Method for directly synthesizing nitrogen-containing organic compounds from nitrogen and catalytic cycle process

Abstract

The present invention relates to a method for directly synthesizing nitrogen-containing organic compounds from nitrogen and a catalytic cycle process, which includes the following steps: A P-S bis(ylide) derivative having a phosphonium ylide and a sulfonium ylide functional group reacts with N2 in the presence of a transition metal complex MLn to directly convert N2 into a nitrogen-containing organic compound 3. Reacting the nitrogen-containing organic compound 3 with the corresponding L ligand can achieve the restoration of the transition metal complex MLn, and at the same time obtain another nitrogen-containing organic compound, a diazaphosphorane derivative 4. In the present invention, the formation of the N-C bond is achieved by directly reacting an N2 molecule with a carbonyl reagent, which is a direct synthesis of nitrogen-containing organic compounds from nitrogen under strict ambient temperature and pressure. The present invention does not require the preparation step of a transition metal-dinitrogen [N2-M] complex and establishes a cyclic catalytic system that can directly convert N2 into nitrogen-containing organic compounds.

Description

Technical Field

[0001] The present invention relates to a method for directly synthesizing nitrogen-containing organic compounds from nitrogen and a catalytic cycle process based on this method, belonging to the technical field of chemical nitrogen fixation. Background Art

[0002] Nitrogen-containing organic compounds are essential for life, and their applications in drug design and polymer materials have greatly improved the quality of human life. As the most abundant component in the earth's atmosphere, the chemical conversion of nitrogen gas (N 2 ) into nitrogen-containing organic compounds is highly desirable. However, the high bond dissociation energy of N 2 (942 kJ / mol) determines that N 2 is very stable, making it difficult for humans to effectively and directly utilize nitrogen. The Haber-Bosch process is a process for fixing nitrogen with hydrogen to produce ammonia, which is a major breakthrough in the field of industrial nitrogen fixation by humans in the 20th century. As the main route for N 2 fixation and conversion in industry, approximately 20% of the NH 3 produced by the Haber-Bosch process is used as a raw material for producing nitrogen-containing chemicals. However, this NH 3 synthesis process requires harsh reaction conditions such as high temperature and high pressure, consumes 1-2% of the world's annual energy supply, and simultaneously emits a large amount of carbon dioxide, making it difficult to meet the requirements of sustainable development of human society. Therefore, achieving the effective activation and conversion of N 2 under mild conditions is a challenging topic in chemistry.

[0003] Using catalysts to achieve chemical nitrogen fixation under mild conditions has also become a research hotspot. For example, prior arts such as CN105271379A, CN114308124A, and CN114749115A have all disclosed catalytic chemical nitrogen fixation technologies. However, these technologies also convert N 2 into ammonia, rather than directly converting N 2 into nitrogen-containing organic compounds. Developing a method for directly synthesizing nitrogen-containing organic compounds from N 2 is even called the "Holy Grail" in the chemical industry by scientists.

[0004] Currently, the research on the direct conversion of N 2 into nitrogen-containing organic compounds under mild conditions mainly focuses on two approaches. First, it is to use transition metal-mediated N 2 to directly convert it into organic compounds by forming an N-C bond on a metal dinitrogen [N2-M] complex, as shown in Technical Route 1:

[0005]

[0006] Inspired by the research on nitrogenase, Allen and Senoff reduced RuCl 3 aqueous solution with hydrazine hydrate to obtain the first transition metal molecular nitrogen compound Ru(N 2 molecule-containing Ru(N 2 )(NH 3 ) 5 Cl 2 . This has promoted the research on transition metal-catalyzed N 2 fixation and its conversion to nitrogen-containing organic compounds for more than half a century.

[0007] Although many great achievements have been made in the field of transition metal-mediated conversion of N 2 to organic compounds, in almost all these works on transition metal-mediated conversion of N 2 to organic compounds, the formation step of the N-C bond is achieved by the reaction of a transition metal-dinitrogen [N 2 -M] complex with a carbon-based reagent. That is to say, in these nitrogen fixation works, the formation of the N-C bond is not achieved by the direct reaction of the N 2 molecule with a carbon-based reagent. Therefore, in a more strict sense, these nitrogen fixation methods cannot be regarded as a method of directly synthesizing nitrogen-containing organic compounds from nitrogen gas in a strict sense. In addition, although through careful design, some synthetic cycles for transition metal-mediated N 2 conversion have been developed. However, all these synthetic cycles are stoichiometric. Due to the reaction conditions involved in the N-C bond formation step and the release step of nitrogen-containing organic compounds in these synthetic cycles, they are incompatible with the preparation step of the N2-M complex. Therefore, a catalytic cycle system for transition metal-mediated conversion of N 2 to nitrogen-containing organic compounds has not been realized.

[0008] Second, it is to use carbene to directly convert N 2 to nitrogen-containing organic compounds, as shown in Technical Route 2:

[0009]

[0010] Technical Route 2 is a metal-free nitrogen fixation strategy. In this nitrogen fixation strategy, carbene species are considered to be a good choice for constructing the N-C bond to directly obtain nitrogen-containing organic compounds. Carbene CR 2 has two electron-sharing bonds between carbon and substituent R and has a σ-type electron lone pair at C. However, so far, people have not realized the direct conversion of N 2 to nitrogen-containing organic compounds through carbene.

[0011] In summary, the current technology for directly synthesizing nitrogen-containing organic compounds from nitrogen mainly has the following two problems: (1) The formation of the N-C bond in the nitrogen-containing organic compound products obtained by the current technology is not achieved by the direct reaction of N 2 molecules with carbon-based reagents, so the current technology cannot be regarded as a method for directly synthesizing nitrogen-containing organic compounds from nitrogen in a strict sense. (2) Due to the problem of incompatible reaction conditions in the catalytic cycle process of converting nitrogen-containing organic compounds mediated by transition metals, the catalytic cycle process of converting N 2 mediated by transition metals into nitrogen-containing organic compounds has not been realized. 2 SUMMARY OF THE INVENTION

[0012] In view of the deficiencies of the prior art, the present invention provides a method for directly synthesizing nitrogen-containing organic compounds from nitrogen and a catalytic cycle process based on this method. The present invention has developed a new technical route for directly synthesizing nitrogen-containing organic compounds from nitrogen. The technical route of the present invention well solves the above two technical problems, that is, (1) The formation of the N-C bond in the nitrogen-containing organic compound products obtained by the technical route of the present invention is achieved by the direct reaction of N 2 molecules with carbon-based reagents, thereby realizing the direct synthesis of nitrogen-containing organic compounds from nitrogen under normal temperature and pressure in a strict sense. (2) Since the preparation step of the transition metal-diazene [N 2 -M] complex is not required in the technical route of the present invention, the problem of incompatible reaction conditions in the catalytic cycle process of converting N 2 mediated by transition metals into nitrogen-containing organic compounds is solved, thereby establishing a catalytic cycle system that can directly convert N 2 into nitrogen-containing organic compounds.

[0013] Term Explanation:

[0014] Schlenk technique: Also called "Schlenk technique", a double-tube operation technique. It is mainly used to provide an inert environment and vacuum conditions, and is mainly composed of glass instruments.

[0015] Room temperature: The room temperature described in the present invention refers to the environmental temperature of 25°C ± 5°C.

[0016] P-S bis(ylide) derivative: Refers to a bis(ylide) derivative having one phosphonium ylide and one sulfonium ylide functional group.

[0017] The technical solution of the present invention is as follows:

[0018] A method for directly synthesizing nitrogen-containing organic compounds from nitrogen, comprising the following steps:

[0019] ​A P-S bis(ylide) derivative (Compound 1) having a phosphonium ylide and a sulfonium ylide functional group reacts with N 2 in the presence of a transition metal complex MLn to directly convert N 2 into a nitrogen-containing organic compound (Compound 3).

[0020] According to the present invention, preferably, the P-S bis(ylide) derivative (Compound 1) reacts with the transition metal complex MLn at room temperature to form a carbene intermediate (Compound 2, as a carbon-based reagent); then the carbene intermediate (Compound 2) reacts with N 2 to generate a nitrogen-containing organic compound (Compound 3), thereby achieving the direct synthesis of a nitrogen-containing organic compound from nitrogen under strict room temperature and atmospheric pressure conditions.

[0021] According to the present invention, preferably, the molar ratio of the P-S bis(ylide) derivative (Compound 1) to the transition metal complex MLn is less than 1:1. That is, a mixture of the P-S bis(ylide) derivative (Compound 1) and an excess of the transition metal complex MLn is required.

[0022] According to the present invention, preferably, the P-S bis(ylide) derivative (Compound 1) has the structure shown in Formula I:

[0023]

[0024] In Formula I: R 1 is selected from alkyl or aryl, R 2 , R 3 are each independently selected from alkylamines, R 2 , R 3 may be the same or different; further preferably, the alkyl is methyl, ethyl or propyl, the aryl is phenyl, and the alkylamine is diisopropylamino or N,N'-diisopropylethylenediamino;

[0025] R 4 , R 5 are independent organic groups, optionally selected from aryl or alkyl. R 4 , R 5 may be the same or different; further preferably, the alkyl is methyl, ethyl, propyl, and the aryl is phenyl.

[0026] According to the present invention, preferably, in the general structural formula of the transition metal complex MLn: M is selected from transition metal atoms or ions, and L is selected from Lewis base ligands; further preferably, the transition metal atoms or ions are nickel, platinum, tungsten, molybdenum or chromium, etc., and the Lewis base ligands are carbonyl or chloride ions with a valence of -1, etc.; n is an integer, and further preferably n = 1, 2, 3, 4, 5 or 6.

[0027] According to the present invention, preferably, the carbene intermediate (Compound 2) has the structure shown in Formula II:

[0028]

[0029] In Formula II, R 1 , R 2 , R 3 have the same meanings as in Formula I; M, L, and n have the same meanings as M, L, and n in the general formula of the transition metal complex MLn.

[0030] According to the present invention, preferably, the nitrogen-containing organic compound (Compound 3) has the structure shown in Formula III:

[0031]

[0032] In Formula III, R 1 , R 2 , R 3 have the same meanings as in Formula I; M, L, and n have the same meanings as M, L, and n in the general formula of the transition metal complex MLn.

