A method for synthesizing 1,2-disubstituted olefins by reacting terminal olefins with sulfoxides

Abstract

The invention discloses a method for synthesizing 1,2-disubstituted olefins by reacting terminal olefins with sulfoxides. The method comprises the following steps: the terminal olefins and sulfoxides are reacted in one pot in the presence of an iron salt and hydrogen peroxide to generate the 1,2-disubstituted olefins. In the method, the sulfoxide serves as both a hydrocarbylating agent and a solvent for the olefins. The reaction product is a 1,2-disubstituted olefin in which a terminal carbon atom in the terminal olefin is coupled to a sulfoxide hydrocarbyl group, thereby lengthening the olefin carbon chain. The method has mild reaction conditions, good selectivity, and high yield, and is conducive to industrial production.

Description

Technical Field

[0001] The present invention relates to a method for synthesizing 1,2-disubstituted olefins, in particular to a method for synthesizing 1,2-disubstituted olefins by reacting terminal olefins with sulfoxides, and belongs to the field of organic synthesis. Background Art

[0002] Olefins are a widely used class of organic compounds, and many compounds in nature contain olefins of varying structures. Steroidal terpenoids, which have neurophysiological effects in vivo, also contain olefins of varying structures. Currently, among the synthesis methods of olefins with different structures, the alkylation of lower olefins is the most commonly used and one of the most effective methods for synthesizing higher olefins (Z. Chen, M.-Y. Rong, J. Nie, X.-F. Zhu, B.-F. Shi and J.-A. Ma, Chem. Soc. Rev., 2019, 48, 4921; T. Irrgang and R. Kempe, Chem. Rev. 2019, 119, 2524; C. Shan, L. Zhu, L.-B. Qu, R. Bai and Y. Lan, Chem. Soc. Rev., 2018, 47, 7552; Z. Dong, Z. Ren, S. Thompson, Y. Xu and G. Dong, Chem. Rev. 2017, 117, 9333). The Heck reaction for the coupling synthesis of halogenated hydrocarbons and olefins under palladium catalysis is a classic direct alkylation reaction of olefins (RF Heck and JP Nolley, J. Org. Chem., 1972, 37, 2320; IP Beletskaya and AV Cheprakov, Chem. Rev., 2000, 100, 3009; AB Dounay and LE Overman, Chem. Rev., 2003, 103, 2945; KC Nicolaou, PG Bulger and D. Sarlah, Angew. Chem., Int. Ed., 2005, 44, 4442; C. Torborg and M. Beller, Adv. Synth. Catal., 2009, 351, 3027; X.-F. Wu, P. Anbarasan, H. Neumann and M. Beller, Angew. Chem., Int. Ed., 2010, 49, 9047; F. Akiyama, H. Miyazaki, K. Kaneda, S. Teranishi, Y. Fujiwara, M. Abe and H. Taniguchi, J. Org. Chem., 1980, 45, 2359). In the past few decades, many organic synthesis workers have proposed some improved Heck reactions to synthesize various olefins.Fujiwara proposed a method for synthesizing 1,2-disubstituted methyl aryl olefins by using alkylamine as a hydrocarbylating agent and a monoaryl-substituted terminal olefin under palladium salt catalysis (Scheme 1, (1a)) (Y. Ikeda, T. Nakamura, H. Yorimitsu and K. Oshima, J. Am. Chem. Soc., 2002, 124, 6514); Oshima proposed a method for synthesizing 1,2-disubstituted methyl aryl olefins by using halogenated hydrocarbons as a hydrocarbylating agent and a monoaryl-substituted terminal olefin under cobalt salt catalysis (Scheme 1, (1b)) (W. Affo, H. Ohmiya, T. Fujioka, Y. Ikeda, T. Nakamura, H. Yorimitsu, K. Oshima, Y. Imamura, T. Mizuta and K. Miyoshi, J. Am. Chem. Soc., 2006, 128, 8068); Brown reported a method for the methylation reaction of N-methyl-N-methylsilyl urea with terminal aromatic olefins and polysubstituted terminal aromatic olefins to produce methyl aromatic olefins (Scheme 1, (1c)) (W. Rauf and J. M. Brown, Angew. Chem., Int. Ed., 2008, 47, 4228); Bao reported a method for the use of alkyl peroxyesters as alkylating agents with terminal aromatic olefins under the catalysis of iron complexes to produce 1,2-disubstituted alkyl aromatic olefins (Scheme 1, (1d)) (N. Zhu, J. Zhao and H. Bao, Chem. Sci., 2017, 8, 2081). These previously published methods achieve the hydrocarbylation of olefin carbon-hydrogen bonds via ionic reactions (Scheme 1, (1a, 1b, 1c)) or free radical reactions (Scheme 1, (1d)). However, these methods utilize complex, difficult-to-obtain compounds containing carbon-halogen, carbon-nitrogen, and carbon-oxygen bonds as hydrocarbylating agents, and expensive metal catalysts. These shortcomings make these methods difficult to apply on an industrial scale, and they can only be used for the hydrocarbylation of aromatic olefin substrates.

