CN113816993B - Synthetic method of containing β-cyanophosphonate derivatives - Google Patents
Synthetic method of containing β-cyanophosphonate derivatives Download PDFInfo
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- 238000006243 chemical reaction Methods 0.000 claims abstract description 46
- 239000003054 catalyst Substances 0.000 claims abstract description 19
- 239000002608 ionic liquid Substances 0.000 claims abstract description 18
- 239000002904 solvent Substances 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 15
- 238000001308 synthesis method Methods 0.000 claims abstract description 13
- 230000035484 reaction time Effects 0.000 claims abstract description 12
- -1 indole compound Chemical class 0.000 claims abstract description 9
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- FTTATHOUSOIFOQ-UHFFFAOYSA-N 1,2,3,4,6,7,8,8a-octahydropyrrolo[1,2-a]pyrazine Chemical compound C1NCCN2CCCC21 FTTATHOUSOIFOQ-UHFFFAOYSA-N 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 150000008301 phosphite esters Chemical class 0.000 claims 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims 2
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- 229910052739 hydrogen Inorganic materials 0.000 claims 1
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- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims 1
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- LXCYSACZTOKNNS-UHFFFAOYSA-N diethoxy(oxo)phosphanium Chemical compound CCO[P+](=O)OCC LXCYSACZTOKNNS-UHFFFAOYSA-N 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 239000012074 organic phase Substances 0.000 description 7
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- 150000001875 compounds Chemical class 0.000 description 4
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 4
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- GZCUYSKAOHTWOW-UHFFFAOYSA-N 1,4-diazabicyclo[2.2.2]octane;hydrobromide Chemical compound Br.C1CN2CCN1CC2 GZCUYSKAOHTWOW-UHFFFAOYSA-N 0.000 description 2
- KXPRLNWTJHJCIX-UHFFFAOYSA-N 1,4-diazabicyclo[2.2.2]octane;sulfuric acid Chemical compound OS(O)(=O)=O.C1CN2CCN1CC2 KXPRLNWTJHJCIX-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 2
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- ZRYZBQLXDKPBDU-UHFFFAOYSA-N 4-bromobenzaldehyde Chemical compound BrC1=CC=C(C=O)C=C1 ZRYZBQLXDKPBDU-UHFFFAOYSA-N 0.000 description 1
- WZWIQYMTQZCSKI-UHFFFAOYSA-N 4-cyanobenzaldehyde Chemical compound O=CC1=CC=C(C#N)C=C1 WZWIQYMTQZCSKI-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- PHENPABYBHPABM-UHFFFAOYSA-N acetic acid;octane Chemical compound CC(O)=O.CCCCCCCC PHENPABYBHPABM-UHFFFAOYSA-N 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
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- 238000004821 distillation Methods 0.000 description 1
- CNUDBTRUORMMPA-UHFFFAOYSA-N formylthiophene Chemical compound O=CC1=CC=CS1 CNUDBTRUORMMPA-UHFFFAOYSA-N 0.000 description 1
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Classifications
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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
- C07F9/28—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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- 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
- C07F9/6553—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having sulfur atoms, with or without selenium or tellurium atoms, as the only ring hetero atoms
- C07F9/655345—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having sulfur atoms, with or without selenium or tellurium atoms, as the only ring hetero atoms the sulfur atom being part of a five-membered ring
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
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- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
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- General Health & Medical Sciences (AREA)
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- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明公开了一种含有β‑氰基膦酸酯类衍生物的合成方法，所述合成方法为：在DABCO基离子液体催化下，将芳香醛、丙二腈、亚磷酸酯、烯酮化合物在溶剂中较为温和的加热反应，制备得到所述含有β‑氰基膦酸酯类衍生物。本发明的合成方法步骤简单，反应时间短，反应收率较高，所使用的离子液体催化剂廉价易得，另外本发明公开的合成方法底物适用范围广，通过四组分“一锅法”即得到了本发明中极其重要的一类多官能团膦酸酯基团的氧化吲哚类化合物，是一高效的四组分反应。The present invention discloses a method for synthesizing β-cyanophosphonate derivatives. The β-cyanophosphonate-containing derivative is prepared by mild heating reaction in a solvent. The synthesis method of the invention has simple steps, short reaction time, high reaction yield, and the used ionic liquid catalyst is cheap and easy to obtain. In addition, the synthesis method disclosed in the invention has a wide range of substrates. That is, an extremely important type of oxidised indole compound with a multifunctional phosphonate group in the present invention is obtained, which is an efficient four-component reaction.
Description
技术领域technical field
本发明属于有机合成技术领域，具体来说涉及一种含有β-氰基膦酸酯类衍生物类衍生物的合成方法。The invention belongs to the technical field of organic synthesis, and in particular relates to a synthesis method containing β-cyanophosphonate derivatives.
背景技术Background technique
β-氰基膦酸酯类衍生物是非常重要的一类化合物，它们是许多天然产物和具有生物活性化合物的重要骨架,这类衍生物丰富的多样性结构，以及它们广谱的生物活性，使得这类化合物极其需要高效的合成方法。而且在本合成体系中，所构建的“碳四中心”仍然是现在有机合成化学中的一个难点，这种同时含有β-氰基膦酸酯类衍生物类衍生物目前还未有报道。β-Cyanophosphonate derivatives are a very important class of compounds. They are important skeletons of many natural products and biologically active compounds. The rich and diverse structures of such derivatives, as well as their broad spectrum of biological activities, This class of compounds is in great need of efficient synthetic methods. Moreover, in this synthesis system, the constructed "carbon four center" is still a difficult point in organic synthesis chemistry, and this kind of derivatives containing β-cyanophosphonate derivatives has not been reported yet.
