CN114805436B - 一种有机膦氧类化合物及其合成方法 - Google Patents
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- -1 phosphine oxide compound Chemical class 0.000 title claims abstract description 25
- 238000001308 synthesis method Methods 0.000 title claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 11
- 150000001875 compounds Chemical class 0.000 claims abstract description 10
- CDVAIHNNWWJFJW-UHFFFAOYSA-N 3,5-diethoxycarbonyl-1,4-dihydrocollidine Chemical compound CCOC(=O)C1=C(C)NC(C)=C(C(=O)OCC)C1C CDVAIHNNWWJFJW-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000003054 catalyst Substances 0.000 claims abstract description 7
- 239000002904 solvent Substances 0.000 claims abstract description 5
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 claims description 6
- 125000000590 4-methylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- 150000001298 alcohols Chemical class 0.000 claims description 4
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 3
- 125000003854 p-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Cl 0.000 claims description 3
- 238000010189 synthetic method Methods 0.000 claims description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims 2
- 229910052757 nitrogen Inorganic materials 0.000 claims 1
- 239000012299 nitrogen atmosphere Substances 0.000 abstract description 11
- 238000000034 method Methods 0.000 abstract description 10
- 239000000654 additive Substances 0.000 abstract description 3
- 238000010438 heat treatment Methods 0.000 abstract description 2
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 abstract 1
- 229910000024 caesium carbonate Inorganic materials 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 11
- 238000004440 column chromatography Methods 0.000 description 10
- 238000002360 preparation method Methods 0.000 description 10
- 239000000203 mixture Substances 0.000 description 9
- 238000000926 separation method Methods 0.000 description 8
- LZKLAOYSENRNKR-LNTINUHCSA-N iron;(z)-4-oxoniumylidenepent-2-en-2-olate Chemical compound [Fe].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O LZKLAOYSENRNKR-LNTINUHCSA-N 0.000 description 7
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 6
- VWBYXJRDIQCSLW-UHFFFAOYSA-N O=[P](c1ccccc1)c1ccccc1 Chemical compound O=[P](c1ccccc1)c1ccccc1 VWBYXJRDIQCSLW-UHFFFAOYSA-N 0.000 description 6
- MPQXHAGKBWFSNV-UHFFFAOYSA-N oxidophosphanium Chemical group [PH3]=O MPQXHAGKBWFSNV-UHFFFAOYSA-N 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 230000002194 synthesizing effect Effects 0.000 description 4
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 description 3
- 150000004820 halides Chemical class 0.000 description 3
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 3
- WRMNZCZEMHIOCP-UHFFFAOYSA-N 2-phenylethanol Chemical compound OCCC1=CC=CC=C1 WRMNZCZEMHIOCP-UHFFFAOYSA-N 0.000 description 2