[0033] According to the present invention, there is also provided a catalytic cycle process for directly synthesizing nitrogen-containing organic compounds from nitrogen, comprising the following steps:

[0034] The P-S bis(ylide) derivative (Compound 1) reacts with N 2 in the presence of a transition metal complex MLn to directly convert N 2 into a nitrogen-containing organic compound (Compound 3). The nitrogen-containing organic compound (Compound 3) reacts with the corresponding L ligand to restore the transition metal complex MLn, and at the same time, another nitrogen-containing organic compound diazaphosphorane derivative (Compound 4) is obtained.

[0035] That is: through the reaction of the nitrogen-containing organic compound (Compound 3) with the corresponding L ligand, the present invention can obtain another nitrogen-containing organic compound diazaphosphorane derivative (Compound 4) and restore the transition metal complex MLn, thereby establishing a cyclic catalytic system that can directly convert N 2 into nitrogen-containing organic compounds.

[0036] According to the present invention, preferably, the nitrogen-containing organic compound diazaphosphorane derivative (Compound 4) has the structure shown in Formula IV:

[0037]

[0038] In Formula IV, R 1 , R 2 , R 3 have the same meanings as in Formula I.

[0039] According to the present invention, the reaction formula of the above catalytic cycle process for directly synthesizing nitrogen-containing organic compounds from nitrogen can be expressed as:

[0040]

[0041] According to the present invention, preferably, the P-S bis(ylide) derivative (Compound 1) has the following structure:

[0042]

[0043] The transition metal complex ML n is Ni(CO) 4 , potassium tetrachloroplatinate(II) K 2 [PtCl 4 2- or W(CO) 6 ;

[0044] The nitrogen-containing organic compound (Compound 3) has the following structure:

[0045]

[0046] The nitrogen-containing organic compound (Compound 4) is a diazomethylphosphane derivative and has the following structure:

[0047]

[0048] Wherein: R = i-Pr 2 N,i-Pr 2 is isopropyl; Ph is phenyl; Me is methyl.

[0049] According to the present invention, taking the above most preferred compound as an example, the reaction mechanism is as follows:

[0050]

[0051] This cyclic reaction includes three concerted chemical processes:

[0052] Step A) Formation of a carbene intermediate 2 by the reaction of the P-S bis(ylide) derivative (Compound 1) with Ni(CO) 4 ;

[0053] Step B) Obtaining the nitrogen-containing organic compound 3 by reacting the carbene intermediate 2 with nitrogen;

[0054] Step C) Restoration of Ni(CO) 4 , and simultaneously forming the nitrogen-containing organic compound diazomethylphosphane derivative 4.

[0055] ​The carbene intermediate 2 formed in step A is crucial for completing the reaction. Since the formation of the N-C bond is achieved by the direct reaction of the N 2 molecule with the carbene intermediate 2, it is a true synthesis of nitrogen-containing organic compounds directly from nitrogen under normal temperature and pressure. Therefore, in the process of the transition metal-mediated conversion of N 2 to nitrogen-containing organic compounds in the present invention, there is no need for the preparation step of the transition metal-diazene [N 2 -M] complex, which well solves the problem of incompatible reaction conditions in the transition metal-mediated conversion of N 2 to nitrogen-containing organic compounds.

[0056] According to the present invention, the P-S bis(ylide) derivative (Compound 1) can be synthesized with reference to the prior art. See: "Dellus, N.; Kato, T.; Bagan, X.; Saffon, N.; Branchadell, V.; Baceiredo, A. Angew. Chem. Int. Ed. 2010, 49, 6798.".

[0057] According to the present invention, preferably, the carbene intermediate 2 and the nitrogen-containing organic compound 3 are obtained by the following method:

[0058] Under the conditions of -30°C to -80°C, nitrogen atmosphere, and without stirring, a solvent is slowly added to the mixture of the P-S bis(ylide) derivative 1 and Ni(CO) 4 . The solvent is preferably THF, and the carbene intermediate 2 can be obtained.

[0059] Then, the reaction mixture is heated to room temperature, and at the same time, the reaction mixture is stirred. The reaction mixture solution is concentrated to obtain a novel nitrogen-containing organic compound 3.

[0060] According to the present invention, preferably, the synthesis method of the diazaphosphorane derivative 4 from the nitrogen-containing organic compound 3 is as follows:

[0061] Under the conditions of room temperature, CO atmosphere, and without stirring, a solvent is slowly added to the nitrogen-containing organic compound 3. The solvent is preferably THF, and then the reaction mixture is stirred. The reaction mixture is filtered, and the filtrate is evaporated to dryness to recover the transition metal complex Ni(CO) 4 , and at the same time, another nitrogen-containing organic compound, the diazaphosphorane derivative 4, is obtained.

[0062] In the catalytic cycle process, Ni(CO) 4 is the reaction catalyst and needs to be kept in excess during the reaction.

[0063] According to the present invention, for the cyclic catalytic process of directly synthesizing nitrogen-containing organic compounds from nitrogen, a preferred implementation scheme includes the following steps:

[0064] Step A): At -30°C to -80°C, in a nitrogen atmosphere, without stirring, add THF to a mixture of P-S bis(ylide) derivative 1 and Ni(CO) 4 to obtain a carbene intermediate 2;

[0065] Step B): Then raise the temperature of the reaction mixture to room temperature, while stirring the reaction mixture, concentrate the reaction mixture solution to obtain a nitrogen-containing organic compound 3;

[0066] Step C): At room temperature, in a CO atmosphere, without stirring, add THF to the nitrogen-containing organic compound 3, then stir the reaction mixture, filter the reaction mixture, and evaporate and dry the filtrate to restore the transition metal complex Ni(CO) 4 while obtaining another nitrogen-containing organic compound, diazaphospholane derivative 4.

[0067] Advantages of the present invention:

[0068] In the present invention, the formation of the N-C bond is achieved by the direct reaction of the N 2 molecule with a carbonyl reagent (carbene intermediate 2), which is a direct synthesis of nitrogen-containing organic compounds from nitrogen under strict normal temperature and pressure conditions. In the scheme for the conversion of the transition metal-mediated N 2 to nitrogen-containing organic compounds in the present invention, there is no need for the preparation step of the transition metal-diazene [N 2 -M] complex, which solves the problem of incompatible reaction conditions in the reaction cycle for the conversion of transition metal-mediated N 2 to nitrogen-containing organic compounds. Thus, a cyclic catalytic system that can directly convert N 2 to nitrogen-containing organic compounds is established. Description of the Drawings

[0069] Figure 1 is the 1 H NMR spectrum of the carbene intermediate 2 in Example 1 of the present invention;

[0070] Figure 2 is the 13 C NMR spectrum of the carbene intermediate 2 in Example 1 of the present invention;

[0071] Figure 3 is the 31 P NMR spectrum of the carbene intermediate 2 in Example 1 of the present invention;

[0072] Figure 4 is the 1 H NMR spectrum of the nitrogen-containing organic compound 3 in Example 1 of the present invention;

[0073] Figure 5It is the 13 13C NMR spectrum of the nitrogen-containing organic compound 3 in Example 1 of the present invention;

[0074] Figure 6 It is the 31 31P NMR spectrum of the nitrogen-containing organic compound 3 in Example 1 of the present invention;

[0075] Figure 7 It is the 1 1H NMR spectrum of the diazomethylphosphorane derivative 4 in Example 1 of the present invention;

[0076] Figure 8 It is the 13 13C NMR spectrum of the diazomethylphosphorane derivative 4 in Example 1 of the present invention;

[0077] Figure 9 It is the 31 31P NMR spectrum of the diazomethylphosphorane derivative 4 in Example 1 of the present invention. Detailed implementation mode

[0078] The present invention will be described in detail below through specific examples in conjunction with the accompanying drawings, but is not limited thereto.

[0079] All operations in the examples were carried out under an inert atmosphere of argon and by using standard Schlenk techniques. Dry and oxygen-free solvents were used. Spectra were recorded on a Bruker-Avance 300 (nuclear magnetic resonance spectrometer) and a 400 MHz spectrometer 1 1H, 13 13C, 31 31P NMR spectra. 1 1H- and 13 13C-NMR chemical shifts relative to Me 4 4Si as an external standard, in ppm, relative to the standard 85% H 3 3PO 4 4, 31 31P-NMR chemical shifts are expressed as positive signs and are in ppm.

[0080] The P-S bis(ylide) derivative 1 used in the examples was synthesized with reference to the prior art "Dellus, N.; Kato, T.; Bagan, X.; Saffon, N.; Branchadell, V.; Baceiredo, A. Angew. Chem. Int. Ed. 2010, 49, 6798."

[0081] Example 1:

[0082] Method for directly synthesizing nitrogen-containing organic compounds from nitrogen, the technical route is as follows:

[0083]

[0084] R = i-Pr 2 N,i-Pr 2 i-Pr is isopropyl; Ph is phenyl; Me is methyl;

[0085] It includes the following steps:

[0086] Step A): Formation of carbene intermediate 2

[0087] At -30 °C to -80 °C, under a nitrogen atmosphere and without stirring, slowly add THF (40 mL) to a mixture of P-S bis(ylide) derivative (Compound 1) (1.00 g, 2.25 mmol) and excess Ni(CO) 4 . The formation of carbene intermediate 2 was monitored by NMR spectroscopy at low temperature. According to the NMR spectroscopy, in the I3 13C NMR spectrum, the central carbon atom appears as a doublet at δ = 36.72 (d, JCP = 47.4 Hz, PCNi), and in the 31 31P NMR spectrum, there is a singlet signal at δ = 41.05 ppm. These spectral features strongly indicate the formation of carbene intermediate 2. The 1 1H NMR spectrum, 13 13C NMR spectrum, 31 31P NMR spectrum of carbene intermediate 2 are shown in Figure 1 , 2 3 respectively.

[0088] Step B): Synthesis of nitrogen-containing organic compound 3

[0089] Then raise the temperature of the reaction mixture to room temperature while vigorously stirring the reaction mixture. After stirring for 4 hours, concentrate the reaction mixture solution to obtain solid nitrogen-containing organic compound 3 (1.622 mmol, 0.696 g, 72% yield).

[0090] In the 31 31P NMR spectrum, nitrogen-containing organic compound 3 shows a signal at δ = 38.97 ppm, and in the 13 13C NMR spectrum, the central carbon appears as a doublet at d = 34.61 ppm (d, JCP = 53.3 Hz, PCNi). The 1 1H NMR spectrum, 13 13C NMR spectrum, 31 31P NMR spectrum of nitrogen-containing organic compound 3 are shown in Figure 4 , 5 6 respectively.