发明内容SUMMARY OF THE INVENTION
针对现有技术的不足，本发明的目的在于提供一种含有β-氰基膦酸酯类衍生物类衍生物的合成方法，该合成方法操作简便，反应时间短，生产成本低，反应绿色污染少，副产物仅为水，后处理简单，该合成方法使用的离子液体催化剂是一种廉价易得且对环境友好的高效催化剂。In view of the deficiencies of the prior art, the object of the present invention is to provide a synthesis method containing β-cyanophosphonate derivatives, which is easy to operate, has short reaction time, low production cost, and causes green pollution in the reaction. The ionic liquid catalyst used in the synthesis method is a cheap, easy-to-obtain and environmentally friendly high-efficiency catalyst.
本发明的目的是通过下述技术方案予以实现的。The purpose of the present invention is achieved through the following technical solutions.
一种含有β-氰基膦酸酯类衍生物的合成方法，包括以下步骤：将反应物、丙二腈、亚磷酸酯、烯酮类化合物、离子液体催化剂和溶剂搅拌反应，萃取，干燥，过滤蒸除，层析柱分离，得到所述含有β-氰基膦酸酯类衍生物，其中，按物质的量份数计，所述反应物、丙二腈、亚磷酸酯、烯酮类化合物和离子液体催化剂的比为1:(1～1.5)：(1～1.5)：(1～1.5)：(0.1～0.2)，所述离子液体催化剂为1,4-二氮双环[2.2.2]辛烷醋酸盐、1,4-二氮双环[2.2.2]辛烷溴酸盐、1,4-二氮双环[2.2.2]辛烷硫酸氢盐、1,4-二氮双环[2.2.2]辛烷盐酸盐或1,4-二氮双环[2.2.2]辛烷四氟硼酸盐。A method for synthesizing β-cyanophosphonate derivatives, comprising the steps of: reacting reactants, malononitrile, phosphite, ketene compounds, ionic liquid catalysts and a solvent by stirring, extracting, drying, Filtration and distillation, separation by chromatography column to obtain the β-cyanophosphonate derivatives, wherein, in terms of the amount of substances, the reactants, malononitrile, phosphite, ketenes The ratio of the compound to the ionic liquid catalyst is 1:(1~1.5):(1~1.5):(1~1.5):(0.1~0.2), and the ionic liquid catalyst is 1,4-diazabicyclo[2.2. 2] Octane acetate, 1,4-diazabicyclo[2.2.2]octane bromide, 1,4-diazabicyclo[2.2.2]octane hydrogen sulfate, 1,4-diaza Bicyclo[2.2.2]octane hydrochloride or 1,4-diazabicyclo[2.2.2]octane tetrafluoroborate.
在上述技术方案中，1,4-二氮双环[2.2.2]辛烷醋酸盐的结构式为
1,4-二氮双环[2.2.2]辛烷溴酸盐的结构式为
1,4-二氮双环[2.2.2]辛烷硫酸氢盐的结构式为
1,4-二氮双环[2.2.2]辛烷盐酸盐的结构式为
1,4-二氮双环[2.2.2]辛烷四氟硼酸盐的结构式为
在上述技术方案中，所述溶剂为甲苯、乙醇、正己烷、四氢呋喃和甲醇中的一种或几种的混合物。In the above technical scheme, the solvent is one or a mixture of toluene, ethanol, n-hexane, tetrahydrofuran and methanol.
在上述技术方案中，所述搅拌反应为20～60℃反应。In the above technical solution, the stirring reaction is a reaction at 20-60°C.
在上述技术方案中，所述反应物为
在上述技术方案中，所述亚磷酸酯为
在上述技术方案中，所述反应物的物质的量份数与所述溶剂的体积份数的比为1：(0.5～1)，其中，所述物质的量份数的单位为mmol，所述体积份数的单位为mL。In the above technical solution, the ratio of the material fraction of the reactant to the volume fraction of the solvent is 1: (0.5-1), wherein the unit of the material fraction is mmol, so The unit of volume fraction is mL.
在上述技术方案中，通过薄层色谱法检测搅拌反应进行的时间。In the above technical solution, the time during which the stirring reaction is carried out is detected by thin layer chromatography.
在上述技术方案中，所述搅拌反应的时间至少为20min，优选为150～210min。In the above technical solution, the stirring reaction time is at least 20 minutes, preferably 150-210 minutes.
在上述技术方案中，先将反应物、丙二腈、亚磷酸酯、离子液体催化剂和溶剂于40～50℃搅拌30～60min，再加入烯酮类化合物进行所述搅拌反应。In the above technical solution, the reactants, malononitrile, phosphite, ionic liquid catalyst and solvent are first stirred at 40-50° C. for 30-60 min, and then ketene compounds are added to carry out the stirring reaction.
在上述技术方案中，所述萃取为先加入水，再加入乙酸乙酯洗涤。In the above technical solution, the extraction is performed by adding water first, and then adding ethyl acetate for washing.
在上述技术方案中，所述干燥采用无水硫酸钠。In the above technical scheme, the drying adopts anhydrous sodium sulfate.
在上述技术方案中，层柱析反应的洗脱剂为石油醚和乙酸乙酯的混合物，按体积份数计，石油醚和乙酸乙酯的比为(1～3):1。In the above technical scheme, the eluent for the column chromatography reaction is a mixture of petroleum ether and ethyl acetate, and the ratio of petroleum ether to ethyl acetate is (1-3):1 in parts by volume.
本发明的合成方法步骤简单，反应时间短，反应收率较高，所使用的离子液体催化剂廉价易得，另外本发明公开的合成方法底物适用范围广，通过四组分“一锅法”即得到了本发明中极其重要的一类多官能团β-氰基膦酸酯类衍生物。The synthesis method of the invention has simple steps, short reaction time, high reaction yield, and the used ionic liquid catalyst is cheap and easy to obtain. In addition, the synthesis method disclosed in the invention has a wide range of substrates. That is, a very important type of multifunctional β-cyanophosphonate derivatives in the present invention is obtained.
具体实施方式Detailed ways
下面结合具体实施例进一步说明本发明的技术方案。The technical solutions of the present invention are further described below in conjunction with specific embodiments.
