A class of nitrogen antimony octane sulfur / selenium derivatives and their efficient synthesis method

Abstract

The present invention discloses a class of nitrogen antimony octane antimony sulfur, antimony selenium derivatives and an efficient synthesis method thereof. The method uses nitrogen antimony octane organic antimony halide and disulfide, diselenide as raw materials, zinc powder as a promoter, and N,N-dimethylformamide as a reaction solvent to obtain nitrogen antimony octane antimony sulfur, antimony selenium derivative compounds in a high yield. The method has the advantages of low cost, high yield, simple operation, no pollution, etc., and has potential industrial application prospects. The method provides a cheap and green way for the preparation of nitrogen antimony octane antimony sulfur, antimony selenium derivative compounds.

Description

[Technical field]

[0001] The invention belongs to the field of organic synthesis, and relates to a class of nitrogen antimony octane sulfur / selenium derivatives and a synthesis method thereof, and specifically relates to disulfide, diselenide, under the action of a reducing agent such as zinc powder, reacts in an N,N-dimethylformamide solvent to form an active intermediate zinc compound, and the nitrogen antimony / bismuth octane organic antimony halide reacts with the formed intermediate zinc compound to obtain a series of nitrogen antimony / bismuth octane sulfur / selenium compounds with a high yield. The method has mild conditions and a high yield in air or nitrogen atmosphere. [Background technology]

[0002] So far, organic antimony compounds containing nitrogen-antimony octane ring skeleton have been widely used in the field of organic synthesis, biological application field and fixation of small molecule gas carbon dioxide. The application in the field of organic synthesis is mainly reflected in: 1. Application as a catalyst in catalytic synthesis, 1 2. Application as ligand, 2 3. Application as organic synthesis reagent. 3,4 The organic antimony halides containing nitrogen-antimony octane skeleton can react with aryl halides, various boric acids, various organic lithium reagents, Grignard reagents, organic zinc reagents, alkyl halides and various terminal alkynes to obtain a series of C(sp)-Sb, C(sp 2 )-Sb,C(sp 3 )-Sb bond organic antimony compounds. Disulfide and diselenide react in N,N-dimethylformamide solvent under the action of zinc powder and other reducing agents to form active intermediate zinc compounds, and nitrogen antimony / bismuth octane ring organic antimony halides react with the formed intermediate zinc compounds to obtain a series of nitrogen antimony / bismuth octane ring sulfur / selenium compounds with high yields. The method is mild in conditions, the yield is high in air or nitrogen atmosphere, and the reaction can be scaled up to 10 grams. As a new type of compound, nitrogen antimony octane ring sulfur / selenium has not been reported in other literature so far. Here we propose an efficient and mild synthesis method to synthesize a series of nitrogen antimony octane ring sulfur / selenium compounds with high yields. [Summary of the invention]

[0003] The purpose of the present invention is to provide a class of nitrogen antimony octane sulfide / selenium compounds and a preparation method thereof, that is, disulfide and diselenide react in a high boiling point polar solvent such as N, N-dimethylformamide under the action of a reducing agent such as zinc powder to form an active intermediate zinc compound, and the nitrogen antimony / bismuth octane organic antimony halide reacts with the formed intermediate zinc compound to obtain a series of nitrogen antimony / bismuth octane sulfide / selenium compounds with a higher yield. It is characterized in that: zinc powder, magnesium powder, manganese powder, sodium borohydride, etc. are used as reducing agents, and zinc powder is preferred, wherein the amount of reducing agent is 0.5-5.0 equivalents, in a high boiling point polar solvent such as N, N-dimethylformamide, wherein N, N-dimethylformamide is preferred, disulfide and diselenide I form an active intermediate zinc compound II, the reaction time is 2-8h, and the active intermediate zinc compound II reacts with the nitrogen antimony octane organic antimony halide III, the reaction temperature is 20-60°C, preferably 30°C, and the reaction time is 1-10mins, preferably 2mins. Nitrogen antimony octane sulfide / selenium compound IV can be obtained in high yield under nitrogen or air atmosphere.

