hz),131.20(d,J=3.9Hz),128.12,120.52,120.25(d,J=8.1Hz),110.55,61.85(d,J=5.5Hz),55.44,26.64(d,J=139.4Hz),16.29(d,J=4.9Hz).31PNMR(202MHz,CDCl3)δ27.13(s)。
实施例9
亚磷酸三乙酯和4-羟基苯甲醇制备4-（羟基）苄基亚膦酸二乙酯
20mL管形反应器中依次加入4-羟基苯甲醇（62.0mg,0.50mmol)，亚磷酸三乙酯（166.0mg,1.0mmol,2.0equiv.）和四丁基碘化铵（3.7mg,0.01mmol,2mol%），抽真空氮气保护，然后在无溶剂条件下加热到120℃反应24h。TLC监测反应完全后，产物用柱色谱分离提纯，分离收率65%。1H NMR(500MHz,CDCl3)δ7.69(brs,1H),7.03(dd,J=8.0,2.0Hz,2H),6.65(d,J=8.0Hz,2H),4.29–3.83(m,4H),3.06(d,J=21.0Hz,2H),1.25(t,J=7.0Hz,6H).13C NMR(125MHz,CDCl3)δ156.18(d,J=3.5Hz),130.67(d,J=6.5Hz),121.04(d,J=9.3Hz),115.99(d,J=3.0Hz),62.49(d,J=7.0Hz),32.59(d,J=139.6Hz),16.36(d,J=5.9Hz).31P NMR(202MHz,CDCl3)δ27.57(s)。
实施例10
亚磷酸三乙酯和3,4,5-三甲氧基苯甲醇制备3,4,5-（三甲氧基）苄基亚膦酸二乙酯
20mL管形反应器中依次加入3,4,5-三甲氧基苯甲醇（99.0mg,0.50mmol)，亚磷酸三乙酯（166.0mg,1.0mmol,2.0equiv.）和四丁基碘化铵（3.7mg,0.01mmol,2mol%），抽真空氮气保护，然后在无溶剂条件下加热到120℃反应24h。TLC监测反应完全后，产物用柱色谱分离提纯，分离收率85%。1H NMR(500MHz,CDCl3)δ6.53(d,J=2.5Hz,2H),4.18–3.98(m,4H),3.86(s,6H),3.83(s,3H),3.10(d,J=21.5Hz,2H),1.28(t,J=7.0Hz,6H).13C NMR(125MHz,CDCl3)δ153.12(d,J=3.2Hz),136.93(d,J=4.0Hz),127.02(d,J=8.9Hz),106.82(d,J=6.7Hz),62.18(d,J=6.8Hz),60.85(d,J=2.1Hz),56.08,33.91(d,J=138.9Hz),16.43(d,J=6.0Hz).31P NMR(202MHz,CDCl3)δ26.41(s)。
实施例11
亚磷酸三乙酯和1-萘甲醇制备1-萘基亚膦酸二乙酯
20mL管形反应器中依次加入1-萘甲醇（79.0mg,0.50mmol)，亚磷酸三乙酯（166.0mg,1.0mmol,2.0equiv.）和四丁基碘化铵（3.7mg,0.01mmol,2mol%），抽真空氮气保护，然后在无溶剂条件下加热到120℃反应24h。TLC监测反应完全后，产物用柱色谱分离提纯，分离收率86%。1H NMR(500MHz,CDCl3)δ8.10(d,J=8.5Hz,1H),7.84(d,J=8.0Hz,1H),7.76(d,J=8.5Hz,1H),7.63–7.37(m,4H),3.99–3.87(m,4H),3.64(d,J=22.0Hz,2H),1.15(t,J=7.0Hz,6H).13C NMR(125MHz,CDCl3)δ133.90(d,J=2.8Hz),132.07(d,J=5.2Hz),128.61,128.46(d,J=7.6Hz),128.09(d,J=9.9Hz),127.74(d,J=4.2Hz),126.06,125.73,125.37(d,J=4.1Hz),124.43(d,J=1.5Hz),62.16(d,J=6.8Hz),30.84(d,J=139.2Hz),16.29(d,J=6.0Hz).31P NMR(202MHz,CDCl3)δ26.25(s)。