在本发明的具体实施方式中，合成所涉及的试剂以及药品为商业途径购买，均购买自天津试剂六厂，药品纯度均为分析纯，试剂和药品都是直接使用，没有经过任何前处理。In the specific embodiment of the present invention, the reagents and medicines involved in the synthesis were purchased through commercial channels, and were purchased from Tianjin Reagent No. 6 Factory. The purity of the medicines were all analytically pure, and the reagents and medicines were used directly without any pretreatment.
本发明合成方法全程持续搅拌，搅拌所使用的电磁加热搅拌器的型号为NUOVAII(美国特马兰公司)；旋转蒸发仪的型号为RE-2000A(巩义市予华仪器责任有限公司)。核磁共振仪器型号：Bruker AV-400 spectrometer，400MHz，DMSO-d6。在本发明的具体实施方式中，物质的量份数的单位为mmol，体积份数的单位为ml。过滤通过玻璃沙芯漏斗(型号：G120～30um)。The synthesis method of the present invention is continuously stirred throughout the whole process, and the model of the electromagnetic heating stirrer used for stirring is NUOVAII (Temalan Company, USA); the model of the rotary evaporator is RE-2000A (Gongyi Yuhua Instrument Co., Ltd.). NMR instrument model: Bruker AV-400 spectrometer, 400MHz, DMSO-d6. In a specific embodiment of the present invention, the unit of the amount and fraction of the substance is mmol, and the unit of the volume fraction is ml. Filter through a glass sand core funnel (model: G120～30um).
通过薄层色谱法(TLC)检测反应进行的程度。在薄层色谱法中，使用尺寸为15mm×50mm的G254型硅胶板；展开剂极性为乙酸乙酯和石油醚混合物，乙酸乙酯和石油醚的体积比为1:2。在检测过程中所使用ZF-I型三用紫外分析仪(上海驰唐)，所使用药品购买自天津试剂六厂，药品纯度都为分析纯，全部都是直接使用，没有经过任何前处理。通过TLC监测，发现产物不再增多时，标志本发明的合成方法反应结束，可以继续进行下一步的分离操作。The extent of reaction progress was checked by thin layer chromatography (TLC). In thin-layer chromatography, a G254 silica gel plate with a size of 15 mm × 50 mm was used; the polarity of the developing solvent was a mixture of ethyl acetate and petroleum ether, and the volume ratio of ethyl acetate and petroleum ether was 1:2. The ZF-I type three-purpose UV analyzer (Shanghai Chitang) was used in the detection process. The drugs used were purchased from Tianjin Reagent No. 6 Factory. The purity of the drugs was analytically pure, and all of them were used directly without any pretreatment. Through TLC monitoring, when it is found that the product is no longer increased, it marks the end of the reaction of the synthesis method of the present invention, and the separation operation of the next step can be continued.
实施例1Example 1
一种含有β-氰基膦酸酯类衍生物的合成方法，包括以下步骤：依次将1.0mmol(0.120g)对甲基苯甲醛、1.0mmol(0.066g)丙二腈、1.0mmol(0.138g)亚磷酸二乙酯和0.2mmol离子液体催化剂1,4-二氮双环[2.2.2]辛烷醋酸盐加入10ml干燥的圆底烧瓶内，再加入1ml THF(四氢呋喃)作溶剂，40℃加热搅拌反应30min，然后加入1.0mmol(0.084g)1-戊烯-3-酮，40℃搅拌反应，通过TLC监测搅拌反应的时间(2h)，待反应结束后，加入10ml水，冷却后，加入10ml乙酸乙酯萃取3次，有机相经无水硫酸钠干燥后，过滤蒸除，粗产品经柱层析分离提纯，采用石油醚和乙酸乙酯作为洗脱剂(按体积份数计，石油醚和乙酸乙酯的比为3:1)，蒸除洗脱剂干燥即得到纯的含有β-氰基膦酸酯类衍生物(分子式C20H27N2O4P)0.183g，纯度大于98％，反应收率47％。A method for synthesizing β-cyanophosphonate derivatives, comprising the steps of: sequentially mixing 1.0 mmol (0.120 g) p-methylbenzaldehyde, 1.0 mmol (0.066 g) malononitrile, 1.0 mmol (0.138 g) ) Diethyl phosphite and 0.2mmol of ionic liquid catalyst 1,4-diazabicyclo[2.2.2]octane acetate were added to a 10ml dry round-bottomed flask, and then 1ml of THF (tetrahydrofuran) was added as solvent, 40°C The reaction was heated and stirred for 30 min, then 1.0 mmol (0.084 g) of 1-penten-3-one was added, the reaction was stirred at 40°C, and the stirring reaction time (2 h) was monitored by TLC. After the reaction was completed, 10 ml of water was added, and after cooling, 10 ml of ethyl acetate was added for extraction 3 times, the organic phase was dried over anhydrous sodium sulfate, filtered and evaporated, and the crude product was separated and purified by column chromatography, using petroleum ether and ethyl acetate as eluents (by volume, The ratio of petroleum ether and ethyl acetate is 3:1), the eluent is evaporated and dried to obtain 0.183g of pure β-cyanophosphonate derivatives (molecular formula C 20 H 27 N 2 O 4 P), The purity is more than 98%, and the reaction yield is 47%.
1H NMR(400MHz,CDCl3):δ＝1.06(t,J＝7.2Hz,3H,CH3),1.15(t,J＝7.2Hz,3H,CH3),1.34(t,J＝7.2Hz,3H,CH3),2.27-2.32(m,1H,CH2),2.36(s,3H,CH3),2.43-2.51(m,3H,CH2),2.83(t,J＝7.2Hz,2H,CH2),3.42(s,0.5H,CH),3.48(s,0.5H,CH),3.81-3.88(m,1H,CH2),4.03-4.09(m,1H,CH2),4.12-4.20(m,2H,CH2),7.22(d,J＝7.8Hz,1H,ArH),7.43(s,1H,ArH). 1 H NMR (400 MHz, CDCl 3 ): δ=1.06 (t, J=7.2 Hz, 3H, CH 3 ), 1.15 (t, J=7.2 Hz, 3H, CH 3 ), 1.34 (t, J=7.2 Hz , 3H, CH 3 ), 2.27-2.32 (m, 1H, CH 2 ), 2.36 (s, 3H, CH 3 ), 2.43-2.51 (m, 3H, CH 2 ), 2.83 (t, J=7.2Hz, 2H, CH 2 ), 3.42(s, 0.5H, CH ), 3.48(s, 0.5H, CH ), 3.81-3.88(m, 1H, CH 2 ), 4.03-4.09(m, 1H, CH 2 ), 4.12-4.20 (m, 2H, CH 2 ), 7.22 (d, J=7.8 Hz, 1H, ArH), 7.43 (s, 1H, ArH).