[0091] Step C): Synthesis of diazomethylphosphane derivative 4 and reduction of Ni(CO) 4 Recovery

[0092] At room temperature, under a CO atmosphere and without stirring, THF was slowly added to the newly formed nitrogen-containing organic compound 3 (0.225 g, 0.524 mmol). Then the reaction mixture was stirred vigorously. After stirring for 4 hours, according to the NMR spectrum, Ni(CO) 4 and diazomethylphosphane derivative 4 were formed in quantitative yield. The reaction mixture was filtered, and all volatiles were evaporated from the filtrate to obtain diazomethylphosphane derivative 4 (0.425 mmol, 0.122 g, 81% yield). I3 The 13C NMR spectrum δ = 36.19 (d, JCP = 56.6 Hz, PCS) and the 31P NMR spectrum δ = 36.04 ppm) confirmed the formation of diazomethylphosphane derivative 4. The 1 1H NMR spectrum, 13 13C NMR spectrum, 31 31P NMR spectrum of diazomethylphosphane derivative 4 are shown in Figure 7 , 8 , 9 respectively.

[0093] Example 2

[0094] Method for directly synthesizing nitrogen-containing organic compounds from nitrogen, the technical route is as follows:

[0095]

[0096] R = i-Pr2N, i-Pr2 is isopropyl; Me is methyl;

[0097] The steps include the following:

[0098] Step A): Formation of carbene intermediate 2

[0099] At -30 °C to -80 °C, under a nitrogen atmosphere and without stirring, THF (40 mL) was slowly added to a mixture of P-S bis(ylide) derivative 1 ((1.00 g, 3.12 mmol) and an excess of Ni(CO)4. The formation of carbene intermediate 2 was monitored by NMR spectroscopy at low temperature.

[0100] Step B): Synthesis of nitrogen-containing organic compound 3

[0101] Then the reaction mixture was warmed to room temperature while stirring the reaction mixture vigorously. After stirring for 4 hours, the formation of nitrogen-containing organic compound 3 could be monitored by NMR spectroscopy. The reaction mixture solution was concentrated to obtain solid nitrogen-containing organic compound 3.

[0102] Step C): Synthesis of diazomethylphosphane derivative 4 and reduction of Ni(CO) 4 recovery

[0103] At room temperature, under a CO atmosphere and without stirring, THF was slowly added to the newly formed nitrogen-containing organic compound 3 (0.263 g, 0.614 mmol). Then the reaction mixture was stirred vigorously. After stirring for 4 hours, according to the NMR spectrum, Ni(CO) 4 and diazomethylphosphane derivative 4 were formed in quantitative yield. The reaction mixture was filtered and all volatiles were evaporated from the filtrate to give diazomethylphosphane derivative 4.

[0104] Example 3:

[0105] Method for directly synthesizing nitrogen-containing organic compounds from nitrogen, with the technical route as follows:

[0106]

[0107] R = i-Pr2N, i-Pr2 is isopropyl; Et is ethyl;

[0108] The steps include:

[0109] Step A): Formation of carbene intermediate 2

[0110] At -30 °C to -80 °C, under a nitrogen atmosphere and without stirring, THF (40 mL) was slowly added to a mixture of P-S bis(ylide) derivative 1 (1.00 g, 2.87 mmol) and excess Ni(CO)4. The formation of carbene intermediate 2 was monitored by NMR spectroscopy at low temperature.

[0111] Step B): Synthesis of nitrogen-containing organic compound 3

[0112] Then the reaction mixture was warmed to room temperature while stirring the reaction mixture vigorously. After stirring for 4 hours, the formation of nitrogen-containing organic compound 3 could be monitored by NMR spectroscopy. The reaction mixture solution was concentrated to give solid nitrogen-containing organic compound 3.

[0113] Step C): Synthesis of diazomethylphosphane derivative 4 and reduction of Ni(CO) 4 recovery

[0114] At room temperature, under a CO atmosphere and without stirring, THF was slowly added to the newly formed nitrogen-containing organic compound 3 (0.273 g, 0.637 mmol). Then the reaction mixture was stirred vigorously. After stirring for 4 hours, according to the NMR spectrum, Ni(CO) 4It is formed with the diazomethylphosphane derivative 4 in quantitative yield. The reaction mixture is filtered, and all volatiles are evaporated from the filtrate to obtain the diazomethylphosphane derivative 4.

[0115] Example 4:

[0116] A method for directly synthesizing nitrogen-containing organic compounds from nitrogen, the technical route is as follows:

[0117]

[0118] R = i-Pr2N, i-Pr2 is isopropyl; Pr is propyl;

[0119] It includes the following steps:

[0120] Step A): Formation of the carbene intermediate 2

[0121] At -30 °C to -80 °C, under a nitrogen atmosphere and without stirring, THF (40 mL) is slowly added to a mixture of P-S bis(ylide) derivative 1 ((1.00 g, 2.66 mmol) and an excess of Ni(CO)4. The formation of the carbene intermediate 2 is monitored by NMR spectroscopy at low temperature.

[0122] Step B): Synthesis of the nitrogen-containing organic compound 3

[0123] Then the reaction mixture is warmed to room temperature while stirring the reaction mixture vigorously. After stirring for 4 hours, the formation of the nitrogen-containing organic compound 3 can be monitored by NMR spectroscopy. The reaction mixture solution is concentrated to obtain the solid nitrogen-containing organic compound 3.

[0124] Step C): Synthesis of the diazomethylphosphane derivative 4 and the restoration of Ni(CO) 4 of

[0125] At room temperature, under a CO atmosphere and without stirring, THF is slowly added to the newly formed nitrogen-containing organic compound 3 (0.293 g, 0.637 mmol). Then the reaction mixture is stirred vigorously. After stirring for 4 hours, according to NMR spectroscopy, Ni(CO) 4 and the diazomethylphosphane derivative 4 are formed in quantitative yield. The reaction mixture is filtered, and all volatiles are evaporated from the filtrate to obtain the diazomethylphosphane derivative 4.

[0126] Example 5:

[0127] A method for directly synthesizing nitrogen-containing organic compounds from nitrogen, the technical route is as follows:

[0128]

[0129] R = i-Pr2N, where i-Pr2 is isopropyl; Ph is phenyl; Et is ethyl;

[0130] The steps are as follows:

[0131] Step A): Formation of carbene intermediate 2

[0132] At -30 °C to -80 °C, under a nitrogen atmosphere and without stirring, slowly add THF (40 mL) to a mixture of P-S bis(ylide) derivative 1 ((1.00 g, 2.18 mmol) and excess Ni(CO) 4 The formation of carbene intermediate 2 was monitored by NMR spectroscopy at low temperature.

[0133] Step B): Synthesis of nitrogen-containing organic compound 3

[0134] Then warm the reaction mixture to room temperature while vigorously stirring the reaction mixture. After stirring for 4 hours, the formation of nitrogen-containing organic compound 3 could be monitored by NMR spectroscopy. Concentrate the reaction mixture solution to obtain solid nitrogen-containing organic compound 3.

[0135] Step C): Synthesis of diazo(methylene)phosphorane derivative 4 and regeneration of Ni(CO) 4 regeneration

[0136] At room temperature, under a CO atmosphere and without stirring, slowly add THF to the newly formed nitrogen-containing organic compound 3 (0.322 g, 0.727 mmol). Then vigorously stir the reaction mixture. After stirring for 4 hours, according to NMR spectroscopy, Ni(CO) 4 and diazo(methylene)phosphorane derivative 4 were formed in quantitative yield. Filter the reaction mixture and evaporate all volatiles from the filtrate to obtain diazo(methylene)phosphorane derivative 4.

[0137] Example 6:

[0138] A method for directly synthesizing nitrogen-containing organic compounds from nitrogen, the technical route is as follows:

[0139]

[0140] R = i-Pr2N, where i-Pr2 is isopropyl; Et is ethyl; Me is methyl;

[0141] The steps are as follows:

[0142] Step A): Formation of carbene intermediate 2

[0143] At -30 °C to -80 °C, under a nitrogen atmosphere and without stirring, slowly add THF to a mixture of P-S bis(ylide) derivative 1 ((1.00 g, 2.99 mmol) and excess Ni(CO)4 Slowly add THF (40 mL) to the mixture. The formation of the carbene intermediate 2 was monitored by NMR spectroscopy at low temperature.

[0144] Step B): Synthesis of the nitrogen-containing organic compound 3

[0145] Then, warm the reaction mixture to room temperature while stirring the reaction mixture vigorously. After stirring for 4 hours, the formation of the nitrogen-containing organic compound 3 was monitored by NMR spectroscopy. Concentrate the solution of the reaction mixture to obtain the solid nitrogen-containing organic compound 3.

[0146] Step C): Synthesis of the diazomethylphosphine derivative 4 and the recovery of Ni(CO) 4

[0147] At room temperature, under a CO atmosphere, without stirring, slowly add THF to the newly formed nitrogen-containing organic compound 3 (0.312 g, 0.704 mmol). Then stir the reaction mixture vigorously. After stirring for 4 hours, according to NMR spectroscopy, Ni(CO) 4 and the diazomethylphosphine derivative 4 were formed in quantitative yield. Filter the reaction mixture and evaporate all volatiles from the filtrate to obtain the diazomethylphosphine derivative 4.

[0148] Example 7:

[0149] A method for directly synthesizing a nitrogen-containing organic compound from nitrogen, the technical route is as follows:

[0150]

[0151] R = i-Pr2N, i-Pr2 is isopropyl; Et is ethyl;

[0152] The steps include:

[0153] Step A): Formation of the carbene intermediate 2

[0154] In this example, the following method was used to obtain the carbene intermediate 2.

[0155] At -30 °C to -80 °C, under a nitrogen atmosphere, without stirring, slowly add THF (40 mL) to the P-S bis(ylide) derivative 1 ((1.00 g, 2.76 mmol) and an excess of Ni(CO) 4 The formation of the carbene intermediate 2 was monitored by NMR spectroscopy at low temperature.

[0156] Step B): Synthesis of the nitrogen-containing organic compound 3

[0157] Then, the reaction mixture was warmed to room temperature while stirring the reaction mixture vigorously. After stirring for 4 hours, the formation of the nitrogen-containing organic compound 3 was monitored by NMR spectroscopy. The reaction mixture solution was concentrated to obtain the solid nitrogen-containing organic compound 3.

