CN115322222A - Photocatalytic preparation method of ((alkylamino) methyl) diphenyl phosphine oxide compound - Google Patents
Photocatalytic preparation method of ((alkylamino) methyl) diphenyl phosphine oxide compound Download PDFInfo
- Publication number
- CN115322222A CN115322222A CN202211004211.3A CN202211004211A CN115322222A CN 115322222 A CN115322222 A CN 115322222A CN 202211004211 A CN202211004211 A CN 202211004211A CN 115322222 A CN115322222 A CN 115322222A
- Authority
- CN
- China
- Prior art keywords
- methyl
- alkylamino
- phosphine oxide
- reaction
- diphenyl phosphine
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 125000003282 alkyl amino group Chemical group 0.000 title claims abstract description 24
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 title claims abstract description 24
- -1 diphenyl phosphine oxide compound Chemical class 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 12
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims abstract description 72
- 238000006243 chemical reaction Methods 0.000 claims abstract description 62
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 43
- 239000003054 catalyst Substances 0.000 claims abstract description 12
- 239000000654 additive Substances 0.000 claims abstract description 7
- 230000000996 additive effect Effects 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims abstract description 7
- ASUOLLHGALPRFK-UHFFFAOYSA-N phenylphosphonoylbenzene Chemical class C=1C=CC=CC=1P(=O)C1=CC=CC=C1 ASUOLLHGALPRFK-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000012046 mixed solvent Substances 0.000 claims abstract description 5
- 238000005286 illumination Methods 0.000 claims abstract description 3
- 239000002994 raw material Substances 0.000 claims abstract description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 63
- 239000012074 organic phase Substances 0.000 claims description 40
- 238000004440 column chromatography Methods 0.000 claims description 21
- 238000001035 drying Methods 0.000 claims description 19
- 150000001875 compounds Chemical class 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 14
- YFPJFKYCVYXDJK-UHFFFAOYSA-N Diphenylphosphine oxide Chemical compound C=1C=CC=CC=1[P+](=O)C1=CC=CC=C1 YFPJFKYCVYXDJK-UHFFFAOYSA-N 0.000 claims description 13
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- PRWATGACIORDEL-UHFFFAOYSA-N 2,4,5,6-tetra(carbazol-9-yl)benzene-1,3-dicarbonitrile Chemical group C12=CC=CC=C2C2=CC=CC=C2N1C1=C(C#N)C(N2C3=CC=CC=C3C3=CC=CC=C32)=C(N2C3=CC=CC=C3C3=CC=CC=C32)C(N2C3=CC=CC=C3C3=CC=CC=C32)=C1C#N PRWATGACIORDEL-UHFFFAOYSA-N 0.000 claims description 4
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 3
- VSTXCZGEEVFJES-UHFFFAOYSA-N 1-cycloundecyl-1,5-diazacycloundec-5-ene Chemical compound C1CCCCCC(CCCC1)N1CCCCCC=NCCC1 VSTXCZGEEVFJES-UHFFFAOYSA-N 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 238000001704 evaporation Methods 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 6
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 239000012429 reaction media Substances 0.000 abstract description 2
- 239000007787 solid Substances 0.000 description 30
- FAGLEPBREOXSAC-UHFFFAOYSA-N tert-butyl isocyanide Chemical compound CC(C)(C)[N+]#[C-] FAGLEPBREOXSAC-UHFFFAOYSA-N 0.000 description 20
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-diisopropylethylamine Substances CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 description 19
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 19
- 238000010790 dilution Methods 0.000 description 14
- 239000012895 dilution Substances 0.000 description 14
- 239000012295 chemical reaction liquid Substances 0.000 description 13
- 238000004949 mass spectrometry Methods 0.000 description 13
- 238000001228 spectrum Methods 0.000 description 13
- 239000000243 solution Substances 0.000 description 8
- 238000001819 mass spectrum Methods 0.000 description 6
- 238000010183 spectrum analysis Methods 0.000 description 6
- 239000012230 colorless oil Substances 0.000 description 5
- CANRZGABCCJJIP-UHFFFAOYSA-N benzyl 2-isocyano-3-phenylpropanoate Chemical compound O=C(OCc1ccccc1)C(Cc1ccccc1)[N+]#[C-] CANRZGABCCJJIP-UHFFFAOYSA-N 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 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 2
- DUVOZUPPHBRJJO-UHFFFAOYSA-N ethyl 2-isocyanatoacetate Chemical compound CCOC(=O)CN=C=O DUVOZUPPHBRJJO-UHFFFAOYSA-N 0.000 description 2
- FPULFENIJDPZBX-UHFFFAOYSA-N ethyl 2-isocyanoacetate Chemical compound CCOC(=O)C[N+]#[C-] FPULFENIJDPZBX-UHFFFAOYSA-N 0.000 description 2
- RIWNFZUWWRVGEU-UHFFFAOYSA-N isocyanomethylbenzene Chemical compound [C-]#[N+]CC1=CC=CC=C1 RIWNFZUWWRVGEU-UHFFFAOYSA-N 0.000 description 2
- ZWTPUHSQAWCFFP-UHFFFAOYSA-N methyl 2-isocyano-4-methylpentanoate Chemical compound COC(=O)C([N+]#[C-])CC(C)C ZWTPUHSQAWCFFP-UHFFFAOYSA-N 0.000 description 2
- HGDIHUZVQPKSMO-UHFFFAOYSA-N methylphosphonoylmethane Chemical compound CP(C)=O HGDIHUZVQPKSMO-UHFFFAOYSA-N 0.000 description 2
- 238000009987 spinning Methods 0.000 description 2
- QDWOIMWUGPSJMU-UHFFFAOYSA-N 1-chloro-4-(4-chlorophenyl)phosphonoylbenzene Chemical compound C1=CC(Cl)=CC=C1P(=O)C1=CC=C(Cl)C=C1 QDWOIMWUGPSJMU-UHFFFAOYSA-N 0.000 description 1
- JNNKFUNOEOWVSD-UHFFFAOYSA-N 1-fluoro-3-(3-fluorophenyl)phosphonoylbenzene Chemical compound FC1=CC=CC(P(=O)C=2C=C(F)C=CC=2)=C1 JNNKFUNOEOWVSD-UHFFFAOYSA-N 0.000 description 1
- CCBDFSFCAHWFJF-UHFFFAOYSA-N 1-methoxy-3-(3-methoxyphenyl)phosphonoylbenzene Chemical compound COC1=CC=CC(P(=O)C=2C=C(OC)C=CC=2)=C1 CCBDFSFCAHWFJF-UHFFFAOYSA-N 0.000 description 1
- KKBXIQVJXZVRHH-UHFFFAOYSA-N C1=CC=C2C(P(C=3C4=CC=CC=C4C=CC=3)=O)=CC=CC2=C1 Chemical compound C1=CC=C2C(P(C=3C4=CC=CC=C4C=CC=3)=O)=CC=CC2=C1 KKBXIQVJXZVRHH-UHFFFAOYSA-N 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- 102000035195 Peptidases Human genes 0.000 description 1
- 108091005804 Peptidases Proteins 0.000 description 1
- 239000004365 Protease Substances 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 150000001371 alpha-amino acids Chemical class 0.000 description 1
- 235000008206 alpha-amino acids Nutrition 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- MIYITCTXDGORJJ-UHFFFAOYSA-N bis(4-fluorophenyl)-oxophosphanium Chemical compound C1=CC(F)=CC=C1[P+](=O)C1=CC=C(F)C=C1 MIYITCTXDGORJJ-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- ACLBAKCXXIZYJV-UHFFFAOYSA-N chembl1463773 Chemical compound C=1C=CC=CC=1CP(=O)CC1=CC=CC=C1 ACLBAKCXXIZYJV-UHFFFAOYSA-N 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- ZGONRPXUNVTWTA-UHFFFAOYSA-N methyl 2-isocyanatoacetate Chemical compound COC(=O)CN=C=O ZGONRPXUNVTWTA-UHFFFAOYSA-N 0.000 description 1
- CRXFROMHHBMNAB-UHFFFAOYSA-N methyl 2-isocyanoacetate Chemical compound COC(=O)C[N+]#[C-] CRXFROMHHBMNAB-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 150000002903 organophosphorus compounds Chemical class 0.000 description 1