13C NMR(100MHz,CDCl3):δ＝7.6,16.1,21.2,31.7,36.1,38.0,39.3,48.9(d,JCP＝187.6Hz,C-P),63.1,64.1,114.1,114.2,114.4,127.1,129.9,130.2,139.5,207.4. 13 C NMR (100 MHz, CDCl 3 ): δ=7.6, 16.1, 21.2, 31.7, 36.1, 38.0, 39.3, 48.9 (d, J CP =187.6 Hz, CP), 63.1, 64.1, 114.1, 114.2, 114.4, 127.1 ,129.9,130.2,139.5,207.4.
31P NMR(162MHz,CDCl3):δ＝18.40. 31 P NMR (162 MHz, CDCl 3 ): δ=18.40.
实施例2Example 2
一种含有β-氰基膦酸酯类衍生物的合成方法，包括以下步骤：依次将1.0mmol(0.131g)对氰基苯甲醛、1.0mmol(0.066g)丙二腈、1.0mmol(0.138g)亚磷酸二乙酯和0.2mmol离子液体催化剂1,4-二氮双环[2.2.2]辛烷醋酸盐加入10ml干燥的圆底烧瓶内，再加入1ml THF作溶剂，40℃加热搅拌反应30min，然后加入1.0mmol(0.084g)1-戊烯-3-酮，40℃搅拌反应，通过TLC监测搅拌反应的时间(2h)，待反应结束后，加入10ml水，冷却后，加入10ml乙酸乙酯萃取3次，有机相经无水硫酸钠干燥后，过滤蒸除，粗产品经柱层析分离提纯，采用石油醚和乙酸乙酯作为洗脱剂(按体积份数计，石油醚和乙酸乙酯的比为3:1)，蒸除洗脱剂干燥即得到纯的含有β-氰基膦酸酯类衍生物(分子式C20H24N3O4P)0.220g，纯度大于98％，反应收率55％。A method for synthesizing β-cyanophosphonate derivatives, comprising the steps of: sequentially mixing 1.0 mmol (0.131 g) p-cyanobenzaldehyde, 1.0 mmol (0.066 g) malononitrile, 1.0 mmol (0.138 g) ) Diethyl phosphite and 0.2mmol of ionic liquid catalyst 1,4-diazabicyclo[2.2.2]octane acetate were added to a 10ml dry round bottom flask, and then 1ml of THF was added as solvent, and the reaction was heated and stirred at 40°C 30min, then add 1.0mmol (0.084g) 1-penten-3-one, stir the reaction at 40°C, monitor the stirring reaction time (2h) by TLC, after the reaction is over, add 10ml water, after cooling, add 10ml acetic acid Ethyl ester was extracted 3 times, the organic phase was dried over anhydrous sodium sulfate, filtered and evaporated, and the crude product was separated and purified by column chromatography, using petroleum ether and ethyl acetate as eluents (in parts by volume, petroleum ether and The ratio of ethyl acetate is 3:1), the eluent is evaporated and dried to obtain pure β-cyanophosphonate derivatives (molecular formula C 20 H 24 N 3 O 4 P) 0.220g, the purity is greater than 98 %, the reaction yield is 55%.
1H NMR(400MHz,CDCl3):δ＝0.97(t,J＝7.2Hz,3H,CH3),1.11(t,J＝6.8Hz,3H,CH3),1.24(t,J＝7.2Hz,3H,CH3),2.16-2.24(m,1H,CH2),2.39-2.44(m,2H,CH2),2.46-2.54(m,1H,CH2),2.72-2.79(m,2H,CH2),3.60(s,0.5H,CH),3.66(s,0.5H,CH),3.86-3.92(m,1H,CH2),3.98-4.14(m,3H,CH2),7.65(s,4H,ArH). 1 H NMR (400 MHz, CDCl 3 ): δ=0.97 (t, J=7.2 Hz, 3H, CH 3 ), 1.11 (t, J=6.8 Hz, 3H, CH 3 ), 1.24 (t, J=7.2 Hz , 3H, CH 3 ), 2.16-2.24 (m, 1H, CH 2 ), 2.39-2.44 (m, 2H, CH 2 ), 2.46-2.54 (m, 1H, CH 2 ), 2.72-2.79 (m, 2H , CH 2 ), 3.60(s, 0.5H, CH ), 3.66(s, 0.5H, CH ), 3.86-3.92(m, 1H, CH 2 ), 3.98-4.14(m, 3H, CH 2 ), 7.65 (s,4H,ArH).
13C NMR(100MHz,CDCl3):δ＝7.6,16.0,16.1,16.2,31.6,36.1,38.0,39.0,48.7(d,JCP＝141.0Hz,C-P),63.7,64.4,113.4,113.7,113.8,113.9,118.0,131.1,132.8,136.2,207.4. 13 C NMR (100 MHz, CDCl 3 ): δ=7.6, 16.0, 16.1, 16.2, 31.6, 36.1, 38.0, 39.0, 48.7 (d, J CP =141.0 Hz, CP), 63.7, 64.4, 113.4, 113.7, 113.8 ,113.9,118.0,131.1,132.8,136.2,207.4.
31P NMR(162MHz,CDCl3):δ＝16.84. 31 P NMR (162 MHz, CDCl 3 ): δ=16.84.