[0158] Step C): Synthesis of diazomethylphosphorane derivative 4 and regeneration of Ni(CO) 4

[0159] At room temperature, under a CO atmosphere and without stirring, THF was slowly added to the newly formed nitrogen-containing organic compound 3 (0.304 g, 0.687 mmol). Then, the reaction mixture was stirred vigorously. After stirring for 4 hours, according to the NMR spectroscopy, Ni(CO) 4 and diazomethylphosphorane derivative 4 were formed in quantitative yield. The reaction mixture was filtered, and all volatiles were evaporated from the filtrate to obtain diazomethylphosphorane derivative 4.

[0160] Example 8:

[0161] Method for directly synthesizing nitrogen-containing organic compounds from nitrogen, with the technical route as follows:

[0162]

[0163] R = i-Pr2N, i-Pr2 is isopropyl; Et is ethyl; Pr is propyl;

[0164] The steps include the following:

[0165] Step A): Formation of carbene intermediate 2

[0166] In this example, the following method was used to obtain carbene intermediate 2.

[0167] At -30 °C to -80 °C, under a nitrogen atmosphere and without stirring, THF (40 mL) was slowly added to a mixture of P-S bis(ylide) derivative 1 ((1.00 g, 2.56 mmol) and an excess of Ni(CO) 4 . The formation of carbene intermediate 2 was monitored by NMR spectroscopy at low temperature.

[0168] Step B): Synthesis of nitrogen-containing organic compound 3

[0169] Then, the reaction mixture was warmed to room temperature while stirring the reaction mixture vigorously. After stirring for 4 hours, the formation of the nitrogen-containing organic compound 3 was monitored by NMR spectroscopy. The reaction mixture solution was concentrated to obtain the solid nitrogen-containing organic compound 3.

[0170] Step C): Synthesis of diazomethylphosphorane derivative 4 and regeneration of Ni(CO) 4 ​​

[0171] At room temperature, in a CO atmosphere, without stirring, THF was slowly added to the newly formed nitrogen-containing organic compound 3 (0.308 g, 0.694 mmol). Then the reaction mixture was stirred vigorously. After stirring for 4 hours, according to the NMR spectrum, Ni(CO) 4 and the diazomethylphosphine derivative 4 were formed in quantitative yield. The reaction mixture was filtered, and all volatiles were evaporated from the filtrate to obtain the diazomethylphosphine derivative 4.

[0172] Example 9:

[0173] Method for directly synthesizing nitrogen-containing organic compounds from nitrogen, the technical route is as follows:

[0174]

[0175] R = i-Pr2N, i-Pr2 is isopropyl; Ph is phenyl; Pr is propyl;

[0176] It includes the following steps:

[0177] Step A): Formation of the carbene intermediate 2

[0178] In this example, the carbene intermediate 2 was obtained by the following method.

[0179] At -30 °C to -80 °C, in a nitrogen atmosphere, without stirring, THF (40 mL) was slowly added to a mixture of P-S bis(ylide) derivative 1 ((1.00 g, 2.12 mmol) and excess Ni(CO) 4 The formation of the carbene intermediate 2 was monitored by NMR spectroscopy at low temperature.

[0180] Step B): Synthesis of the nitrogen-containing organic compound 3

[0181] Then the reaction mixture was warmed to room temperature while stirring the reaction mixture vigorously. After stirring for 4 hours, the formation of the nitrogen-containing organic compound 3 was monitored by NMR spectroscopy. The reaction mixture solution was concentrated to obtain the solid nitrogen-containing organic compound 3.

[0182] Step C): Synthesis of the diazomethylphosphine derivative 4 and the restoration of Ni(CO) 4 restoration

[0183] At room temperature, in a CO atmosphere, without stirring, THF was slowly added to the newly formed nitrogen-containing organic compound 3 (0.273 g, 0.598 mmol). Then the reaction mixture was stirred vigorously. After stirring for 4 hours, according to the NMR spectrum, Ni(CO) 4It forms with the diazomethylphosphane derivative 4 in quantitative yield. The reaction mixture is filtered, and all volatiles are evaporated from the filtrate to obtain the diazomethylphosphane derivative 4.

[0184] Example 10:

[0185] A method for directly synthesizing nitrogen-containing organic compounds from nitrogen, the technical route is as follows:

[0186]

[0187] R = i-Pr2N, i-Pr2 is isopropyl; Me is methyl; Pr is propyl;

[0188] It includes the following steps:

[0189] Step A): Formation of the carbene intermediate 2

[0190] At -30 °C to -80 °C, under a nitrogen atmosphere and without stirring, THF (40 mL) is slowly added to a mixture of the P-S bis(ylide) derivative 1 ((1.00 g, 2.87 mmol) and an excess of Ni(CO) 4 The formation of the carbene intermediate 2 is monitored by NMR spectroscopy at low temperature.

[0191] Step B): Synthesis of the nitrogen-containing organic compound 3

[0192] Then the reaction mixture is warmed to room temperature while stirring the reaction mixture vigorously. After stirring for 4 hours, the formation of the nitrogen-containing organic compound 3 can be monitored by NMR spectroscopy. The reaction mixture solution is concentrated to obtain the solid nitrogen-containing organic compound 3.

[0193] Step C): Synthesis of the diazomethylphosphane derivative 4 and the recovery of Ni(CO) 4 restoration

[0194] At room temperature, under a CO atmosphere and without stirring, THF is slowly added to the newly formed nitrogen-containing organic compound 3 (0.279 g, 0.629 mmol). Then the reaction mixture is stirred vigorously. After stirring for 4 hours, according to NMR spectroscopy, Ni(CO) 4 and the diazomethylphosphane derivative 4 form in quantitative yield. The reaction mixture is filtered, and all volatiles are evaporated from the filtrate to obtain the diazomethylphosphane derivative 4.

[0195] Example 11:

[0196] A method for directly synthesizing nitrogen-containing organic compounds from nitrogen, the technical route is as follows:

[0197]

[0198] R = i-Pr2N, where i-Pr2 is isopropyl; Et is ethyl; Pr is propyl;

[0199] The steps are as follows:

[0200] Step A): Formation of carbene intermediate 2

[0201] At -30 °C to -80 °C, under a nitrogen atmosphere and without stirring, slowly add THF (40 mL) to a mixture of P-S bis(ylide) derivative 1 ((1.00 g, 2.66 mmol) and excess Ni(CO) 4 The formation of carbene intermediate 2 was monitored by NMR spectroscopy at low temperature.

[0202] Step B): Synthesis of nitrogen-containing organic compound 3

[0203] Then, warm the reaction mixture to room temperature while vigorously stirring the reaction mixture. After stirring for 4 hours, the formation of nitrogen-containing organic compound 3 could be monitored by NMR spectroscopy. Concentrate the reaction mixture solution to obtain solid nitrogen-containing organic compound 3.

[0204] Step C): Synthesis of diazomethylphosphine derivative 4 and regeneration of Ni(CO) 4 regeneration

[0205] At room temperature, under a CO atmosphere and without stirring, slowly add THF to the newly formed nitrogen-containing organic compound 3 (0.300 g, 0.676 mmol). Then, vigorously stir the reaction mixture. After stirring for 4 hours, according to NMR spectroscopy, Ni(CO) 4 and diazomethylphosphine derivative 4 were formed in quantitative yield. Filter the reaction mixture and evaporate all volatiles from the filtrate to obtain diazomethylphosphine derivative 4.

[0206] Example 12:

[0207] A method for directly synthesizing nitrogen-containing organic compounds from nitrogen, the technical route is as follows:

[0208]

[0209] R = i-Pr2N, where i-Pr2 is isopropyl; Pr is propyl;

[0210] The steps are as follows:

[0211] Step A): Formation of carbene intermediate 2

[0212] At -30 °C to -80 °C, under a nitrogen atmosphere and without stirring, slowly add THF to a mixture of P-S bis(ylide) derivative 1 ((1.00 g, 2.48 mmol) and excess Ni(CO) 4Slowly add THF (40 mL) to the mixture. The formation of carbene intermediate 2 was monitored by NMR spectroscopy at low temperature.

[0213] Step B): Synthesis of nitrogen-containing organic compound 3

[0214] Then warm the reaction mixture to room temperature while stirring the reaction mixture vigorously. After stirring for 4 h, the formation of nitrogen-containing organic compound 3 could be monitored by NMR spectroscopy. The reaction mixture solution was concentrated to give solid nitrogen-containing organic compound 3.

[0215] Step C): Synthesis of diazomethylphosphine derivative 4 and 4 recovery of Ni(CO)

[0216] At room temperature, under a CO atmosphere and without stirring, slowly add THF to the newly formed nitrogen-containing organic compound 3 (0.293 g, 0.661 mmol). Then stir the reaction mixture vigorously. After stirring for 4 h, according to NMR spectroscopy, Ni(CO) 4 and diazomethylphosphine derivative 4 were formed in quantitative yield. The reaction mixture was filtered and all volatiles were evaporated from the filtrate to give diazomethylphosphine derivative 4.

[0217] Example 13:

[0218] A method for directly synthesizing nitrogen-containing organic compounds from nitrogen, the technical route is as follows:

[0219]

[0220] R = i-Pr2N, i-Pr2 is isopropyl; Ph is phenyl;

[0221] The steps include the following:

[0222] Step A): Formation of carbene intermediate 2

[0223] At -30 °C to -80 °C, under a nitrogen atmosphere and without stirring, slowly add THF (40 mL) to the mixture of P-S bis(ylide) derivative 1 ((1.00 g, 1.98 mmol) and excess Ni(CO) 4 The formation of a novel carbene intermediate 2 was monitored by NMR spectroscopy at low temperature.

[0224] Step B): Synthesis of novel nitrogen-containing organic compound 3

[0225] Then warm the reaction mixture to room temperature while stirring the reaction mixture vigorously. After stirring for 4 h, the formation of novel nitrogen-containing organic compound 3 could be monitored by NMR spectroscopy. The reaction mixture solution was concentrated to give solid novel nitrogen-containing organic compound 3.

[0226] Step C): Synthesis of diazomethylphosphane derivative 4 and regeneration of Ni(CO) 4

[0227] At room temperature, under a CO atmosphere and without stirring, THF was slowly added to the newly formed nitrogen-containing organic compound 3 (0.321 g, 0.654 mmol). Then the reaction mixture was stirred vigorously. After stirring for 4 hours, according to the NMR spectrum, Ni(CO) 4 and diazomethylphosphane derivative 4 were formed in quantitative yield. The reaction mixture was filtered and all volatiles were evaporated from the filtrate to obtain diazomethylphosphane derivative 4.