[0004]

[0005] When E is sulfur, R 1 R is a methyl, n-propyl, isopropyl, n-octyl, n-hexyl, cyclohexyl, alkyl substituent, phenyl, 2-fluorophenyl, 2-chlorophenyl, 2-nitrophenyl, 2-aminophenyl, 3-fluorophenyl, 3-chlorophenyl, 4-fluorophenyl, 4-methoxyphenyl, 4-chlorophenyl, 4-bromophenyl, 4-nitrophenyl, 4-aminophenyl, 4-hydroxyphenyl, 4-cyanophenyl, 2,5-dichlorophenyl, 3,5-dichlorophenyl, 2-thienyl, 3-(2-methyl)furanyl, benzyl, 2-furfuryl and the like functional groups; 2 is a functional group such as phenyl, 2-ethylphenyl, 3-ethylphenyl, 4-tert-butylphenyl, 4-methylphenyl, cyclohexyl, tert-butyl, etc.; when E is selenium, R 1 is a functional group such as phenyl, 4-chlorophenyl, 1-naphthyl, benzyl, etc.; R 2 It is a functional group such as phenyl.

[0006] The method has the advantages of low cost, high yield, simple operation and no pollution, and has certain feasibility for realizing its industrial production. In order to achieve the above invention object, the present invention proposes the following technical solution:

[0007] In order to achieve the above-mentioned object of the invention, the present invention proposes the following technical solutions:

[0008]

Brief Description of the Drawings

[0009] Figure 1The invention provides a reaction route for preparing an active intermediate zinc compound from disulfide, diselenide and zinc powder, and then reacting the compound with nitrogen-antimony-octane organic antimony halide to obtain nitrogen-antimony-octane organic antimony sulfur / selenium derivatives. [Specific implementation method]

[0010] The present invention provides a method for synthesizing nitrogen antimony octane ring organic antimony sulfur / selenium derivatives, see the attached Figure 1 : 0.1mmol of disulfide / diselenide and 0.2mmol of reducing agent zinc powder are placed in a reaction container, and solvent N,N-dimethylformamide is added, and the reaction is carried out at 80°C for 4 hours. Then 0.2mmol of nitrogen antimony octane ring organic antimony halide is added, and the reaction is carried out at room temperature for 2.0 minutes. After the reaction is completed, the target compound nitrogen antimony octane ring organic antimony sulfur / selenium derivative is separated by column.

[0011] The present invention will be further described below in conjunction with specific preparation examples:

[0012] Preparation Example 1

[0013] Add p-toluene disulfide (R 1 =4-methylphenyl) 0.1mmol, zinc powder 0.2mmol and reaction solvent N, N-dimethylformamide 1.5ml were added, the reaction was stirred at 80°C for 4h, and nitrogen antimony octyl ring phenyl antimony chloride (R 2 =Ph)0.20mmol was reacted at room temperature for 2mins. After the reaction was completed, the target compound (R 1 =4-methylphenyl, R 2 =phenyl) to give a white solid in 88% yield.

[0014] Characterization data:

[0015] 1 H NMR(400MHz,Chloroform-d)δ8.47(d,J=7.3Hz,2H),7.47(dd,J=19.1,7.1Hz,4H),7.39(t,J=7.3Hz,2H),7.35–7.25(m,4H ),7.20(d,J=8.0Hz,2H),7.10(s,1H),7.06(d,J=7.3Hz,2H),4.73(d,J=15.0Hz,2H),4.47(d,J=15.0Hz,2H),2.33(s,3H).

[0016] 13 C{ 1H}NMR(101MHz,Chloroform-d)δ148.2,143.4,137.5,135.9,135.1,134.2,133.5,129.4,129.2,128.0,128.7,126.0,123.4,118.5,59.1,20.9.

[0017] HRMS-ESI(m / z)[M+H] + Calcd for C 27 H 25 NSSb,516.0740; Found,516.0747.