[0003]

[0004] Scheme 1. Reported olefin alkylation reactions Summary of the Invention

[0005] To address the shortcomings of existing methods for preparing 1,2-disubstituted olefins from terminal olefins, the present invention aims to provide a universal method using sulfoxides as the hydrocarbylating agent, applicable to both aromatic and non-aromatic terminal olefins. This synthesis method utilizes a one-pot reaction in which a hydrogen atom on the olefin carbon is replaced by a hydrocarbyl group, resulting in a 1,2-disubstituted olefin with a sulfoxide hydrocarbyl group coupled to the terminal olefin carbon atom. The readily available raw materials, mild reaction conditions, good selectivity, and high yield facilitate industrial production.

[0006] The terminal olefin has the structure of Formula 1:

[0007]

[0008] The sulfoxide has a structure of Formula 2:

[0009]

[0010] in,

[0011] R is an alkyl group such as methyl, ethyl, phenyl, benzyl, etc.;

[0012] R1 and R2 can be simple aromatic ring groups or substituted aromatic ring groups or C1-C 10 The substituted aryl group contains 1 to 2 substituents, and the substituents are selected from at least one of halogen substituents, alkyl, hydroxyl, amino, nitro, aldehyde, and carboxyl groups. Halogen substituents are such as fluorine, chlorine, bromine, iodine, etc. The alkyl group is C1 to C 10 alkyl, more preferably a C1-C5 short-chain alkyl, such as methyl, ethyl, propyl, etc., and may also be a branched alkyl, such as isopropyl, tert-butyl, etc.; R1 or R2 may be hydrogen, but not both;

[0013] The metal salt can be an iron salt, a copper salt, a nickel salt, or a cobalt salt, preferably an iron salt;

[0014] The peroxide is hydrogen peroxide, tert-butyl hydroperoxide, or di-tert-butane peroxide, preferably hydrogen peroxide.

[0015] In a preferred embodiment, the ratio of hydrogen peroxide to terminal olefin is 2 to 8:1, more preferably 4:1.

[0016] In a preferred embodiment, the reaction temperature is 80-160°C, more preferably 140°C.

[0017] In a preferred embodiment, the reaction is carried out at 80-160°C in an air atmosphere for 2-12 hours. More preferably, the reaction is carried out at 140°C in an air atmosphere for 6 hours.

[0018] The present invention uses the reaction of styrene and dimethyl sulfoxide to synthesize (Z)-2-methylstyrene (a) to illustrate the reaction mechanism. After consulting and referencing relevant literature, a series of mechanism research experiments were designed. The results are shown in Scheme 2:

[0019]

[0020] Scheme 2 Reaction control experiment

[0021] First, under standard reaction conditions, a small amount of free radical scavenger 2,6-di-tert-butyl-4-methylphenol (BHT) was added, and the reaction of styrene with DMF to produce the desired product a was inhibited, and the methyl radical extraction product E and the 1-phenylpropyl radical A extraction product D were detected (Scheme 2.a), indicating that the reaction was a free radical reaction and that methyl radicals and 1-phenylpropyl radicals A were present. In addition, the reaction of styrene with deuterated DMF gave the deuterated product ad 3 (Scheme 2.f) shows that in the reaction, DMF is the alkylating agent that provides the hydrocarbon group to the double bond carbon of styrene. 3+ When the reaction mixture was stirred in the presence of H₂O₂, product a was barely detectable (Scheme 2.c), and no methyl radicals were detected (Scheme 2.d). GC-MS analysis of the product after a one-hour reaction under standard conditions revealed the presence of intermediate F (Scheme 6.d). Further investigation revealed that product a could be obtained in a 95% yield under standard conditions using intermediate F as the starting material (Scheme 6.e), indicating that compound F is the intermediate in the reaction of olefins and sulfoxides to form alkyl olefins in the presence of iron salts and hydrogen peroxide.