实施例3Example 3
一种含有β-氰基膦酸酯类衍生物的合成方法，包括以下步骤：依次将1.0mmol(0.185g)对溴苯甲醛、1.0mmol(0.066g)丙二腈、1.0mmol(0.138g)亚磷酸二乙酯和0.2mmol离子液体催化剂1,4-二氮双环[2.2.2]辛烷醋酸盐加入10ml干燥的圆底烧瓶内，再加入1mlTHF作溶剂，50℃加热搅拌反应30min，然后加入1.0mmol(0.084g)1-戊烯-3-酮，50℃搅拌反应，通过TLC监测搅拌反应的时间(2h)，待反应结束后，加入10ml水，冷却后，加入10ml乙酸乙酯萃取3次，有机相经无水硫酸钠干燥后，过滤蒸除，粗产品经柱层析分离提纯，采用石油醚和乙酸乙酯作为洗脱剂(按体积份数计，石油醚和乙酸乙酯的比为3:1)，蒸除洗脱剂干燥即得到纯的含有β-氰基膦酸酯类衍生物(分子式C19H24BrN2O4P)0.336g，纯度大于98％，反应收率74％。A method for synthesizing β-cyanophosphonate derivatives, comprising the steps of: sequentially mixing 1.0 mmol (0.185 g) p-bromobenzaldehyde, 1.0 mmol (0.066 g) malononitrile, 1.0 mmol (0.138 g) Diethyl phosphite and 0.2mmol of ionic liquid catalyst 1,4-diazabicyclo[2.2.2]octane acetate were added to a 10ml dry round-bottomed flask, then 1ml of THF was added as solvent, and the reaction was heated and stirred at 50°C for 30min. Then 1.0 mmol (0.084 g) 1-penten-3-one was added, the reaction was stirred at 50°C, and the stirring reaction time (2 h) was monitored by TLC. After the reaction was completed, 10 ml of water was added, and after cooling, 10 ml of ethyl acetate was added. Extracted 3 times, the organic phase was dried over anhydrous sodium sulfate, filtered and evaporated, and the crude product was separated and purified by column chromatography, using petroleum ether and ethyl acetate as eluents (in parts by volume, petroleum ether and ethyl acetate) The ratio of ester is 3:1), and the eluent is evaporated and dried to obtain pure β-cyanophosphonate derivatives (molecular formula C 19 H 24 BrN 2 O 4 P) 0.336g, the purity is greater than 98%, The reaction yield was 74%.
1H NMR(400MHz,CDCl3):δ＝1.07(t,J＝7.8Hz,3H,CH3),1.88(t,J＝7.2Hz,3H,CH3),1.35(t,J＝7.2Hz,3H,CH3),2.24-2.32(m,1H,CH2),2.47-2.52(m,3H,CH2),2.82-2.86(m,2H,CH2),3.44(s,0.5H,CH),4.00(s,0.5H,CH),3.88-3.94(m,1H,CH2),4.08-4.10(m,1H,CH2),4.15-4.21(m,2H,CH2),7.44(d,J＝6.8Hz,1H,ArH),7.57(d,J＝8.4Hz,1H,ArH). 1 H NMR (400 MHz, CDCl 3 ): δ=1.07 (t, J=7.8 Hz, 3H, CH 3 ), 1.88 (t, J=7.2 Hz, 3H, CH 3 ), 1.35 (t, J=7.2 Hz , 3H, CH 3 ), 2.24-2.32 (m, 1H, CH 2 ), 2.47-2.52 (m, 3H, CH 2 ), 2.82-2.86 (m, 2H, CH 2 ), 3.44 (s, 0.5H, CH), 4.00 (s, 0.5H, CH), 3.88-3.94 (m, 1H, CH 2 ), 4.08-4.10 (m, 1H, CH 2 ), 4.15-4.21 (m, 2H, CH 2 ), 7.44 (d,J=6.8Hz,1H,ArH),7.57(d,J=8.4Hz,1H,ArH).
13C NMR(100MHz,CDCl3):δ＝7.6,16.1,31.6,36.0,38.0,39.1,48.3,49.7,63.4(d,JCP＝87.6Hz,C-P),113.9,114.0,114.1,123.9,129.6,131.9,132.4,207.3. 13 C NMR (100 MHz, CDCl 3 ): δ=7.6, 16.1, 31.6, 36.0, 38.0, 39.1, 48.3, 49.7, 63.4 (d, J CP =87.6 Hz, CP), 113.9, 114.0, 114.1, 123.9, 129.6 ,131.9,132.4,207.3.
31P NMR(162MHz,CDCl3):δ＝17.61. 31 P NMR (162 MHz, CDCl 3 ): δ=17.61.
实施例4Example 4
一种含有β-氰基膦酸酯类衍生物的合成方法，包括以下步骤：依次将1.0mmol(0.185g)间溴苯甲醛、1.0mmol(0.066g)丙二腈、1.0mmol(0.138g)亚磷酸二乙酯和0.2mmol离子液体催化剂1,4-二氮双环[2.2.2]辛烷醋酸盐加入10ml干燥的圆底烧瓶内，再加入1mlTHF作溶剂，40℃加热搅拌反应30min，然后加入1.0mmol(0.084g)1-戊烯-3-酮，40℃搅拌反应，通过TLC监测搅拌反应的时间2h)，待反应结束后，加入10ml水，冷却后，加入10ml乙酸乙酯萃取3次，有机相经无水硫酸钠干燥后，过滤蒸除，粗产品经柱层析分离提纯，采用石油醚和乙酸乙酯作为洗脱剂(按体积份数计，石油醚和乙酸乙酯的比为3:1)，蒸除洗脱剂干燥即得到纯的含有β-氰基膦酸酯类衍生物(分子式C19H24BrN2O4P)0.286g，纯度大于98％，反应收率63％。A method for synthesizing β-cyanophosphonate derivatives, comprising the steps of: sequentially mixing 1.0 mmol (0.185 g) m-bromobenzaldehyde, 1.0 mmol (0.066 g) malononitrile, 1.0 mmol (0.138 g) Diethyl phosphite and 0.2mmol of ionic liquid catalyst 1,4-diazabicyclo[2.2.2]octane acetate were added to a 10ml dry round-bottomed flask, then 1ml of THF was added as solvent, and the reaction was heated and stirred at 40°C for 30min. Then 1.0 mmol (0.084 g) 1-penten-3-one was added, the reaction was stirred at 40 °C, and the stirring reaction time was monitored by TLC for 2 h). After the reaction was completed, 10 ml of water was added. After cooling, 10 ml of ethyl acetate was added for extraction. 3 times, the organic phase was dried over anhydrous sodium sulfate, filtered and evaporated, and the crude product was separated and purified by column chromatography, using petroleum ether and ethyl acetate as eluents (in parts by volume, petroleum ether and ethyl acetate) The ratio of β-cyanophosphonates (molecular formula C 19 H 24 BrN 2 O 4 P) 0.286g, the purity is greater than 98%, the reaction Yield 63%.
