一类氮锑辛环烷基锑类衍生物及其合成方法
The synthesis of N-antimony octylcycloalkyl antimony derivatives via reductive coupling reaction solves the problem of poor stability of organoantimony compounds in traditional methods, achieving high-yield and low-cost synthesis of N-antimony octylcycloalkyl antimony derivatives, expanding the substrate range and improving functional group tolerance.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- HUNAN UNIV
- Filing Date
- 2022-07-16
- Publication Date
- 2026-05-19
AI Technical Summary
There are few types of organoantimony compounds in the existing technology, and traditional synthesis methods have problems such as poor stability, complicated operation and low selectivity, making it difficult to synthesize stable water-resistant and antioxidant organoantimony compounds.
A reducing coupling reaction was employed, using nickel acetylacetone as a catalyst, zinc powder as a reducing agent, anhydrous lithium chloride as an additive, and terpyridine as a ligand. The reaction was carried out in N,N-dimethylformamide solvent under a nitrogen atmosphere to synthesize N-antimony octylcycloalkyl antimony derivatives. The reaction conditions were mild and the operation was simple.
This method enables the high-yield, low-cost synthesis of nitrogen-antimony octylcycloalkyl antimony derivatives, expands the substrate range, improves functional group tolerance, and simplifies the operation process.
Smart Images
Figure CN115093448B_ABST
Abstract
Description
[Technical Field]
[0001] This invention belongs to the field of catalytic organic synthesis, and relates to a class of nitrogen-antimony octylcycloalkyl antimony derivatives and their synthetic methods. Specifically, it relates to a novel method for synthesizing nitrogen-antimony octylcycloalkyl antimony derivatives via a reductive coupling reaction between nitrogen-antimony octylcycloalkyl antimony halides and alkyl halide compounds under the conditions of nickel acetylacetonate as a catalyst and zinc powder as a reducing agent. This method uses nitrogen-antimony octylcycloalkyl antimony halides and alkyl halide compounds as main raw materials, nickel acetylacetonate as a catalyst, zinc powder as a reducing agent, anhydrous lithium chloride as an additive, and terpyridine as a ligand. Under N,N-dimethylformamide (DMF) as a solvent and a nitrogen atmosphere, the reaction proceeds for 12 hours to obtain nitrogen-antimony octylcycloalkyl antimony derivatives in high yield. [Background Technology]
[0002] Organoantimony compounds, as organometallic compounds, have been extensively studied. Due to their unique biological activities, they are widely used in anti-inflammatory, antibacterial, and antitumor research. Their special catalytic activity has led to their use as Lewis acid catalysts in Friedel-Crafts alkylation, Friedel-Crafts acylation, and Mannich reactions. Due to their unique coordination properties, they have been synthesized into various chelating ligands such as NCN, OCO, and NCN. Furthermore, due to their excellent reactivity, they are also used as arylating, alkenylating, and alkynylating agents. However, the variety of organoantimony compounds remains relatively small, mainly due to: 1) the lack of a stable core framework, resulting in fewer stable, water-resistant, and antioxidant organoantimony compounds; and 2) the lack of effective methods for directly synthesizing organoantimony compounds. Therefore, developing new methods for synthesizing stable, water-resistant, and antioxidant organoantimony compounds is essential.