[0228] Example 14:

[0229] A method for directly synthesizing nitrogen-containing organic compounds from nitrogen, with the technical route as follows:

[0230]

[0231] R = i-Pr2N, i-Pr2 is isopropyl; Ph is phenyl; Me is methyl;

[0232] The steps include the following:

[0233] Step A): Formation of carbene intermediate 2

[0234] At -30 °C to -80 °C, under a nitrogen atmosphere and without stirring, THF (40 mL) was slowly added to a mixture of P-S bis(ylide) derivative 1 ((1.00 g, 2.62 mmol) and an excess of Ni(CO) 4 . The formation of the novel carbene intermediate 2 was monitored by NMR spectroscopy at low temperature.

[0235] Step B): Synthesis of nitrogen-containing organic compound 3

[0236] Then the reaction mixture was warmed to room temperature while stirring the reaction mixture vigorously. After stirring for 4 hours, the formation of the novel nitrogen-containing organic compound 3 was monitored by NMR spectroscopy. The reaction mixture solution was concentrated to obtain the solid novel nitrogen-containing organic compound 3.

[0237] Step C): Synthesis of diazomethylphosphane derivative 4 and regeneration of Ni(CO) 4

[0238] At room temperature, under a CO atmosphere and without stirring, THF was slowly added to the newly formed nitrogen-containing organic compound 3 (0.359 g, 0.731 mmol). Then the reaction mixture was stirred vigorously. After stirring for 4 hours, according to the NMR spectrum, Ni(CO) 4 ​​It forms with the diazomethylphosphane derivative 4 in quantitative yield. The reaction mixture is filtered, and all volatiles are evaporated from the filtrate to obtain the diazomethylphosphane derivative 4.

[0239] Example 15:

[0240] A method for directly synthesizing nitrogen-containing organic compounds from nitrogen, with the technical route as follows:

[0241]

[0242] R = i-Pr2N, i-Pr2 is isopropyl; Ph is phenyl; Et is ethyl;

[0243] It includes the following steps:

[0244] Step A): Formation of the carbene intermediate 2

[0245] At -30 °C to -80 °C, under a nitrogen atmosphere and without stirring, slowly add THF (40 mL) to a mixture of the P-S bis(ylide) derivative 1 ((1.00 g, 2.44 mmol) and an excess of Ni(CO) 4 The formation of the novel carbene intermediate 2 is monitored by NMR spectroscopy at low temperature.

[0246] Step B): Synthesis of the novel nitrogen-containing organic compound 3

[0247] Then raise the temperature of the reaction mixture to room temperature while vigorously stirring the reaction mixture. After stirring for 4 hours, the formation of the novel nitrogen-containing organic compound 3 can be monitored by NMR spectroscopy. Concentrate the reaction mixture solution to obtain the solid novel nitrogen-containing organic compound 3.

[0248] Step C): Synthesis of the diazomethylphosphane derivative 4 and the restoration of Ni(CO) 4 restoration

[0249] At room temperature, under a CO atmosphere and without stirring, slowly add THF to the newly formed nitrogen-containing organic compound 3 (0.352 g, 0.716 mmol). Then vigorously stir the reaction mixture. After stirring for 4 hours, as shown by NMR spectroscopy, Ni(CO) 4 and the diazomethylphosphane derivative 4 form in quantitative yield. Filter the reaction mixture, and evaporate all volatiles from the filtrate to obtain the diazomethylphosphane derivative 4.

[0250] Example 16:

[0251] A method for directly synthesizing nitrogen-containing organic compounds from nitrogen, with the technical route as follows:

[0252]

[0253] R = i-Pr₂N, where i-Pr₂ is isopropyl; Ph is phenyl; Pr is propyl;

[0254] It includes the following steps:

[0255] Step A): Formation of carbene intermediate 2

[0256] At -30 °C to -80 °C, under a nitrogen atmosphere and without stirring, slowly add THF (40 mL) to a mixture of P-S bis(ylide) derivative 1 ((1.00 g, 2.28 mmol) and excess Ni(CO) 4 The formation of the novel carbene intermediate 2 is monitored by NMR spectroscopy at low temperature.

[0257] Step B): Synthesis of nitrogen-containing organic compound 3

[0258] Then warm the reaction mixture to room temperature while vigorously stirring the reaction mixture. After stirring for 4 hours, the formation of the novel nitrogen-containing organic compound 3 can be monitored by NMR spectroscopy. Concentrate the reaction mixture solution to obtain the solid novel nitrogen-containing organic compound 3.

[0259] Step C): Synthesis of diazomethylphosphine derivative 4 and regeneration of Ni(CO) 4

[0260] At room temperature, under a CO atmosphere and without stirring, slowly add THF to the newly formed nitrogen-containing organic compound 3 (0.352 g, 0.717 mmol). Then vigorously stir the reaction mixture. After stirring for 4 hours, according to NMR spectroscopy, Ni(CO) 4 and diazomethylphosphine derivative 4 are formed in quantitative yield. Filter the reaction mixture and evaporate all volatiles from the filtrate to obtain diazomethylphosphine derivative 4.

[0261] Example 17:

[0262] A method for directly synthesizing nitrogen-containing organic compounds from nitrogen, the technical route is as follows:

[0263]

[0264] i-Pr₂ is isopropyl; Me is methyl;

[0265] It includes the following steps:

[0266] Step A): Formation of carbene intermediate 2

[0267] ​In the temperature range of -30 °C to -80 °C, under a nitrogen atmosphere and without stirring, slowly add THF (40 mL) to a mixture of P-S bis(ylide) derivative 1 ((1.00 g, 2.23 mmol) and an excess of Ni(CO) 4 The formation of the novel carbene intermediate 2 was monitored by NMR spectroscopy at low temperature.

[0268] Step B): Synthesis of the novel nitrogen-containing organic compound 3

[0269] Then, allow the reaction mixture to warm to room temperature while vigorously stirring the reaction mixture. After stirring for 4 hours, the formation of the novel nitrogen-containing organic compound 3 was monitored by NMR spectroscopy. Concentrate the reaction mixture solution to obtain the solid novel nitrogen-containing organic compound 3.

[0270] Step C): Synthesis of the diazomethylphosphine derivative 4 and regeneration of Ni(CO) 4

[0271] At room temperature, under a CO atmosphere and without stirring, slowly add THF to the newly formed nitrogen-containing organic compound 3 (0.274 g, 0.633 mmol). Then, vigorously stir the reaction mixture. After stirring for 4 hours, according to NMR spectroscopy, Ni(CO) 4 and the diazomethylphosphine derivative 4 were formed in quantitative yield. Filter the reaction mixture and evaporate all volatiles from the filtrate to obtain the diazomethylphosphine derivative 4.

[0272] Example 18:

[0273] A method for directly synthesizing nitrogen-containing organic compounds from nitrogen, with the technical route as follows:

[0274]

[0275] i-Pr2 is isopropyl; Me is methyl;

[0276] The steps include the following:

[0277] Step A): Formation of the carbene intermediate 2

[0278] In the temperature range of -30 °C to -80 °C, under a nitrogen atmosphere and without stirring, slowly add THF (40 mL) to a mixture of P-S bis(ylide) derivative 1 ((1.00 g, 3.09 mmol) and an excess of Ni(CO) 4 The formation of the novel carbene intermediate 2 was monitored by NMR spectroscopy at low temperature.

[0279] Step B): Synthesis of the nitrogen-containing organic compound 3

[0280] ​Then, the reaction mixture was warmed to room temperature while stirring the reaction mixture vigorously. After stirring for 4 hours, the formation of the novel nitrogen-containing organic compound 3 could be monitored by NMR spectroscopy. The reaction mixture solution was concentrated to obtain the solid novel nitrogen-containing organic compound 3.

[0281] Step C): Synthesis of diazomethylphosphorane derivative 4 and regeneration of Ni(CO) 4

[0282] At room temperature, under a CO atmosphere and without stirring, THF was slowly added to the newly formed nitrogen-containing organic compound 3 (0.293 g, 0.677 mmol). Then, the reaction mixture was stirred vigorously. After stirring for 4 hours, according to the NMR spectroscopy, Ni(CO) 4 and diazomethylphosphorane derivative 4 were formed in quantitative yield. The reaction mixture was filtered, and all volatiles were evaporated from the filtrate to obtain diazomethylphosphorane derivative 4.

[0283] Example 19:

[0284] A method for directly synthesizing nitrogen-containing organic compounds from nitrogen, with the technical route as follows:

[0285]

[0286] i-Pr2 is isopropyl; Me is methyl; Et is ethyl;

[0287] Including the following steps:

[0288] Step A): Formation of carbene intermediate 2

[0289] At -30 °C to -80 °C, under a nitrogen atmosphere and without stirring, THF (40 mL) was slowly added to a mixture of P-S bis(ylide) derivative 1 ((1.00 g, 2.84 mmol) and an excess of Ni(CO) 4 . The formation of the novel carbene intermediate 2 was monitored by NMR spectroscopy at low temperature.

[0290] Step B): Synthesis of novel nitrogen-containing organic compound 3

[0291] Then, the reaction mixture was warmed to room temperature while stirring the reaction mixture vigorously. After stirring for 4 hours, the formation of the novel nitrogen-containing organic compound 3 could be monitored by NMR spectroscopy. The reaction mixture solution was concentrated to obtain the solid novel nitrogen-containing organic compound 3.

[0292] Step C): Synthesis of diazomethylphosphorane derivative 4 and regeneration of Ni(CO) 4

[0293] ​​At room temperature, in a CO atmosphere, without stirring, THF was slowly added to the newly formed nitrogen-containing organic compound 3 (0.300 g, 0.693 mmol). Then the reaction mixture was stirred vigorously. After stirring for 4 hours, according to the NMR spectrum, Ni(CO) 4 and the diazomethylphosphine derivative 4 were formed in quantitative yield. The reaction mixture was filtered, and all volatiles were evaporated from the filtrate to obtain the diazomethylphosphine derivative 4.

[0294] Example 20:

[0295] A method for directly synthesizing nitrogen-containing organic compounds from nitrogen, the technical route is as follows:

[0296]

[0297] i-Pr2 is isopropyl; Me is methyl; Pr is propyl;

[0298] It includes the following steps:

[0299] Step A): Formation of the carbene intermediate 2

[0300] At -30 °C to -80 °C, in a nitrogen atmosphere, without stirring, THF (40 mL) was slowly added to a mixture of the P-S bis(ylide) derivative 1 ((1.00 g, 2.63 mmol) and an excess of Ni(CO) 4 . The formation of the novel carbene intermediate 2 was monitored by NMR spectroscopy at low temperature.