[0018] Preparation Example 2

[0019] Add 2-fluorodiphenyl disulfide (R 1 =2-fluorophenyl) 0.1mmol, 0.2mmol zinc powder and 1.5ml N,N-dimethylformamide as reaction solvent were added, and the reaction was stirred at 80°C for 4h, and then nitrogen antimony octyl ring phenyl antimony chloride (R 2 =Ph)0.20mmol was reacted at room temperature for 2mins. After the reaction was completed, the target compound (R 1 =2-fluorophenyl, R 2 =phenyl) to give a white solid in 82% yield.

[0020] Preparation Example 3

[0021] Add 2-chlorodiphenyl disulfide (R 1 =2-chlorophenyl) 0.1mmol, zinc powder 0.2mmol and reaction solvent N, N-dimethylformamide 1.5ml were added, the reaction was stirred at 80°C for 4h, and nitrogen antimony octyl ring phenyl antimony chloride (R 2 =Ph)0.20mmol was reacted at room temperature for 2mins. After the reaction was completed, the target compound (R 1 =2-chlorophenyl, R 2 =phenyl) to give a white solid in 83% yield.

[0022] Preparation Example 4

[0023] Add 2-nitrodiphenyl disulfide (R 1 =2-nitrophenyl) 0.1mmol, zinc powder 0.2mmol and reaction solvent N, N-dimethylformamide 1.5ml were added, the reaction was stirred at 80°C for 4h, and nitrogen antimony octyl ring phenyl antimony chloride (R 2=Ph)0.20mmol was reacted at room temperature for 2mins. After the reaction was completed, the target compound (R 1 =2-nitrophenyl, R 2 =phenyl) to give a yellow solid in 68% yield.

[0024] Preparation Example 5

[0025] Add 2-aminodiphenyl disulfide (R 1 =2-aminophenyl) 0.1mmol, 0.2mmol zinc powder and 1.5ml N,N-dimethylformamide as reaction solvent were added, and the reaction was stirred at 80°C for 4h, and then nitrogen antimony octyl ring phenyl antimony chloride (R 2 =Ph)0.20mmol was reacted at room temperature for 2mins. After the reaction was completed, the target compound (R 1 =2-aminophenyl, R 2 =phenyl) to give a white solid in 58% yield.

[0026] Preparation Example 6

[0027] Add 3-fluorodiphenyl disulfide (R 1 =3-fluorophenyl) 0.1mmol, 0.2mmol zinc powder and 1.5ml N,N-dimethylformamide as reaction solvent were added, and the reaction was stirred at 80°C for 4h, and then nitrogen antimony octyl ring phenyl antimony chloride (R 2 =Ph)0.20mmol was reacted at room temperature for 2mins. After the reaction was completed, the target compound (R 1 =3-fluorophenyl, R 2 =phenyl) to give a white solid in 81% yield.

[0028] Preparation Example 7

[0029] Add 3-chlorodiphenyl disulfide (R 1 =3-chlorophenyl) 0.1mmol, 0.2mmol zinc powder and 1.5ml N,N-dimethylformamide as reaction solvent were added, and the reaction was stirred at 80°C for 4h, and then nitrogen antimony octyl ring phenyl antimony chloride (R 2 =Ph)0.20mmol was reacted at room temperature for 2mins. After the reaction was completed, the target compound (R 1 =3-chlorophenyl, R 2 =phenyl) to give a white solid in 80% yield.

[0030] Preparation Example 8

[0031] Add diphenyl disulfide (R) into a 10 mL reaction tube. 1 =H) 0.1mmol, 0.2mmol zinc powder and 1.5ml N,N-dimethylformamide as reaction solvent were added, and the reaction was stirred at 80°C for 4h, and then nitrogen antimony octyl ring phenyl antimony chloride (R 2 =Ph)0.20mmol was reacted at room temperature for 2mins. After the reaction was completed, the target compound (R 1 =H, R 2 =phenyl) to give a white solid in 92% yield.

[0032] Preparation Example 9

[0033] Add 4-methoxydiphenyl disulfide (R 1 =4-methoxyphenyl) 0.1mmol, zinc powder 0.2mmol and reaction solvent N, N-dimethylformamide 1.5ml were added, the reaction was stirred at 80°C for 4h, and nitrogen antimony octyl ring phenyl antimony chloride (R 2 =Ph)0.20mmol was reacted at room temperature for 2mins. After the reaction was completed, the target compound (R 1 =4-methoxyphenyl, R 2 =phenyl) to give a white solid in 83% yield.