- MSHFRERJPWKJFX-UHFFFAOYSA-N 4-Methoxybenzyl alcohol Chemical compound COC1=CC=C(CO)C=C1 MSHFRERJPWKJFX-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 235000019445 benzyl alcohol Nutrition 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- NLFBCYMMUAKCPC-KQQUZDAGSA-N ethyl (e)-3-[3-amino-2-cyano-1-[(e)-3-ethoxy-3-oxoprop-1-enyl]sulfanyl-3-oxoprop-1-enyl]sulfanylprop-2-enoate Chemical compound CCOC(=O)\C=C\SC(=C(C#N)C(N)=O)S\C=C\C(=O)OCC NLFBCYMMUAKCPC-KQQUZDAGSA-N 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000000575 pesticide Substances 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- PTHGDVCPCZKZKR-UHFFFAOYSA-N (4-chlorophenyl)methanol Chemical compound OCC1=CC=C(Cl)C=C1 PTHGDVCPCZKZKR-UHFFFAOYSA-N 0.000 description 1
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 1
- KMTDMTZBNYGUNX-UHFFFAOYSA-N 4-methylbenzyl alcohol Chemical compound CC1=CC=C(CO)C=C1 KMTDMTZBNYGUNX-UHFFFAOYSA-N 0.000 description 1
- YFPJFKYCVYXDJK-UHFFFAOYSA-N Diphenylphosphine oxide Chemical compound C=1C=CC=CC=1[P+](=O)C1=CC=CC=C1 YFPJFKYCVYXDJK-UHFFFAOYSA-N 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Natural products P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000002152 alkylating effect Effects 0.000 description 1
- 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 description 1
- 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 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 238000006880 cross-coupling reaction Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 150000004795 grignard reagents Chemical class 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 1
- 125000001979 organolithium group Chemical group 0.000 description 1
- FVEINXLJOJPHLH-UHFFFAOYSA-N p-tert-Butylbenzyl alcohol Chemical compound CC(C)(C)C1=CC=C(CO)C=C1 FVEINXLJOJPHLH-UHFFFAOYSA-N 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
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- 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 Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/50—Organo-phosphines
- C07F9/53—Organo-phosphine oxides; Organo-phosphine thioxides
- C07F9/5333—Arylalkane phosphine oxides or thioxides
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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 Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/655—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having oxygen atoms, with or without sulfur, selenium, or tellurium atoms, as the only ring hetero atoms
- C07F9/65515—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having oxygen atoms, with or without sulfur, selenium, or tellurium atoms, as the only ring hetero atoms the oxygen atom being part of a five-membered ring
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Abstract
本发明揭示了一种有机膦氧类化合物及其合成方法,该方法以醇类化合物与P(O)‑H化合物为反应原料,使用5 mol%乙酰丙酮铁为催化剂,1当量碳酸铯,环己烷为溶剂,在氮气氛围下,加热到130℃,有效反应24 h,以较高产率获得有机膦氧类化合物。该方法具有产率高,操作简便,添加剂少,成本低,无污染等优点,对于实现其工业化生产具有一定的可行性。
Description
【技术领域】
本发明属于过渡金属催化有机合成领域,具体地说涉及一种有机膦氧类化合物及其合成方法。
【背景技术】
有机膦氧类化合物广泛应用于杀虫剂,阻燃剂,表面活性剂等,且有机膦氧基团是药物分子、农药分子以及材料结构分子中的重要组成部分。有机膦氧类化合物还可以还原为三价膦化合物,作为配体应用于不对称催化以及过渡金属催化等反应中。因此,有机膦氧类化合物的合成也一直是科研工作者关注的重点。