[0022] Based on the above experimental results, the following reaction mechanism (Scheme 3) is proposed for the reaction of olefins and sulfoxides to generate alkyl olefins in the presence of iron salts and hydrogen peroxide. 3+ or Fe 2+ The reaction generates a hydroxyl radical OH·, which then reacts with DMSO to produce a methyl radical CH3·. The methyl radical CH3· further reacts with styrene to produce a 1-phenylpropyl radical A. The 1-phenylpropyl radical A then couples with the hydroxyl radical OH· to produce intermediate F. Finally, under heating conditions, intermediate F undergoes trans-elimination dehydration to yield the product (Z)-2-methylstyrene (a).

[0023]

[0024] Scheme 3. Reaction mechanism

[0025] In the technical solution of the present invention, sulfoxide acts as a hydrocarbylating agent and reacts with terminal olefins to generate a 1,2-disubstituted olefin by substitution of the double carbon-hydrogen bond. This adds a hydrocarbyl carbon chain to the terminal carbon atom of the starting olefin. The sulfoxide primarily serves two functions: first, it acts as a benign solvent; second, as a reaction substrate, it provides an alkyl group as the hydrocarbyl group on the double bond of the product. While the structure or structural unit of a peroxide does not appear in the product structure, the peroxide is essential for the hydrocarbyl formation reaction between the olefin and the sulfoxide, providing hydroxyl radicals. Hydroxyl radicals have two functions: reacting with sulfoxide to generate alkyl radicals and reacting with olefin alkylation radicals to generate hydroxyl products. Metal ions promote the formation of hydroxyl radicals from peroxides.

[0026] Compared with the prior art, the technical solution of the present invention brings the following beneficial technical effects:

[0027] 1) The raw materials used in the method for synthesizing alkyl olefins via coupling double carbon-hydrogen bonds with saturated carbon-hydrogen bonds proposed in the present invention are olefins and sulfoxides, and the auxiliary reagents iron salts and hydrogen peroxide are all common chemical raw materials with low cost and wide raw material sources, which is conducive to industrial production.

[0028] 2) The method proposed in the present invention for synthesizing alkyl olefins by coupling double carbon-hydrogen bonds with saturated carbon-hydrogen bonds adopts a one-pot reaction to form the product, which is simple to operate and convenient for industrial application.

[0029] 3) The method proposed in the present invention for synthesizing alkyl olefins by coupling double carbon-hydrogen bonds with saturated carbon-hydrogen bonds is carried out in an atmospheric atmosphere with mild conditions and simple operation, thus meeting the requirements of industrial production.

[0030] 4) The method proposed in the present invention for synthesizing hydrocarbon-based olefins by coupling double carbon-hydrogen bonds with saturated carbon-hydrogen bonds has a wide range of adaptability to substrate raw materials and can construct various multi-substituted olefins. DETAILED DESCRIPTION

[0031] The following examples are intended to further illustrate the present invention, but are not intended to limit the scope of protection of the claims of the present invention.

[0032] Unless otherwise stated, all reactions were performed in Schlenk tubes.

[0033] All reaction starting solvents were obtained from commercial sources and used without further purification.

[0034] The products were separated using a silica gel chromatography column with silica gel (particle size 300-400 mesh).

[0035] 1H NMR (400 MHz), 13C NMR (100 MHz) and 19F NMR (376 MHz) were detected using a Bruker ADVANCE III spectrometer with CDCl3 as the solvent and TMS as the internal standard. Chemical shifts were measured in parts per million (ppm) with 0.0 ppm of tetramethylsilane as the reference shift. The following abbreviations (or combinations thereof) are used to explain multiplicity: s = singlet, d = doublet, t = triplet, q = quartet, m = multiplet, br = broad peak. The unit of the coupling constant J is Hertz (Hz). Chemical shifts are expressed in ppm, with reference to the center line of the triplet state of deuterated chloroform at 77.0 ppm or the center line of the septet state of deuterated DMSO at 39.52 ppm.

[0036] GC-MS was detected by GC-MS QP2010 equipment, HRMS was measured by electron ionization (EI) method, the mass analyzer type was TOF, and EI was detected by Esquire 3000plus instrument.

[0037] 1. Condition optimization experiment:

[0038] Taking the synthesis of (Z)-2-methylstyrene (a) from styrene and dimethyl sulfoxide as an example, the type of metal salt used in the reaction, the type and amount of peroxide, reaction temperature, etc. were screened to find the optimal reaction conditions.

[0039]

[0040] Reaction formula 1: Synthesis of (Z)-2-methylstyrene (a) by reaction of styrene with DMSO

[0041] 1.1 Screening of metal salts

[0042] First, the metal salts used in the reaction were screened. Ferrous, copper, nickel, cobalt, and ferric salts were screened, with the results shown in Table 1. All metal salts produced reaction products, but ferrous and ferric salts produced higher yields than the other metal salts.