[0034] Preparation Example 10

[0035] Add 4-fluorodiphenyl disulfide (R 1 =4-fluorophenyl) 0.1mmol, 0.2mmol zinc powder and 1.5ml N,N-dimethylformamide as reaction solvent were added, and the reaction was stirred at 80°C for 4h, and then nitrogen antimony octyl ring phenyl antimony chloride (R 2 =Ph)0.20mmol was reacted at room temperature for 2mins. After the reaction was completed, the target compound (R 1 =4-fluorophenyl, R 2 =phenyl) to give a white solid in 78% yield.

[0036] Preparation Example 11

[0037] Add 4-chlorodiphenyl disulfide (R 1 =4-chlorophenyl) 0.1mmol, 0.2mmol zinc powder and 1.5ml N,N-dimethylformamide as reaction solvent were added, and the reaction was stirred at 80°C for 4h, and then nitrogen antimony octyl ring phenyl antimony chloride (R 2=Ph)0.20mmol was reacted at room temperature for 2mins. After the reaction was completed, the target compound (R 1 =4-chlorophenyl, R 2 =phenyl) to give a white solid in 77% yield.

[0038] Preparation Example 12

[0039] Add 4-bromodiphenyl disulfide (R 1 =4-bromophenyl) 0.1mmol, 0.2mmol zinc powder and 1.5ml N,N-dimethylformamide as reaction solvent were added, and the reaction was stirred at 80°C for 4h, and then nitrogen antimony octyl ring phenyl antimony chloride (R 2 =Ph)0.20mmol was reacted at room temperature for 2mins. After the reaction was completed, the target compound (R 1 =4-bromophenyl, R 2 =phenyl) to give a white solid in 85% yield.

[0040] Preparation Example 13

[0041] Add 4-nitrodiphenyl disulfide (R 1 =4-nitrophenyl) 0.1mmol, zinc powder 0.2mmol and reaction solvent N, N-dimethylformamide 1.5ml were added, the reaction was stirred at 80°C for 4h, and nitrogen antimony octyl ring phenyl antimony chloride (R 2 =Ph)0.20mmol was reacted at room temperature for 2mins. After the reaction was completed, the target compound (R 1 =4-nitrophenyl, R 2 =phenyl) to give a yellow solid in 63% yield.

[0042] Preparation Example 14

[0043] Add 4-hydroxydiphenyl disulfide (R 1 =4-hydroxyphenyl) 0.1mmol, 0.2mmol zinc powder and 1.5ml N,N-dimethylformamide as reaction solvent were added, and the reaction was stirred at 80°C for 4h, and then nitrogen antimony octyl ring phenyl antimony chloride (R 2 =Ph)0.20mmol was reacted at room temperature for 2mins. After the reaction was completed, the target compound (R 1 =4-hydroxyphenyl, R 2 =phenyl) to give a white solid in 88% yield.

[0044] Preparation Example 15

[0045] Add 4-aminodiphenyl disulfide (R 1 =4-aminophenyl) 0.1mmol, 0.2mmol zinc powder and 1.5ml N,N-dimethylformamide as reaction solvent were added, and the reaction was stirred at 80°C for 4h, and then nitrogen antimony octyl ring phenyl antimony chloride (R 2 =Ph)0.20mmol was reacted at room temperature for 2mins. After the reaction was completed, the target compound (R) was obtained by column chromatography. 1 =4-aminophenyl, R 2 =phenyl) to give a white solid in 83% yield.

[0046] Preparation Example 16

[0047] Add 4-cyanodiphenyl disulfide (R 1 =4-cyanophenyl) 0.1mmol, zinc powder 0.2mmol and reaction solvent N, N-dimethylformamide 1.5ml were added, the reaction was stirred at 80°C for 4h, and nitrogen antimony octyl ring phenyl antimony chloride (R 2 =Ph)0.20mmol was reacted at room temperature for 2mins. After the reaction was completed, the target compound (R 1 =4-cyanophenyl, R 2 =phenyl) to give a white solid in 88% yield.