[0003] Over the past decade, the synthesis of organoantimony compounds and their derivatives has primarily relied on highly reactive organometallic reagents, such as common organolithium, Grignard, and organozinc reagents. However, these highly reactive organometallic reagents are known to have limitations: a) they are generally water- and oxygen-sensitive; b) they require harsh reaction conditions, typically very low temperatures, making operation inconvenient; c) they exhibit low functional group tolerance; and d) their high reactivity leads to low selectivity. Compared to traditional coupling reactions, reductive coupling reactions offer the following advantages: 1) reductive coupling reactions require milder reaction conditions and generally only require inexpensive transition metal catalysts, such as nickel, iron, and cobalt, and inexpensive elemental reducing agents such as zinc and manganese powder; 2) reductive coupling reactions exhibit high chemoselectivity; and 3) they have good substrate functional group tolerance. Therefore, based on the research background of organoantimony compounds and the limitations of traditional organoantimony compound synthesis methods, and combining the advantages of reduction reactions, this patent proposes to adopt a reductive coupling strategy to construct C(sp) compounds using a stable nitrogen-antimony octyl ring as the core skeleton. 3 The -Sb bond is broken, resulting in a series of water- and antioxidant N-antimony octylcycloalkylantimony compounds. Current research indicates that the construction of most carbon-metal bonds still utilizes traditional highly reactive organometallic reagents. This reductive coupling reaction is used for C(sp... 3 The construction of the α-Sb bond provides a new approach to the construction of carbon-metal bonds, significantly shortens the synthetic route, improves efficiency, and most importantly, greatly expands the substrate range and enhances the tolerance of functional groups. We designed mild reaction conditions and optimized the reaction conditions using N-antimony octylcycloalkyl antimony halides and alkyl halides as templates and substrates. Finally, we established a method using nickel acetylacetone as a catalyst, zinc powder as a reducing agent, anhydrous lithium chloride as an additive, terpyridine as a ligand, and N,N-dimethylformamide as a reaction solvent to successfully synthesize N-antimony octylcycloalkyl antimony derivatives. This method requires no special equipment. [Summary of the Invention]
[0004] The purpose of this invention is to provide a class of nitrogen-antimony octylcycloalkyl antimony derivatives and their preparation method. This catalytic synthesis method uses nickel acetylacetone as a catalyst, N,N-dimethylformamide as a reaction solvent, and a nitrogen atmosphere, reacting at 100 degrees Celsius for 12 hours to obtain nitrogen-antimony octylcycloalkyl antimony derivatives in high yield. This method has advantages such as low cost, high yield, simple operation, and no pollution, and is feasible for industrial production. To achieve the above-mentioned objective, this invention proposes the following technical solution:
[0005] To achieve the above-mentioned objectives, the present invention proposes the following technical solution:
[0006] A class of N-antimony octyl ring organic antimony halide derivatives I and II, and their synthetic methods, wherein the structural formulas of N-antimony octyl ring organic antimony halide derivatives I and II are as follows:
[0007]
[0008] Wherein R is selected from cyclohexyl, tert-butyl, phenyl, 4-tert-butylphenyl, 2-ethylphenyl, 3-ethylphenyl, 3,5-dimethylphenyl; Alkyl is selected from methyl, n-butyl, n-octyl, n-dodecyl, n-hexadecyl, n-octadecyl, 2-phenylethyl, 3-phenylpropyl, 4-phenylbutyl, 2-(4-fluorophenyl)ethyl, 2-(4-nitrophenyl)ethyl, 5-chloropentyl, 3-(trimethoxy)silylpropyl, 2-Thiophenylethyl, 3-(dimethyltert-butylsiloxy)propyl, 3-(diethylamino)propyl, 2-(ethoxycarbonyl)ethyl, 4-cyanobutyl, 4-methoxybutyl, 4-alkynylbutyl, 4-fluorobutyl, 4-carbonylpentyl, 2-alkenylethyl; X is selected from fluorine, chlorine, bromine, and iodine; wherein the green catalytic synthesis method of compound III is characterized by using nickel acetylacetone as a catalyst, using antimony octanecycloantimony halide I and alkyl halide II as reactants, reacting effectively at 100°C in N,N-dimethylformamide solvent, and obtaining high yields of antimony octanecycloalkylantimony derivatives III within 12 hours;
[0009] The present invention provides a highly efficient catalytic synthesis method for a class of nitrogen-antimony octylcycloalkyl antimony derivatives, opening up a new low-cost "green" route. Its advantages are: the sources of alkyl halides as raw materials are more extensive, the yield of the target product is higher, the reaction conditions are mild, and the reaction operation is simple. [Attached Image Description]
[0010]
[0011] Figure 1 The diagram shown is a roadmap for preparing nitrogen-antimony octylcycloalkyl antimony derivatives provided by the present invention.
