CN103102228B - Preparation method of aryl eneyne compound - Google Patents

Preparation method of aryl eneyne compound Download PDF

Info

Publication number
CN103102228B
CN103102228B CN201210326046.3A CN201210326046A CN103102228B CN 103102228 B CN103102228 B CN 103102228B CN 201210326046 A CN201210326046 A CN 201210326046A CN 103102228 B CN103102228 B CN 103102228B
Authority
CN
China
Prior art keywords
preparation
arylalkyne
reaction
cdcl
nmr
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
CN201210326046.3A
Other languages
Chinese (zh)
Other versions
CN103102228A (en
Inventor
徐华栋
何维杰
蔡茂强
张人伟
郑庆
胡文浩
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
East China Normal University
Original Assignee
East China Normal University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by East China Normal University filed Critical East China Normal University
Priority to CN201210326046.3A priority Critical patent/CN103102228B/en
Publication of CN103102228A publication Critical patent/CN103102228A/en
Application granted granted Critical
Publication of CN103102228B publication Critical patent/CN103102228B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Landscapes

  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention discloses a preparation method of an aryl eneyne compound. The method uses an aryl alkyne compound or propargyl alcohol or a propargyl amine compound as a raw material, a rhodium complex produced through the reaction of [Rh(COD)Cl]2 and ligand as a catalyst to react to obtain the aryl eneyne compound represented by the formula (I) in the presence of an organic solvent. The preparation method disclosed by the invention has easily obtained raw materials, and is low in catalyst dosage, efficient and easy to operate, good in region selectivity, good in reaction yield and strong in practicability. The prepared aryl eneyne compound is an important chemical synthesis intermediate.

Description

A kind of preparation method of arylalkyne ene compound
Technical field
The present invention relates to compou nd synthesis technical field, be specifically related to a kind of preparation method of arylalkyne ene compound.
Background technology
Conjugation alkynes vinyl compound is the very important synthetic intermediate of a class, and it is important structure unit and the building block of many natural products, pharmaceutical intermediate.The synthetic existing bibliographical information of alkynes vinyl compound at present, for example: document (1) Helio A, Stefani; Marlito Gomes, Jr.Tetrahedron Lett.2005,46,563; (2) K, Sonogashira; Y, Tohda; N, Hagihara.Tetrahedron Lett.1975,16,4467; (3) Hong Mei Peng; Jing Zhao; Xingwei Li.Adv.Synth.Catal.2009,351,1371; (4) H, Katayama; H, Yari; F, Ozawa.Chem.Commun.2005,34,4336 (5) M, Nishiura; Z, Hou; T, Miyamoto.J.Am.Chem.Soc.2003,125,1184.The synthetic method of the above bibliographical information of prior art makes alkynes self dimerization by metal catalytic or makes alkynes and alkene coupling obtains arylalkyne vinyl compound.Almost seldom there are document or report to propose directly to intersect hydrogen alkynyl by two kinds of end alkynes and prepare the synthetic method of the Atom economy of arylalkyne ene compound.
Summary of the invention
The present invention overcomes the above-mentioned defect of prior art, and a kind of preparation method of important chemosynthesis intermediate arylalkyne ene compound is provided.
The present invention proposes a kind of preparation method of arylalkyne ene compound, taking arylalkyne compounds and propargyl alcohol or propargylamine compounds as raw material, with [Rh (COD) Cl] 2the rhodium complex generating with part effect is catalyzer, and in organic solvent, reaction obtains the described arylalkyne ene compound shown in formula (I);
Described preparation method's reaction scheme is as shown in following reaction formula (A):
Wherein, R 1for hydrogen, methoxyl group, carboxaldehyde radicals, nitro, bromine, amino or-NHAc;
R 2for-OH or-NHTs.
The product that preparation method of the present invention obtains is suc as formula the arylalkyne ene compound shown in (I),
In formula (I), R 1for hydrogen, methoxyl group, carboxaldehyde radicals, nitro, bromine, amino or-NHAc; R 2for-OH or-NHTs.