[0043] Table 1. Screening of metal salt types

[0044]

[0045] 1.2 Screening of peroxide types and dosage

[0046] Under standard conditions, different peroxide types and dosages were screened. Commonly used peroxides included hydrogen peroxide, dibenzoyl peroxide (BPO), di-tert-butyl peroxide (DTBP), tert-butyl hydroperoxide (TBHP), and potassium peroxydisulfate (K2S2O8). The screening results are shown in Table 2. Dibenzoyl peroxide and potassium peroxydisulfate produced little to no product, while hydrogen peroxide was the most effective. Experiments using varying amounts of hydrogen peroxide showed that 6 equivalents of hydrogen peroxide produced the highest yield.

[0047] Table 2. Screening of peroxides

[0048]

[0049] 1.3 Screening of reaction temperature

[0050] Reaction temperature is an important factor affecting the reaction yield. The effect of gradient temperature on the reaction was further studied, and the results are shown in Table 3. The experiment was carried out from 80℃ to 160℃, and the reaction yield was the highest at 140℃.

[0051] Table 3. Screening of reaction temperature

[0052]

[0053] 1.4 Standard reaction process

[0054] After optimization, the standard reaction process was as follows: 3 ml of DMSO, 0.5 mmol of olefin, 2 mmol (4.0 equiv) of 30% H₂O₂, and 15 mg of FeCl₃·6H₂O were added to a 25 ml Schlenk tube. After mixing, the tube was sealed with a stopper and heated in a 140°C oil bath with magnetic stirring. After 6 h of reaction, heating was stopped. After the tube cooled, the product was extracted with ethyl acetate. The extract was washed with water to remove DMSO, dried over anhydrous Na₂SO₄, and the solvent was evaporated in vacuo. The dried sample was separated by silica gel column chromatography using petroleum ether / ethyl acetate as the eluent to obtain the product, which was then dried in vacuo and characterized by NMR, MS, and MS.

[0055] 1.5 Special reaction process

[0056] To a 25 ml Schlenk tube, 3 ml of DMSO, 0.25 mmol of olefin, 1 mmol (4.0 equiv) of 30% H₂O₂, and 15 mg of FeCl₃.6H₂O were added. After mixing thoroughly, the tube was sealed with a stopper and heated in a 160°C oil bath with magnetic stirring. After 12 hours of reaction, heating was stopped. After the tube cooled, the product was extracted with ethyl acetate. The extract was washed with water to remove DMSO, dried over anhydrous Na₂SO₄, and the solvent was evaporated in vacuo. The dried sample was separated by silica gel column chromatography using petroleum ether / ethyl acetate as the eluent to obtain the product, which was then dried in vacuo and characterized by NMR, MS, and MS.

[0057] 2. Reaction substrate expansion

[0058] Under standard reaction conditions, the applicability of the present invention to partially substituted terminal olefin derivatives was investigated, and the results are shown in Table 4 below. The product a corresponding to styrene was finally isolated with a yield of 85%. t When Bu is substituted, the yield of the corresponding products b and c can also reach more than 81%. When the para position contains -F substitution, the product yield is also 75%. We continue to investigate the reaction of -Cl substitution at different positions on the styrene benzene ring. The results show that the corresponding yields of the three substrates containing Cl substitutions at different positions are 78%, 75% and 72%, respectively. When we use 2-vinylnaphthalene instead of styrene, the corresponding product i can also be separated with a yield of 84%. The disclosed technology can be used for the sterically hindered 1,1,2-triarylethylene (product p) that is difficult to synthesize. When the fatty olefin 1-heptene is used, the product m can also be obtained with a separation yield of 50%. Other current carbon-hydrogen bond coupling alkylation methods cannot be used for fatty olefin substrates and cannot synthesize triarylethylenes.

[0059] In terminal olefins, the double bond carbon atom can be one substituent or two substituents, and the substituents can be aromatic or non-aromatic. When the starting material is a monosubstituted terminal olefin, the product is an E-type 1,2-disubstituted olefin; when the starting material is an asymmetric disubstituted terminal olefin, the product is an E-type trisubstituted olefin.

[0060] Table 4 Study on the reaction of terminal olefins with sulfoxides

[0061]

[0062] Reaction conditions: olefin (0.25 mmol, 1.0 eq), FeCl3 (0.1 mmol), DMSO (2 ml), heated at 140°C in a pressure tube for 6 h. Yield is isolated yield.