- MPQXHAGKBWFSNV-UHFFFAOYSA-N oxidophosphanium Chemical class [PH3]=O MPQXHAGKBWFSNV-UHFFFAOYSA-N 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010490 three component reaction Methods 0.000 description 1
Classifications
-
- 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
- C07F9/50—Organo-phosphines
- C07F9/53—Organo-phosphine oxides; Organo-phosphine thioxides
- C07F9/5325—Aromatic phosphine oxides or thioxides (P-C aromatic linkage)
-
- 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
- C07F9/50—Organo-phosphines
- C07F9/53—Organo-phosphine oxides; Organo-phosphine thioxides
- C07F9/5333—Arylalkane phosphine oxides or thioxides
-
- 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
- Y02P20/584—Recycling of catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a photocatalytic preparation method of ((alkylamino) methyl) diphenyl phosphine oxide compounds, belonging to the technical field of organic synthesis. The technical scheme provided by the invention has the key points that: the method comprises the steps of taking an isocyano compound and a diphenyl phosphine oxide compound as initial raw materials, taking acetonitrile and water as a mixed solvent under the action of an additive and a catalyst, and carrying out a blue light illumination reaction at room temperature under the air condition to obtain a target product ((alkylamino) methyl) diphenyl phosphine oxide compound. The preparation method is simple, convenient and safe to operate, mild in reaction conditions, green and pollution-free due to the fact that a light source used by the preparation method is visible light, the catalyst and the reaction medium are friendly to the environment, and the yield of the synthesized target product is relatively high.
Description
Technical Field
The invention belongs to the technical field of synthesis of substituted phosphine oxide compounds, and particularly relates to a photocatalytic preparation method of ((alkylamino) methyl) diphenyl phosphine oxide compounds.
Background
Organophosphorus compounds are widely applied in pharmaceutical industry (chem.Rev.2006, 106, 3868), pesticides (plantas 2019,8, 341) and functional materials, so that the construction of carbon-phosphorus bonds has important research value. Alpha-aminomethylphosphoryl compounds are used as isosteres of alpha-amino acids in inhibitors of various proteases (J.Med.chem.1986, 29).
The kabechnik-feeds reaction is currently the most commonly used method for constructing alpha-aminomethyl phosphoryl compounds, and the method obtains target compounds through three-component reaction of one molecule of amine, paraformaldehyde and phosphoryl compounds (Synthetic Communications,2019, 49,1047 molecules 2019,24, 1640), however, the reaction needs high-temperature heating. Therefore, the development of a preparation method of ((alkylamino) methyl) diphenylphosphine oxide compounds with mild conditions has important significance.
Disclosure of Invention
The invention solves the technical problem of providing a photocatalytic preparation method of ((alkylamino) methyl) diphenyl phosphine oxide compounds, which has simple synthesis process and mild reaction conditions, can effectively solve the problem that the prior art needs high-temperature heating, and provides a new method for synthesizing ((alkylamino) methyl) diphenyl phosphine oxide compounds.
The invention adopts the following technical scheme for solving the technical problems: a photocatalytic preparation method of ((alkylamino) methyl) diphenyl phosphine oxide compounds is characterized by comprising the following specific steps: the method comprises the following steps of taking an isocyanic compound and a diphenyl phosphine oxide compound as initial raw materials, taking acetonitrile and water as a mixed solvent under the action of an additive and a catalyst, carrying out blue light illumination reaction at room temperature under the condition of air, evaporating the solvent after the reaction is finished, extracting a reaction solution by ethyl acetate, drying, removing an organic phase by rotation, and carrying out column chromatography separation on residues to obtain a target product ((alkylamino) methyl) diphenyl phosphine oxide compound, wherein the additive is one or more of triethylamine, N-diisopropylethylamine DIPEA, 1, 8-diazabicycloundec-7-ene DBU or tetramethylethylenediamine TMEDA, the catalyst is 2,4,5, 6-tetra (9-carbazolyl) -isophthalonitrile 4-CzIPN, the structural formula of the isocyanic compound is shown as A, the structural formula of the diphenyl phosphine oxide compound is shown as B, and the structural formula of the ((alkylamino) methyl) diphenyl phosphine oxide compound is shown as C:
in the formula R 1 Is tert-butyl, benzyl or an ester-containing alkyl radical, R 2 Is halogen, C 1-5 Alkyl or C 1-5 An alkoxy group.
Further limiting, the specific structural formula of the ((alkylamino) methyl) diphenylphosphine oxide compound is as follows:
further limiting, the charging molar ratio of the isocyanic compound, the diphenyl phosphine oxide compound, the catalyst and the additive is 1-3.
Further limiting, the volume ratio of acetonitrile to water in the mixed solvent is 200-50, and preferably is 100.
Further defined, the reaction equation in the preparation process of the ((alkylamino) methyl) diphenyl phosphine oxide compound is as follows:
the structural formula of the catalyst 2,4,5, 6-tetra (9-carbazolyl) -isophthalonitrile 4-CzIPN is as follows:
further limited, the light source of the blue light in the reaction process is a blue LED lamp, the wavelength of the blue LED lamp is 405nm, and the power of the blue LED lamp is 10W.
Compared with the prior art, the invention has the following advantages and beneficial effects: compared with the prior art, the preparation method does not need high-temperature heating, and synthesizes the target product ((alkylamino) methyl) diphenyl phosphine oxide compound through one-pot reaction by using an organic photosensitizer as a catalyst under the catalysis of visible light. The preparation method is simple, convenient and safe to operate, mild in reaction conditions, green and pollution-free due to the fact that a light source used by the preparation method is visible light, the catalyst and the reaction medium are friendly to the environment, and the yield of the synthetic target product is relatively high.
Detailed Description
The technical solution of the present invention is specifically described below by way of examples. It is to be noted that the following examples are only for further illustration of the present invention and should not be construed as limiting the scope of the present invention. Many non-essential modifications and adaptations of the present invention will occur to those skilled in the art in view of the foregoing description, and are intended to be within the scope of the present invention. In addition, the starting materials used are all commercially available, unless otherwise specified.