传统合成有机膦氧类化合物的方法主要依赖于有机卤化物的转化,如Michaelis–Arbusov反应,有机锂试剂或者格氏试剂与P(O)-X化合物的亲核取代反应,或者过渡金属催化的卤化物与P(O)-H化合物的交叉偶联等。然而,这些化学反应通常反应条件苛刻,原料对水和空气敏感、不稳定且毒性较大,同时产生计量的副产物,原子利用率低,污染严重。
醇类化合物广泛存在于自然界中,廉价易得,毒性低,被当作理想的原料广泛地应用于有机合成中。2019年,徐课题组发明了醇为烷基化试剂,在卤硅烷催化条件下,实现了P(O)-H化合物与醇进行反应制备三取代氧膦化合物的方法 (于静 马献涛 燕然 徐清.一种三取代氧膦化合物的合成方法.中国.2019. CN 109678901 A)。该方法虽然避免了使用有机卤化物为原料,但是采用对空气和水敏感的卤硅烷作为催化剂,且部分反应催化剂用量较大。廉价金属铁在地球上的储量丰富,价格低廉,而且具有相当高的生物相容性。因此,我们发明了一种有机膦氧类化合物的合成方法,既以苯甲醇与P(O)-H化合物为原料,通过乙酰丙酮铁催化合成有机膦氧类化合物,此方法无需特殊的设备要求,操作简单,添加剂少,产率高,适用范围广,具有一定的工业应用价值。目前,国内外还没有关于乙酰丙酮铁催化合成有机氧化膦类化合物的公开文献和专利。
【发明内容】
本发明的目的在于提供一种以乙酰丙酮铁为催化剂,以醇类化合物和P(O)-H化合物为原料,高效合成有机膦氧类化合物的方法,该方法具有操作简便,添加剂少,产率高等优点,对于实现其工业化生产具有一定的可行性。
为达到上述发明目的,本发明提出以下技术方案:
一种有机膦氧类化合物及其合成方法,其中有机膦氧类化合物Ⅰ结构通式如下:
其中所述R1为苯基、4-甲基苯基、4-甲氧基苯基、4-氯苯基、4-叔丁基苯基、苄基、呋喃;R2为苯基、4-甲基苯基、4-甲氧基苯基。其中化合物Ⅰ的合成方法,其特征在于,以苯甲醇为Ⅱ与P(O)-H化合物Ⅲ为原料,环己烷为溶剂,使用5 mol%乙酰丙酮铁为催化剂,在130℃温度下有效反应24 h,高产率得到有机膦氧类化合物Ⅰ。
上述合成方法中,原料醇II和P(O)-H化合物III的结构式如下:
其中所述R1为苯基、4-甲基苯基、4-甲氧基苯基、4-氯苯基、4-叔丁基苯基、苄基、呋喃;R2为苯基、4-甲基苯基、4-甲氧基苯基。
上述合成方法中,铁催化剂为5 mol%,环己烷为溶剂,反应时间为24 h,反应温度为130 ℃。
本发明所提供的一类有机膦氧类化合物的合成方法是一类绿色高效的合成途径,其优点在于:目标产物产率高,添加剂少,反应操作简单,绿色无污染。
【附图说明】
附图所示是本发明所提供的制备有机膦氧类化合物的路线图。
【具体实施方式】
本发明所提供的一种有机膦氧类化合物的合成方法,请参见附图:以醇类化合物和P(O)-H化合物为原料,环己烷为溶剂,使用5 mol%乙酰丙酮铁为催化剂,置入反应容器内,在氮气氛围下,加热到130 ℃,反应24小时,反应完成后通过柱色谱分离提纯得到相应的目标产物。
下面结合具体的制备实例对本发明做进一步说明:
制备例1
向25 mL管形反应器中加入苯甲醇0.2 mmol,二苯基磷氧0.4 mmol,加入乙酰丙酮铁5 mol%,1 mL环己烷,在氮气氛围下,加热到130 ℃反应24 h。反应结束后,产物经柱色谱分离提纯,分离收率为96%。1H NMR (400 MHz, CDCl3): δ 7.64-7.59 (m, 4H), 7.46-7.41(m, 2H), 7.38-7.34 (m, 4H), 7.14-7.09 (m, 3H), 7.05-7.02 (m, 2H), 3.58 (d, J=14.0 Hz, 2H). 13C NMR (100 MHz, CDCl3): δ 132.8, 131.8 (d, J C-P = 2.6 Hz),131.1 (d, J C-P = 9.1 Hz), 130.1 (d, J C-P = 5.2 Hz), 128.5, 128.4, 128.3 (d, J C-P = 2.4 Hz), 126.7 (d, J C-P=2.8 Hz), 38.1 (d, J C-P = 66.1 Hz). 31P NMR (162 MHz,CDCl3): δ29.4.
制备例2
向25 mL管形反应器中加入4-甲基苯甲醇0.2 mmol,二苯基磷氧0.4 mmol,加入乙酰丙酮铁5 mol%,1 mL环己烷,在氮气氛围下,加热到130 ℃反应24 h。反应结束后,产物经柱色谱分离提纯,分离收率为95%。1H NMR (400 MHz, CDCl3): δ 7.72-7.67 (m, 4H),7.50-7.47 (m, 2H), 7.44-7.40 (m, 4H), 6.99 (s, 4H), 3.61 (d, J = 13.6 Hz,2H), 2.25 (d, J = 1.6 Hz, 3H). 31C NMR (100 MHz, CDCl3) δ 136.2 (d, J C-P = 3.0Hz), 132.3 (d, J C-P = 98.0 Hz), 131.6 (d, J C-P = 2.5 Hz), 131.1 (d, J C-P = 9.1Hz), 129.9 (d, J C-P = 5.1 Hz), 129.0 (d, J C-P = 2.4 Hz), 128.4 (d, J C-P = 11.7Hz), 127.8 (d, J C-P = 8.0 Hz), 37.5 (d, J C-P = 66.5 Hz), 20.9. 31P NMR (162 MHz,CDCl3): δ 29.4.
制备例3
向25 mL管形反应器中加入4-甲氧基苯甲醇0.2 mmol,二苯基磷氧0.4 mmol,加入乙酰丙酮铁5 mol%,1 mL环己烷,在氮气氛围下,加热到130 ℃反应24 h。反应结束后,产物经柱色谱分离提纯,分离收率为85%。1H NMR (400 MHz, CDCl3): δ 7.71-7.66 (m, 4H),7.51-7.48 (m, 2H), 7.45-7.40 (m, 4H), 7.02-7.00 (m, 2H), 6.72 (d, J = 13.2Hz, 2H), 3.73 (s, 3H), 3.59 (d, J = 13.2 Hz, 2H). 31C NMR (100 MHz, CDCl3): δ158.4 (d, J C-P = 2.7 Hz), 132.2 (d, J C-P = 98.0 Hz), 131.7 (d, J C-P = 2.4 Hz),131.1 (d, J C-P = 9.0 Hz), 131.0 (d, J C-P = 3.1 Hz), 128.4 (d, J C-P = 11.6 Hz),122.8 (d, J C-P = 8.0 Hz), 113.8 (d, J C-P = 2.1 Hz), 55.1, 37.0 (d, J C-P = 67.1Hz). 31P NMR (162 MHz, CDCl3): δ 29.6.