Detailed Implementation Methods
[0012] The present invention provides a highly efficient catalytic synthesis method for a class of nitrogen-antimony octylcycloalkyl antimony derivatives, as shown in the attached figure: 0.20 mmol of nitrogen-antimony octylcycloalkyl antimony halide and 0.3 mmol of alkyl halide are added to a 10 mL reaction tube, along with 0.1 mmol of nickel acetylacetone catalyst, 2.0 equivalents of zinc powder, 0.1 equivalents of terpyridine, 2.0 equivalents of anhydrous lithium chloride, and 1.5 mL of N,N-dimethylformamide solvent. The reaction is carried out at 100 °C for 12 hours to obtain the target compound, nitrogen-antimony octylcycloalkyl antimony derivative.
[0013] The invention will be further illustrated below with specific preparation examples:
[0014] Preparation Example 1
[0015] N-phenylantimony(R=phenyl, X=10mL) was added to a 10mL reaction tube. 1 =CI)0.20mmol and 2-chloroethylbenzene (Alkyl = 2-phenylethyl, X 2 =0.30 mmol of nickel acetylacetone, 0.02 mmol of zinc powder, 0.40 mmol of anhydrous lithium chloride, 0.40 mmol of terpyridine, and 1.5 mL of N,N-dimethylformamide were added. The reaction was carried out at 100 °C for 12 h. After the reaction was completed, N-phenylantimony octylcyclophenylethyl antimony derivatives (R = Ph, Alkyl = 2-phenylethyl) were separated by column chromatography to give a white solid in 88% yield.
[0016] Its NMR structure data are as follows;
[0017] 1 H NMR (400MHz, CDCl3) δ7.56–7.51(m,2H),7.32(d,J=4.1Hz,4H),7.25–7.22(m,7H),7.19–7.16(m, 2H), 6.99 (d, J = 8.0Hz, 2H), 6.89 (t, J = 7.3Hz, 1H), 4.66 (d, J = 15.0Hz, 2H), 4.32 (d, J = 15.0Hz, 2H), 3.07–2.99 (m, 2H), 2.15–2.08 (m, 2H).
[0018] 13 C NMR (101MHz, CDCl3) δ148.8,145.2,144.1,134.6,133.9,128.9,128.5,128.2,128.1,127.9,126.9,125.8,120.6,116.3,56.9,33.8,20.7.
[0019] Preparation Example 2
[0020] N-phenylantimony(R=phenyl, X=10mL) was added to a 10mL reaction tube. 1 =CI)0.20mmol and 3-chloropropylbenzene (Alkyl = 3-phenylpropyl, X 2=0.30 mmol of nickel acetylacetonate, 0.02 mmol of zinc powder, 0.40 mmol of anhydrous lithium chloride, 0.40 mmol of terpyridine, and 1.5 mL of N,N-dimethylformamide were added. The reaction was carried out at 100 °C for 12 h. After the reaction was completed, N-phenylantimony octylcyclophenylpropyl antimony derivatives (R = Ph, Alkyl = 3-phenylpropyl) were separated by column chromatography to give a white solid in 84% yield.
[0021] Preparation Example 3
[0022] N-phenylantimony(R=phenyl, X=10mL) was added to a 10mL reaction tube. 1 =CI)0.20mmol and 4-chlorobutylbenzene (Alkyl = 4-phenylbutyl, X 2 =0.30 mmol of nickel acetylacetone, 0.02 mmol of zinc powder, 0.40 mmol of anhydrous lithium chloride, 0.40 mmol of terpyridine, and 1.5 mL of N,N-dimethylformamide were added. The reaction was carried out at 100 °C for 12 h. After the reaction was completed, N-phenylantimony octyl phenylbutyl antimony derivatives (R = Ph, Alkyl = 4-phenylbutyl) were separated by column chromatography to give a white solid in 84% yield.