Example 1
Adding 2-isocyano-2-methylpropane (0.2 mmol), diphenylphosphine oxide (0.4 mmol), N-diisopropylethylamine (0.4 mmol) and 4-CZIPN (5 mol% equivalent) in sequence into a 10mL reaction tube containing magnetons, then adding solvents acetonitrile (2 mL) and water (20 mu L), reacting for 12 hours at room temperature under the irradiation of a 405nm blue LED lamp under the air condition, adding water for dilution after the reaction is finished, extracting reaction liquid by using ethyl acetate, combining organic phases, drying by using anhydrous sodium sulfate, removing the organic phases, and separating residues by using column chromatography to obtain the target product which is a white solid. The yield of the target product was 85% based on 100% by mole of 2-isocyano-2-methylpropane.
The structural formula of the target product is as follows:
the white solid was analyzed by nuclear magnetic spectrum and mass spectrometry, and the data were as follows:
1 H NMR(400MHz,CDCl 3 )δ7.83-7.78(m,4H),7.55-7.51(m,2H),7.48-7.44(m,4H),3.40(d,J＝9.8Hz,2H),1.07(s,9H)。
13 C NMR(100MHz,CDCl 3 )δ132.2(d,J＝98.0Hz),132.0(d,J＝3.0Hz),131.4(d,J＝9.0Hz),128.6(d,J＝11.0Hz),51.3(d,J＝13.0Hz),42.8(d,J＝84.0Hz),28.6。
31 P NMR(162MHz,CDCl 3 )δ30.6。
HRMS(ESI-TOF)m/z:[M+H] + Calcd for C 17 H 23 NOP + 288.1512,Found:288.1512。
example 2
Adding (isocyanmethyl) benzene (0.2 mmol), diphenylphosphine oxide (0.4 mmol), N-diisopropylethylamine (0.4 mmol) and 4-CzIPN (5 mol% equivalent) into a 10mL reaction tube containing magnetons in sequence, then adding solvents acetonitrile (2 mL) and water (20 mu L), reacting at room temperature for 12 hours under the irradiation of a 405nm blue LED lamp under the air condition, adding water for dilution after the reaction is finished, extracting the reaction liquid with ethyl acetate, combining organic phases, drying with anhydrous sodium sulfate, removing the organic phases by rotation, and separating residues by column chromatography to obtain the target product which is a white solid. The yield of the target product was 50% based on the molar amount of (isocyanmethyl) benzene taken as 100%.
The structural formula of the target product is as follows:
the white solid was analyzed by nuclear magnetic spectrum and mass spectrometry, and the data were as follows:
1 H NMR(600MHz,CDCl 3 )δ7.77-7.74(m,4H),7.55-7.52(m,2H),7.47-7.44(m,4H),7.30-7.23(m,5H),3.87(s,2H),3.42(d,J＝7.9Hz,2H)。
13 C NMR(100MHz,CDCl 3 )δ139.2,132.1(d,J＝3.0Hz),132.0(d,J＝97.0Hz),131.3(d,J＝9.0Hz),128.8,128.7,128.5(d,J＝14.0Hz),127.4,55.2(d,J＝14.0Hz),48.2(d,J＝80.0Hz)。
31 P NMR(162MHz,CDCl 3 )δ29.5。
HRMS(ESI-TOF)m/z:[M+H] + Calcd for C 20 H 21 NOP + 322.1355,Found:322.1352。
example 3
Adding 2-isocyano-2-methylpropane (0.2 mmol), di (naphthalene-1-yl) phosphine oxide (0.4 mmol), N-diisopropylethylamine (0.4 mmol) and 4-CzIPN (5 mol% equivalent) in sequence into a 10mL reaction tube filled with magnetons, then adding acetonitrile (2 mL) and water (20 mu L), reacting at room temperature for 12 hours under the irradiation of a 405nm blue LED lamp under the air condition, adding water for dilution after the reaction is finished, extracting a reaction solution by using ethyl acetate, combining organic phases, drying by using anhydrous sodium sulfate, removing the organic phases, and separating the residue by using column chromatography to obtain the target product which is a white solid. The yield of the objective product was 40% based on the molar amount of 2-isocyano-2-methylpropane taken as 100%.
The structural formula of the target product is as follows:
the white solid was analyzed by nuclear magnetic spectrum and mass spectrometry, and the data were as follows:
1 H NMR(400MHz,CDCl 3 )δ8.74(d,J＝8.1Hz,2H),8.01(dd,J＝13.9Hz,6.1Hz4H),7.88(d,J＝7.7Hz,2H),7.50-7.43(m,6H),3.71(d,J＝10.0Hz,2H),1.07(s,9H)。
13 C NMR(100MHz,CDCl 3 )δ133.9(q,J＝8.0Hz),133.2(d,J＝3Hz),132.8,132.7,129.1,128.9(d,J＝95.0Hz),127.4,126.9(d,J＝5.0Hz),126.5,124.7(d,J＝14.0Hz),51.4(d,J＝14.0Hz),43.8(d,J＝83.0Hz),28.6。
31 P NMR(162MHz,CDCl 3 )δ36.6。
HRMS(ESI-TOF)m/z:[M+H] + Calcd for C 25 H 27 NOP + 388.1825,Found:388.1844。
example 4
Adding 2-isocyano-2-methylpropane (0.2 mmol), bis (4-fluorophenyl) phosphine oxide (0.4 mmol), N-diisopropylethylamine (0.4 mmol) and 4-CzIPN (5 mol% equivalent) in sequence into a 10mL reaction tube filled with magnetons, then adding acetonitrile (2 mL) and water (20 mu L), reacting at room temperature for 12 hours under the irradiation of a 405nm blue LED lamp under the air condition, adding water for dilution after the reaction is finished, extracting a reaction solution by using ethyl acetate, combining organic phases, drying by using anhydrous sodium sulfate, removing the organic phases, and separating the residue by using column chromatography to obtain a target product which is a light yellow solid. The yield of the objective product was 78% based on the molar amount of 2-isocyano-2-methylpropane taken as 100%.
The structural formula of the target product is as follows:
the light yellow solid is subjected to nuclear magnetic spectrum and mass spectrum analysis, and the data are as follows:
1 H NMR(600MHz,CDCl 3 )δ7.83-7.79(m,4H),7.18-7.15(m,4H),3.36(d,J＝10.0Hz,2H),1.06(s,9H)。
13 C NMR(150MHz,CDCl 3 )δ165.2(dd,J 1 ＝252.0Hz，J 2 ＝3.0Hz),134.0(t,J＝9.0Hz),128.0(dd,J 1 ＝102.0Hz，J 2 ＝3.0Hz),116.1(dd,J 1 ＝21.0Hz，J 2 ＝12.0Hz),51.4(d,J＝13.5Hz),43.2(d,J＝87.0Hz),29.1。
19 F NMR(564MHz,CDCl 3 )δ-106.5。
31 P NMR(243MHz,CDCl 3 )δ29.1。
HRMS(ESI-TOF)m/z:[M+H] + Calcd for C 17 H 21 F 2 NOP + 324.1323,Found:324.1323。
example 5
Adding 2-isocyano-2-methylpropane (0.2 mmol), bis (3-methoxyphenyl) phosphine oxide (0.4 mmol), N-diisopropylethylamine (0.4 mmol) and 4-CzIPN (5 mol% equivalent) in sequence into a 10mL reaction tube filled with magnetons, then adding acetonitrile (2 mL) and water (20 mu L), reacting at room temperature for 12 hours under the irradiation of a 405nm blue LED lamp under the air condition, adding water for dilution after the reaction is finished, extracting a reaction solution by using ethyl acetate, combining organic phases, drying by using anhydrous sodium sulfate, removing the organic phases, and separating the residue by using column chromatography to obtain the target product which is a white solid. The yield of the objective product was 38% based on the molar amount of 2-isocyano-2-methylpropane taken as 100%.