实施例12
亚磷酸三乙酯和2-萘甲醇制备2-萘基亚膦酸二乙酯
20mL管形反应器中依次加入2-萘甲醇（79.0mg,0.50mmol)，亚磷酸三乙酯（166.0mg,1.0mmol,2.0equiv.）和四丁基碘化铵（3.7mg,0.01mmol,2mol%），抽真空氮气保护，然后在无溶剂条件下加热到120℃反应24h。TLC监测反应完全后，产物用柱色谱分离提纯，分离收率90%。1H NMR(500MHz,CDCl3)δ7.82–7.73(m,4H),7.48–7.42(m,3H),4.20–3.90(m,4H),3.32(d,J=21.7Hz,2H),1.23(t,J=7.1Hz,6H).13C NMR(125MHz,CDCl3)δ133.45(d,J=3.1Hz),132.34(d,J=2.6Hz),129.16(d,J=9.5Hz),128.48(d,J=8.4Hz),128.14(d,J=2.5Hz),127.91(d,J=5.1Hz),127.63(dd,J=5.9,1.4Hz),126.14(d,J=0.8Hz),125.74(d,J=1.4Hz),62.20(d,J=6.7Hz),33.98(d,J=138.1Hz),16.40(d,J=5.9Hz).31P NMR(202MHz,CDCl3)δ26.33(s)。
实施例13
亚磷酸三乙酯和2-噻吩甲醇制备2-噻吩甲基亚膦酸二乙酯
20mL管形反应器中依次加入2-噻吩甲醇（57.0mg,0.50mmol)，亚磷酸三乙酯（166.0mg,1.0mmol,2.0equiv.）和四丁基碘化铵（9.3mg,0.025mmol,5mol%），抽真空氮气保护，然后在无溶剂条件下加热到120℃反应24h。TLC监测反应完全后，产物用柱色谱分离提纯，分离收率70%。1H NMR(500MHz,CDCl3)δ7.19(d,J=5.0Hz,1H),7.00–6.94(m,2H),4.11–4.00(m,4H),3.38(d,J=20.5Hz,2H),1.28(t,J=7.0Hz,6H).13C NMR(125MHz,CDCl3)δ132.43(d,J=10.2Hz),127.34(d,J=8.5Hz),127.05(d,J=3.3Hz),124.74(d,J=3.9Hz),62.43(d,J=6.7Hz),27.98(d,J=143.9Hz),16.36(d,J=6.0Hz).31PNMR(202MHz,CDCl3)δ24.24(s)。
实施例14
亚磷酸三乙酯和3-吲哚甲醇制备3-吲哚甲基亚膦酸二乙酯
20mL管形反应器中依次加入3-吲哚甲醇（73.5mg,0.50mmol)，亚磷酸三乙酯（166.0mg,1.0mmol,2.0equiv.）和四丁基碘化铵（9.3mg,0.025mmol,5mol%），抽真空氮气保护，然后在无溶剂条件下加热到120℃反应24h。TLC监测反应完全后，产物用柱色谱分离提纯，分离收率83%。1H NMR(500MHz,CDCl3)δ8.75(brs,1H),7.55(d,J=7.8Hz,1H),7.36–7.17(m,1H),7.12–7.00(m,3H),4.11–3.74(m,4H),3.24(d,J=20.0Hz,2H),1.15(t,J=6.5Hz,6H).13C NMR(125MHz,CDCl3)δ136.06,127.44(d,J=5.4Hz),123.91(d,J=7.3Hz),121.95(s),119.39,118.78,111.33,104.54(d,J=9.1Hz),62.19(d,J=6.2Hz),23.12(d,J=142.9Hz),16.42(d,J=5.5Hz).31P NMR(202MHz,CDCl3)δ27.87(s)。
