CN101018794A - 烷基次膦酸酯的制备方法 - Google Patents
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- 239000002253 acid Substances 0.000 claims description 14
- GJYJYFHBOBUTBY-UHFFFAOYSA-N alpha-camphorene Chemical group CC(C)=CCCC(=C)C1CCC(CCC=C(C)C)=CC1 GJYJYFHBOBUTBY-UHFFFAOYSA-N 0.000 claims description 12
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- GKASDNZWUGIAMG-UHFFFAOYSA-N triethyl orthoformate Chemical compound CCOC(OCC)OCC GKASDNZWUGIAMG-UHFFFAOYSA-N 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 6
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 claims description 6
- PYOKUURKVVELLB-UHFFFAOYSA-N trimethyl orthoformate Chemical compound COC(OC)OC PYOKUURKVVELLB-UHFFFAOYSA-N 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims description 4
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 230000001476 alcoholic effect Effects 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 229910001380 potassium hypophosphite Inorganic materials 0.000 claims description 2
- CRGPNLUFHHUKCM-UHFFFAOYSA-M potassium phosphinate Chemical compound [K+].[O-]P=O CRGPNLUFHHUKCM-UHFFFAOYSA-M 0.000 claims description 2
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 2
- 125000003944 tolyl group Chemical group 0.000 claims 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical class O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 abstract description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 14
- 235000014347 soups Nutrition 0.000 description 13
- ZKNJRUPWSFSOFM-UHFFFAOYSA-N diethoxymethyl-ethoxy-oxophosphanium Chemical compound CCOC(OCC)[P+](=O)OCC ZKNJRUPWSFSOFM-UHFFFAOYSA-N 0.000 description 12
- 238000003756 stirring Methods 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
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- -1 phospho Chemical class 0.000 description 6
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 5
- 235000017557 sodium bicarbonate Nutrition 0.000 description 5
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- 238000004679 31P NMR spectroscopy Methods 0.000 description 4
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- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 125000004494 ethyl ester group Chemical group 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 239000012266 salt solution Substances 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