[0048] Preparation Example 17

[0049] Add 2,5-dichlorodiphenyl disulfide (R 1 =2,5-dichlorophenyl) 0.1mmol, zinc powder 0.2mmol and reaction solvent N, N-dimethylformamide 1.5ml were added, the reaction was stirred at 80°C for 4h, and nitrogen antimony octyl ring phenyl antimony chloride (R 2 =Ph)0.20mmol was reacted at room temperature for 2mins. After the reaction was completed, the target compound (R 1 =2,5-dichlorophenyl, R 2 =phenyl) to give a white solid in 74% yield.

[0050] Preparation Example 18

[0051] Add 3,5-dichlorodiphenyl disulfide (R 1=3,5-dichlorophenyl) 0.1mmol, 0.2mmol zinc powder and 1.5ml N,N-dimethylformamide as reaction solvent were added, and the reaction was stirred at 80°C for 4h, and then nitrogen antimony octyl ring phenyl antimony chloride (R 2 =Ph)0.20mmol was reacted at room temperature for 2mins. After the reaction was completed, the target compound (R 1 =3,5-dichlorophenyl, R 2 =phenyl) to give a white solid in 77% yield.

[0052] Preparation Example 19

[0053] Add 2-thiophene disulfide (R 1 =2-thienyl) 0.1mmol, zinc powder 0.2mmol and reaction solvent N, N-dimethylformamide 1.5ml were added, the reaction was stirred at 80°C for 4h, and nitrogen antimony octyl ring phenyl antimony chloride (R 2 =Ph)0.20mmol was reacted at room temperature for 2mins. After the reaction was completed, the target compound (R 1 =2-thienyl, R 2 =phenyl) to give a white solid in 62% yield.

[0054] Preparation Example 20

[0055] Add 3-(2-methyl)furan disulfide (R 1 =3-(2-methyl)furanyl) 0.1mmol, 0.2mmol zinc powder and 1.5ml N,N-dimethylformamide as reaction solvent were added, and the reaction was stirred at 80°C for 4h, and then nitrogen antimony octyl ring phenyl antimony chloride (R 2 =Ph)0.20mmol was reacted at room temperature for 2mins. After the reaction was completed, the target compound (R 1 =3-(2-methyl)furanyl, R 2 =phenyl) to give a white solid in 88% yield.

[0056] Preparation Example 21

[0057] Add dibenzyl disulfide (R 1 =benzyl) 0.1mmol, 0.2mmol zinc powder and 1.5ml N,N-dimethylformamide as reaction solvent were added, and the reaction was stirred at 80°C for 4h, and then nitrogen antimony octyl ring phenyl antimony chloride (R 2 =Ph)0.20mmol was reacted at room temperature for 2mins. After the reaction was completed, the target compound (R1 =3 benzyl, R 2 =phenyl) to give a white solid in 65% yield.

[0058] Preparation Example 22

[0059] Add difurfuryl disulfide (R 1 = furfuryl) 0.1mmol, zinc powder 0.2mmol and reaction solvent N, N-dimethylformamide 1.5ml were added, the reaction was stirred at 80°C for 4h, and then nitrogen antimony octyl ring phenyl antimony chloride (R 2 =Ph)0.20mmol was reacted at room temperature for 2mins. After the reaction was completed, the target compound (R 1 = furfuryl, R 2 =phenyl) to give a white solid in 61% yield.

[0060] Preparation Example 23

[0061] Add dicyclohexyl disulfide (R 1 =cyclohexyl) 0.1mmol, 0.2mmol zinc powder and 1.5ml N,N-dimethylformamide as reaction solvent were added, and the reaction was stirred at 80°C for 4h, and then nitrogen antimony octyl ring phenyl antimony chloride (R 2 =Ph)0.20mmol was reacted at room temperature for 2mins. After the reaction was completed, the target compound (R 1 = cyclohexyl, R 2 =phenyl) to give a colorless liquid in 69% yield.

[0062] Preparation Example 24

[0063] Add dimethyl disulfide (R) into a 10 mL reaction tube. 1 = methyl) 0.1mmol, 0.2mmol zinc powder and 1.5ml N, N-dimethylformamide as reaction solvent were added, and the reaction was stirred at 80°C for 4h, and then nitrogen antimony octyl ring phenyl antimony chloride (R 2 =Ph)0.20mmol was reacted at room temperature for 2mins. After the reaction was completed, the target compound (R 1 = methyl, R 2 =phenyl) to give a white solid in 65% yield.

[0064] Preparation Example 25

[0065] Add diisopropyl disulfide (R 1= isopropyl) 0.1mmol, zinc powder 0.2mmol and reaction solvent N, N-dimethylformamide 1.5ml were added, the reaction was stirred at 80°C for 4h, and nitrogen antimony octyl ring phenyl antimony chloride (R 2 =Ph)0.20mmol was reacted at room temperature for 2mins. After the reaction was completed, the target compound (R 1 = isopropyl, R 2 =phenyl), to give a light yellow liquid with a yield of 38%.

[0066] Preparation Example 26

[0067] Add di-n-propyl disulfide (R 1 =n-propyl) 0.1mmol, 0.2mmol zinc powder and 1.5ml N,N-dimethylformamide as reaction solvent were added, and the reaction was stirred at 80°C for 4h, and then nitrogen antimony octyl ring phenyl antimony chloride (R 2 =Ph)0.20mmol was reacted at room temperature for 2mins. After the reaction was completed, the target compound (R 1 =n-propyl, R 2 =phenyl) to give a white solid in 64% yield.

[0068] Preparation Example 27

[0069] Add dioctyl disulfide (R 1 =n-octyl) 0.1mmol, 0.2mmol zinc powder and 1.5ml N,N-dimethylformamide as reaction solvent were added, and the reaction was stirred at 80°C for 4h, and then nitrogen antimony octyl ring phenyl antimony chloride (R 2 =Ph)0.20mmol was reacted at room temperature for 2mins. After the reaction was completed, the target compound (R 1 = n-octyl, R 2 =phenyl) to give a white solid in 68% yield.

[0070] Preparation Example 28

[0071] Add di-n-decyl disulfide (R 1 =n-decyl) 0.1mmol, 0.2mmol zinc powder and 1.5ml N,N-dimethylformamide as reaction solvent were added, and the reaction was stirred at 80°C for 4h, and then nitrogen antimony octyl ring phenyl antimony chloride (R 2 =Ph)0.20mmol was reacted at room temperature for 2mins. After the reaction was completed, the target compound (R 1 = n-decyl, R 2=phenyl) to give a colorless liquid in 27% yield.

[0072] Preparation Example 29

[0073] Add diphenyl diselenide (R 1 =phenyl) 0.1mmol, 0.2mmol zinc powder and 1.5ml N,N-dimethylformamide as reaction solvent were added, and the reaction was stirred at 80°C for 4h, and then nitrogen antimony octyl ring phenyl antimony chloride (R 2 =Ph)0.20mmol was reacted at room temperature for 2mins. After the reaction was completed, the target compound (R 1 =phenyl, R 2 =phenyl) to give a pale yellow solid in 85% yield.

[0074] Preparation Example 30

[0075] Add 4-chlorophenyl diselenide (R 1 =4-chlorophenyl) 0.1mmol, 0.2mmol zinc powder and 1.5ml N,N-dimethylformamide as reaction solvent were added, and the reaction was stirred at 80°C for 4h, and then nitrogen antimony octyl ring phenyl antimony chloride (R 2 =Ph)0.20mmol was reacted at room temperature for 2mins. After the reaction was completed, the target compound (R 1 =4-chlorophenyl, R 2 =phenyl) to give a pale yellow solid with a yield of 86%.

[0076] Preparation Example 31

[0077] Add 1-naphthyl diselenide (R 1 =1-naphthyl) 0.1mmol, 0.2mmol zinc powder and 1.5ml N,N-dimethylformamide as reaction solvent were added, and the reaction was stirred at 80°C for 4h, and then nitrogen antimony octyl ring phenyl antimony chloride (R 2 =Ph)0.20mmol was reacted at room temperature for 2mins. After the reaction was completed, the target compound (R 1 =1-naphthyl, R 2 =phenyl) to give a pale yellow solid in 75% yield.