实施例15
亚磷酸三乙酯和肉桂醇制备肉桂基磷亚膦二乙酯
20mL管形反应器中依次加入肉桂醇（67.0mg,0.50mmol)，亚磷酸三乙酯（166.0mg,1.0mmol,2.0equiv.）和四丁基碘化铵（3.7mg,0.01mmol,2mol%），抽真空氮气保护，然后在无溶剂条件下加热到120℃反应24h。TLC监测反应完全后，产物用柱色谱分离提纯，分离收率90%。1H NMR(500MHz,CDCl3)δ7.28(d,J=7.5Hz,3H),7.25(t,J=7.5Hz,3H),7.15(t,J=7.5Hz,1H),6.45(dd,J=16.0,5.0Hz,1H),6.09(dt,J=16.0,7.5Hz,1H),4.10–3.99(m,4H),2.69(dd,J=22.5,7.5Hz,2H),1.24(t,J=7.0Hz,7H).13C NMR(125MHz,CDCl3)δ136.79(d,J=3.4Hz),134.71(d,J=14.9Hz),128.56,127.60,126.22(d,J=1.9Hz),118.76(d,J=12.0Hz),62.09(d,J=6.7Hz),31.06(d,J=138.9Hz),15.47(d,J=6.0Hz).31P NMR(202MHz,CDCl3)δ26.94(s)。
实施例16
亚磷酸三乙酯和（E）-2-己烯-1-醇制备(E）-2-己烯-1-亚膦酸二乙酯
20mL管形反应器中依次加入（E）-2-己烯-1-醇（50.0mg,0.50mmol)，亚磷酸三乙酯（166.0mg,1.0mmol,2.0equiv.）和四丁基碘化铵（3.7mg,0.01mmol,2mol%），抽真空氮气保护，然后在无溶剂条件下加热到120℃反应24h。TLC监测反应完全后，产物用柱色谱分离提纯，分离收率87%。1H NMR(500MHz,CDCl3)δ5.75–5.52(m,1H),5.44–5.36(m,1H),4.21–3.98(m,4H),2.56(dd,J=21.5,7.5Hz,2H),2.12–1.93(m,2H),1.39(q,J=7.5Hz,2H),1.32(t,J=7.0Hz,6H),0.90(t,J=7.5Hz,3H).13C NMR(125MHz,CDCl3)δ136.05(d,J=14.5Hz),118.51(d,J=11.2Hz),61.83(d,J=6.6Hz),34.64(d,J=2.3Hz),30.44(d,J=139.7Hz),22.30(d,J=3.6Hz),16.42(d,J=6.0Hz),13.56.31P NMR(202MHz,CDCl3)δ28.12(s)。
实施例17
亚磷酸三异丙酯和苯甲醇制备苄基亚膦酸二异丙酯
20mL管形反应器中依次加入苯甲醇（54.0mg,0.50mmol)，亚磷酸三异丙酯（208.0mg,1.0mmol,2.0equiv.）和四丁基碘化铵（3.7mg,0.01mmol,2mol%），抽真空氮气保护，然后在无溶剂条件下加热到120℃反应24h。TLC监测反应完全后，产物用柱色谱分离提纯，分离收率83%。1H NMR(500MHz,CDCl3)δ7.51–7.13(m,5H),4.60(dq,J=12.5,6.5Hz,2H),3.11(d,J=21.5Hz,2H),1.27(d,J=6.0Hz,6H),1.16(d,J=6.5Hz,6H).13C NMR(125MHz,CDCl3)δ132.00(d,J=9.0Hz),129.90(d,J=6.6Hz),128.36(d,J=3.0Hz),126.71(d,J=3.6Hz),70.58(d,J=7.0Hz),34.82(d,J=139.7Hz),24.06(d,J=3.8Hz),23.78(d,J=5.0Hz).31P NMR(202MHz,CDCl3)δ26.65(s)。
实施例18
亚磷酸三丁酯和4-甲氧基苯甲醇制备4-甲氧基苄基亚膦酸二丁酯