[0063] Structural characterization of some alkyl olefin products

[0064] (E)-prop-1-en-1-ylbenzene (a): Synthesized according to the standard reaction procedure, the product was purified by silica gel column chromatography using a 100:1 ratio of petroleum ether to ethyl acetate as the eluent. The product was a colorless liquid, 50.02 mg, in an 85% yield. Structural analysis data are as follows: 1 H NMR (400MHz, Chloroform-d) δ 7.39–7.26 (m, 4H), 7.25–7.16 (m, 1H), 6.42 (d, J = 15.0Hz, 1H), 6.26 (m, 6.5Hz, 1H), 1.90 (d, J = 6.5Hz, 3H). 13 C NMR(101MHz,Chloroform-d)δ 137.92,131.01,128.44,126.70,125.79,125.65,18.46.

[0065] (E)-1-methyl-4-(prop-1-en-1-yl)benzene (b): Synthesized according to the standard reaction procedure, the product was purified by silica gel column chromatography using a 100:1 ratio of petroleum ether to ethyl acetate as the eluent. The product was a colorless liquid, 54.76 mg, in an 83% yield. Structural analysis data are as follows: 1 H NMR(400 MHz,Chloroform-d)δ7.26(d,J=7.9Hz,2H),7.13(d,J=7.9Hz,2H),6.41(d,J=15.8Hz,1H),6.27–6.17(m,1H),2.36(s,3H),1.91(d,J=6.6Hz,3H). 13 C NMR(101MHz,Chloroform-d)δ136.39,135.18,130.85,129.16, 125.71,124.61,21.13,18.45.

[0066] (E)-1-methyl-3-(prop-1-en-1-yl)benzene (c): Synthesized according to the standard reaction procedure, the product was purified by silica gel column chromatography using a 100:1 ratio of petroleum ether to ethyl acetate as the eluent. The product was a colorless liquid, 52.84 mg, in an 80% yield. Structural analysis data are as follows: 1H NMR (400 MHz, Chloroform-d) δ7.18 (m, 3H), 7.03 (d, J = 7.4Hz, 1H), 6.40 (d, J = 15.4Hz, 1H), 6.25 (m, 1H), 2.36 (s, 3H), 1.90 (d, J = 6.5Hz, 3H). 13 CNMR(101 MHz,Chloroform-d)δ137.92,137.87,131.06,128.34,127.50,126.56,125.42,122.92,21.38,18.45.

[0067] (E)-1-(tert-butyl)-4-(prop-1-en-1-yl)benzene (d): Synthesized according to the standard reaction procedure, the product was purified by silica gel column chromatography using a 100:1 ratio of petroleum ether to ethyl acetate as the eluent. The product was a colorless liquid, 70.46 mg, in an 81% yield. Structural analysis data are as follows: 1 H NMR (400 MHz, Chloroform-d) δ7.38–7.28(m,4H),6.42(d,J=15.7Hz,1H),6.23(m,1H),1.91(d,J=6.6Hz,3H),1.35(s,9H). 13 C NMR (101MHz, Chloroform-d) δ149.67,135.18,130.72,125.50,125.34,124.82,34.45,31.31,18.46.

[0068] (E)-1-chloro-4-(prop-1-en-1-yl)benzene(e): Synthesized according to the standard reaction procedure, the product was purified by silica gel column chromatography using a 100:1 ratio of petroleum ether to ethyl acetate as the eluent. The product was a colorless liquid, 59.28 mg, in a 78% yield. Structural analysis data are as follows: 1 H NMR (400 MHz, Chloroform-d) δ7.25 (s, 4H), 6.36 (d, J=15.8Hz, 1H), 6.26–6.17 (m, 1H), 1.88 (d, J=6.6Hz, 3H). 13 C NMR(101MHz,Chloroform-d)δ136.40, 132.24,129.86,128.56,126.99,126.43,18.44.

[0069] (E)-1-chloro-3-(prop-1-en-1-yl)benzene (f): Synthesized according to the standard reaction procedure, the product was purified by silica gel column chromatography using a 100:1 ratio of petroleum ether to ethyl acetate as the eluent. The product was a colorless liquid, 57.06 mg, in a 75% yield. Structural analysis data are as follows: 1 H NMR (400 MHz, Chloroform-d) δ7.32 (s, 1H), 7.24–7.15 (m, 3H), 6.35 (d, J = 14.1Hz, 1H), 6.31–6.21 (m, 1H), 1.89 (d, J = 6.7Hz, 3H). 13 C NMR (101MHz, Chloroform-d) δ139.80,134.38,129.80,129.62,127.33,126.64,125.75,124.00,18.42.