In the present invention, raw material arylalkyne compounds structure is: r 1for hydrogen, methoxyl group, carboxaldehyde radicals, nitro, bromine, amino or-NHAc.Raw material propargyl alcohol or propargylamine compounds structure are: r 2for :-OH or-NHTs.
In the present invention, described arylalkyne compounds, propargyl alcohol or propargylamine compounds, [Rh (COD) Cl] 2, part mol ratio be 1: 1-1.5: 0.05: 0.2-0.3.Preferably, arylalkyne compounds, propargyl alcohol or propargylamine compounds, [Rh (COD) Cl] 2, part mol ratio be 1: 1.5: 0.05: 0.2.
In the present invention, described part is:
Preferably, part is
In the present invention, described organic solvent is methylene dichloride, trichloromethane, tetrahydrofuran (THF), 1,2-ethylene dichloride.Described organic solvent can make polarity or non-polar solvent.
In the present invention, the described reaction times is 10-12 hour.For example, reaction overnight.
In the present invention, described temperature of reaction is 25 DEG C to 40 DEG C.Preferably, temperature of reaction is 40 DEG C.
Preparation method of the present invention, taking arylalkyne compounds and propargyl alcohol or propargylamine compounds as raw material, under the condition existing at organic solvent, with [Rh (COD) Cl] 2the rhodium complex generating with ligand L effect is catalyzer, and reaction overnight makes arylalkyne ene compound.Adopt the inventive method products therefrom to be separated through column chromatography method.Column chromatography for separation developping agent used is the mixed solvent of polar solvent and non-polar solvent, preferably, the mixed solvents such as solvent can be ethyl acetate-sherwood oil, ethyl acetate-normal hexane, its volume ratio can be respectively: polar solvent: non-polar solvent=1: 2-10.For example: ethyl acetate: sherwood oil=1: 2-10.
The present invention studies discovery, uses with [Rh (COD) Cl] 2the rhodium complex catalyzed lower hydrogen alkynylation reaction that intersects with ligand L effect generates, can highly synthesize multiple together with 2-alkynyl vinyl carbinol with together with 2-alkynyl propylamine compound together with selectivity.
Prior art is to generate the formula coupling of meeting and discussing of alkynes alkene or certain two kinds of acetylene compound head with a certain acetylene compound self dimerization to generate alkynes ene compound.And the synthetic method of arylalkyne ene compound of the present invention is to adopt metal rhodium complex catalysis, innovation ground proposes with Rh (COD) Cl] 2, make to touch tail formula as two class acetylene compounds of raw material with head and generate new alkynes ene compound as catalyzer with the rhodium complex of ligand L effect generation, realize high regioselectivity.The present invention adopts atomic economy reaction to prepare arylalkyne ene compound, has catalyst levels low, and raw material is easy to get, efficient easy handling, and regioselectivity is good, and product yield is high, practical, efficient Atom economy, the advantages such as highly selective.The product that preparation method of the present invention provides is a class important intermediate arylalkyne ene compound.
Embodiment
Below in conjunction with embodiment, the invention will be further described.Implement process of the present invention, condition, experimental technique etc., except the content of mentioning specially below, be universal knowledege and the common practise of this area, the present invention is not particularly limited content.
The preparation method of a kind of arylalkyne ene compound of the present invention, taking arylalkyne compounds and propargyl alcohol or propargylamine compounds as raw material, with [Rh (COD) Cl] 2the rhodium complex generating with part effect is catalyzer, and in organic solvent, reaction obtains the described arylalkyne ene compound shown in formula (I); Described preparation method's reaction scheme as shown in following formula (A), wherein, R 1for hydrogen, methoxyl group, carboxaldehyde radicals, nitro, bromine, amino or-NHAc; R 2for-OH or-NHTs.
Reaction formula (A)
preferred part is
Embodiment 1:
With [Rh (COD) Cl] 2prepare reacting of arylalkyne ene compound with the metal rhodium complex catalysis that part forms, under argon atmosphere, in dry reaction tubes, add [Rh (COD) Cl] 2and part, add successively subsequently anhydrous methylene chloride and starting compound (1), finally inject starting compound (2) with peristaltic pump, reaction overnight under 40 DEG C or room temperature.After finishing, reaction obtains product (ethyl acetate: sherwood oil=1: 2-10, V/V) by concentrated reacting liquid filtering through column chromatography for separation.Reaction scheme, reaction raw materials, experiment condition and product etc. are listed as follows.