1H NMR(400MHz,CDCl3):δ＝0.98(t,J＝7.2Hz,3H,CH3),1.11(t,J＝7.2Hz,3H,CH3),1.27(t,J＝6.8Hz,3H,CH3),2.18-2.24(m,1H,CH2),2.39-2.49(m,3H,CH2),2.72-2.79(m,2H,CH2),3.43(s,0.5H,CH),3.49(s,0.5H,CH),3.83-3.90(m,1H,CH2),4.01-4.13(m,3H,CH2),7.24(t,J＝8.0Hz,1H,ArH),7.48(d,J＝7.6Hz,1H,ArH),7.61(s,1H,ArH). 1 H NMR (400 MHz, CDCl 3 ): δ=0.98 (t, J=7.2 Hz, 3H, CH 3 ), 1.11 (t, J=7.2 Hz, 3H, CH 3 ), 1.27 (t, J=6.8 Hz , 3H, CH 3 ), 2.18-2.24 (m, 1H, CH 2 ), 2.39-2.49 (m, 3H, CH 2 ), 2.72-2.79 (m, 2H, CH 2 ), 3.43 (s, 0.5H, CH), 3.49 (s, 0.5H, CH), 3.83-3.90 (m, 1H, CH 2 ), 4.01-4.13 (m, 3H, CH 2 ), 7.24 (t, J=8.0 Hz, 1H, ArH) ,7.48(d,J=7.6Hz,1H,ArH),7.61(s,1H,ArH).
13C NMR(100MHz,CDCl3):δ＝7.6,16.1,31.7,36.1,38.0,39.0,48.8(d,JCP＝141.5Hz,C-P),63.8,64.5,113.5,113.6,113.8,113.8,117.9,131.1,132.9,136.1,207.4. 13 C NMR (100 MHz, CDCl 3 ): δ=7.6, 16.1, 31.7, 36.1, 38.0, 39.0, 48.8 (d, J CP =141.5 Hz, CP), 63.8, 64.5, 113.5, 113.6, 113.8, 113.8, 117.9 ,131.1,132.9,136.1,207.4.
31P NMR(162MHz,CDCl3):δ＝16.89. 31 P NMR (162 MHz, CDCl 3 ): δ=16.89.
实施例5Example 5
一种含有β-氰基膦酸酯类衍生物的合成方法，包括以下步骤：依次将1.0mmol(0.185g)邻溴苯甲醛、1.0mmol(0.066g)丙二腈、1.0mmol(0.138g)亚磷酸二乙酯和0.2mmol离子液体催化剂1,4-二氮双环[2.2.2]辛烷醋酸盐加入10ml干燥的圆底烧瓶内，再加入1mlTHF作溶剂，40℃加热搅拌反应30min，然后加入1.0mmol(0.084g)1-戊烯-3-酮，40℃搅拌反应，通过TLC监测搅拌反应的时间(2h)，待反应结束后，加入10ml水，冷却后，加入10ml乙酸乙酯萃取3次，有机相经无水硫酸钠干燥后，过滤蒸除，粗产品经柱层析分离提纯，采用石油醚和乙酸乙酯作为洗脱剂(按体积份数计，石油醚和乙酸乙酯的比为3:1)，蒸除洗脱剂干燥即得到纯的含有β-氰基膦酸酯类衍生物(分子式C19H24BrN2O4P)0.322g，纯度大于98％，反应收率71％。A method for synthesizing β-cyanophosphonate derivatives, comprising the steps of: sequentially mixing 1.0mmol (0.185g) o-bromobenzaldehyde, 1.0mmol (0.066g) malononitrile, 1.0mmol (0.138g) Diethyl phosphite and 0.2mmol of ionic liquid catalyst 1,4-diazabicyclo[2.2.2]octane acetate were added to a 10ml dry round-bottomed flask, then 1ml of THF was added as solvent, and the reaction was heated and stirred at 40°C for 30min. Then 1.0 mmol (0.084 g) 1-penten-3-one was added, the reaction was stirred at 40°C, and the stirring reaction time (2 h) was monitored by TLC. After the reaction was completed, 10 ml of water was added, and after cooling, 10 ml of ethyl acetate was added. Extracted 3 times, the organic phase was dried over anhydrous sodium sulfate, filtered and evaporated, and the crude product was separated and purified by column chromatography, using petroleum ether and ethyl acetate as eluents (in parts by volume, petroleum ether and ethyl acetate) The ratio of ester is 3:1), evaporate the eluent and dry to obtain 0.322g of pure β-cyanophosphonate derivatives (molecular formula C 19 H 24 BrN 2 O 4 P), the purity is greater than 98%, The reaction yield was 71%.