[0023] Preparation Example 4
[0024] N-phenylantimony(R=phenyl, X=10mL) was added to a 10mL reaction tube. 1 =CI)0.20mmol and 2-phenylthioethyl chloride (Alkyl = 2-phenylthioethyl, X 2 =0.30 mmol of nickel acetylacetone, 0.02 mmol of zinc powder, 0.40 mmol of anhydrous lithium chloride, 0.40 mmol of terpyridine, and 1.5 mL of N,N-dimethylformamide were added. The reaction was carried out at 100 °C for 12 h. After the reaction was completed, N-phenylazine octylcyclophenylthioethyl antimony derivatives (R = Ph, Alkyl = 2-phenylthioethyl) were separated by column chromatography to give a white solid in 78% yield.
[0025] Preparation Example 5
[0026] N-phenylantimony(R=phenyl, X=10mL) was added to a 10mL reaction tube. 1 =CI)0.20mmol and 3-(trimethoxysilylpropylchloro(Alkyl=3-(trimethoxysilyl)propyl, X 2=CI)0.30mmol, added 0.02mmol of nickel acetylacetonate, 0.40mmol of zinc powder, 0.40mmol of anhydrous lithium chloride, 0.02mmol of terpyridine, and 1.5mL of N,N-dimethylformamide. The reaction was carried out at 100℃ for 12h. After the reaction was completed, N-phenylazistinocyclo(3-(trimethoxysilyl)propyl)antimony derivative (R=Ph, Alkyl=3-(trimethoxysilyl)propyl) was separated by column chromatography to give a white solid in 68% yield.
[0027] Preparation Example 6
[0028] N-phenylantimony(R=phenyl, X=10mL) was added to a 10mL reaction tube. 1 =CI)0.20mmol and iodomethane (Alkyl = methyl, X 2 =I) 0.30 mmol, added 0.02 mmol of nickel acetylacetonate, 0.40 mmol of zinc powder, 0.40 mmol of anhydrous lithium chloride, 0.02 mmol of terpyridine, and 1.5 mL of N,N-dimethylformamide. The reaction was carried out at 100 °C for 12 h. After the reaction was completed, N-phenylantimony octyl methyl antimony derivatives (R = Ph, Alkyl = methyl) were separated by column chromatography to give a white solid in 78% yield.
[0029] Preparation Example 7
[0030] N-phenylantimony(R=phenyl, X=10mL) was added to a 10mL reaction tube. 1 =CI)0.20mmol and 1-chloro-5-bromopentane (Alkyl=5-chloropentyl, X 2 0.30 mmol of (Br) was added, along with 0.02 mmol of nickel acetylacetonate, 0.40 mmol of zinc powder, 0.40 mmol of anhydrous lithium chloride, 0.02 mmol of terpyridine, and 1.5 mL of N,N-dimethylformamide. The reaction was carried out at 100 °C for 12 h. After the reaction was completed, N-phenylazine octyl ring 5-chloropentyl antimony derivative (R = Ph, Alkyl = 5-chloropentyl) was separated by column chromatography to give a white solid in 77% yield.
[0031] Preparation Example 8
[0032] N-phenylantimony(R=phenyl, X=10mL) was added to a 10mL reaction tube. 1 =CI)0.20mmol and 3-(dimethyl tert-butylsilyl)propyl chloride (Alkyl=3-(dimethyl tert-butylsilyl)propyl, X 2=CI)0.30mmol, added 0.02mmol of nickel acetylacetonate, 0.40mmol of zinc powder, 0.40mmol of anhydrous lithium chloride, 0.02mmol of terpyridine, and 1.5mL of N,N-dimethylformamide. The reaction was carried out at 100℃ for 12h. After the reaction was completed, the N-phenylazine octylcyclo-3-(dimethyl tert-butylsilyl ether)propyl antimony derivative (R = Ph, Alkyl = 3-(dimethyl tert-butylsilyl ether)propyl) was separated by column chromatography to give a white solid in 74% yield.