Wherein, ligand L is respectively:
Embodiment 2:
With [Rh (COD) Cl] 2prepare reacting of arylalkyne ene compound with the metal rhodium complex catalysis that part forms, under argon atmosphere, in dry reaction tubes, add 5mol%[Rh (COD) Cl] 2with 20mol%PPh 3, add successively subsequently solvent and starting compound (1), finally inject starting compound (2) with peristaltic pump, reaction overnight under 40 DEG C or room temperature.After finishing, reaction obtains product (ethyl acetate: sherwood oil=1: 2-10, V/V) by concentrated reacting liquid filtering through column chromatography for separation.Reaction scheme, reaction raw materials, optimal conditions and product etc. are listed as follows.
Wherein, DCM is methylene dichloride, and THF is tetrahydrofuran (THF), and DCE is 1,2-ethylene dichloride.
Embodiment 3: aryl ethane and propargyl alcohol are prepared 2-alkynyl vinyl carbinol under metal rhodium complex catalysis
Under argon atmosphere, in dry reaction tubes, add [Rh (COD) Cl] 2(5mol%) and PPh 3(30mol%), add successively subsequently 1ml anhydrous methylene chloride and 0.5mmol aryl ethane.Finally inject 0.75mmol propargyl alcohol with peristaltic pump, reaction overnight at 40 DEG C.After finishing, reaction obtains product (ethyl acetate: sherwood oil=1: 2-10, V/V) by concentrated reacting liquid filtering through column chromatography for separation.
Raw materials used arylalkyne compounds in, R 1be respectively: hydrogen, methoxyl group, carboxaldehyde radicals, nitro, bromine, amino or-NHAc, corresponding product formula (I) the arylalkyne ene compound preparing is P1-P10, refers to shown below.
Yield: 70%. 1h NMR (500MHz, CDCl 3): δ ppm 7.47-7.45 (m, 2H), 7.33-7.32 (m, 3H), 5.61 (d, J=1.2Hz, 1H), 5.58 (s, 1H), 4.25 (d, J=3.1Hz, 2H), 1.90 (bs, 1H); 13c NMR (100MHz, CDCl 3): δ ppm 131.7,131.2,128.5,128.4,122.8,120.2,90.8,87.0, and 65.3; HRMS (ESI): calculated value C 11h 10o[M+Na] +: 181.0624; Detected value: 181.0623..
Yield: 55%. 1h NMR (500MHz, CDCl 3): δ ppm 7.41 (d, J=8.7Hz, 2H), 6.87 (d, J=8.7Hz, 2H), 5.58 (d, J=1.2Hz, 1H), 5.55 (s, 1H), 4.24 (s, 2H), 3.83 (s, 3H), 1.90 (bs, 1H); 13c NMR (100MHz, CDCl 3): δ ppm 159.8,133.2,119.7,118.4,114.9,114.0,90.6,85.5,65.4,55.2; HRMS (ESI): calculated value C 12h 12o 2[M+Na] +: 211.0733, detected value: 211.0730.
Yield: 52%. 1h NMR (400MHz, CDCl 3): δ ppm 8.20 (d, J=8.4Hz, 2H), 7.60 (d, J=8.8Hz, 2H), 5.73 (s, 1H), 5.68 (s, 1H), 4.27 (s, 2H); 13c NMR (100MHz, CDCl 3): δ ppm 152.4,132.4,129.7,123.6,122.7,92.2,88.8,65.1.HRMS (ESI): calculated value C 11h 9nO 3[M+Na] +: 226.0475, detected value: 226.0474.
Yield: 65%. 1h NMR (500MHz, CDCl 3): δ ppm 10.0 (s, 1H), 7.85 (d, J=7.5Hz, 2H), 7.61 (d, J=7.5Hz, 2H), 5.70 (s, 1H), 5.66 (s, 1H), 4.27 (s, 2H), 1.86 (bs, 1H). 13c NMR (125MHz, CDCl 3): δ ppm 191.5,135.5,132.2,130.8,129.5,129.1,122.0,91.0,89.8,65.1.HRMS (ESI): calculated value C 12h 10o 2[M+Na] +: 209.0573, detected value: 209.0571.