The structural formula of the target product is as follows:
the above white solid was analyzed by nuclear magnetic spectrum and mass spectrometry, and the data were as follows:
1 H NMR(400MHz,CDCl 3 )δ7.45-7.41(m,2H),7.39-7.34(m,2H),7.32-7.28(m,2H),7.06-7.03(m,2H),3.82(s,6H),3.38(d,J＝9.8Hz,2H),1.08(s,9H)。
13 C NMR(100MHz,CDCl 3 )δ159.7(d,J＝14.0Hz),133.5(d,J＝97.0Hz),129.8(d,J＝14.0Hz),123.5(d,J＝9.0Hz),118.4(d,J＝2.0Hz),116.2(d,J＝9.0Hz),55.6,51.3(d,J＝14.0Hz),43.0(d,J＝84.0Hz),28.6。
31 P NMR(162MHz,CDCl 3 )δ30.7。
HRMS(ESI-TOF)m/z:[M+H] + Calcd for C 19 H 27 NO 3 P + 348.1723,Found:348.1723。
example 6
Adding 2-isocyano-2-methyl propane (0.2 mmol), di-p-methyl phosphine oxide (0.4 mmol), N-diisopropylethylamine (0.4 mmol) and 4-CZIPN (5 mol% equivalent) into a 10mL reaction tube filled with magnetons in sequence, then adding solvents acetonitrile (2 mL) and water (20 mu L), reacting at room temperature for 12 hours under the irradiation of a 405nm blue LED lamp under the air condition, adding water for dilution after the reaction is finished, extracting reaction liquid by using ethyl acetate, combining organic phases, drying by using anhydrous sodium sulfate, removing the organic phases, and separating residues by using column chromatography to obtain the target product which is a white solid. The yield of the objective product was 56% based on the molar amount of 2-isocyano-2-methylpropane taken as 100%.
The structural formula of the target product is as follows:
the above white solid was analyzed by nuclear magnetic spectrum and mass spectrometry, and the data were as follows:
1 H NMR(600MHz,CDCl 3 )δ7.68(dd,J 1 ＝11.1Hz，J 2 ＝8.0Hz,4H),7.27-7.25(m,4H),3.35(d,J＝9.9Hz,2H),2.39(s,6H),1.06(s,9H)。
13 C NMR(100MHz,CDCl 3 )δ142.3(d,J＝3.0Hz),131.5(d,J＝9.0Hz),129.4(d,J＝12.0Hz),129.2(d,J＝101.0Hz),51.3(d,J＝14.0Hz),43.0(d,J＝84.0Hz),28.6,21.7。
31 P NMR(162MHz,CDCl 3 )δ30.7。
HRMS(ESI-TOF)m/z:[M+H] + Calcd for C 19 H 27 NOP + 316.1825,Found:316.1808。
example 7
Adding 2-isocyano-2-methylpropane (0.2 mmol), dibenzylphosphine oxide (0.4 mmol), N-diisopropylethylamine (0.4 mmol) and 4-CZIPN (5 mol% equivalent) into a 10mL reaction tube filled with magnetons in sequence, then adding solvents of acetonitrile (2 mL) and water (20 mu L), reacting at room temperature for 12 hours under the irradiation of a 405nm blue LED lamp under the air condition, adding water to dilute after the reaction is finished, extracting reaction liquid with ethyl acetate, combining organic phases, drying with anhydrous sodium sulfate, removing the organic phases, and separating residues through column chromatography to obtain the target product which is light red solid. The yield of the objective product was 45% based on 100% by mole of 2-isocyano-2-methylpropane.
The structural formula of the target product is as follows:
the light red solid is subjected to nuclear magnetic spectrum and mass spectrum analysis, and the data are as follows:
1 H NMR(400MHz,CDCl 3 )δ7.34-7.26(m,10H),3.28-3.12(m,4H),2.72(d,J＝9.3Hz,2H),1.02(s,9H)。
13 C NMR(100MHz,CDCl 3 )δ132.0(d,J＝6.0Hz),130.0(d,J＝6.0Hz),129.0(d,J＝3.0Hz),127.1(d,J＝3.0Hz),34.7,34.1,29.9,28.5。
31 P NMR(243MHz,CDCl 3 )δ44.6。
HRMS(ESI-TOF)m/z:[M+H] + Calcd for C 19 H 27 NOP + 316.1825,Found:316.1826。
example 8
2-isocyano-2-methylpropane (0.2 mmol), bis (3-fluorophenyl) phosphine oxide (0.4 mmol), N-diisopropylethylamine (0.4 mmol) and 4-CzIPN (5 mol% equivalent) were sequentially added to a 10mL reaction tube containing magnetons, followed by addition of acetonitrile (2 mL) and water (20. Mu.L), reaction at room temperature for 12 hours under irradiation of a 405nm blue LED lamp under air conditions, dilution with water was added after the reaction was completed, the reaction solution was extracted with ethyl acetate, the organic phases were combined, dried over anhydrous sodium sulfate, the organic phase was removed by spinning, and the residue was separated by column chromatography to give the target product as a white solid. The yield of the objective product was 72% based on the molar amount of 2-isocyano-2-methylpropane taken as 100%.
The structural formula of the target product is as follows:
the above white solid was analyzed by nuclear magnetic spectrum and mass spectrometry, and the data were as follows:
1 H NMR(400MHz,CDCl 3 )δ7.60-7.52(m,4H),7.50-7.44(m,2H),7.26-7.22(m,2H),3.40(d,J＝9.8Hz,2H),1.08(s,9H)。
13 C NMR(150MHz,CDCl 3 )δ162.7(dd,J 1 ＝249.0Hz，J 2 ＝16.5Hz),134.4(dd,J 1 ＝97.5Hz，J 2 ＝6.0Hz),130.8(dd,J 1 ＝13.5Hz，J 2 ＝7.5Hz),127.1(dd,J 1 ＝7.5Hz，J 2 ＝3.0Hz),119.5(dd,J 1 ＝21.0Hz，J 2 ＝1.5Hz),118.4(dd,J 1 ＝22.5Hz，J 2 ＝10.5Hz),51.5(d,J＝13.5Hz),42.8(d,J＝87.0Hz),28.5。
19 F NMR(564MHz,CDCl 3 )δ-110.8。
31 P NMR(243MHz,CDCl 3 )δ28.4。
HRMS(ESI-TOF)m/z:[M+H] + Calcd for C 17 H 21 F 2 NOP + 324.1323,Found:324.1323。
example 9
Adding 2-isocyano-2-methylpropane (0.2 mmol), bis (4-methoxyphenyl) phosphine oxide (0.4 mmol), N-diisopropylethylamine (0.4 mmol) and 4-CzIPN (5 mol% equivalent) into a 10mL reaction tube filled with magnetons in sequence, then adding solvents acetonitrile (2 mL) and water (20 mu L), reacting at room temperature for 12 hours under the irradiation of a 405nm blue LED lamp under the air condition, adding water for dilution after the reaction is finished, extracting reaction liquid by using ethyl acetate, combining organic phases, drying by using anhydrous sodium sulfate, removing the organic phases in a rotary manner, and separating the residue by using column chromatography to obtain the target product which is a white solid. The yield of the objective product was 65% based on 100% by mole of 2-isocyano-2-methylpropane.