[0033] Preparation Example 9
[0034] N-phenylantimony(R=phenyl, X=10mL) was added to a 10mL reaction tube. 1 =CI)0.20mmol and 2-(ethoxycarbonyl)ethyl chloride (Alkyl=2-(ethoxycarbonyl)ethyl, X 2 =CI)0.30mmol, added 0.02mmol of nickel acetylacetone, 0.40mmol of zinc powder, 0.40mmol of anhydrous lithium chloride, 0.02mmol of terpyridine, and 1.5mL of N,N-dimethylformamide. The reaction was carried out at 100℃ for 12h. After the reaction was completed, the N-phenylazantimony octyl ring 2-(ethoxycarbonyl)ethyl antimony derivative (R=Ph, Alkyl=2-(ethoxycarbonyl)ethyl) was separated by column chromatography to give a white solid in 72% yield.
[0035] Preparation Example 10
[0036] N-phenylantimony(R=phenyl, X=10mL) was added to a 10mL reaction tube. 1 =CI)0.20mmol and 4-cyano-1-chlorobutane (Alkyl = 2-phenylethyl, X 2 =0.30 mmol of nickel acetylacetonate, 0.02 mmol of zinc powder, 0.40 mmol of anhydrous lithium chloride, 0.40 mmol of terpyridine, and 1.5 mL of N,N-dimethylformamide were added. The reaction was carried out at 100 °C for 12 h. After the reaction was completed, N-phenylazantimonyoctylcyclo-4-cyanobutane antimony derivative (R = Ph, Alkyl = 4-cyanobutyl) was separated by column chromatography to give a white solid in 76% yield.
[0037] Preparation Example 11
[0038] N-phenylantimony(R=phenyl, X=10mL) was added to a 10mL reaction tube. 1 =CI)0.20mmol and 3-(dimethoxymethyl)1-chloropropane (Alkyl=3-(dimethoxymethyl)propyl, X2 =0.30 mmol of nickel acetylacetonate, 0.02 mmol of zinc powder, 0.40 mmol of anhydrous lithium chloride, 0.40 mmol of terpyridine, and 1.5 mL of N,N-dimethylformamide were added. The reaction was carried out at 100 °C for 12 h. After the reaction was completed, N-phenylazistinocyclo(3-(dimethoxymethyl)propyl) antimony derivative (R = Ph, Alkyl = 3-(dimethoxymethyl)propyl) was separated by column chromatography to give a white solid in 84% yield.
[0039] Preparation Example 12
[0040] N-phenylantimony(R=phenyl, X=10mL) was added to a 10mL reaction tube. 1 =CI)0.20mmol and 1-bromo-3-butene (Alkyl=3-butenyl, X 2 0.30 mmol of (Br) was added, along with 0.02 mmol of nickel acetylacetonate, 0.40 mmol of zinc powder, 0.40 mmol of anhydrous lithium chloride, 0.02 mmol of terpyridine, and 1.5 mL of N,N-dimethylformamide. The reaction was carried out at 100 °C for 12 h. After the reaction was completed, N-phenylazine-antimony octylcyclo-3-butenyl antimony derivatives (R = Ph, Alkyl = 3-butenyl) were separated by column chromatography to give a white solid in 69% yield.
[0041] Preparation Example 13
[0042] N-phenylantimony(R=phenyl, X=10mL) was added to a 10mL reaction tube. 1 =CI)0.20mmol and 4-carbonyl-1-chloropentane (Alkyl=4-carbonylpentyl, X 2 =0.30 mmol of nickel acetylacetone, 0.02 mmol of zinc powder, 0.40 mmol of anhydrous lithium chloride, 0.40 mmol of terpyridine, and 1.5 mL of N,N-dimethylformamide were added. The reaction was carried out at 100 °C for 12 h. After the reaction was completed, N-phenylazine octyl ring 4-carbonylpentyl antimony derivative (R = Ph, Alkyl = 4-carbonylpentyl) was separated by column chromatography to give a white solid in 66% yield.