[0078] Preparation Example 32

[0079] Add dibenzyl diselenide (R 1=benzyl) 0.1mmol, 0.2mmol zinc powder and 1.5ml N,N-dimethylformamide as reaction solvent were added, and the reaction was stirred at 80°C for 4h, and then nitrogen antimony octyl ring phenyl antimony chloride (R 2 =Ph)0.20mmol was reacted at room temperature for 2mins. After the reaction was completed, the target compound (R 1 =benzyl, R 2 =phenyl) to give a pale yellow solid in 34% yield.

[0080] Preparation Example 33

[0081] Add diphenyl disulfide (R) into a 10 mL reaction tube. 1 =phenyl) 0.1mmol, 0.2mmol zinc powder and 1.5ml N,N-dimethylformamide as reaction solvent were added, and the reaction was stirred at 80°C for 4h, and then nitrogen antimony octane 4-methylphenyl antimony chloride (R 2 =4-methylphenyl) 0.20mmol was reacted at room temperature for 2mins. After the reaction was completed, the target compound (R 1 =phenyl, R 2 =4-methylphenyl) to give a white solid in 76% yield.

[0082] Preparation Example 34

[0083] Add diphenyl disulfide (R) into a 10 mL reaction tube. 1 =phenyl) 0.1mmol, 0.2mmol zinc powder and 1.5ml N,N-dimethylformamide as reaction solvent were added, and the reaction was stirred at 80°C for 4h, and then nitrogen antimony octane 4-tert-butylphenyl antimony chloride (R 2 =4-tert-butylphenyl) 0.20mmol was reacted at room temperature for 2mins. After the reaction was completed, the target compound (R 1 =phenyl, R 2 =4-tert-butylphenyl) to give a white solid with a yield of 88%.

[0084] Preparation Example 35

[0085] Add diphenyl disulfide (R) into a 10 mL reaction tube. 1 =phenyl) 0.1mmol, 0.2mmol zinc powder and 1.5ml N,N-dimethylformamide as reaction solvent were added, and the reaction was stirred at 80°C for 4h, and then nitrogen antimony octane 2-ethylphenyl antimony chloride (R 2 =2-ethylphenyl) 0.20mmol was reacted at room temperature for 2mins. After the reaction was completed, the target compound (R1 =phenyl, R 2 =2-ethylphenyl) to give a white solid in 87% yield.

[0086] Preparation Example 36

[0087] Add diphenyl disulfide (R) into a 10 mL reaction tube. 1 =phenyl) 0.1mmol, 0.2mmol zinc powder and 1.5ml N,N-dimethylformamide as reaction solvent were added, and the reaction was stirred at 80°C for 4h, and then nitrogen antimony octane 3-ethylphenyl antimony chloride (R 2 =3-ethylphenyl) 0.20mmol was reacted at room temperature for 2mins. After the reaction was completed, the target compound (R 1 =phenyl, R 2 =3-ethylphenyl) to give a white solid in 92% yield.

[0088] Preparation Example 37

[0089] Add diphenyl disulfide (R) into a 10 mL reaction tube. 1 =phenyl) 0.1mmol, 0.2mmol zinc powder and 1.5ml N,N-dimethylformamide as reaction solvent were added, and the reaction was stirred at 80°C for 4h, and then nitrogen antimony octane 3,5-dimethylphenyl antimony chloride (R 2 =3,5-dimethylphenyl) 0.20mmol was reacted at room temperature for 2mins. After the reaction was completed, the target compound (R 1 =phenyl, R 2 =3,5-dimethylphenyl) to give a white solid with a yield of 76%.

[0090] Preparation Example 38

[0091] Add diphenyl disulfide (R) into a 10 mL reaction tube. 1 =phenyl) 0.1mmol, 0.2mmol zinc powder and 1.5ml N,N-dimethylformamide as reaction solvent were added, and the reaction was stirred at 80°C for 4h, and then nitrogen antimony octyl ring cyclohexyl antimony chloride (R 2 =3,5-dimethylphenyl) 0.20mmol was reacted at room temperature for 2mins. After the reaction was completed, the target compound (R 1 =phenyl, R 2 =cyclohexyl) to give a white solid in 43% yield.