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- 230000002194 synthesizing effect Effects 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- NJSUFZNXBBXAAC-UHFFFAOYSA-N ethanol;toluene Chemical compound CCO.CC1=CC=CC=C1 NJSUFZNXBBXAAC-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
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- 229910052757 nitrogen Inorganic materials 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
- C07F9/48—Phosphonous acids [RP(OH)2] including [RHP(=O)(OH)]; Thiophosphonous acids including [RP(SH)2], [RHP(=S)(SH)]; Derivatives thereof
- C07F9/4808—Phosphonous acids [RP(OH)2] including [RHP(=O)(OH)]; Thiophosphonous acids including [RP(SH)2], [RHP(=S)(SH)]; Derivatives thereof the acid moiety containing a substituent or structure which is considered as characteristic
- C07F9/4816—Acyclic saturated acids or derivatices which can have further substituents on alkyl
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Abstract
本发明涉及一种制备烷基二烷氧基烷基次膦酸酯的新方法。该方法中使用了次磷酸盐。
Description
发明领域
本发明涉及一种制备烷基二烷氧基烷基次膦酸酯的新方法。
发明背景
Gallagher,M J.Honegger,H.Aust.J.Chem.1980,33,287-294(见下文)中描述了乙基(二乙氧基甲基)次膦酸酯的制备。次膦酸是通过市售水溶液(50wt%水)的蒸发而得到的。
EP307362A2描述了从次膦酸水溶液制备脂族次膦酸(aliphatyl phosphinicacid)衍生物。
Deprèle,S.Montchamp,J.-L.J.Organomet.Chem.2002,643-644,154-165公开了次磷酸盐的酯化方法并概述如下:
次磷酸铵 100%
本发明的一个目的是开发一种制备烷基二烷氧基烷基次膦酸酯的方法,它更适合于大规模生产。
发明概述
本发明涉及一种制备通式(I)的烷基二烷氧基烷基次膦酸酯的新方法:
其中
R1、R2和R3各自独立表示甲基或乙基;R4表示氢或甲基;
是将次磷酸盐和通式(II)化合物在溶剂和酸存在下反应:
其中
R1、R2、R3和R4定义如上。
根据本发明的方法尤其可用于乙基(二乙氧基甲基)次膦酸酯的合成。通过使用该方法能避免危险的纯次膦酸处理。另外能控制副产物的量。
制备方法
在本发明的一个实施方案中,将通式(II)化合物加入到搅动的次磷酸盐和合适的溶剂例如甲苯-乙醇(20∶1)的浆状物中。小心地将该混合物惰化并以控制的速度加入酸。将该浆状物在0℃到20℃下搅拌1到20小时或直到大部分中间体烷基酯耗尽为止。加入碳酸氢钠水溶液猝灭该反应并浓缩有机层。
在本发明的一个实施方案中,次磷酸盐选自次磷酸铵、次磷酸钠和次磷酸钾。
在本发明的一个实施方案中,通式(II)化合物选自原甲酸三甲酯、原甲酸三乙酯、原乙酸三甲酯和原乙酸三乙酯。
在本发明的一个实施方案中,反应中所用的酸选自甲磺酸、硫酸、醚合三氟化硼和三氟甲磺酸。在本发明另一个实施方案中,该酸基本上是无水的。在一个实施方案中,该酸包含最多10%的水、最多5%的水或最多2%的水。
在一个实施方案中,根据本发明的方法所用的溶剂是甲苯、乙腈、四氢呋喃(THF)、二氯甲烷、苯或甲苯和乙醇的混合物。
实施例
用甲磺酸合成乙基(二乙氧基甲基)次膦酸酯
将原甲酸三乙酯(42.1mL,253mmol,2.1当量)在氮气氛围下加入到冷的(0℃)研细的次磷酸铵(10g,120mmol,1.0当量)、甲苯(50mL)和乙醇(3.5mL)的混合物中。惰化该浆状物并冷却到大约0℃。在4分钟内(Ti保持在10℃以下)加入甲磺酸(8.4mL,127mmol,1.05当量)(放热)。在0℃下搅拌该浆状物,1小时后GC-分析显示从乙基酯到预期产品的转化率为93%。2小时后,用饱和碳酸氢钠水溶液(37mL)猝灭该反应混合物。相分离后有机层在40℃下减压浓缩为无色液体,其包含~50%甲苯(28.0g,GC-纯度95%,测定含量51.2%)。(乙基(二乙氧基甲基)次膦酸酯的量:14.3g,73.1mmol,产率61%)。13C-NMR(CD3CN):δ14.2(2xCH3),15.4(CH3),62.4+62.5(CH2O),64.5+64.6(CH2O),64.9+65.0(CH2O)和99.1+100.5(CHO2)。31P-NMR:δ26.8(ddd)。
用甲磺酸在2-L-规模内合成乙基(二乙氧基甲基)次膦酸酯