20mL管形反应器中依次加入4-甲氧基苯甲醇（69.0mg,0.50mmol)，亚磷酸三丁酯（250.0mg,1.0mmol,2.0equiv.）和四丁基碘化铵（3.7mg,0.01mmol,2mol%），抽真空氮气保护，然后在无溶剂条件下加热到120℃反应24h。TLC监测反应完全后，产物用柱色谱分离提纯，分离收率85%。1H NMR(500MHz,CDCl3)δ7.21(d,J=7.0Hz,2H),6.84(d,J=8.0Hz,2H),3.98–3.88(m,4H),3.79(s,3H),3.09(d,J=21.1Hz,2H),1.61–1.48(m,4H),1.38–1.30(m,4H),0.89(t,J=7.5Hz,6H).13C NMR(125MHz,CDCl3)δ158.6(d,J=3.3Hz),130.7(d,J=6.6Hz),123.6(d,J=9.3Hz),114.0(d,J=2.7Hz),65.8(d,J=7.0Hz),55.3,32.7(d,J=138.8Hz),32.6(d,J=5.9Hz),18.7,13.6.31P NMR(202MHz,CDCl3)δ26.76(s)。
实施例19
亚磷酸三异丙酯和2-苯乙醇制备2-苯乙基亚膦酸二乙酯
20mL管形反应器中依次加入2-苯乙醇（61.0mg,0.50mmol)，亚磷酸异丙酯（208.0mg,1.0mmol,2.0equiv.）和四丁基碘化铵（27.8mg,0.075mmol,15mol%），抽真空氮气保护，然后在无溶剂条件下加热到150℃反应24h。TLC监测反应完全后，产物用柱色谱分离提纯，分离收率68%。1H NMR(500MHz,CDCl3)δ7.31–7.27(m,2H),7.22–7.19(m,3H),4.75–4.68(m,2H),2.93–2.87(m,2H),2.07–1.97(m,2H),1.33(d,J=6.0Hz,6H),1.31(d,J=6.5Hz,6H).13C NMR(125MHz,CDCl3)δ141.22(d,J=18.1Hz),128.54,128.04,126.25,70.03(d,J=6.7Hz),28.92(d,J=139.8Hz),28.82(d,J=4.5Hz),24.06(d,J=3.8Hz).31P NMR(202MHz,CDCl3)δ28.68(s)。
实施例20
甲基亚膦酸二乙酯和苯甲醇制备苄基甲基次膦酸乙酯
20mL管形反应器中依次加入苯甲醇（54.0mg,0.50mmol)，甲基亚磷酸二乙酯（136.0mg,1.0mmol,2.0equiv.）和四丁基碘化铵（3.7mg,0.01mmol,2mol%），抽真空氮气保护，然后在无溶剂条件下加热到100℃反应24h。TLC监测反应完全后，产物用柱色谱分离提纯，分离收率80%。1H NMR(500MHz,CDCl3)δ7.42–7.18(m,3H),4.21–3.89(m,1H),3.15(d,J=17.5Hz,1H),1.36(d,J=13.5Hz,2H),1.29(t,J=7.0Hz,1H).13C NMR(125MHz,CDCl3)δ132.1(d,J=7.2Hz),129.6(d,J=5.7Hz),128.7(d,J=2.7Hz),126.9(d,J=3.3Hz),60.5(d,J=6.6Hz),38.0(d,J=88.3Hz),16.6(d,J=5.9Hz),13.4(d,J=94.7Hz).31P NMR(202MHz,CDCl3)δ51.04(s)。
Claims (6)
1.一种烷基亚膦酸二酯化合物或烷基次膦酸酯化合物的合成方法，
其特征在于：
以碘盐为催化剂，亚磷酸三酯或亚膦酸二酯与醇在直接反应得到烷基亚膦酸二酯，反应温度为80～160℃，反应时间为1～60小时，分别制备烷基亚膦酸二酯化合物或烷基次膦酸酯化合物，其具体反应式为：
其中：
R1为各种官能团取代在2-、3-、4-、5-或6-位的苯基或其他取代芳基、稠环，或各种官能团取代的杂芳基，还可以是各种碳链长度和支链官能团取代的烷基；