制备例4
向25 mL管形反应器中加入4-氯苯甲醇0.2 mmol,二苯基磷氧0.4 mmol,加入乙酰丙酮铁5 mol%,1 mL环己烷,在氮气氛围下,加热到130 ℃反应24 h。反应结束后,产物经柱色谱分离提纯,分离收率为72%。1H NMR (400 MHz, CDCl3): δ 7.71-7.66 (m, 4H), 7.54-7.45 (m, 2H), 7.16-7.14 (m, 2H), 7.05-7.02 (m, 2H), 3.63-3.59 (m, 2H), 3.61(d, J = 13.2 Hz, 2H). 31C NMR (100 MHz, CDCl3): δ 132.8 (d, J C-P = 3.5 Hz),132.0 (d, J C-P = 98.8 Hz), 131.9 (d, J C-P = 2.5 Hz), 131.3 (d, J C-P = 5.1 Hz),131.1 (d, J C-P = 9.1), 129.7 (d, J C-P = 8.0 Hz), 128.6 (d, J C-P = 12.0 Hz),128.5 (d, J C-P = 3.0 Hz), 37.4 (d, J C-P = 65.8 Hz).31P NMR (162 MHz, CDCl3): δ29.2
制备例5
向25 mL管形反应器中加入4-叔丁基苯甲醇0.2 mmol,二苯基磷氧0.4 mmol,加入乙酰丙酮铁5 mol%,1 mL环己烷,在氮气氛围下,加热到130 ℃反应24 h。反应结束后,产物经柱色谱分离提纯,分离收率为91%。1H NMR (400 MHz, CDCl3): δ 7.71-7.67 (m, 4H),7.50-7.46 (m, 2H), 7.43-7.39 (m, 4H), 7.20-7.18 (m, 2H), 7.04-7.01 (m, 2H),3.62 (d, J = 13.6 Hz, 2H), 1.24 (s, 9H). 31C NMR (100 MHz, CDCl3): δ149.5 (d,J C-P = 3.2 Hz), 132.4 (d, J C-P = 98.0 Hz), 131.6 (d, J C-P = 2.6 Hz), 131.1 (d,J C-P = 9.1 Hz), 129.7 (d, J C-P = 5.3 Hz), 128.3 (d, J C-P = 11.6 Hz), 127.8 (d,J C-P = 8.1 Hz), 125.2 (d, J C-P = 2.6 Hz), 37.4 (d, J C-P = 66.6 Hz), 34.2, 37.2.31P NMR (162 MHz, CDCl3): δ 29.6.
制备例6
向25 mL管形反应器中加入苯乙醇0.2 mmol,二苯基磷氧0.4 mmol,加入乙酰丙酮铁5 mol%,1 mL环己烷,在氮气氛围下,加热到130 ℃反应24 h。反应结束后,产物经柱色谱分离提纯,分离收率为67%。1H NMR (400 MHz, CDCl3): δ 7.79-7.74 (m, 4H), 7.53-7.44(m, 6H), 7.27-7.23 (m, 2H), 7.18-7.14 (m, 3H), 2.96-2.90 (m, 2H), 2.61-2.54(m, 2H). 31C NMR (100 MHz, CDCl3): δ141.0 (d, J C-P = 15.2 Hz), 132.6 (d, J C-P =97.9 Hz), 131.7 (d, J C-P = 2.5 Hz), 130.6 (d, J C-P = 9.3 Hz), 128.7, 128.5 (d,J C-P = 7.0 Hz), 127.9, 126.2, 31.2 (d, J C-P = 69.4 Hz), 27.4 (d, J C-P = 2.9 Hz).31P NMR (162 MHz, CDCl3): δ 29.6.