1H NMR(400MHz,CDCl3):δ＝1.07(t,J＝7.2Hz,3H,CH3),1.16(t,J＝7.2Hz,3H,CH3),1.37(t,J＝7.2Hz,3H,CH3),2.22-2.30(m,1H,CH2),2.47-2.52(m,2H,CH2),2.55-2.63(m,2H,CH2),2.80-2.92(m,1H,CH2),3.87-3.94(m,1H,CH2),4.04-4.13(m,2H,CH2),4.18-4.28(m,2H,CH2),4.38(s,0.5H,CH),4.43(s,0.5H,CH),7.27-7.31(m,1H,ArH),7.44(t,J＝8.0Hz,1H,ArH),7.69(d,J＝8.0Hz,1H,ArH),8.03(d,J＝8.0Hz,1H,ArH). 1 H NMR (400 MHz, CDCl 3 ): δ=1.07 (t, J=7.2 Hz, 3H, CH 3 ), 1.16 (t, J=7.2 Hz, 3H, CH 3 ), 1.37 (t, J=7.2 Hz , 3H, CH 3 ), 2.22-2.30 (m, 1H, CH 2 ), 2.47-2.52 (m, 2H, CH 2 ), 2.55-2.63 (m, 2H, CH 2 ), 2.80-2.92 (m, 1H , CH 2 ), 3.87-3.94 (m, 1H, CH 2 ), 4.04-4.13 (m, 2H, CH 2 ), 4.18-4.28 (m, 2H, CH 2 ), 4.38 (s, 0.5H, CH ) ,4.43(s,0.5H,CH),7.27-7.31(m,1H,ArH),7.44(t,J=8.0Hz,1H,ArH),7.69(d,J=8.0Hz,1H,ArH), 8.03(d,J=8.0Hz,1H,ArH).
13C NMR(100MHz,CDCl3):δ＝7.5,15.9,16.1,31.4,35.9,37.7,38.9,46.1,47.5,63.4(d,JCP＝68.4Hz,C-P),113.5,113.6,114.0,126.8,128.3,130.4,130.9,133.6,207.0. 13 C NMR (100 MHz, CDCl 3 ): δ=7.5, 15.9, 16.1, 31.4, 35.9, 37.7, 38.9, 46.1, 47.5, 63.4 (d, J CP =68.4 Hz, CP), 113.5, 113.6, 114.0, 126.8 ,128.3,130.4,130.9,133.6,207.0.
31P NMR(162MHz,CDCl3):δ＝17.40. 31 P NMR (162 MHz, CDCl 3 ): δ=17.40.
实施例6Example 6
一种含有β-氰基膦酸酯类衍生物的合成方法，包括以下步骤：依次将1.0mmol(0.175g)3,4-二氯苯甲醛、1.0mmol(0.066g)丙二腈、1.0mmol(0.138g)亚磷酸二乙酯、和0.2mmol离子液体催化剂1,4-二氮双环[2.2.2]辛烷醋酸盐加入10ml干燥的圆底烧瓶内，再加入1ml THF作溶剂，40℃加热搅拌反应30min，然后加入1.0mmol(0.084g)1-戊烯-3-酮，40℃搅拌反应，通过TLC监测搅拌反应的时间(3h)，待反应结束后，加入10ml水，冷却后，加入10ml乙酸乙酯萃取3次，有机相经无水硫酸钠干燥后，过滤蒸除，粗产品经柱层析分离提纯，采用石油醚和乙酸乙酯作为洗脱剂(按体积份数计，石油醚和乙酸乙酯的比为3:1)，蒸除洗脱剂干燥即得到纯的含有β-氰基膦酸酯类衍生物(分子式C19H23Cl2N2O4P)0.320g，纯度大于98％，反应收率72％。A method for synthesizing β-cyanophosphonate derivatives, comprising the steps of: sequentially mixing 1.0mmol (0.175g) 3,4-dichlorobenzaldehyde, 1.0mmol (0.066g) malononitrile, 1.0mmol (0.138g) diethyl phosphite and 0.2mmol ionic liquid catalyst 1,4-diazabicyclo[2.2.2]octane acetate were added to a 10ml dry round bottom flask, and then 1ml THF was added as solvent, 40 The reaction was heated and stirred for 30 min at ℃, then 1.0 mmol (0.084 g) 1-penten-3-one was added, and the reaction was stirred at 40 ℃. The stirring reaction time (3h) was monitored by TLC. After the reaction was completed, 10 ml of water was added, and after cooling , 10 ml of ethyl acetate was added for extraction 3 times, the organic phase was dried over anhydrous sodium sulfate, filtered and evaporated, and the crude product was separated and purified by column chromatography, using petroleum ether and ethyl acetate as eluents (by volume fractions) , the ratio of petroleum ether and ethyl acetate is 3:1), evaporate the eluent and dry to obtain pure β-cyanophosphonate derivatives (molecular formula C 19 H 23 Cl 2 N 2 O 4 P) 0.320g, the purity is more than 98%, and the reaction yield is 72%.
1H NMR(400MHz,CDCl3):δ＝1.08(t,J＝7.2Hz,3H,CH3),1.24(t,J＝7.2Hz,3H,CH3),1.36(t,J＝6.8Hz,3H,CH3),2.25-2.32(m,1H,CH2),2.48-2.58(m,3H,CH2),2.83-2.88(m,2H,CH2),3.45(s,0.5H,CH),3.50(s,0.5H,CH),3.96-4.03(m,1H,CH2),4.11-4.22(m,3H,CH2),7.45(d,J＝7.2Hz,1H,ArH),7.53(d,J＝8.4Hz,1H,ArH),7.64(s,1H,ArH). 1 H NMR (400 MHz, CDCl 3 ): δ=1.08 (t, J=7.2 Hz, 3H, CH 3 ), 1.24 (t, J=7.2 Hz, 3H, CH 3 ), 1.36 (t, J=6.8 Hz , 3H, CH 3 ), 2.25-2.32 (m, 1H, CH 2 ), 2.48-2.58 (m, 3H, CH 2 ), 2.83-2.88 (m, 2H, CH 2 ), 3.45 (s, 0.5H, CH), 3.50 (s, 0.5H, CH), 3.96-4.03 (m, 1H, CH 2 ), 4.11-4.22 (m, 3H, CH 2 ), 7.45 (d, J=7.2Hz, 1H, ArH) ,7.53(d,J=8.4Hz,1H,ArH),7.64(s,1H,ArH).