Yield: 88%. 1h NMR (500MHz, CDCl 3): δ ppm 7.59 (d, J=7.9Hz, 1H), 7.49 (d, J=1.3Hz, 1H), 7.28 (m, 1H), 7.18 (m, 1H), 5.64 (s, 2H), 4.27 (s, 2H). 13c NMR (100MHz, CDCl 3): δ ppm 133.3,132.4,131.1,129.7,127.1,125.7,124.9,121.1,91.6,89.6,65.2.HRMS (ESI): calculated value C 11h 9brO[M+Na] +: 258.9729, detected value: 258.9730.
Yield: 87%. 1h NMR (400MHz, CDCl 3): δ ppm 7.32-7.28 (m, 1H), 7.17-7.13 (m, 1H), 6.77-6.71 (m, 2H), 5.57 (m, 2H), 4.27 (s, 2H), 3.77 (br, 2H). 13c NMR (100MHz, CDCl 3): δ ppm147.9,132.0,131.3,129.9,120.1,118.0,114.5,107.6,92.7,87.6,65.4.HRMS (ESI): calculated value C 11h 11nO[M+Na] +: 196.0733, detected value: 196.0728.
Yield: 65%. 1h NMR (500MHz, CDCl 3): δ ppm 7.46-7.44 (m, 2H), 7.32-7.30 (m, 2H), 5.63 (s, 1H), 5.59 (s, 1H), 4.23 (s, 2H), 1.80 (br, 1H). 13c NMR (100MHz, CDCl 3): δ ppm 133.1,131.6,131.0,122.7,121.8,121.0,89.4,88.1,65.2.HRMS (ESI): calculated value C 11h 9brO[M+Na] +258.9729, detected value: 258.9729.
Yield: 73%. 1h NMR (500MHz, CDCl 3): δ ppm 8.41 (d, J=8.4Hz, 1H), 8.23 (bs, 1H), 7.42 (d, J=7.6Hz, 1H), 7.36-7.33 (m, 1H), 7.06-7.03 (m, 1H), 5.60 (s, 1H), 5.59 (s, 1H), 4.31 (d, J=3.6Hz, 2H), 2.35 (bs, 1H), 2.23 (s, 3H). 13c NMR (125MHz, CDCl 3): δ ppm169.0,139.4,131.2,130.9,123.3,120.9,119.4,111.6,94.5,86.4,65.5,24.6.HRMS (ESI): calculated value C 13h 13nO 2[M+Na] +: 238.0838, detected value: 238.0842.
Yield: 64%. 1h NMR (400MHz, CDCl 3): δ ppm7.60 (t, J=1.6Hz, 1H), 7.46-7.43 (m, 1H), 7.38 (d, J=7.7Hz, 1H), 7.18 (t, J=7.9Hz, 1H), 5.64 (d, J=1.4Hz, 1H), 5.59 (d, J=1.4Hz, 1H), 4.23 (s, 2H), 2.04 (bs, 1H). 13c NMR (100MHz, CDCl3) :δ ppm134.4,131.6,130.9,130.2,129.8,124.8,122.1,121.3,89.2,88.3,76.7,65.2.HRMS (ESI): calculated value C 13h 13brNO 2[M+Na] +: 258.9729, detected value: 258.9727.
Embodiment 4: aryl ethane and propargylamine are prepared 2-alkynyl allylamine under metal rhodium complex catalysis
Wherein Ts is p-toluenesulfonyl, and DCM is methylene dichloride.
Under argon atmosphere, in dry reaction tubes, add [Rh (COD) Cl] 2(5mol%) and PPh 3(30mol%), add successively subsequently 1ml anhydrous methylene chloride and 0.5mmol aryl ethane.Finally inject 0.75mmol propargylamine with peristaltic pump, reaction overnight at 40 DEG C.After finishing, reaction obtains product (ethyl acetate: sherwood oil=1:2-10, V/V) by concentrated reacting liquid filtering through column chromatography for separation.