[0301] Step B): Synthesis of the nitrogen-containing organic compound 3

[0302] Then the reaction mixture was warmed to room temperature while stirring the reaction mixture vigorously. After stirring for 4 hours, the formation of the novel nitrogen-containing organic compound 3 could be monitored by NMR spectroscopy. The reaction mixture solution was concentrated to obtain the solid novel nitrogen-containing organic compound 3.

[0303] Step C): Synthesis of the diazomethylphosphine derivative 4 and the restoration of Ni(CO) 4

[0304] At room temperature, in a CO atmosphere, without stirring, THF was slowly added to the newly formed nitrogen-containing organic compound 3 (0.318 g, 0.734 mmol). Then the reaction mixture was stirred vigorously. After stirring for 4 hours, according to the NMR spectrum, Ni(CO) 4 and the diazomethylphosphine derivative 4 were formed in quantitative yield. The reaction mixture was filtered, and all volatiles were evaporated from the filtrate to obtain the diazomethylphosphine derivative 4.

[0305] Example 21:

[0306] A method for directly synthesizing nitrogen-containing organic compounds has the following technical route:

[0307]

[0308] i-Pr2 is isopropyl; Ph is phenyl; Et is ethyl;

[0309] It includes the following steps:

[0310] Step A): Formation of carbene intermediate 2

[0311] At -30°C to -80°C, in a nitrogen atmosphere and without stirring, slowly add THF (40 mL) to a mixture of P-S bis(ylide) derivative 1 ((1.00 g, 2.16 mmol) and excess Ni(CO) 4 The formation of the novel carbene intermediate 2 is monitored by NMR spectroscopy at low temperature.

[0312] Step B): Synthesis of nitrogen-containing organic compound 3

[0313] Then raise the temperature of the reaction mixture to room temperature while vigorously stirring the reaction mixture. After stirring for 4 hours, the formation of the novel nitrogen-containing organic compound 3 can be monitored by NMR spectroscopy. Concentrate the reaction mixture solution to obtain the solid novel nitrogen-containing organic compound 3.

[0314] Step C): Synthesis of diazo methylene phosphine derivative 4 and regeneration of Ni(CO) 4 regeneration

[0315] At room temperature, in a CO atmosphere and without stirring, slowly add THF to the newly formed nitrogen-containing organic compound 3 (0.320 g, 0.715 mmol). Then vigorously stir the reaction mixture. After stirring for 4 hours, according to NMR spectroscopy, Ni(CO) 4 and diazo methylene phosphine derivative 4 are formed in quantitative yield. Filter the reaction mixture and evaporate all volatiles from the filtrate to obtain diazo methylene phosphine derivative 4.

[0316] Example 22:

[0317] A method for directly synthesizing nitrogen-containing organic compounds has the following technical route:

[0318]

[0319] i-Pr2 is isopropyl; Et is ethyl; Me is methyl;

[0320] It includes the following steps:

[0321] Step A): Formation of carbene intermediate 2

[0322] At -30 °C to -80 °C, under a nitrogen atmosphere and without stirring, slowly add THF (40 mL) to a mixture of P-S bis(ylide) derivative 1 ((1.00 g, 2.96 mmol) and excess Ni(CO) 4 Monitor the formation of the novel carbene intermediate 2 by NMR spectroscopy at low temperature.

[0323] Step B): Synthesis of nitrogen-containing organic compound 3

[0324] Then raise the temperature of the reaction mixture to room temperature while vigorously stirring the reaction mixture. After stirring for 4 hours, the formation of the novel nitrogen-containing organic compound 3 can be monitored by NMR spectroscopy. Concentrate the reaction mixture solution to obtain the solid novel nitrogen-containing organic compound 3.

[0325] Step C): Synthesis of diazo methylene phosphine derivative 4 and regeneration of Ni(CO) 4 Regeneration

[0326] At room temperature, under a CO atmosphere and without stirring, slowly add THF to the newly formed nitrogen-containing organic compound 3 (0.308 g, 0.688 mmol). Then vigorously stir the reaction mixture. After stirring for 4 hours, according to NMR spectroscopy, Ni(CO) 4 and diazo methylene phosphine derivative 4 are formed in quantitative yield. Filter the reaction mixture and evaporate all volatiles from the filtrate to obtain diazo methylene phosphine derivative 4.

[0327] Example 23:

[0328] Method for directly synthesizing nitrogen-containing organic compounds from nitrogen, the technical route is as follows:

[0329]

[0330] i-Pr2 is isopropyl; Et is ethyl;

[0331] The steps include the following:

[0332] Step A): Formation of carbene intermediate 2

[0333] At -30 °C to -80 °C, under a nitrogen atmosphere and without stirring, slowly add THF (40 mL) to a mixture of P-S bis(ylide) derivative 1 ((1.00 g, 2.66 mmol) and excess Ni(CO) 4 Monitor the formation of the novel carbene intermediate 2 by NMR spectroscopy at low temperature.

[0334] Step B): Synthesis of nitrogen-containing organic compound 3

[0335] Then, the reaction mixture was warmed to room temperature while stirring the reaction mixture vigorously. After stirring for 4 hours, the formation of the novel nitrogen-containing organic compound 3 could be monitored by NMR spectroscopy. The reaction mixture solution was concentrated to obtain the solid novel nitrogen-containing organic compound 3.

[0336] Step C): Synthesis of diazomethylphosphorane derivative 4 and regeneration of Ni(CO) 4 regeneration

[0337] At room temperature, under a CO atmosphere and without stirring, THF was slowly added to the newly formed nitrogen-containing organic compound 3 (0.334 g, 0.748 mmol). Then, the reaction mixture was stirred vigorously. After stirring for 4 hours, according to the NMR spectroscopy, Ni(CO) 4 and diazomethylphosphorane derivative 4 were formed in quantitative yield. The reaction mixture was filtered, and all volatiles were evaporated from the filtrate to obtain diazomethylphosphorane derivative 4.

[0338] Example 24:

[0339] Method for directly synthesizing nitrogen-containing organic compounds from nitrogen, with the technical route as follows:

[0340]

[0341] i-Pr2 is isopropyl; Et is ethyl; Pr is propyl;

[0342] The steps include the following:

[0343] Step A): Formation of carbene intermediate 2

[0344] At -30 °C to -80 °C, under a nitrogen atmosphere and without stirring, THF (40 mL) was slowly added to a mixture of P-S bis(ylide) derivative 1 ((1.00 g, 2.48 mmol) and an excess of Ni(CO) 4 . The formation of the novel carbene intermediate 2 was monitored by NMR spectroscopy at low temperature.

[0345] Step B): Synthesis of novel nitrogen-containing organic compound 3

[0346] Then, the reaction mixture was warmed to room temperature while stirring the reaction mixture vigorously. After stirring for 4 hours, the formation of the novel nitrogen-containing organic compound 3 could be monitored by NMR spectroscopy. The reaction mixture solution was concentrated to obtain the solid novel nitrogen-containing organic compound 3.

[0347] Step C): Synthesis of diazomethylphosphorane derivative 4 and regeneration of Ni(CO) 4Restoration

[0348] At room temperature, in a CO atmosphere, without stirring, THF was slowly added to the newly formed nitrogen-containing organic compound 3 (0.300 g, 0.672 mmol). Then the reaction mixture was stirred vigorously. After stirring for 4 hours, according to the NMR spectrum, Ni(CO) 4 and the diazomethylenephosphane derivative 4 were formed in quantitative yield. The reaction mixture was filtered, and all volatiles were evaporated from the filtrate to obtain the diazomethylenephosphane derivative 4.

[0349] Example 25:

[0350] Method for directly synthesizing nitrogen-containing organic compounds from nitrogen, the technical route is as follows:

[0351]

[0352] i-Pr2 is isopropyl; Ph is phenyl; Pr is propyl;

[0353] Including the following steps:

[0354] Step A): Formation of the carbene intermediate 2

[0355] At -30 °C to -80 °C, in a nitrogen atmosphere, without stirring, THF (40 mL) was slowly added to a mixture of the P-S bis(ylide) derivative 1 ((1.00 g, 2.10 mmol) and excess Ni(CO) 4 The formation of the novel carbene intermediate 2 was monitored by NMR spectroscopy at low temperature.

[0356] Step B): Synthesis of the nitrogen-containing organic compound 3

[0357] Then the reaction mixture was warmed to room temperature while stirring the reaction mixture vigorously. After stirring for 4 hours, the formation of the novel nitrogen-containing organic compound 3 could be monitored by NMR spectroscopy. The reaction mixture solution was concentrated to obtain the solid novel nitrogen-containing organic compound 3.

[0358] Step C): Synthesis of the diazomethylenephosphane derivative 4 and restoration of Ni(CO) 4 Restoration

[0359] At room temperature, in a CO atmosphere, without stirring, THF was slowly added to the newly formed nitrogen-containing organic compound 3 (0.350 g, 0.759 mmol). Then the reaction mixture was stirred vigorously. After stirring for 4 hours, according to the NMR spectrum, Ni(CO) 4 and the diazomethylenephosphane derivative 4 were formed in quantitative yield. The reaction mixture was filtered, and all volatiles were evaporated from the filtrate to obtain the diazomethylenephosphane derivative 4.

[0360] Example 26:

[0361] A method for directly synthesizing nitrogen-containing organic compounds from nitrogen, the technical route is as follows:

[0362]

[0363] i-Pr2 is isopropyl; Me is methyl; Pr is propyl;

[0364] It includes the following steps:

[0365] Step A): Formation of carbene intermediate 2

[0366] At -30°C to -80°C, in a nitrogen atmosphere and without stirring, slowly add THF (40 mL) to a mixture of P-S bis(ylide) derivative 1 ((1.00 g, 2.84 mmol) and excess Ni(CO) 4 Monitor the formation of the novel carbene intermediate 2 by NMR spectroscopy at low temperature.

[0367] Step B): Synthesis of nitrogen-containing organic compound 3

[0368] Then raise the temperature of the reaction mixture to room temperature while vigorously stirring the reaction mixture. After stirring for 4 hours, the formation of the novel nitrogen-containing organic compound 3 can be monitored by NMR spectroscopy. Concentrate the reaction mixture solution to obtain the solid novel nitrogen-containing organic compound 3.