将原甲酸三乙酯(632mL,3.80mol,2.1当量)在氮气氛围下加入到冷的(0℃)次磷酸铵(150g,1.81mol,1.0当量)、甲苯(750mL)和乙醇(75mL)的混合物中。惰化该浆状物并冷却到~0℃。在8分钟内(Ti保持在10℃以下)加入甲磺酸(126mL,1.90mol,1.05当量)(放热)。在0℃下搅拌该浆状物,1小时后GC-分析显示从乙基酯到预期产品的转化率为90%。1.5小时后,用饱和碳酸氢钠水溶液(600mL)猝灭该反应混合物。相分离后有机层在40℃下减压浓缩为无色液体,其包含~65%甲苯(579g,GC-纯度88%,测定含量34.4%)。(乙基(二乙氧基甲基)次膦酸酯的量:199.2g,1.02mol,产率~56%)。用甲磺酸在500-L-规模内合成乙基(二乙氧基甲基)次膦酸酯
将原甲酸三乙酯(133.6kg,901.4mol,2.1当量)在氮气氛围下加入到冷的(0℃)剧烈搅拌的次磷酸铵(35.6kg,429.2mol,1.0当量)、甲苯(107L)和乙醇(11L)的混合物中。将该浆状物在冷却到~0℃时小心地惰化。随后持续地用氮气吹扫该浆状物以减少氧化的副产物的量。随后在30分钟内(Ti保持在10℃以下)加入甲磺酸(43.3kg,450.7mol,1.05当量)(放热)。在0℃下搅拌该浆状物,2.5小时后通过控制地加入(Ti≤10℃)碳酸氢钠(14.4kg,171.7mol,0.4当量)和水(128L)的混合物猝灭该反应混合物。用水(14L)冲洗加料管并剧烈搅拌该反应混合物10分钟。相分离后有机层在40℃下减压浓缩为1/3的体积(82L,0.991kg/L,81.3kg,GC-纯度89.6%,测定含量61%)。(乙基(二乙氧基甲基)次膦酸酯的量:49.6kg,252.7mol,产率58.9%)。用硫酸合成乙基(二乙氧基甲基)次膦酸酯
将浓硫酸(1.65mL,29.7mmol,0.5当量)在室温下加入到次磷酸铵(5g,60.2mmol,1当量)、甲苯(45mL)和乙醇(5mL)的混合物中。2小时后加入原甲酸三乙酯(26.0mL,156.3mmol,2.6当量)并搅拌该浆状物过夜。GC-分析显示几乎所有的中间体乙基酯都转化为预期产品。随后用1∶1的饱和碳酸氢钠水溶液和盐水(50mL)混合物猝灭该反应混合物。相分离并洗涤有机层两次,第一次用1∶1的饱和碳酸氢钠水溶液和盐水(50mL)混合物,随后只用盐水(25mL)。该有机层随后干燥(Na2SO4)并减压浓缩。分离出无色油状物乙基(二乙氧基甲基)亚膦酸酯(5.7g,GC-纯度~93%,产率~44%)。用醚合三氟化硼合成乙基(二乙氧基甲基)次膦酸酯
在3分钟内将醚合三氟化硼(3.47mL,13.3mmol,1.1当量)加入到次磷酸铵(1g,12.0mmol,1当量)、甲苯(8mL)、乙醇(2mL)和原甲酸三乙酯(5.2mL,25.2mmol,2.1当量)的混合物中。室温下搅拌该反应,4小时后GC-分析显示到预期产品的良好转化。
用三氟甲磺酸合成乙基(二乙氧基甲基)次膦酸酯
在3分钟内将三氟甲磺酸(1.2mL,13.6mmol,1.1当量)加入到冷的(0℃)次磷酸铵(1g,12.0mmol,1当量)、甲苯(10mL)和原甲酸三乙酯(4.2mL,31.3mmol,2.6当量)的混合物中。室温下搅拌该反应,2小时后GC-分析显示到预期产品的良好转化。产品未分离。
用甲磺酸合成乙基(二乙氧基乙基)次膦酸酯
将原乙酸三乙酯(4.6mL,25.1mmol,2.1当量)加入到冷的(0℃)次磷酸铵(1.0g,12.0mmol,1.0当量)和甲苯(5mL)的混合物中。将该浆状物冷却到~0℃并惰化。在4分钟内(Ti保持在10℃以下)加入甲磺酸(0.84mL,12.7mmol,1.05当量)(放热)。反应在0℃下搅拌,1小时后GC-分析显示~40%转化为预期产物。3小时后加入饱和的碳酸氢钠水溶液(3.6mL)猝灭该反应混合物。相分离后有机层浓缩为无色油状物(1.1g,GC-纯度~81%,产率~35%)。
13C-NMR(CD3CN):δ14.4(2 xCH3),15.4(CH3),18.0(CH3),57.0+57.1(CH2O),57.4+57.5(CH2O),62.5+62.6(CH2O)和98.9+100.4(CHO2)。31P-NMR:δ30.0(dm)。
用甲磺酸合成甲基(二甲氧基乙基)次膦酸酯
将原乙酸三甲酯(3.2mL,25.1mmol,2.1当量)加入到冷的(0℃)次磷酸铵(1.0g,12.0mmol,1.0当量)和甲苯(5mL)的混合物中。将该浆状物冷却到~0℃并惰化。在4分钟内(Ti保持在10℃以下)加入甲磺酸(0.84mL,12.7mmol,1.05当量)(放热)。反应在0℃下搅拌,1小时后GC-分析显示有~50%转化为预期产物。3小时后加入饱和的碳酸氢钠水溶液(3.6mL)猝灭该反应混合物。相分离后有机层浓缩为无色油状物(0.21g,GC-纯度~92%,产率~10%)。
13C-NMR(CD3CN):δ17.0+17.1(CH3),48.8+48.9(CH3O),49.2+49.3(CH3O),52.5+52.6(CH3O)和99.2+100.7(CHO2)。31P-NMR:δ32.4(dm)。
用甲磺酸合成甲基(二甲氧基甲基)次膦酸酯
将原甲酸三甲酯(2.8mL,25.6mmol,2.1当量)加入到冷的(0℃)次磷酸铵(1.0g,12.0mmol,1.0当量)和甲苯(5mL)的混合物中。将该浆状物冷却到~0℃并惰化。在4分钟内(Ti保持在10℃以下)加入甲磺酸(0.84mL,12.7mmol,1.05当量)(放热)。反应在0℃下搅拌,1小时后GC-分析显示有~84%转化为预期产物。3小时后加入饱和的碳酸氢钠水溶液(3.6mL)猝灭该反应混合物。相分离后有机层浓缩为无色油状物(0.12g,GC-纯度~78%,产率~7%)。