Raw materials used arylalkyne compounds in, R1 is respectively: hydrogen, methoxyl group, carboxaldehyde radicals, nitro, bromine, amino or-NHAc, corresponding product formula (I) the arylalkyne ene compound preparing is respectively P11-P20, refers to shown below.
Yield: 84%. 1h NMR (500MHz, CDCl 3): δ ppm7.79 (d, J=5.4Hz, 2H), 7.38-7.36 (m, 2H), 7.31-7.29 (m, 3H), 7.25 (d, J=8.0Hz, 2H), 5.46 (m, 2H), 5.27 (br, 1H), 3.74 (d, J=6.4Hz, 2H), 2.37 (s, 3H). 13c NMR (100MHz, CDCl 3): δ ppm143.4,137.3,131.7,129.7,128.6,128.3,127.2,127.1,122.7,122.5,90.9,87.0,47.6,21.4.HRMS (ESI): calculated value C 18h 17nO 2s[M+Na] +: 334.0872, detected value: 334.0910..
Yield: 92%. 1h NMR (500MHz, CDCl 3): δ ppm 7.78 (d, J=8.2Hz, 2H), 7.31 (d, J=8.7Hz, 2H), 7.24 (d.J=8.1Hz, 2H), 6.82 (d, J=8.6Hz, 2H), 5.40 (s, 1H), 5.39 (s, 1H), 5.27 (br, 1H), 3.78 (s, 3H), 3.72 (d, J=6.4Hz, 2H), 2.36 (s, 3H). 13c NMR (100MHz, CDCl 3): δ ppm 160.0,143.5,137.3,133.2,132.1,129.7,127.2,121.9,114.6,114.0,91.2,85.8,55.2,47.8,21.4.HRMS (ESI): calculated value C 19h 19nO 3s[M+Na] +: 364.0978, detected value: 364.1000.
Yield: 77%. 1h NMR (400MHz, CDCl 3): δ ppm 8.10 (d, J=8.4Hz, 2H), 7.71 (d, J=8.0Hz, 2H), 7.46 (d, J=8.0Hz, 2H), 7.22 (d, J=8.0Hz, 2H), 5.50 (s, 2H), 5.07 (t, J=6.0Hz, 1H), 3.7 (d, J=6.4Hz, 2H), 2.33 (s, 3H). 13c NMR (100MHz, CDCl 3): δ ppm 147.2,143.6,137.2,132.4,129.7,129.4,127.1,126.6,124.8,123.6,91.9,89.1,47.5,21.5.HRMS (ESI): calculated value C 18h 16n 2o 4s[M+Na] +: 379.0723, detected value: 379.0741.
Yield: 70%. 1h NMR (500MHz, CDCl 3): δ ppm 9.97 (s, 1H), 7.79-7.75 (m, 4H), 7.51 (d, J=7.9Hz, 2H), 7.25 (d, J=7.9Hz, 2H), 5.54 (s, 1H), 5.52 (s, 1H), 5.46 (br, 1H), 3.75 (d, J=6.4Hz, 2H), 2.37 (s, 3H). 13c NMR (100MHz, CDCl 3): δ ppm 191.7,143.6,137.3,135.7,132.3,129.8,129.6,128.9,127.2,126.9,124.3,90.9,90.0,47.5,21.4.HRMS (ESI): calculated value C 19h 17nO 3s[M+Na] +: 362.0861, detected value: 362.0864.
Yield: 95%. 1h NMR (500MHz, CDCl 3): δ ppm 7.78 (d, J=8.2Hz, 2H), 7.56 (d, J=8.1Hz, 1H), 7.39 (d, J=6.9Hz, 1H), 7.23-7.22 (m, 3H), 7.17-7.14 (m, 1H), 5.48 (s, 2H), 5.27 (br, 1H), 3.78 (d, J=6.0 Hz, 2H), 2.35 (s, 3H). 13c NMR (100MHz, CDCl 3): δ ppm143.6,137.2,133.4,132.5,130.0,129.7,127.4,127.2,126.8,125.7,124.6,123.6,91.3,90.0,47.8,21.6.HRMS (ESI): calculated value C 19h 17brNO 3s[M+Na] +: 411.9977, detected value: 412.0017.