The structural formula of the target product is as follows:
the above white solid was analyzed by nuclear magnetic spectrum and mass spectrometry, and the data were as follows:
1 H NMR(400MHz,CDCl 3 )δ7.74-7.68(m,4H),6.97-6.94(m,4H),3.83(s,6H)，3.32(d,J＝10.1Hz,2H),1.06(s,9H)。
13 C NMR(100MHz,CDCl 3 )δ162.5(d,J＝3.0Hz),133.3(d,J＝10.0Hz),123.7(d,J＝105.0Hz),114.1(d,J＝13Hz),55.4,51.3(d,J＝14.0Hz),43.2(d,J＝85.0Hz),28.6。
31 P NMR(162MHz,CDCl 3 )δ30.4。
HRMS(ESI-TOF)m/z:[M+H] + Calcd for C 19 H 27 NO 3 P + 348.1723,Found:348.1723。
example 10
Adding 2-isocyano-2-methylpropane (0.2 mmol), di-m-methyl phosphine oxide (0.4 mmol), N-diisopropylethylamine (0.4 mmol) and 4-CzIPN (5 mol% equivalent) into a 10mL reaction tube filled with magnetons in sequence, then adding acetonitrile (2 mL) and water (20 mu L), reacting at room temperature for 12 hours under the irradiation of a 405nm blue LED lamp under the air condition, adding water to dilute after the reaction is finished, extracting the reaction liquid by ethyl acetate, combining organic phases, drying by anhydrous sodium sulfate, removing the organic phases, and separating the residue by column chromatography to obtain the target product which is a white solid. The yield of the objective product was 81% based on the molar amount of 2-isocyano-2-methylpropane taken as 100%.
The structural formula of the target product is as follows:
the above white solid was analyzed by nuclear magnetic spectrum and mass spectrometry, and the data were as follows:
1 H NMR(400MHz,CDCl 3 )δ7.66(d,J＝11.8Hz,2H),7.55-7.52(m,2H),7.35-7.31(m,4H),3.37(d,J＝9.6Hz,2H),2.37(s,6H),1.07(s,9H)。
13 C NMR(100MHz,CDCl 3 )δ138.5(d,J＝12.0Hz),132.7(d,J＝3.0Hz),132.1(d,J＝98.0Hz),131.9(d,J＝8.0Hz),128.5(d,J＝12.0Hz),128.3(d,J＝9.0Hz),51.4(d,J＝13.0Hz),42.8(d,J＝84.0Hz),28.5,21.5。
31 P NMR(162MHz,CDCl 3 )δ30.6。
HRMS(ESI-TOF)m/z:[M+H] + Calcd for C 19 H 27 NOP + 316.1825,Found:316.1825。
example 11
2-isocyano-2-methylpropane (0.2 mmol), bis (4-chlorophenyl) phosphine oxide (0.4 mmol), N-diisopropylethylamine (0.4 mmol) and 4-CzIPN (5 mol% equivalent) were sequentially added to a 10mL reaction tube containing magnetons, followed by addition of acetonitrile (2 mL) and water (20. Mu.L), reaction at room temperature for 12 hours under irradiation of a 405nm blue LED lamp under air conditions, dilution with water was added after the reaction was completed, the reaction solution was extracted with ethyl acetate, the organic phases were combined, dried over anhydrous sodium sulfate, the organic phase was removed by spinning, and the residue was separated by column chromatography to give the target product as a white solid. The yield of the objective product was 51% based on the molar amount of 2-isocyano-2-methylpropane taken as 100%.
Target productThe structural formula of (A) is as follows:
the above white solid was analyzed by nuclear magnetic spectrum and mass spectrometry, and the data were as follows:
1 H NMR(400MHz,CDCl 3 )δ7.73(dd,J 1 ＝10.8Hz，J 2 ＝2.4Hz,4H),7.45(dd,J 1 ＝8.5Hz，J 2 ＝2.2Hz,4H),3.36(d,J＝9.9Hz,2H),1.06(s,9H)。
13 C NMR(100MHz,CDCl 3 )δ138.9(d,J＝3.0Hz),132.8(d,J＝10.0Hz),130.3(d,J＝99.0Hz),129.1(d,J＝12.0Hz),51.4(d,J＝15.0Hz),42.9(d,J＝86.0Hz),28.6。
31 P NMR(162MHz,CDCl 3 )δ29.2。
HRMS(ESI-TOF)m/z:[M+H] + Calcd for C 17 H 21 Cl 2 NOP + 356.0732,Found:356.0767。
example 12
Adding methyl 2-isocyanoacetate (0.2 mmol), diphenylphosphine oxide (0.4 mmol), N-diisopropylethylamine (0.4 mmol) and 4-CZIPN (5 mol% equivalent) into a 10mL reaction tube containing magnetons in sequence, then adding acetonitrile (2 mL) and water (20 mu L) serving as solvents, reacting for 12 hours at room temperature under the irradiation of a 405nm blue LED lamp under the air condition, adding water for dilution after the reaction is finished, extracting the reaction liquid by using ethyl acetate, combining organic phases, drying by using anhydrous sodium sulfate, removing the organic phases by rotation, and separating residues by column chromatography to obtain the target product which is a white solid. The yield of the target product was 68% based on the molar amount of methyl 2-isocyanatoacetate (100%).
The structural formula of the target product is as follows:
the above white solid was analyzed by nuclear magnetic spectrum and mass spectrometry, and the data were as follows:
1 H NMR(600MHz,CDCl 3 )δ7.82-7.79(m,4H),7.56-7.53(m,2H),7.50-7.47(m,4H),3.70(s,3H),3.55(d,J＝7.8Hz,2H),3.51(s,2H)。
13 C NMR(100MHz,CDCl 3 )δ172.4,132.2(d,J＝2.0Hz),131.7(d,J＝98.0Hz),131.3(d,J＝9.0Hz),128.9(d,J＝12.0Hz),52.0,51.8(d,J＝13.0Hz),49.0(d,J＝82.0Hz)。
31 P NMR(162MHz,CDCl 3 )δ29.1。
HRMS(ESI-TOF)m/z:[M+H] + Calcd for C 16 H 19 NO 3 P + 304.1097,Found:304.1095。
example 13
Adding 2-isocyanoacetic acid ethyl ester (0.2 mmol), diphenyl phosphine oxide (0.4 mmol), N-diisopropylethylamine (0.4 mmol) and 4-CZIPN (5 mol% equivalent) into a 10mL reaction tube filled with magnetons in sequence, then adding solvents acetonitrile (2 mL) and water (20 mu L), reacting for 12 hours at room temperature under the irradiation of a 405nm blue LED lamp under the air condition, adding water for dilution after the reaction is finished, extracting the reaction liquid with ethyl acetate, combining organic phases, drying with anhydrous sodium sulfate, removing the organic phases by rotation, and separating residues by column chromatography to obtain the target product which is light yellow oily. The yield of the target product was 74% based on the molar amount of ethyl 2-isocyanatoacetate (100%).