13C-NMR(CD3CN):δ48.4(CH3O),56.3 (CH3O),56.4(CH3O)和101.4+102.9(CHO2)。31P-NMR:δ31.6(dm)。
Claims (11)
2、根据权利要求1所述的方法,其中所述的次磷酸盐选自次磷酸铵、次磷酸钠和次磷酸钾。
3、根据权利要求1或2所述的方法,其中所述通式(II)化合物选自原甲酸三甲酯、原甲酸三乙酯、原乙酸三甲酯和原乙酸三乙酯。
4、根据权利要求1-3任一项所述的方法,其中所述的酸选自甲磺酸、硫酸、醚合三氟化硼和三氟甲磺酸。
5、根据权利要求4所述的方法,其中所述的酸包含少于5%的水。
6、根据权利要求5所述的方法,其中所述的酸包含少于2%的水。
7、根据权利要求1-6任一项所述的方法,其中所述的溶剂选自甲苯或甲苯和乙醇的混合物。
8、根据权利要求1-7任一项所述的方法,其中该方法在0℃到20℃的温度下进行。
9、根据权利要求1-8任一项所述的方法,其中该方法进行1到20小时。
10、根据权利要求1-9任一项所述的方法,其中R1是乙基;R2是乙基和R3是乙基。
11、根据权利要求1-10任一项所述的方法,其中R4是乙基。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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SE04021994 | 2004-09-13 | ||
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EP (1) | EP1791851B1 (zh) |
JP (1) | JP2008512451A (zh) |
CN (1) | CN100575355C (zh) |
AT (1) | ATE490259T1 (zh) |
DE (1) | DE602005025140D1 (zh) |
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WO (1) | WO2006031180A1 (zh) |
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CN103755605A (zh) * | 2013-12-30 | 2014-04-30 | 中国科学院上海硅酸盐研究所 | 对己硫基苯甲醛的制备方法 |
WO2015165295A1 (zh) * | 2014-04-28 | 2015-11-05 | 湖南大学 | 一种以含p(o)-oh类化合物制备次膦酸/亚膦酸/磷酸酯类化合物的方法 |
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TW201840578A (zh) * | 2017-02-22 | 2018-11-16 | 以色列商亞當阿甘公司 | 製備甲基膦酸丁基酯的方法 |
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US20040167330A1 (en) | 2001-07-17 | 2004-08-26 | Ivan Lukes | Novel chelating agents and conjugates thereof, their synthesis and use as diagnois and therapeutic agents |
WO2006000043A1 (en) * | 2004-06-25 | 2006-01-05 | The University Of Sydney | Neurologically-active compounds |
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CN103755605A (zh) * | 2013-12-30 | 2014-04-30 | 中国科学院上海硅酸盐研究所 | 对己硫基苯甲醛的制备方法 |
CN103755605B (zh) * | 2013-12-30 | 2016-08-17 | 中国科学院上海硅酸盐研究所 | 对己硫基苯甲醛的制备方法 |
WO2015165295A1 (zh) * | 2014-04-28 | 2015-11-05 | 湖南大学 | 一种以含p(o)-oh类化合物制备次膦酸/亚膦酸/磷酸酯类化合物的方法 |
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US7557234B2 (en) | 2009-07-07 |
JP2008512451A (ja) | 2008-04-24 |
CN100575355C (zh) | 2009-12-30 |
US20080319231A1 (en) | 2008-12-25 |
SE0402199D0 (sv) | 2004-09-13 |
EP1791851A4 (en) | 2010-03-10 |
ATE490259T1 (de) | 2010-12-15 |
WO2006031180A1 (en) | 2006-03-23 |
DE602005025140D1 (de) | 2011-01-13 |
EP1791851A1 (en) | 2007-06-06 |
EP1791851B1 (en) | 2010-12-01 |
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