[0070] (E)-1-chloro-2-(prop-1-en-1-yl)benzene (g): Synthesized according to the standard reaction procedure, the product was purified by silica gel column chromatography using a 100:1 ratio of petroleum ether to ethyl acetate as the eluent. The product was a colorless liquid, 54.74 mg, in a 72% yield. Structural analysis data are as follows: 1 H NMR(400MHz, Chloroform-d)δ7.49(d,J=7.7Hz,1H),7.33(d,J=7.8Hz,1H),7.20(m,1H),7.13(m,1H),6.79(d,J=15.7Hz,1H),6.23(m,6.7Hz,1H),1.94(d,J=6.7 Hz,3H). 13 C NMR (101MHz, Chloroform-d) δ135.95,132.36,129.54,128.69,127.76,127.29,126.71,126.57,18.72.

[0071] (E)-1-bromo-4-(prop-1-en-1-yl)benzene(h): Synthesized according to the standard reaction procedure, the product was purified by silica gel column chromatography using a 100:1 ratio of petroleum ether to ethyl acetate as the eluent. The product was a colorless liquid, 75.46 mg, in a 77% yield. Structural analysis data are as follows: 1H NMR (400 MHz, Chloroform-d) δ7.41 (m, 2H), 7.19 (d, J = 8.3Hz, 2H), 6.34 (d, J = 15.8Hz, 1H), 6.23 (m, J = 15.7, 6.4Hz, 1H), 1.88 (d, J = 6.4Hz, 3H). 13 C NMR (101MHz, Chloroform-d) δ136.84,131.49,129.91,127.34,126.58,120.31,18.46.

[0072] (E)-1-bromo-3-(prop-1-en-1-yl)benzene(i): Synthesized according to the standard reaction procedure, the product was purified by silica gel column chromatography using a 100:1 ratio of petroleum ether to ethyl acetate as the eluent. The product was a colorless liquid, 77.42 mg, in a 79% yield. Structural analysis data are as follows: 1 H NMR(400 MHz,Chloroform-d)δ7.50(s,1H),7.33(d,J=7.7Hz,1H),7.25(d,J=7.8Hz,1H),7.17(t,J=7.8Hz,1H),6.35(d,J=17.1Hz,1H),6.31–6.21(m,1H), 1.91(d,J=6.2Hz,3H). 13 C NMR(101MHz,Chloroform-d)δ140.07, 129.92,129.68,129.54,128.69,127.39,124.43,122.66,18.43.

[0073] (E)-1-fluoro-4-(prop-1-en-1-yl)benzene (j): Synthesized according to the standard reaction procedure, the product was purified by silica gel column chromatography using a 100:1 ratio of petroleum ether to ethyl acetate as the eluent. The product was a colorless liquid, 47.64 mg, in a 70% yield. Structural analysis data are as follows: 1 H NMR (400MHz, Chloroform-d) δ7.28(m,2H),6.97(t,J=8.6Hz,2H),6.48–6.27(d,1H),6.15(m,1H),1.87(d,J=6.5Hz,3H). 13C NMR (101MHz, Chloroform-d) δ 161.82 (d, J = 245.3Hz), 134.07 (d, J = 3.2Hz), 129.84, 127.17 (d, J = 7.9Hz), 125.40(d,J=2.3Hz), 115.27(d,J=21.4Hz), 18.38.

[0074] (E)-1-methoxy-4-(prop-1-en-1-yl)benzene (k): Synthesized according to the standard reaction procedure, the product was purified by silica gel column chromatography using a 100:1 ratio of petroleum ether to ethyl acetate as the eluent. The product was a colorless liquid, 46.64 mg, in a 63% yield. Structural analysis data are as follows: 1 H NMR (400 MHz, Chloroform-d) δ7.35–7.18(m,2H),6.84(d,J=8.5Hz,2H),6.36(d,J=15.7Hz,1H),6.18–6.03(m,1H),3.81(s,3H),1.87(d,J=6.6Hz,3H). 13 C NMR(101MHz,Chloroform-d)δ130.81,130.32,126.84,123.46,113.88, 55.25,18.39.

[0075] (E)-2-(prop-1-en-1-yl)naphthalene(l): Synthesized according to the standard reaction procedure, the product was purified by silica gel column chromatography using a 100:1 ratio of petroleum ether to ethyl acetate as the eluent. The product was obtained as a white solid, 70.56 mg, in an 84% yield. Structural analysis data are as follows: 1 H NMR(400MHz, Chloroform-d)δ7.86–7.79(m,3H),7.71(d,J=1.6Hz,1H),7.62(dd,J=8.6,1.7Hz,1H),7.53–7.43(m,2H),6.63(d,J=15.6Hz,1H),6.42(m,1H),2.00 (d,J=6.6Hz,3H). 13 C NMR(101MHz,Chloroform-d)δ135.37,133.71,132.61,131.15,128.01,127.79,127.58,126.11,126.06,125.37,125.14, 123.49,18.58.