R2是各种直链或支链取代的烷基，或各类官能团取代的芳基；
R3是各种直链或支链取代的烷基、或各类官能团取代的芳基、稠环以及各类官能团取代杂芳基。
2.根据权利要求1所述的一种烷基亚膦酸二酯化合物或烷基次膦酸酯化合物的合成方法，其特征在于：所述的催化剂无机碘盐、有机碘盐、以及碘单质或碘代烷烃通过反应原位生成的碘盐。
3.根据权利要求1所述的一种烷基亚膦酸二酯化合物或烷基次膦酸酯化合物的合成方法，其特征在于：催化剂的用量为0.1～100mol％。
4.根据权利要求1所述的一种烷基亚膦酸二酯化合物或烷基次膦酸酯化合物的合成方法，其特征在于：所述反应在无溶剂条件下进行。
5.根据权利要求1所述的一种烷基亚膦酸二酯化合物或烷基次膦酸酯化合物的合成方法，其特征在于：所述反应在在惰性气体保护下进行。
6.根据权利要求1所述的一种烷基亚膦酸二酯化合物或烷基次膦酸酯化合物的合成方法，其特征在于：反应温度为100～150℃，反应时间为12～48小时。
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| CN110922427A (zh) * | 2019-11-26 | 2020-03-27 | 温州大学 | 大位阻烷基取代亚膦酸二酯的制备方法 |
| CN111909199A (zh) * | 2020-08-06 | 2020-11-10 | 浙江新安化工集团股份有限公司 | 一种甲基亚膦酸二乙酯精馏高沸物资源化利用的方法 |
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| CN114213457A (zh) * | 2022-01-21 | 2022-03-22 | 杭州师范大学 | 一种化工中间体有机膦及其衍生物的制备方法 |
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| CN110726801A (zh) * | 2019-10-31 | 2020-01-24 | 山东泰星新材料股份有限公司 | 一种监测烷基次膦酸反应状态的方法 |
| CN110922427A (zh) * | 2019-11-26 | 2020-03-27 | 温州大学 | 大位阻烷基取代亚膦酸二酯的制备方法 |
| CN110922427B (zh) * | 2019-11-26 | 2022-07-15 | 温州大学 | 大位阻烷基取代亚膦酸二酯的制备方法 |
| CN111909199A (zh) * | 2020-08-06 | 2020-11-10 | 浙江新安化工集团股份有限公司 | 一种甲基亚膦酸二乙酯精馏高沸物资源化利用的方法 |
| CN111909199B (zh) * | 2020-08-06 | 2021-09-14 | 浙江新安化工集团股份有限公司 | 一种甲基亚膦酸二乙酯精馏高沸物资源化利用的方法 |
| CN112321638A (zh) * | 2020-10-23 | 2021-02-05 | 杭州燕麟科技有限公司 | 单烷基亚膦酸二烷基酯、二烷基膦酸酯及其金属盐的制备方法 |
| CN112321638B (zh) * | 2020-10-23 | 2022-11-25 | 杭州燕麟科技有限公司 | 单烷基亚膦酸二烷基酯、二烷基膦酸酯及其金属盐的制备方法 |
| CN114213457A (zh) * | 2022-01-21 | 2022-03-22 | 杭州师范大学 | 一种化工中间体有机膦及其衍生物的制备方法 |
| CN114213457B (zh) * | 2022-01-21 | 2022-09-09 | 杭州师范大学 | 一种化工中间体有机膦及其衍生物的制备方法 |
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