[0043] Preparation Example 14
[0044] N-phenylantimony(R=phenyl, X=10mL) was added to a 10mL reaction tube. 1 =CI)0.20mmol and 4-fluoro-1-chlorobutane (Alkyl=4-fluorobutyl, X 2=0.30 mmol of nickel acetylacetonate, 0.02 mmol of zinc powder, 0.40 mmol of anhydrous lithium chloride, 0.40 mmol of terpyridine, and 1.5 mL of N,N-dimethylformamide were added. The reaction was carried out at 100 °C for 12 h. After the reaction was completed, N-phenylazine octyl ring 4-fluorobutyl antimony derivative (R = Ph, Alkyl = 4-fluorobutyl) was separated by column chromatography to give a white solid with a yield of 79%.
[0045] Preparation Example 15
[0046] N-phenylantimony(R=phenyl, X=10mL) was added to a 10mL reaction tube. 1 =CI)0.20mmol and 1-chloro-5-hexyne (Alkyl=50 hexyne group, X 2 =CI)0.30mmol, added 0.02mmol of nickel acetylacetone, 0.40mmol of zinc powder, 0.40mmol of anhydrous lithium chloride, 0.02mmol of terpyridine, and 1.5mL of N,N-dimethylformamide. The reaction was carried out at 100℃ for 12h. After the reaction was completed, N-phenylazantimonyoctylcyclohexynylantimony derivatives (R=Ph, Alkyl=2-phenylethyl) were separated by column chromatography to give a white solid in 74% yield.
[0047] Preparation Example 16
[0048] N-phenylantimony(R=phenyl, X=10mL) was added to a 10mL reaction tube. 1 =CI)0.20mmol and 4-methoxy-1-chlorobutane (Alkyl = 4-methoxybutyl, X 2 =0.30 mmol of nickel acetylacetonate, 0.02 mmol of zinc powder, 0.40 mmol of anhydrous lithium chloride, 0.40 mmol of terpyridine, and 1.5 mL of N,N-dimethylformamide were added. The reaction was carried out at 100 °C for 12 h. After the reaction was completed, N-phenylazine octyl ring 4-methoxybutyl antimony derivative (R = Ph, Alkyl = 4-methoxybutyl) was separated by column chromatography to give a white solid in 80% yield.
[0049] Preparation Example 17
[0050] N-phenylantimony(R=phenyl, X=10mL) was added to a 10mL reaction tube. 1 =CI)0.20mmol and 1-chlorobutane (Alkyl=butyl, X 2=0.30 mmol of nickel acetylacetonate, 0.02 mmol of zinc powder, 0.40 mmol of anhydrous lithium chloride, 0.40 mmol of terpyridine, and 1.5 mL of N,N-dimethylformamide were added. The reaction was carried out at 100 °C for 12 h. After the reaction was completed, N-phenylazine octylcyclobutyl antimony derivatives (R = Ph, Alkyl = butyl) were separated by column chromatography to give a white solid in 83% yield.
[0051] Preparation Example 18
[0052] N-phenylantimony(R=phenyl, X=10mL) was added to a 10mL reaction tube. 1 =CI)0.20mmol and 1-n-octyl chloride (Alkyl = n-octyl, X 2 =0.30 mmol of nickel acetylacetone, 0.02 mmol of zinc powder, 0.40 mmol of anhydrous lithium chloride, 0.40 mmol of terpyridine, and 1.5 mL of N,N-dimethylformamide were added. The reaction was carried out at 100 °C for 12 h. After the reaction was completed, N-phenylazine antimony octyl ring n-octyl antimony derivatives (R = Ph, Alkyl = n-octyl) were separated by column chromatography to give a white solid in 83% yield.
[0053] Preparation Example 19
[0054] N-phenylantimony(R=phenyl, X=10mL) was added to a 10mL reaction tube. 1 =CI)0.20mmol and n-dodecyl chloride (Alkyl=n-dodecyl, X 2 =0.30 mmol of nickel acetylacetone, 0.02 mmol of zinc powder, 0.40 mmol of anhydrous lithium chloride, 0.40 mmol of terpyridine, and 1.5 mL of N,N-dimethylformamide were added. The reaction was carried out at 100 °C for 12 h. After the reaction was completed, N-phenylazine-antimony octyl ring n-dodecyl antimony derivative (R = Ph, Alkyl = n-dodecyl) was separated by column chromatography to give a white solid in 78% yield.