[0076] 2-Octene(m): Synthesized according to the standard reaction procedure, the product was purified by silica gel column chromatography using a 150:1 ratio of petroleum ether to ethyl acetate as the eluent. The product was a colorless liquid, 28.05 mg, in a 50% yield. Structural analysis data are as follows: 1 HNMR(400MHz,Chloroform-d)δ6.22–6.27(m, 1H),5.47–5.52(m,1H),2.10(q,J=7.1Hz,2H),1.24–1.44(m,6H),0.89(t,J=6.8Hz,3H),0.20(s,9H). 13 C NMR(101MHz,Chloroform-d)δ132.2, 125.2,33.4,32.0,29.7,19.2,14.1.

[0077] (E)-But-2-en-2-ylbenzene(n): Synthesized according to the standard reaction procedure, the product was purified by silica gel column chromatography using a 100:1 ratio of petroleum ether to ethyl acetate as the eluent. The product was a colorless liquid, 42.65 mg, in a 65% yield. Structural analysis data are as follows: 1 H NMR (400MHz, Chloroform-d): 7.41(m,2H),7.34(m,2H),7.25(m,1H),5.90(m,1H),2.07(m,3H),1.84(m,3H); 13 C NMR (101MHz, Chloroform-d): 144.0, 135.5, 128.1, 126.4, 125.5, 122.4, 15.5, 14.3.

[0078] Prop-1-ene-1,1-diyldibenzene(o): Synthesized according to the standard reaction procedure, the product was purified by silica gel column chromatography using a 10:1 ratio of petroleum ether to ethyl acetate as the eluent. The product was obtained as a white solid, 54.31 mg, in a 56% yield. Structural analysis data are as follows: 1 H NMR (500MHz, CDCl3) δ7.37(t,J=8.0Hz,2H),7.30(t,J=7.5Hz,1H),7.25(t,J=7.5,2H),7.22-7.18(m,5H),6.17(q,J=7.0Hz,1H),1.76(d,J=7.0Hz,3H); 13CNMR (125MHz, CDCl3) δ143.2,142.6,140.2,130.2,128.3,128.2,127.4,127.0, 126.9,124.3,15.9.

[0079] Ethene-1,1,2-triyltribenzene (p): Synthesized according to a specific reaction process, the product was purified by silica gel column chromatography using a 100:1 ratio of petroleum ether to ethyl acetate as the eluent. The product was obtained as a white solid, 22.41 mg, in a 35% yield. Structural analysis data are as follows: 1 H NMR (400MHz, Chloroform-d) δ7.33 (s, 8H), 7.24–7.18 (m, 2H), 7.13 (m, 3H), 7.03 (d, J = 7.3Hz, 2H), 6.97 (s, 1H). 13 C NMR (101MHz, Chloroform-d) δ144.42,143.58,141.35,138.38,131.38,130.53,129.61,129.18,129.15,128.94,128.59,128.48,128.38,127.72.

[0080] (E)-prop-1-ene-1,3-diyldibenzene (q): Synthesized according to a specific reaction procedure, the product was purified by silica gel column chromatography using a 100:1 ratio of petroleum ether to ethyl acetate as the eluent. The product was obtained as a white solid, 26.68 mg, in a 55% yield. Structural analysis data are as follows: 1 H NMR(400MHz, Chloroform-d)δ7.50–7.43(m,3H),7.43–7.38(m,3H),7.38–7.33(m,3H),7.33–7.29(m,1H),6.58(d,J=15.8Hz,1H),6.48(m,1H),3.66(d,J=6.6Hz, 2H). 13 C NMR (101MHz, Chloroform-d) δ137.43,131.03,129.16,128.62,128.45,127.05,126.13,126.09,39.30.

[0081] (E)-1-methyl-3-(3-phenylprop-1-en-1-yl)benzene(r): Synthesized according to a specific reaction procedure, the product was purified by silica gel column chromatography using a 100:1 ratio of petroleum ether to ethyl acetate as the eluent. The product was obtained as a white solid, 25.48 mg, in a 49% yield. Structural analysis data are as follows: 1 H NMR (400MHz, Chloroform-d) δ7.32(t,J=7.5Hz,3H),7.23(d,J=8.3Hz,2H),7.18(d,J=5.8Hz,3H),7.03(d,J=6.9Hz,1H),6.44(d,J=15.9Hz,1H), 6.35(m,1H),3.55(d,J=6.5Hz,2H),2.33(s,3H). 13 C NMR (101MHz, Chloroform-d) δ140.23,138.00,137.41,131.12,129.00,128.65,128.45,128.38,127.87,126.83,126.13,123.27,39.35,21.37.