The structural formula of the target product is as follows:
nuclear magnetic spectrum and mass spectrum analysis were performed on the pale yellow oil, and the data were as follows:
1 H NMR(400MHz,CDCl 3 )δ7.83-7.78(m,4H),7.55-7.51(m,2H),7.49-7.45(m,4H),4.15(q,J＝7.1Hz,2H),3.55(d,J＝7.8Hz,2H),3.48(s,2H),1.24(t,J＝7.1Hz,3H)。
13 C NMR(100MHz,CDCl 3 )δ171.9,132.21,132.18,131.3,(d,J＝9.0Hz),131.2,128.8(d,J＝11.0Hz),61.0,52.0(d,J＝13.0Hz),49.0(d,J＝82.0Hz),14.3。
31 P NMR(162MHz,CDCl 3 )δ29.0。
HRMS(ESI-TOF)m/z:[M+H] + Calcd for C 17 H 21 NO 3 P + 318.1254,Found:318.1254。
example 14
Adding benzyl 2-isocyano-3-phenylpropionate (0.2 mmol), diphenylphosphine oxide (0.4 mmol), N-diisopropylethylamine (0.4 mmol) and 4-CZIPN (5 mol% equivalent) into a 10mL reaction tube filled with magnetons in sequence, then adding solvents acetonitrile (2 mL) and water (20 mu L), reacting at room temperature for 12 hours under the irradiation of a 405nm blue LED lamp under the air condition, adding water for dilution after the reaction is finished, extracting reaction liquid by using ethyl acetate, combining organic phases, drying by using anhydrous sodium sulfate, removing the organic phases, and separating residues by using column chromatography to obtain the target product which is a white solid. The yield of the target product is 48 percent based on the molar weight of the 2-isocyano-3-benzyl phenylpropionate as 100 percent.
The structural formula of the target product is as follows:
the white solid was analyzed by nuclear magnetic spectrum and mass spectrometry, and the data were as follows:
1 H NMR(600MHz,CDCl 3 )δ7.71-7.65(m,4H),7.53-7.50(m,2H),7.42-7.38(m,4H),7.35-7.32(m,3H),7.2(dd,J 1 ＝7.6Hz，J 2 ＝2.8Hz,2H),7.21-7.20(m,3H),7.05-7.04(m,2H),5.11-5.07(m,2H),3.63-3.61(m,1H),3.55(q,J＝7.1Hz,1H),3.25(dd,J 1 ＝14.2Hz，J 2 ＝11.2Hz,1H),2.97(dd,J 1 ＝13.7Hz，J 2 ＝6.0Hz,1H),2.84(dd,J 1 ＝13.7Hz，J 2 ＝7.7Hz,1H)。
13 C NMR(150MHz,CDCl 3 )δ173.5,137.1,135.5,132.1,131.48(d,J＝99.0Hz),131.45(d,J＝4.5Hz),131.4(d,J＝3.0Hz),129.4,128.7(d,J＝1.5Hz),128.62,128.55,128.53,126.8,66.8,64.37(d,J＝13.5Hz),47.9(d,J＝82.5Hz),39.4。
31 P NMR(243MHz,CDCl 3 )δ28.7。
HRMS(ESI-TOF)m/z:[M+H] + Calcd for C 29 H 29 NO 3 P + 470.1880,Found:470.1876。
example 15
Adding 2-isocyano-4-methyl valerate (0.2 mmol), diphenyl phosphine oxide (0.4 mmol), N-diisopropylethylamine (0.4 mmol) and 4-CZIPN (5 mol% equivalent) into a 10mL reaction tube filled with magnetons in sequence, then adding solvents of acetonitrile (2 mL) and water (20 mu L), reacting at room temperature for 12 hours under the irradiation of a 405nm blue LED lamp under the air condition, adding water to dilute after the reaction is finished, extracting reaction liquid with ethyl acetate, combining organic phases, drying with anhydrous sodium sulfate, removing the organic phases, and separating residues through column chromatography to obtain the target product which is a white solid. The yield of the desired product was 48% based on 100% by mole of methyl 2-isocyano-4-methylpentanoate.
The structural formula of the target product is as follows:
the white solid was analyzed by nuclear magnetic spectrum and mass spectrometry, and the data were as follows:
1 H NMR(600MHz,CDCl 3 )δ7.84-7.73(m,4H),7.56-7.50(m,2H),7.49-7.43(m,4H),3.68(s,3H),3.57(dd,J 1 ＝14.2Hz，J 2 ＝6.7Hz,1H),3.34-3.23(m,2H),1.70-1.60(m,1H),1.41(t,J＝7.1Hz,2H),0.82(dd,J 1 ＝13.4Hz，J 2 ＝6.8Hz,6H)。
13 C NMR(100MHz,CDCl 3 )δ175.4,132.1(dd,J 1 ＝8.0Hz，J 2 ＝3.0Hz),131.8(d,J＝122Hz),131.4(dd,J 1 ＝8.0Hz，J 2 ＝2.0Hz),128.7(dd,J 1 ＝11.0Hz，J 2 ＝2.0Hz),61.4(d,J＝14Hz),51.9,47.8(d,J＝11Hz),42.3,24.8,23.0,21.9。
31 P NMR(162MHz,CDCl 3 )δ29.1。
HRMS(ESI-TOF)m/z:[M+H] + Calcd for C 20 H 27 NO 3 P + 360.1723,Found:360.1723。
example 16
Adding benzyl 2-isocyano-3-phenylpropionate (0.2 mmol), di-methyl phosphine oxide (0.4 mmol), N-diisopropylethylamine (0.4 mmol) and 4-CZIPN (5 mol% equivalent) into a 10mL reaction tube filled with magnetons in sequence, then adding solvents acetonitrile (2 mL) and water (20 mu L), reacting at room temperature for 12 hours under the irradiation of a 405nm blue LED lamp under the air condition, adding water to dilute after the reaction is finished, extracting reaction liquid with ethyl acetate, combining organic phases, drying with anhydrous sodium sulfate, removing the organic phases, separating residues by column chromatography to obtain a target product, wherein the target product is colorless oil. The yield of the target product is 51 percent based on the molar weight of the 2-isocyano-3-benzyl phenylpropionate as 100 percent.