13C NMR(100MHz,CDCl3):δ＝7.6,16.2,31.7,36.1,38.0,39.1,48.3(d,JCP＝141.7Hz,C-P),63.6,64.4,113.7,113.8,113.9,129.4,130.8,131.2,132.2,133.5,134.1,207.2. 13 C NMR (100 MHz, CDCl 3 ): δ=7.6, 16.2, 31.7, 36.1, 38.0, 39.1, 48.3 (d, J CP =141.7 Hz, CP), 63.6, 64.4, 113.7, 113.8, 113.9, 129.4, 130.8 ,131.2,132.2,133.5,134.1,207.2.
31P NMR(162MHz,CDCl3):δ＝17.05. 31 P NMR (162 MHz, CDCl 3 ): δ=17.05.
实施例7Example 7
一种含有β-氰基膦酸酯类衍生物的合成方法，包括以下步骤：依次将1.0mmol(0.112g)2-噻吩甲醛、1.0mmol(0.066g)丙二腈、1.0mmol(0.138g)亚磷酸二乙酯、和0.2mmol离子液体催化剂1,4-二氮双环[2.2.2]辛烷醋酸盐加入10ml干燥的圆底烧瓶内，再加入1ml THF作溶剂，50℃加热搅拌反应30min，然后加入1.0mmol(0.084g)1-戊烯-3-酮，50℃搅拌反应，通过TLC监测搅拌反应的时间(3h)，待反应结束后，加入10ml水，冷却后，加入10ml乙酸乙酯萃取3次，有机相经无水硫酸钠干燥后，过滤蒸除，粗产品经柱层析分离提纯，采用石油醚和乙酸乙酯作为洗脱剂(按体积份数计，石油醚和乙酸乙酯的比为3:1)，蒸除洗脱剂干燥即得到纯的含有β-氰基膦酸酯类衍生物(分子式C17H23N2O4PS)0.275g，纯度大于98％，反应收率72％。A method for synthesizing β-cyanophosphonate derivatives, comprising the steps of: sequentially mixing 1.0 mmol (0.112 g) 2-thiophenecarboxaldehyde, 1.0 mmol (0.066 g) malononitrile, 1.0 mmol (0.138 g) Diethyl phosphite and 0.2mmol of ionic liquid catalyst 1,4-diazabicyclo[2.2.2]octane acetate were added to a 10ml dry round-bottomed flask, and then 1ml of THF was added as a solvent, and the reaction was heated and stirred at 50°C 30min, then add 1.0mmol (0.084g) 1-penten-3-one, stir the reaction at 50 ℃, monitor the stirring reaction time (3h) by TLC, after the reaction is over, add 10ml water, after cooling, add 10ml acetic acid Ethyl ester was extracted 3 times, the organic phase was dried over anhydrous sodium sulfate, filtered and evaporated, and the crude product was separated and purified by column chromatography, using petroleum ether and ethyl acetate as eluents (in parts by volume, petroleum ether and The ratio of ethyl acetate is 3:1), the eluent is evaporated and dried to obtain pure β-cyanophosphonate derivatives (molecular formula C 17 H 23 N 2 O 4 PS) 0.275g, the purity is greater than 98 %, the reaction yield is 72%.
1H NMR(400MHz,CDCl3):δ＝1.09(t,J＝7.8Hz,3H,CH3),1.22(t,J＝7.2Hz,3H,CH3),1.37(t,J＝7.2Hz,3H,CH3),2.32-2.39(m,1H,CH2),2.48-2.56(m,3H,CH2),2.85(t,J＝7.8Hz,2H,CH2),3.79(s,0.5H,CH),3.84(s,0.5H,CH),3.89-3.98(m,1H,CH2),4.11-4.26(m,3H,CH2),7.10(t,J＝4.0Hz,1H,ArH),7.40(t,J＝5.2Hz,2H,ArH). 1 H NMR (400 MHz, CDCl 3 ): δ=1.09 (t, J=7.8 Hz, 3H, CH 3 ), 1.22 (t, J=7.2 Hz, 3H, CH 3 ), 1.37 (t, J=7.2 Hz , 3H, CH 3 ), 2.32-2.39 (m, 1H, CH 2 ), 2.48-2.56 (m, 3H, CH 2 ), 2.85 (t, J=7.8Hz, 2H, CH 2 ), 3.79 (s, 0.5H, CH), 3.84 (s, 0.5H, CH), 3.89-3.98 (m, 1H, CH 2 ), 4.11-4.26 (m, 3H, CH 2 ), 7.10 (t, J=4.0Hz, 1H ,ArH),7.40(t,J=5.2Hz,2H,ArH).
13C NMR(100MHz,CDCl3):δ＝7.7,16.2,31.4,36.1,38.1,39.8,44.2,45.6,63.6,63.7,64.6,113.8,114.0,127.5,127.8,130.2,207.3. 13 C NMR (100 MHz, CDCl 3 ): δ=7.7, 16.2, 31.4, 36.1, 38.1, 39.8, 44.2, 45.6, 63.6, 63.7, 64.6, 113.8, 114.0, 127.5, 127.8, 130.2, 207.3.
31P NMR(162MHz,CDCl3):δ＝16.29. 31 P NMR (162 MHz, CDCl 3 ): δ=16.29.
以上对本发明做了示例性的描述，应该说明的是，在不脱离本发明的核心的情况下，任何简单的变形、修改或者其他本领域技术人员能够不花费创造性劳动的等同替换均落入本发明的保护范围。The present invention has been exemplarily described above. It should be noted that, without departing from the core of the present invention, any simple deformation, modification or other equivalent replacements that can be performed by those skilled in the art without creative effort fall into the scope of the present invention. the scope of protection of the invention.
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