制备例7
向25 mL管形反应器中加入2-呋喃甲醇0.2 mmol,二苯基磷氧0.4 mmol,加入乙酰丙酮铁5 mol%,1 mL环己烷,在氮气氛围下,加热到130 ℃反应24 h。反应结束后,产物经柱色谱分离提纯,分离收率为45%。1H NMR (400 MHz, CDCl3): δ 7.73-7.68 (m, 4H), 7.54-7.43 (m, 6H), 7.23 (s, 1H), 6.23-6.07 (m, 2H), 3.76 (d, J = 14.0 Hz, 2H). 31CNMR (100 MHz, CDCl3): δ145.3 (d, J C-P = 7.8 Hz), 141.9 (d, J C-P = 2.7 Hz),132.1 (d, J C-P = 14.4 Hz), 132.0 (d, J C-P = 99.9Hz), 131.1 (d, J C-P = 9.4 Hz),128.6 (d, J C-P = 11.8 Hz), 110.9 (d, J C-P = 2.4 Hz), 109.1 (d, J C-P = 5.8 Hz),37.4 (d, J C-P = 69.0 Hz). 31P NMR (162 MHz, CDCl3): δ 28.2.
制备例8
向25 mL管形反应器中加入苯甲醇0.2 mmol,二(4-甲基苯基)氧化膦0.4 mmol,加入乙酰丙酮铁5 mol%,1 mL环己烷,在氮气氛围下,加热到130 ℃反应24 h。反应结束后,产物经柱色谱分离提纯,分离收率为90%。1H NMR (400 MHz, CDCl3): δ7.58-7.53 (m, 4H),7.23-7.21 (m, 4H), 7.18-7.16 (m, 3H), 7.11-7.09 (m, 2H), 3.61 (d, J C-P = 13.6Hz, 2H), 2.37 (s, 6H). 31C NMR (100 MHz, CDCl3):δ 142.1 (d, J C-P = 2.6 Hz),132.0 (d, J C-P = 10.1 Hz), 131.1 (d, J C-P = 9.4 Hz), 130.1 (d, J C-P = 5.2 Hz),129.5 (d, J C-P = 12.8 Hz), 129.1 (d, J C-P = 100.7 Hz), 128.2 (d, J C-P = 2.2 Hz),126.6 (d, J C-P = 2.8 Hz), 38.1 (d, J C-P = 66.3 Hz), 21.5 (d, J C-P = 0.9 Hz). 31PNMR (162 MHz, CDCl3): δ 30.0.
制备例9
向25 mL管形反应器中加入苯甲醇0.2 mmol,二(4-甲氧基苯基)氧化膦0.4 mmol,加入乙酰丙酮铁5 mol%,1 mL环己烷,在氮气氛围下,加热到130 ℃反应24 h。反应结束后,产物经柱色谱分离提纯,分离收率为85%。1H NMR (400 MHz, CDCl3): δ 7.60-7.55 (m,4H), 7.17-16 (m, 5H), 7.17-7.09 (m, 4H), 3.79 (s, 6H), 3.58 (d, J = 14.0 Hz,2H). 31C NMR (100 MHz, CDCl3):δ 162.2 (d, J C-P = 2.7 Hz), 133.0 (d, J C-P = 10.4Hz), 131.6 (d, J C-P = 7.8 Hz), 130.1 (d, J C-P = 5.2 Hz), 128.3 (d, J C-P = 2.3Hz), 126.6 (d, J C-P = 2.8 Hz), 123.7 (d, J C-P = 104.9 Hz), 113.9 (d, J C-P = 12.6Hz), 55.3, 38.6 (d, J C-P = 66.9 Hz). 31P NMR (162 MHz, CDCl3): δ 29.6.
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 (1)
1.一种有机膦氧类化合物的合成方法,其中有机膦氧类化合物Ⅰ以及合成所需的的原料醇类化合物II和P(O)-H化合物III结构通式如下:
其中所述R1为苯基、4-甲基苯基、4-甲氧基苯基、4-氯苯基、4-叔丁基苯基、苄基、呋喃;R2为苯基、4-甲基苯基、4-甲氧基苯基;其中化合物I的合成方法,其特征在于,以醇类化合物II和P(O)-H化合物III为原料,环己烷为溶剂,使用5mol%乙酰丙酮铁为催化剂,在130℃下,氮气环境下有效反应24h,高产率得到有机膦氧类化合物Ⅰ。
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CN110143982A (zh) * | 2019-07-05 | 2019-08-20 | 湖南第一师范学院 | 一种二芳基苄基膦氧化合物的合成方法 |
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EP2281860A1 (en) * | 2009-08-03 | 2011-02-09 | Morgan Adhesives Company | Adhesive compositions for easy application and improved durability |
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