The structural formula of the target product is as follows:
nuclear magnetic spectrum and mass spectrum analysis were performed on the colorless oil, and the data were as follows:
1 H NMR(600MHz,CDCl 3 )δ7.58(dd,J 1 ＝27.5Hz，J 2 ＝11.8Hz,2H),7.44-7.41(m,2H),7.32-7.27(m,7H),7.23-7.22(m,2H),7.19-7.18(m,3H),7.04-7.03(m,2H),5.10-5.06(m,2H),3.63(t,J＝6.8Hz,1H),3.53(dd,J 1 ＝14.2Hz，J 2 ＝6.8Hz,1H),3.25(dd,J 1 ＝14.0Hz，J 2 ＝11.0Hz,1H),2.95(dd,J 1 ＝13.6Hz，J 2 ＝6.2Hz,1H),2.87(dd,J 1 ＝13.6Hz，J 2 ＝7.3Hz,1H),2.35(s,6H)。
13 C NMR(150MHz,CDCl 3 )δ173.5,138.6(dd,J 1 ＝12Hz，J 2 ＝3.0Hz),137.1,135.6,132.9(t,J＝3.0Hz),132.0-131.9(m),131.6(dd,J 1 ＝97.5Hz，J 2 ＝34.5Hz),129.3,128.7,128.6(d,J＝3.0Hz),128.52,128.50,128.47,128.3(dd,J 1 ＝18.0Hz，J 2 ＝9.0Hz),126.8,66.8,64.3(d,J＝13.5Hz),47.9(d,J＝82.5Hz),39.4,21.6。
31 P NMR(243MHz,CDCl 3 )δ27.3。
HRMS(ESI-TOF)m/z:[M+H] + Calcd for C 31 H 33 NO 3 P + 498.2193,Found:498.2178。
example 17
Adding 2-isocyano-4-methyl pentanoate (0.2 mmol), di-methyl phosphine oxide (0.4 mmol), N-diisopropylethylamine (0.4 mmol) and 4-CZIPN (5 mol% equivalent) into a 10mL reaction tube filled with magnetons in sequence, then adding solvents acetonitrile (2 mL) and water (20 mu L), reacting for 12 hours at room temperature under the irradiation of a 405nm blue LED lamp under the air condition, adding water to dilute after the reaction is finished, extracting reaction liquid with ethyl acetate, combining organic phases, drying with anhydrous sodium sulfate, removing the organic phases, separating residues by column chromatography to obtain the target product, wherein the target product is a white solid. The yield of the desired product was 48% based on 100% by mole of methyl 2-isocyano-4-methylpentanoate.
The structural formula of the target product is as follows:
the white solid was analyzed by nuclear magnetic spectrum and mass spectrometry, and the data were as follows:
1 H NMR(600MHz,CDCl 3 )δ7.65(dd,J 1 ＝23.2Hz，J 2 ＝11.8Hz,2H),7.58-7.55(m,1H),7.50-7.47(m,1H),7.37-7.33(m,4H),3.69(s,3H),3.55(dd,J 1 ＝14.2Hz，J 2 ＝6.6Hz,1H),3.33(t,J＝7.2Hz,1H),3.25(dd,J 1 ＝14.2Hz，J 2 ＝10.5Hz,1H),2.38(d,J＝5.3Hz,6H),1.71-1.64(m,1H),1.42(t,J＝7.1Hz,2H),0.88(dd,J 1 ＝18.0Hz，J 2 ＝6.7Hz,6H)。
13 C NMR(150MHz,CDCl 3 )δ175.5,138.6(q,J＝6Hz),132.9(dd,J 1 ＝13.5Hz，J 2 ＝3Hz,),132.0(d,J＝7.5Hz),131.7(dd,J 1 ＝97.5Hz，J 2 ＝42.0Hz),128.5(q,J＝6.0Hz),128.3(dd,J 1 ＝9.0Hz，J 2 ＝1.5Hz),61.4(d,J＝15.0Hz),51.9,47.8(d,J＝84.0Hz),42.3,24.8,23.0,21.9,21.5。
31 P NMR(243MHz,CDCl 3 )δ29.3。
HRMS(ESI-TOF)m/z:[M+H] + Calcd for C 22 H 31 NO 3 P + 388.2036,Found:388.2034。
example 18
Adding 2-isocyanoacetic acid ethyl ester (0.2 mmol), di-p-methyl phosphine oxide (0.4 mmol), N-diisopropylethylamine (0.4 mmol) and 4-CzIPN (5 mol% equivalent) into a 10mL reaction tube filled with magnetons in sequence, then adding acetonitrile (2 mL) and water (20 mu L), reacting for 12 hours at room temperature under the irradiation of a 405nm blue LED lamp under the air condition, adding water for dilution after the reaction is finished, extracting the reaction liquid by using ethyl acetate, combining organic phases, drying by using anhydrous sodium sulfate, removing the organic phases, and separating residues by using column chromatography to obtain the target product which is colorless oil. The yield of the target product was 46% based on the molar amount of ethyl 2-isocyanatoacetate (100%).
The structural formula of the target product is as follows:
nuclear magnetic spectrum and mass spectrum analysis were performed on the colorless oil, and the data were as follows:
1 H NMR(400MHz,CDCl 3 )δ7.68(dd,J＝11.2Hz,8.1Hz,4H),7.29-7.26(m,4H),4.16(q,J＝7.1Hz,2H),3.50(d,J＝7.9Hz,2H),3.48(s,2H),2.39(s,6H),1.25(t,J＝7.1Hz,3H)。
13 C NMR(100MHz,CDCl 3 )δ172.0,142.6(d,J＝2.0Hz),131.4,(d,J＝9.0Hz),129.6(d,J＝12.0Hz),128.6(d,J＝101.0Hz),61.0,52.1(d,J＝13.0Hz),49.1(d,J＝81.0Hz),21.8,14.4。
31 P NMR(162MHz,CDCl 3 )δ29.4。
HRMS(ESI-TOF)m/z:[M+H] + Calcd for C 19 H 25 NO 3 P + 346.1567,Found:346.1567。
example 19
Adding benzyl 2-isocyano-3-phenylpropionate (0.2 mmol), bis (4-methoxyphenyl) phosphine oxide (0.4 mmol), N-diisopropylethylamine (0.4 mmol) and 4-CzIPN (5 mol% equivalent) into a 10mL reaction tube filled with magnetons in sequence, then adding acetonitrile (2 mL) and water (20 mu L) serving as solvents, reacting at room temperature for 12 hours under the irradiation of a 405nm blue LED lamp under the air condition, adding water for dilution after the reaction is finished, extracting a reaction solution by using ethyl acetate, combining organic phases, drying by using anhydrous sodium sulfate, removing the organic phase, and carrying out column chromatography separation on residues to obtain a target product which is colorless oily. The yield of the target product is 40% based on 100% of the molar weight of the 2-isocyano-3-benzyl phenylpropionate.