[0082] (E)-1-(but-1-en-1-yl)-4-methylbenzene(s): Synthesized according to the standard reaction procedure, the product was purified by silica gel column chromatography using a 100:1 ratio of petroleum ether to ethyl acetate as the eluent. The product was a colorless liquid, 51.84 mg, in a 71% yield. Structural analysis data are as follows: 1 H NMR(400MHz, Chloroform-d)δ7.24(d,J=7.8Hz,2H),7.10(d,J=7.8Hz,2H),6.35(d,J=15.8Hz,1H),6.21(m,J=15.9,6.4Hz,1H),2.32(s,3H),2.22(p,J=7.2Hz, 2H),1.09(t,J=7.5Hz,3H). 13 C NMR (101MHz, Chloroform-d) δ136.39,135.15,131.60,129.14,128.59,125.77,26.03,21.11,13.70.

[0083] (E)-1-(but-1-en-1-yl)-4-chlorobenzene(t): Synthesized according to the standard reaction procedure, the product was purified by silica gel column chromatography using a 100:1 ratio of petroleum ether to ethyl acetate as the eluent. The product was a colorless liquid, 58.16 mg, in a 70% yield. Structural analysis data are as follows:1 H NMR (400MHz, CDCl3) δ7.25 (s, 4H), 6.38-6.18 (m, 2H), 2.28-2.16 (m, 2H), 1.09 (t, J = 8.0 Hz, 3H). 13 C NMR(101MHz,Chloroform-d)δ136.44,133.38,132.26,128.58, 127.64,127.11,26.04,13.54.

[0084] (E)-1-chloro-4-(3-phenylprop-1-en-1-yl)benzene(u): Synthesized according to a specific reaction procedure, the product was purified by silica gel column chromatography using a 100:1 ratio of petroleum ether to ethyl acetate as the eluent. The product was obtained as a white solid, 29.07 mg, in a 51% yield. Structural analysis data are as follows: 1 H NMR (400MHz, Chloroform-d) δ7.38–7.33(m,2H),7.30(d,J=2.9Hz,4H),7.27(d,J=7.2Hz,3H),6.44(d,J=15.9Hz,1H),6.37(m,1H),3.58(d,J=6.1Hz, 2H). 13 C NMR (101MHz, Chloroform-d) δ139.84,135.95,130.00,129.82,128.64,128.60,128.52,127.30,126.26,39.29.

Claims

1. A method for synthesizing 1,2-disubstituted olefins by reacting terminal olefins with sulfoxides, characterized in that: The terminal olefin reacts with sulfoxide in a one-pot reaction in the presence of a metal salt and hydrogen peroxide. A hydrogen atom on the terminal carbon of the olefin is replaced by a hydrocarbon group, and the resulting product is a 1,2-disubstituted olefin with a sulfoxide hydrocarbon group coupled to the terminal carbon atom of the olefin. The terminal olefin has the structure of Formula 1: ； The sulfoxide has a structure of Formula 2: ； in, R1 is an aromatic ring group or a substituted aromatic group or a C1-C 10 The substituted aryl group contains 1 to 2 substituents, and the substituents are selected from at least one of a halogen substituent, an alkyl group, a hydroxyl group, an amino group, a nitro group, an aldehyde group, and a carboxyl group. The halogen substituent is fluorine, chlorine, bromine, or iodine. The alkyl group is C1 to C 10 Alkyl; R2 is hydrogen; R is methyl, ethyl, phenyl or benzyl; The metal salt is an iron salt, a copper salt, a nickel salt or a cobalt salt.

2. The method for synthesizing 1,2-disubstituted olefins by reacting terminal olefins with sulfoxides according to claim 1, characterized in that: The ratio of hydrogen peroxide to terminal olefin is 2~8:

1.

3. The method for synthesizing 1,2-disubstituted olefins by reacting terminal olefins with sulfoxides according to claim 2, characterized in that: The ratio of hydrogen peroxide to terminal olefin is 4:

1.

4. The method for synthesizing 1,2-disubstituted olefins by reacting terminal olefins with sulfoxides according to claim 1, characterized in that: The reaction conditions are: under atmospheric atmosphere, at a temperature of 80-160° C., and for 2-12 hours.

5. The method for synthesizing 1,2-disubstituted olefins by reacting terminal olefins with sulfoxides according to claim 4, characterized in that: The reaction conditions are: under atmospheric atmosphere, at a temperature of 140° C., and for 6 h.

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