[0055] Preparation Example 20
[0056] N-phenylantimony(R=phenyl, X=10mL) was added to a 10mL reaction tube. 1 =CI)0.20mmol and n-hexadecyl chloride (Alkyl = n-hexadecyl, X 2=CI)0.30mmol, added 0.02mmol of nickel acetylacetonate, 0.40mmol of zinc powder, 0.40mmol of anhydrous lithium chloride, 0.02mmol of terpyridine, and 1.5mL of N,N-dimethylformamide. The reaction was carried out at 100℃ for 12h. After the reaction was completed, the N-phenylazantimony octylcyclohexadecyl antimony derivative (R=Ph, Alkyl=n-hexadecyl) was separated by column chromatography to give a white solid in 76% yield.
[0057] Preparation Example 21
[0058] N-phenylantimony(R=phenyl, X=10mL) was added to a 10mL reaction tube. 1 =CI)0.20mmol and n-octadecyl chloride (Alkyl = n-octadecyl, X 2 =0.30 mmol of nickel acetylacetonate, 0.02 mmol of zinc powder, 0.40 mmol of anhydrous lithium chloride, 0.40 mmol of terpyridine, and 1.5 mL of N,N-dimethylformamide were added. The reaction was carried out at 100 °C for 12 h. After the reaction was completed, N-phenylazine-antimony octylcycloetradecyl antimony derivative (R = Ph, Alkyl = n-octyl) was separated by column chromatography to give a white solid in 70% yield.
[0059] Preparation Example 22
[0060] N-tert-butylantimony(R = tert-butyl, X) chloride was added to a 10 mL reaction tube. 1 =CI)0.20mmol and 2-chloroethylbenzene (Alkyl = 2-phenylethyl, X 2 =0.30 mmol of nickel acetylacetone, 0.02 mmol of zinc powder, 0.40 mmol of anhydrous lithium chloride, 0.40 mmol of terpyridine, and 1.5 mL of N,N-dimethylformamide were added. The reaction was carried out at 100 °C for 12 h. After the reaction was completed, N-tert-butylantimony(R) octyl cycloantimony phenethyl antimony derivative (R = tert-butyl, Alkyl = 2-phenylethyl) was obtained by column chromatography to give a white solid in 70% yield.
[0061] Preparation Example 23
[0062] Add N-cyclohexylantimony(R = cyclohexyl, X) to a 10 mL reaction tube. 1 =CI)0.20mmol and 2-chloroethylbenzene (Alkyl = 2-phenylethyl, X 2=CI)0.30mmol, added 0.02mmol of nickel acetylacetone, 0.40mmol of zinc powder, 0.40mmol of anhydrous lithium chloride, 0.02mmol of terpyridine, and 1.5mL of N,N-dimethylformamide. The reaction was carried out at 100℃ for 12h. After the reaction was completed, N-phenylantimony(R)-Cy, Alkyl=2-phenylethyl antimony derivatives were obtained by column chromatography to give a white solid with a yield of 68%.
[0063] Preparation Example 24
[0064] Add N-(4-tert-butyl)phenyl azirmonoantimony chloride (R = (4-tert-butyl)phenyl, X) to a 10 mL reaction tube. 1 =CI)0.20mmol and 2-chloroethylbenzene (Alkyl = 2-phenylethyl, X 2 =CI)0.30mmol, added 0.02mmol of nickel acetylacetone, 0.40mmol of zinc powder, 0.40mmol of anhydrous lithium chloride, 0.02mmol of terpyridine, and 1.5mL of N,N-dimethylformamide. The reaction was carried out at 100℃ for 12h. After the reaction was completed, N-(4-tert-butyl)phenyl antimony octylcycloantimony phenethyl antimony derivatives (R=(4- t Bu)Ph, Alkyl (2-phenylethyl), yielded a white solid in 87% yield.