The structural formula of the target product is as follows:
nuclear magnetic spectrum and mass spectrum analysis were performed on the colorless oil, and the data were as follows:
1 H NMR(600MHz,CDCl 3 )δ7.62-7.55(m,4H),7.35-7.31(m,3H),7.24-7.23(m,2H),7.21-7.20(m,3H),7.05-7.04(m,2H),6.90-6.87(m,4H),5.09(t,J＝12.6,2H),3.84(s,6H),3.59(t,J＝6.8,1H),3.50-3.46(m,1H),3.17(dd,J 1 ＝13.7Hz，J 2 ＝11.8Hz,1H),2.96(dd,J 1 ＝13.6Hz，J 2 ＝6.0Hz,1H),2.83(dd,J 1 ＝13.6Hz，J 2 ＝7.7Hz,1H)。
13 C NMR(150MHz,CDCl 3 )δ173.6,162.5,137.2,135.6,133.3(d,J＝10.5Hz),129.4,128.7,128.6,128.5,126.8,123.1(dd,J 1 ＝105Hz，J 2 ＝58.5Hz),114.2(dd,J 1 ＝12.0Hz，J 2 ＝3.0Hz),66.8,64.4(d,J＝13.5Hz),55.4(d,J＝1.5Hz),48.3(d,J＝84.0Hz),39.4。
31 P NMR(243MHz,CDCl 3 )δ28.6。
HRMS(ESI-TOF)m/z:[M+H] + Calcd for C 31 H 33 NO 5 P + 530.2091,Found:530.2069。
while the foregoing embodiments have described the general principles, features and advantages of the present invention, it will be understood by those skilled in the art that the present invention is not limited thereto, and that the foregoing embodiments and descriptions are only illustrative of the principles of the present invention, and various changes and modifications can be made without departing from the scope of the principles of the present invention, and these changes and modifications are within the scope of the present invention.
Claims (6)
1. A photocatalytic preparation method of ((alkylamino) methyl) diphenyl phosphine oxide compounds is characterized by comprising the following specific steps: the method comprises the following steps of taking an isocyanic compound and a diphenyl phosphine oxide compound as initial raw materials, taking acetonitrile and water as a mixed solvent under the action of an additive and a catalyst, carrying out blue light illumination reaction at room temperature under the condition of air, evaporating the solvent after the reaction is finished, extracting a reaction solution by ethyl acetate, drying, removing an organic phase by rotation, and carrying out column chromatography separation on residues to obtain a target product ((alkylamino) methyl) diphenyl phosphine oxide compound, wherein the additive is one or more of triethylamine, N-diisopropylethylamine DIPEA, 1, 8-diazabicycloundec-7-ene DBU or tetramethylethylenediamine TMEDA, the catalyst is 2,4,5, 6-tetra (9-carbazolyl) -isophthalonitrile 4-CzIPN, the structural formula of the isocyanic compound is shown as A, the structural formula of the diphenyl phosphine oxide compound is shown as B, and the structural formula of the ((alkylamino) methyl) diphenyl phosphine oxide compound is shown as C:
in the formula R 1 Is tert-butyl, benzyl or an ester-containing alkyl radical, R 2 Is halogen, C 1-5 Alkyl or C 1-5 An alkoxy group.
2. The photocatalytic production method of ((alkylamino) methyl) diphenylphosphine oxide-based compound according to claim 1, characterized in that the specific structural formula of the ((alkylamino) methyl) diphenylphosphine oxide-based compound is:
3. the photocatalytic production method of ((alkylamino) methyl) diphenylphosphine oxide-based compound according to claim 1, characterized in that: the charging molar ratio of the isocyano compound, the diphenyl phosphine oxide compound, the catalyst and the additive is 1-3.
4. The photocatalytic production method of ((alkylamino) methyl) diphenylphosphine oxide-based compound according to claim 1, characterized in that: the volume ratio of acetonitrile to water in the mixed solvent is 200.
5. The photocatalytic production method of ((alkylamino) methyl) diphenylphosphine oxide-based compound according to claim 1, characterized in that the reaction equation in the production process of ((alkylamino) methyl) diphenylphosphine oxide-based compound is:
the structural formula of the catalyst 2,4,5, 6-tetra (9-carbazolyl) -isophthalonitrile 4-CzIPN is as follows:
6. the photocatalytic production method of ((alkylamino) methyl) diphenylphosphine oxide-based compound according to claim 1, characterized in that: in the reaction process, a blue LED lamp is used as a light source of blue light, the wavelength of the blue LED lamp is 405nm, and the power of the blue LED lamp is 10W.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211004211.3A CN115322222A (en) | 2022-08-22 | 2022-08-22 | Photocatalytic preparation method of ((alkylamino) methyl) diphenyl phosphine oxide compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211004211.3A CN115322222A (en) | 2022-08-22 | 2022-08-22 | Photocatalytic preparation method of ((alkylamino) methyl) diphenyl phosphine oxide compound |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115322222A true CN115322222A (en) | 2022-11-11 |
Family
ID=83926961
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211004211.3A Pending CN115322222A (en) | 2022-08-22 | 2022-08-22 | Photocatalytic preparation method of ((alkylamino) methyl) diphenyl phosphine oxide compound |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115322222A (en) |
-
2022
- 2022-08-22 CN CN202211004211.3A patent/CN115322222A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109265360B (en) | Synthetic method of alpha-aryl substituted glycine ester derivative | |
| CN108727427A (en) | A kind of succinct glufosinate-ammonium synthetic method | |
| CN109718851B (en) | Chiral quaternary phosphonium salt phase transfer catalyst and preparation method and application thereof | |
| EP2797931B1 (en) | Process for the preparation of 2-cyanophenylboronic acid and esters thereof | |
| CN109879731B (en) | Diaryl methane halogenated olefin derivative and preparation method thereof | |
| CN110437068A (en) | A kind of preparation method of aromatic hydrocarbons methylation | |
| CN111187298B (en) | C2-phosphono methylene indole compound and preparation method and application thereof | |
| CN100548979C (en) | A kind of method of synthetic 3-methyl amino indole compound | |
| CN115322222A (en) | Photocatalytic preparation method of ((alkylamino) methyl) diphenyl phosphine oxide compound | |
| CN109293700A (en) | Chiral diphosphine ligand, preparation method, intermediate and application | |
| CN108948077A (en) | A kind of the a-amino acid esters compound and its synthetic method of α-phosphorylated | |
| CN114685335B (en) | Hydrogen bond organic catalyst, preparation method and application thereof | |
| CN110026244B (en) | Alpha alkylation reaction catalyst of nitrile and application thereof | |
| CN103209978B (en) | Phase-transfer catalyst | |
| CN104945434A (en) | (2-disubstituted phosphino-phenyl)-1-alkyl-indol-phosphine ligand and synthetic method and application thereof | |
| CN111170885A (en) | Preparation of levomilnacipran hydrochloride | |
| JP5943387B2 (en) | Novel triflon derivative and method for producing the same | |
| CN102933589A (en) | Strecker reagents, their derivatives, methods for forming the same and improved strecker reaction | |
| CN115448949B (en) | Synthesis method of chiral allylphosphine compound | |
| TWI589584B (en) | Compound, method for producing the same, and method for producing optically active α-aminophosphonic acid derivative | |
| CN110878024B (en) | Synthesis method of (1R,2R) -nitroalcohol compound | |
| Yuan et al. | Facile and Efficient Asymmetric Synthesis of α‐Aminoalkylphosphonic Acids | |
| CN116284114A (en) | Method for synthesizing chiral 1, 3-phosphine alcohol | |
| CN117050026A (en) | Synthesis method of fluoroalkyl substituted quinoxalinone derivative | |
| CN115974920A (en) | Method for constructing carbon-phosphorus bond by copper catalysis |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |