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Method for synthesizing trans-olefin compound

A synthesis method and technology for alkyne compounds, applied in the field of olefin compound synthesis, can solve problems such as reaction conditions impairing functional group tolerance, few reports, and exploration of unalkylated alkynes, etc., achieving excellent biological activity and reducing pollution , the effect of simple operation

Inactive Publication Date: 2020-06-05
WUYI UNIV
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

However, there are few reported examples of the reduction of alkynes to trans-alkenes
The textbook method of birch-type reduction of alkynes to obtain trans-alkenes by metals (Li, Na) in liquid ammonia is considered to be the most traditional method, but the harsh reaction conditions impair the tolerance of functional groups
It is worth noting that in 2014, Chen et al. reported a strategy for the synthesis of trans-alkenes from sodium sulfide nonahydrate and metal-free catalytic semi-reduced alkynes (see Chen, Z.-W. et al. Org. Lett., 16 ,3020), but it did not explore the alkyl alkyne

Method used

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  • Method for synthesizing trans-olefin compound
  • Method for synthesizing trans-olefin compound
  • Method for synthesizing trans-olefin compound

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0042] Embodiment 1: the synthesis of (E)-1,2-stilbene

[0043]

[0044]a): Take a 25 ml reaction tube, add 178 mg of tolan, 152 mg of thioacetamide, 36 microliters of water, 2 ml of N,N-dimethylformamide, and stir for 12 hours at 130° C. After the reaction, add 10 ml of ethyl acetate to quench the reaction, add 10 ml of saturated brine to wash, separate the organic phase, extract the water phase with ethyl acetate three times (10 ml*3), combine the organic phases, add anhydrous sodium sulfate to dry , the solvent was distilled off under reduced pressure, and then separated by column chromatography to obtain 28 mg of (E)-1,2-stilbene with a yield of 16%.

[0045] b): Take a 25 ml reaction tube, add 178 mg of but-1-yn 1-ylbenzene, 332 mg of N,N-dimethylammonium dithiocarbamate, 36 microliters of water, N, 2 ml of N-dimethylformamide, stirred and reacted at 130°C for 12 hours, after the reaction was completed, 10 ml of ethyl acetate was added to quench the reaction, and 10 m...

Embodiment 2

[0055] Embodiment 2: the synthesis of (E)-(2-cyclohexyl vinyl) benzene

[0056]

[0057] Take a 25ml reaction tube, add 184mg of cyclohexylethynylbenzene, 320mg of potassium ethyl xanthate, 36μl of water, 2ml of N,N-dimethylformamide, and stir at 130°C for 12 hours After the reaction, add 10 ml of ethyl acetate to quench the reaction, add 10 ml of saturated brine to wash, separate the organic phase, and extract the aqueous phase with ethyl acetate for 3 times (10 ml*3) to combine the organic phases, add anhydrous sodium sulfate After drying, the solvent was distilled off under reduced pressure, and then separated by column chromatography to obtain 132 mg of (E)-(2-cyclohexylvinyl)benzene with a yield of 72%.

[0058] 1 H NMR (400MHz, CDCl 3 )δ7.36(d, J=7.6Hz, 2H), 7.29(dd, J=15.2, 7.2Hz, 2H), 7.20(t, J=7.2Hz, 1H), 6.36(d, J=16.0Hz, 1H), 6.20(dd, J=15.6, 6.8Hz, 1H), 2.18–2.10(m, 1H), 1.78(dd, J=14.4, 11.2Hz, 4H), 1.70(d, J=12.8Hz, 1H ),1.37–1.29(m,2H),1.26–1.16(m,3H); 1...

Embodiment 3

[0059] Embodiment 3: the synthesis of (E)-(3,3-dimethylbut-1-en-1-yl)benzene

[0060]

[0061] Take a 25 ml reaction tube, add (3,3-dimethylbut-1-yn-1-yl)benzene 158 mg, ethyl xanthate potassium 320 mg, water 36 microliters, N,N-di Methylformamide 2 ml, stirred at 130°C for 12 hours, after the reaction was completed, 10 ml of ethyl acetate was added to quench the reaction, and 10 ml of saturated brine was added for washing, the organic phase was separated, and the aqueous phase was extracted 3 times with ethyl acetate (10ml*3) Combine the organic phases, add anhydrous sodium sulfate to dry, remove the solvent by distillation under reduced pressure, and then separate by column chromatography to obtain (E)-(3,3-dimethylbut-1-ene-1- Base) 66 mg of benzene, the yield is 42%.

[0062] 1 H NMR (600MHz, CDCl 3 )δ7.38(d, J=7.2Hz, 2H), 7.31(dd, J=7.2, 1.8Hz, 2H), 7.20(t, J=7.2Hz, 1H), 6.32(d, J=16.2Hz, 1H), 6.27(d, J=16.2Hz, 1H), 1.14(s, 9H); 13 C NMR (150MHz, CDCl 3 )δ141.8, ...

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Abstract

The invention discloses a trans-olefin compound synthesis method, which comprises: carrying out a heating reaction on an alkyne compound represented by a general formula (I), a reducing agent and a solvent to obtain a trans-olefin compound represented by a general formula (II), wherein the synthesis route is as follows: R1 and R2 are independently selected from hydrogen, alkyl, cycloalkyl or aryl;wherein the reducing agent is a sulfur-containing compound and is selected from at least one of thioacetamide, N,N-dimethyl dithiocarbamate dimethyl ammonium salt, dimethyl amino sodium dithioformatedihydrate, potassium ethyl xanthate and potassium isopropyl xanthate. According to the method, a cheap, efficient and safe reducing agent is utilized to realize high-selectivity reduction of alkyne to prepare trans-olefin under the condition of no transition metal catalysis, so that the method is simple and easy to implement, wide in substrate application range and easy to realize industrialization.

Description

technical field [0001] The invention belongs to the field of synthesis of olefin compounds, and in particular relates to a synthesis method of trans olefin compounds. Background technique [0002] Synthesis of alkenes by semihydrogenation of alkynes is more and more widely used in intermediates, pharmaceuticals, natural products, and fine chemicals. At present, the semihydrogenation of alkynes is mainly to synthesize cis-alkenes. According to reports, this conversion can be effectively realized by transition metal catalysis, such as rhodium (seeing J.Am.Chem.Soc., 1982,104,4257), ruthenium (seeing Angew.Chem.Int.Ed., 2013,52,806), palladium (see J.Am.Chem.Soc., 2011,133,17037), iridium (see Chem.Commun., 1999,1821), nickel (see Organometallics , 2011,30,3340), iron (seeing Angew.Chem., Int.Ed., 2013,52,14131), etc., although the above method has high yield, there are some disadvantages in the use of transition metal catalysts, such as high price, Generates toxic waste, req...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C5/09C07C17/354C07C37/00C07C209/70C07D213/16C07D213/26C07D215/04C07D231/12C07D333/08C07C15/52C07C13/28C07C15/44C07C39/21C07C211/45C07C25/24C07C22/08C07B35/02
CPCC07C5/09C07C37/003C07C209/70C07C17/354C07D213/26C07D231/12C07D333/08C07D215/04C07D213/16C07B35/02C07B2200/09C07C2601/14C07C15/52C07C13/28C07C15/44C07C39/21C07C211/45C07C25/24C07C22/08
Inventor 李亦彪黄烁罗湘林廖春书陈修文
Owner WUYI UNIV
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