[0369] Step C): Synthesis of diazomethylphosphine derivative 4 and regeneration of Ni(CO) 4 regeneration

[0370] At room temperature, in a CO atmosphere and without stirring, slowly add THF to the newly formed nitrogen-containing organic compound 3 (0.320 g, 0.693 mmol). Then vigorously stir the reaction mixture. After stirring for 4 hours, according to NMR spectroscopy, Ni(CO) 4 and diazomethylphosphine derivative 4 are formed in quantitative yield. Filter the reaction mixture and evaporate all volatiles from the filtrate to obtain diazomethylphosphine derivative 4.

[0371] Example 27:

[0372] A method for directly synthesizing nitrogen-containing organic compounds from nitrogen, the technical route is as follows:

[0373]

[0374] i-Pr2 is isopropyl; Et is ethyl; Pr is propyl;

[0375] It includes the following steps:

[0376] Step A): Formation of novel carbene intermediate 2

[0377] Under the conditions of -30°C to -80°C, nitrogen atmosphere, and without stirring, slowly add THF (40 mL) to a mixture of P-S bis(ylide) derivative 1 ((1.00 g, 2.64 mmol) and excess Ni(CO) 4 The formation of novel carbene intermediate 2 is monitored by NMR spectroscopy at low temperature.

[0378] Step B): Synthesis of nitrogen-containing organic compound 3

[0379] Then raise the temperature of the reaction mixture to room temperature while vigorously stirring the reaction mixture. After stirring for 4 hours, the formation of novel nitrogen-containing organic compound 3 can be monitored by NMR spectroscopy. Concentrate the reaction mixture solution to obtain solid novel nitrogen-containing organic compound 3.

[0380] Step C): Synthesis of diazomethylenephosphane derivative 4 and regeneration of Ni(CO) 4 regeneration

[0381] Under the conditions of room temperature, CO atmosphere, and without stirring, slowly add THF to the newly formed nitrogen-containing organic compound 3 (0.271 g, 0.587 mmol). Then vigorously stir the reaction mixture. After stirring for 4 hours, according to NMR spectroscopy, Ni(CO) 4 and diazomethylenephosphane derivative 4 are formed in quantitative yield. Filter the reaction mixture and evaporate all volatiles from the filtrate to obtain diazomethylenephosphane derivative 4.

[0382] Example 28:

[0383] Method for directly synthesizing nitrogen-containing organic compounds from nitrogen, the technical route is as follows:

[0384]

[0385] i-Pr2 is isopropyl; Pr is propyl;

[0386] It includes the following steps:

[0387] Step A): Formation of carbene intermediate 2

[0388] Under the conditions of -30°C to -80°C, nitrogen atmosphere, and without stirring, slowly add THF to a mixture of P-S bis(ylide) derivative 1 ((1.00 g, 2.45 mmol) and excess Ni(CO) 4Slowly add THF (40 mL) to the mixture. The formation of the novel carbene intermediate 2 was monitored by NMR spectroscopy at low temperature.

[0389] Step B): Synthesis of the nitrogen-containing organic compound 3

[0390] Then, the reaction mixture was warmed to room temperature while stirring the reaction mixture vigorously. After stirring for 4 hours, the formation of the novel nitrogen-containing organic compound 3 could be monitored by NMR spectroscopy. The reaction mixture solution was concentrated to obtain the solid novel nitrogen-containing organic compound 3.

[0391] Step C): Synthesis of the diazomethylphosphine derivative 4 and the recovery of Ni(CO) 4 recovery

[0392] At room temperature, under a CO atmosphere and without stirring, slowly add THF to the newly formed nitrogen-containing organic compound 3 (0.286 g, 0.621 mmol). Then, stir the reaction mixture vigorously. After stirring for 4 hours, according to the NMR spectroscopy, Ni(CO) 4 and the diazomethylphosphine derivative 4 were formed in quantitative yield. The reaction mixture was filtered, and all volatiles were evaporated from the filtrate to obtain the diazomethylphosphine derivative 4.

[0393] Example 29:

[0394] A method for directly synthesizing nitrogen-containing organic compounds from nitrogen, the technical route is as follows:

[0395]

[0396] i-Pr2 is isopropyl;; Ph is phenyl;

[0397] The steps include the following:

[0398] Step A): Formation of the carbene intermediate 2

[0399] At -30 °C to -80 °C, under a nitrogen atmosphere and without stirring, slowly add THF (40 mL) to the mixture of the P-S bis(ylide) derivative 1 ((1.00 g, 1.96 mmol) and an excess of Ni(CO) 4 The formation of the novel carbene intermediate 2 was monitored by NMR spectroscopy at low temperature.

[0400] Step B): Synthesis of the nitrogen-containing organic compound 3

[0401] Then, the reaction mixture was warmed to room temperature while stirring the reaction mixture vigorously. After stirring for 4 hours, the formation of the novel nitrogen-containing organic compound 3 could be monitored by NMR spectroscopy. The reaction mixture solution was concentrated to give the solid novel nitrogen-containing organic compound 3 (1.370 mmol, 0.680 g, 70% yield).

[0402] Step C): Synthesis of diazomethylphosphane derivative 4 and regeneration of Ni(CO) 4

[0403] At room temperature, under a CO atmosphere and without stirring, THF was slowly added to the freshly formed nitrogen-containing organic compound 3 (0.334 g, 0.674 mmol). Then the reaction mixture was stirred vigorously. After stirring for 4 hours, according to the NMR spectroscopy, Ni(CO) 4 and diazomethylphosphane derivative 4 were formed in quantitative yield. The reaction mixture was filtered and all volatiles were evaporated from the filtrate to give diazomethylphosphane derivative 4.

[0404] Example 30:

[0405] Method for directly synthesizing nitrogen-containing organic compounds from nitrogen, the technical route is as follows:

[0406]

[0407] i-Pr2 is isopropyl; Ph is phenyl; Me is methyl;

[0408] It includes the following steps:

[0409] Step A): Formation of carbene intermediate 2

[0410] At -30 °C to -80 °C, under a nitrogen atmosphere and without stirring, THF (40 mL) was slowly added to a mixture of P-S bis(ylide) derivative 1 ((1.00 g, 2.59 mmol) and an excess of Ni(CO) 4 . The formation of the novel carbene intermediate 2 was monitored by NMR spectroscopy at low temperature.

[0411] Step B): Synthesis of nitrogen-containing organic compound 3

[0412] The reaction mixture was warmed to room temperature while stirring the reaction mixture vigorously. After stirring for 4 hours, the formation of the novel nitrogen-containing organic compound 3 could be monitored by NMR spectroscopy. The reaction mixture solution was concentrated to give the solid novel nitrogen-containing organic compound 3.

[0413] Step C): Synthesis of diazomethylphosphane derivative 4 and regeneration of Ni(CO) 4 ​​

[0414] At room temperature, under a CO atmosphere, without stirring, THF was slowly added to the newly formed nitrogen-containing organic compound 3 (0.305 g, 0.617 mmol). Then the reaction mixture was stirred vigorously. After stirring for 4 hours, according to the NMR spectrum, Ni(CO) 4 and the diazomethylphosphine derivative 4 were formed in quantitative yield. The reaction mixture was filtered, and all volatiles were evaporated from the filtrate to obtain the diazomethylphosphine derivative 4.

[0415] Example 31:

[0416] A method for directly synthesizing nitrogen-containing organic compounds from nitrogen, with the technical route as follows:

[0417]

[0418] i-Pr2 is isopropyl; Ph is phenyl; Et is ethyl;

[0419] Including the following steps:

[0420] Step A): Formation of the carbene intermediate 2

[0421] At -30 °C to -80 °C, under a nitrogen atmosphere, without stirring, THF (40 mL) was slowly added to a mixture of the P-S bis(ylide) derivative 1 ((1.00 g, 2.42 mmol) and an excess of Ni(CO) 4 . The formation of the novel carbene intermediate 2 was monitored by NMR spectroscopy at low temperature.

[0422] Step B): Synthesis of the nitrogen-containing organic compound 3

[0423] Then the reaction mixture was warmed to room temperature while stirring the reaction mixture vigorously. After stirring for 4 hours, the formation of the novel nitrogen-containing organic compound 3 was monitored by NMR spectroscopy. The reaction mixture solution was concentrated to obtain the solid novel nitrogen-containing organic compound 3.

[0424] Step C): Synthesis of the diazomethylphosphine derivative 4 and the 4 recovery of Ni(CO)

[0425] At room temperature, under a CO atmosphere, without stirring, THF was slowly added to the newly formed nitrogen-containing organic compound 3 (0.346 g, 0.699 mmol). Then the reaction mixture was stirred vigorously. After stirring for 4 hours, according to the NMR spectrum, Ni(CO) 4 and the diazomethylphosphine derivative 4 were formed in quantitative yield. The reaction mixture was filtered, and all volatiles were evaporated from the filtrate to obtain the diazomethylphosphine derivative 4.

[0426] Example 32:

[0427] A method for directly synthesizing nitrogen-containing organic compounds from nitrogen, with the technical route as follows:

[0428]

[0429] i-Pr2 is isopropyl; Ph is phenyl; Pr is propyl;

[0430] Including the following steps:

[0431] Step A): Formation of carbene intermediate 2

[0432] At -30 °C to -80 °C, under a nitrogen atmosphere, without stirring, slowly add THF (40 mL) to a mixture of P-S bis(ylide) derivative 1 ((1.00 g, 2.26 mmol) and excess Ni(CO) 4 Monitor the formation of the novel carbene intermediate 2 by NMR spectroscopy at low temperature.

[0433] Step B): Synthesis of nitrogen-containing organic compound 3

[0434] Then raise the temperature of the reaction mixture to room temperature while vigorously stirring the reaction mixture. After stirring for 4 hours, the formation of the novel nitrogen-containing organic compound 3 can be monitored by NMR spectroscopy. Concentrate the reaction mixture solution to obtain the solid novel nitrogen-containing organic compound 3.

[0435] Step C): Synthesis of diazomethylphosphine derivative 4 and regeneration of Ni(CO) 4 regeneration

[0436] At room temperature, under a CO atmosphere, without stirring, slowly add THF to the newly formed nitrogen-containing organic compound 3 (0.380 g, 0.767 mmol). Then vigorously stir the reaction mixture. After stirring for 4 hours, as shown by NMR spectroscopy, Ni(CO) 4 and diazomethylphosphine derivative 4 are formed in quantitative yield. Filter the reaction mixture and evaporate all volatiles from the filtrate to obtain diazomethylphosphine derivative 4.