[0065] Preparation Example 25
[0066] Add N-(3,5-dimethyl)phenylantimony(N,N,O, ... 1 =CI)0.20 mmol and 2-chloroethylbenzene (Alkyl = 2-phenylethyl, X 2 =0.30 mmol of nickel acetylacetone, 0.02 mmol of zinc powder, 0.40 mmol of anhydrous lithium chloride, 0.40 mmol of terpyridine, and 1.5 mL of N,N-dimethylformamide were added. The reaction was carried out at 100 °C for 12 h. After the reaction was completed, N-(3,5-dimethyl)phenyl-azomoni ...
[0067] Preparation Example 26
[0068] Add N-(2-ethyl)phenylazine-antimony-octane-antimony chloride (R = (2-ethyl)phenyl, X) to a 10 mL reaction tube. 1=CI)0.20mmol and 2-chloroethylbenzene (Alkyl = 2-phenylethyl, X 2 =0.30 mmol of nickel acetylacetone, 0.02 mmol of zinc powder, 0.40 mmol of anhydrous lithium chloride, 0.40 mmol of terpyridine, and 1.5 mL of N,N-dimethylformamide were added. The reaction was carried out at 100 °C for 12 h. After the reaction was completed, N-(2-ethyl)phenylazine-antimony-octylcycloantimony-phenethyl antimony derivatives (R = (2-ethyl)phenyl, Alkyl = 2-phenylethyl) were separated by column chromatography to give a white solid in 68% yield.
[0069] Preparation Example 27
[0070] Add N-(3-ethyl)phenylazine-antimony-octane-antimony chloride (R = (3-ethyl)phenyl, X) to a 10 mL reaction tube. 1 =CI)0.20mmol and 2-chloroethylbenzene (Alkyl = 2-phenylethyl, X 2 =0.30 mmol of nickel acetylacetone, 0.02 mmol of zinc powder, 0.40 mmol of anhydrous lithium chloride, 0.40 mmol of terpyridine, and 1.5 mL of N,N-dimethylformamide were added. The reaction was carried out at 100 °C for 12 h. After the reaction was completed, N-(3-ethyl)phenylazine-antimony-octylcycloantimony-phenethyl antimony derivatives (R = (3-ethyl)phenyl, Alkyl = 2-phenylethyl) were separated by column chromatography to give a white solid in 89% yield.
[0071] The embodiments described above are merely illustrative of several implementations of the present invention, and while the descriptions are specific and detailed, they should not be construed as limiting the scope of the present invention. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of the present invention, and these modifications and improvements all fall within the scope of protection of the present invention. Therefore, the scope of protection of this patent should be determined by the appended claims.
Claims
1. A method for synthesizing a class of alkyl-antimony-nitrogen-antimony-octyl ring organoantimony derivatives III, characterized in that, Using antimony-nitrogen-antimony-octyl ring antimony halide I and alkyl halide II as reactants, nickel acetylacetonate as catalyst (10%), zinc powder as reducing agent (2 equivalents), terpyridine as ligand (0.1 equivalents), anhydrous lithium chloride as additive (2 equivalents), and N,N-dimethylformamide (DMF) as solvent, the reaction was carried out at 100 °C for 12 h to obtain alkylantimony-nitrogen-antimony-octyl ring organoantimony derivative III. ， R is one of phenyl, tert-butyl, cyclohexyl, 4-tert-butylphenyl, 3,5-dimethylphenyl, 2-ethylphenyl, and 3-ethylphenyl; X 1 X 2 It is one of F, CI, Br, and I; Alkyl is one of methyl, ethyl, butyl, pentyl, hexyl, octyl, dodecyl, hexadecyl, octadecyl, 2-phenylethyl, 3-phenylpropyl, 4-phenylbutyl, 5-chloropentyl, 3-(trimethoxy)silylpropyl, 2-phenylthioethyl, 3-(dimethyltert-butylsiloxy)propyl, 3-diethylaminopropyl, 2-(ethoxycarbonyl)ethyl, 4-cyanobutyl, 3-(dimethoxymethyl)propyl, 2-(4-fluorophenyl)ethyl, 2-(4-nitrophenyl)ethyl, 4-methoxybutyl, 4-hexynyl, 4-fluorobutyl, 4-carbonylpentyl, and 3-butenyl.