[0092] Preparation Example 39

[0093] Add diphenyl disulfide (R) into a 10 mL reaction tube. 1 =phenyl) 0.1mmol, 0.2mmol zinc powder and 1.5ml N,N-dimethylformamide as reaction solvent were added, and the reaction was stirred at 80°C for 4h, and then tert-butyl antimony chloride (R 2 =3,5-dimethylphenyl) 0.20mmol was reacted at room temperature for 2mins. After the reaction was completed, the target compound (R 1 =phenyl, R 2 =tert-butyl) to give a white solid in 72% yield.

[0094] The above-mentioned embodiments only express several implementation methods of the present invention, and the descriptions thereof are relatively specific and detailed, but they cannot be understood as limiting the scope of the patent of the present invention. It should be pointed out that, for ordinary technicians in this field, several variations and improvements can be made without departing from the concept of the present invention, and these all belong to the protection scope of the present invention. Therefore, the protection scope of the patent of the present invention should be based on the attached claims.

[0095] References:

[0096] 1.Chen, Y.; Qiu, R.; Xu,

[0097] 2. Benjamin, SL; Reid, G., Neutral organoantimony(III)and organobismuth(III)ligands as acceptors in transition metal complexes–Role of substituents and co-ligands.Coord.Chem.Rev.2015,297-298,168-180.

[0098] 3. Zhang, D.; Le, L.; Qiu, R.; Wong, W.-Y.; Kambe, N., Nickel-and Palladium-Catalyzed Cross-Coupling Reactions of Organostibines with OrganoboronicAcids. Angew. Chem. Int. Ed. 2021, 60, 3104-3114.

[0099] 4.Zhang,Z.;Zhang,D.;Zhu,L.;Zeng,D.;Kambe,N.;Qiu,R.,Pd-CatalyzedCross-Coupling of Organostibines with Styrenes to Give Unsymmetric(E)-Stilbenes and(1E,3E)-1,4-Diarylbuta-1,3-dienes and Fluorescence Properties ofthe Products.Org.Lett.2021,23,5317-5322.

Claims

1. An efficient synthesis method of a nitrogen-antimony-octane-ring organic antimony-sulfur / selenium derivative IV, characterized in that: Compound I is reacted in a reaction solvent at elevated temperature under the action of a reducing agent to form an intermediate zinc compound II, and then nitrogen antimony octane ring organic antimony halide III is added to react at room temperature to obtain nitrogen antimony octane ring organic antimony sulfur / selenium derivative IV; When E is sulfur, R 1 is a methyl, n-propyl, isopropyl, n-hexyl, n-octyl, n-hexyl, cyclohexyl, phenyl, 2-fluorophenyl, 2-chlorophenyl, 2-nitrophenyl, 2-aminophenyl, 3-fluorophenyl, 3-chlorophenyl, 4-fluorophenyl, 4-methoxyphenyl, 4-chlorophenyl, 4-bromophenyl, 4-nitrophenyl, 4-aminophenyl, 4-hydroxyphenyl, 4-cyanophenyl, 2,5-dichlorophenyl, 3,5-dichlorophenyl, 2-thienylphenyl, 3-(2-methyl)furyl, benzyl or 2-furfuryl functional group, R 2 is a phenyl, 2-ethylphenyl, 3-ethylphenyl, 4-tert-butylphenyl, 4-methylphenyl, cyclohexyl or tert-butyl functional group; When E is selenium, R 1 is a phenyl, 4-chlorophenyl, 1-naphthyl or benzyl functional group, R 2 is a phenyl functional group; X is chlorine, the reducing agent is zinc powder, the amount of the reducing agent is 0.5-5.0 equivalents, and the reaction solvent is DMF.

2. The efficient synthesis method according to claim 1, characterized in that The reaction temperature of the temperature-raising reaction is 25-140° C., and the reaction time is 4 to 8 hours.

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