[0437] Example 33:

[0438] A method for directly synthesizing nitrogen-containing organic compounds from nitrogen, with the technical route as follows:

[0439]

[0440] R = i-Pr 2 N,i-Pr 2 is isopropyl; Ph is phenyl; Me is methyl;

[0441] It includes the following steps:

[0442] Step A): Formation of carbene intermediate 2

[0443] Under the conditions of -30°C to -80°C, nitrogen atmosphere, and without stirring, slowly add THF (40 mL) to the mixture of P-S bis(ylide) derivative 1 ((1.00 g, 2.25 mmol) and excess potassium tetrachloroplatinate(II) K 2 [PtCl 4 2- . Monitor the formation of the novel carbene intermediate 2 by NMR spectroscopy at low temperature.

[0444] Step B): Synthesis of nitrogen-containing organic compound 3

[0445] Then raise the temperature of the reaction mixture to room temperature while vigorously stirring the reaction mixture. After stirring for 4 hours, the formation of the novel nitrogen-containing organic compound 3 can be monitored by NMR spectroscopy. Concentrate the reaction mixture solution to obtain the solid novel nitrogen-containing organic compound 3.

[0446] Step C): Synthesis of diazomethylenephosphane derivative 4 and recovery of potassium tetrachloroplatinate(II) K 2 [PtCl 4 2-

[0447] Under the conditions of room temperature and without stirring, slowly add THF to the mixture of the newly formed nitrogen-containing organic compound 3 (0.568 g, 0.624 mmol) and excess potassium chloride. Then vigorously stir the reaction mixture. After stirring for 4 hours, according to the NMR spectroscopy, potassium tetrachloroplatinate(II) K 2 [PtCl 4 2- and diazomethylenephosphane derivative 4 are formed in quantitative yield. Filter the reaction mixture and evaporate all volatiles from the filtrate to obtain diazomethylenephosphane derivative 4.

[0448] Example 34:

[0449] Method for directly synthesizing nitrogen-containing organic compounds from nitrogen, the technical route is as follows:

[0450]

[0451] R = i-Pr 2 N,i-Pr 2 is isopropyl; Ph is phenyl; Me is methyl;

[0452] It includes the following steps:

[0453] ​​​​Step A): Formation of carbene intermediate 2

[0454] At -30 °C to -80 °C, under a nitrogen atmosphere and without stirring, slowly add THF (40 mL) to a mixture of P-S bis(ylide) derivative 1 ((1.00 g, 2.25 mmol) and an excess of W(CO) 6 The formation of the novel carbene intermediate 2 was monitored by NMR spectroscopy at low temperature.

[0455] Step B): Synthesis of nitrogen-containing organic compound 3

[0456] Then, allow the reaction mixture to warm to room temperature while vigorously stirring the reaction mixture. After stirring for 4 hours, the formation of the novel nitrogen-containing organic compound 3 could be monitored by NMR spectroscopy. Concentrate the reaction mixture solution to obtain the solid novel nitrogen-containing organic compound 3.

[0457] Step C): Synthesis of diazomethylenephosphorane derivative 4 and regeneration of W(CO) 6 Regeneration

[0458] At room temperature, under a CO atmosphere and without stirring, slowly add THF to the newly formed nitrogen-containing organic compound 3 (0.376 g, 0.617 mmol). Then, vigorously stir the reaction mixture. After stirring for 4 hours, as shown by NMR spectroscopy, W(CO) 6 and diazomethylenephosphorane derivative 4 were formed in quantitative yield. Filter the reaction mixture and evaporate all volatiles from the filtrate to obtain diazomethylenephosphorane derivative 4.

[0459] The foregoing has shown and described the basic principles, principal features and advantages of the invention. Those skilled in the art should understand that the above embodiments do not limit the invention in any way, and all technical solutions obtained by means of equivalent substitution or equivalent transformation fall within the scope of protection of the invention.

Claims

1. A method for directly synthesizing nitrogen-containing organic compounds from nitrogen, comprising the following steps: The P-S bis(ylide) derivative 1 having a phosphonium ylide and a sulfonium ylide functional group reacts with N 2 in the presence of a transition metal complex MLn to directly convert N 2 into a nitrogen-containing organic compound 3; The P-S bis(ylide) derivative 1 reacts with the transition metal complex MLn at room temperature to form the carbene intermediate 2; then the carbene intermediate 2 reacts with N 2 to produce the nitrogen-containing organic compound 3; The P-S bis(ylide) derivative 1 has the structure shown in Formula I: In Formula I: R 1 is selected from alkyl or aryl, R 2 , R 3 are each independently selected from alkylamines, R 2 , R 3 are the same or different; R 4 , R 5 are independent organic groups, selected from aryl or alkyl, R 4 , R 5 are the same or different; In the general structural formula of the transition metal complex MLn: M is selected from transition metal atoms or ions, and L is selected from Lewis base ligands; the transition metal atom or ion is nickel, platinum, tungsten, molybdenum or chromium, and the Lewis base ligand is carbonyl or chloride ion with a valence of -1, and n is an integer greater than 1; The carbene intermediate 2 has the structure shown in Formula II: In formula II, R 1 , R 2 , R 3 have the same meanings as in formula I; M, L, and n have the same meanings as M, L, and n in the general formula of the transition metal complex MLn; The nitrogen-containing organic compound 3 has the structure shown in Formula III: In formula III, R 1 , R 2 , R 3 have the same meanings as in formula I; M, L, and n have the same meanings as M, L, and n in the general formula of the transition metal complex MLn.

2. The method for directly synthesizing nitrogen-containing organic compounds from nitrogen according to claim 1, characterized in that the molar ratio of the P-S bis(ylide) derivative 1 to the transition metal complex MLn is less than 1:

1.

3. The method for directly synthesizing nitrogen-containing organic compounds from nitrogen according to claim 1, characterized in that the alkyl group is methyl, ethyl or propyl, the aryl group is phenyl, and the alkylamine is diisopropylamino or N,N'-diisopropylethylenediamino.

4. A catalytic cycle process for directly synthesizing nitrogen-containing organic compounds from nitrogen, comprising the following steps: The P-S bis(ylide) derivative 1 reacts with N 2 in the presence of a transition metal complex MLn to directly convert N 2 into a nitrogen-containing organic compound 3. Reacting the nitrogen-containing organic compound 3 with the corresponding L ligand enables the recovery of the transition metal complex MLn while obtaining another nitrogen-containing organic compound, a diazaphosphorane derivative 4; The P-S bis(ylide) derivative 1 has the structure shown in Formula I: In formula I: R 1 is selected from alkyl or aryl, R 2 , R 3 are each independently selected from alkylamines, R 2 , R 3 are the same or different; R 4 , R 5 are independent organic groups, selected from aryl or alkyl, R 4 , R 5 are the same or different; In the general structural formula of the transition metal complex MLn: M is selected from transition metal atoms or ions, and L is selected from Lewis base ligands; the transition metal atom or ion is nickel, platinum, tungsten, molybdenum or chromium, and the Lewis base ligand is carbonyl or chloride ion with a valence of -1, and n is an integer greater than 1; The nitrogen-containing organic compound 3 has the structure shown in Formula III: In formula III, R 1 , R 2 , R 3 have the same meanings as in formula I; M, L, and n have the same meanings as M, L, and n in the general formula of the transition metal complex MLn.

5. The catalytic cycle process for directly synthesizing nitrogen-containing organic compounds from nitrogen according to claim 4, characterized in that it comprises the following steps: Step A) Forming a carbene intermediate 2 by reacting the P-S bis(ylide) derivative 1 with MLn; Step B) Obtaining a nitrogen-containing organic compound 3 by reacting the carbene intermediate 2 with nitrogen; Step C) Restoration of MLn, and simultaneously forming a nitrogen-containing organic compound diazaphosphorane derivative 4; The carbene intermediate 2 has the structure shown in Formula II: In Formula II, R 1 , R 2 , R 3 have the same meanings as in Formula I; M, L, and n have the same meanings as M, L, and n in the general formula of the transition metal complex MLn; The nitrogen-containing organic compound diazaphosphorane derivative 4 has the structure shown in Formula IV: In formula IV, R 1 , R 2 , R 3 have the same meanings as in formula I.

6. The catalytic cycle process for directly synthesizing nitrogen-containing organic compounds from nitrogen according to claim 4, characterized in that the P-S bis(ylide) derivative 1 has the following structure:

7. The catalytic cycle process for directly synthesizing nitrogen-containing organic compounds from nitrogen according to claim 4, characterized in that The transition metal complex ML n is Ni(CO) 4 , potassium tetrachloroplatinate(II) K 2 [PtCl 4 2- or W(CO) 6 .​ 8. The catalytic cycle process for directly synthesizing nitrogen-containing organic compounds from nitrogen according to claim 4, characterized in that the nitrogen-containing organic compound 3 has the following structure: The nitrogen-containing organic compound diazaphosphorane derivative 4 has the following structure: Wherein: R = i-Pr 2 N,i-Pr 2 i-Pr is isopropyl; Ph is phenyl; Me is methyl.

9. The catalytic cycle process for directly synthesizing nitrogen-containing organic compounds from nitrogen according to claim 5, characterized in that the carbene intermediate 2 and the nitrogen-containing organic compound 3 are obtained by the following method: In the case of -30 °C to -80 °C, nitrogen atmosphere, without stirring, slowly add a solvent to a mixture of P-S bis(ylide) derivative 1 and Ni(CO) 4 to obtain the carbene intermediate 2; Then the reaction mixture is heated to room temperature, and while stirring the reaction mixture, the reaction mixture solution is concentrated to obtain the nitrogen-containing organic compound 3.

10. The catalytic cycle process for directly synthesizing nitrogen-containing organic compounds from nitrogen as claimed in claim 9, characterized in that, the solvent is THF.

11. The catalytic cycle process for directly synthesizing nitrogen-containing organic compounds from nitrogen as claimed in claim 5, characterized in that, the synthesis method from nitrogen-containing organic compound 3 to nitrogen-containing organic compound diazaphospholane derivative 4 is as follows: At room temperature and without stirring, a solvent is slowly added to a mixture of nitrogen-containing organic compound 3 and the corresponding ligand, then the reaction mixture is stirred, the reaction mixture is filtered, and the filtrate is evaporated to dryness to obtain another nitrogen-containing organic compound diazaphospholane derivative 4.

12. The catalytic cycle process for directly synthesizing nitrogen-containing organic compounds from nitrogen as claimed in claim 11, characterized in that, the solvent is THF.

Images