Yield: 65%. 1h NMR (400MHz, CDCl 3): δ ppm7.69 (d, J=8.0Hz, 2H), 7.17 (d, J=8.4Hz, 2H), 7.13 (d, J=8.0Hz, 1H), 7.05 (t, J=7.7Hz, 1H), 6.61-6.56 (m, 2H), 5.35 (s, 1H), 5.32 (s, 1H), 5.26 (br, 1H), 3.86 (s, 2H), 3.65 (d, J=6.4Hz, 2H), 2.30 (s, 3H). 13c NMR (100MHz, CDCl 3): δ ppm147.9,143.5,137.1,132.1,130.1,129.7,127.3,127.1,122.4,117.9,114.6,107.3,92.3,88.1,48.1,21.5.HRMS (ESI): calculated value C 18h 18n 2o 2s[M+Na] +: 349.0981, detected value: 349.1026.
Yield: 90%, 1h NMR (500MHz, CDCl 3): δ ppm7.76 (d, J=8.0Hz, 2H), 7.42 (d, J=6.8Hz, 2H), 7.26-7.21 (m, 4H), 5.47 (s, 1H), 5.46 (s, 1H), 5.32 (br, 1H), 3.73 (d, J=6.5Hz, 2H), 2.37 (s, 3H). 13cNMR (100MHz, CDCl 3): δ ppm143.4,137.2,133.1,132.0,131.6,129.7,127.2,126.9,123.2,122.9,121.5,89.9,88.1,47.6,21.5.HRMS (ESI): calculated value C 18h 16brNO 2s[M+Na] +: 411.9977, detected value: 412.0024.
Yield: 89%. 1h NMR (400MHz, CDCl 3): δ ppm8.21 (d, J=8Hz, 1H), 7.91 (s, 1H), 7.65 (d, J=8.4Hz, 2H), 7.25-7.18 (m, 2H), 7.16-7.14 (m, 2H), 5.42 (d, J=0.4Hz, 1H), 5.37 (d, J=1.2Hz, 1H), 5.18 (br, 1H), 3.62 (d, J=6.4Hz, 2H), 2.29 (s, 3H), 2.13 (s, 3H). 13c NMR (100MHz, CDCl 3): δ ppm169.0,143.7,139.1,136.9,132.1,129.9,129.8,127.2,127.0,124.0,123.2,120.0,111.8,93.6,86.5,48.2,24.8,21.5.HRMS (ESI): calculated value C 20h 20n 2o 3s[M+Na] +: 391.1087, detected value: 391.1105.
Yield: 72%. 1h NMR (400MHz, CDCl 3): δ ppm 7.78 (d, J=8.4Hz, 1H), 7.49 (s, 1H), 7.45 (d, J=8.0Hz, 1H), 7.30-7.26 (m, 3H), 7.16 (t, J=7.9Hz, 1H), 5.50 (s, 1H), 5.48 (s, 1H), 5.17 (br, 1H), 3.75 (d, J=6.4Hz, 2H), 2.39 (s, 3H). 13c NMR (100MHz, CDCl 3): δ ppm 143.5,137.1,134.3,131.7,130.2,129.8,129.7,127.2,126.7,124.5,123.6,122.1,89.4,88.1,47.7,21.5.HRMS (ESI): calculated value C 18h 16brNO 2s[M+Na] +: 411.9977, detected value: 412.0013.
Yield: 68%. 1h NMR (500MHz, CDCl 3): δ ppm 8.15 (d, J=8.1Hz, 1H), (7.79 d, J=8.0Hz, 2H), 7.73 (s, 1H), 7.57 (d, J=7.8Hz, 1H), 7.39 (t, J=7.8Hz, 1H), 7.31-7.27 (m, 2H), 5.50 (s, 1H), 5.47 (s, 1H), 4.77 (br, 1H), 3.81 (d, J=6.0Hz, 2H), 2.38 (s, 3H), 1.68 (s, 9H). 13c NMR (125MHz, CDCl 3): δ ppm 148.8,143.3,137.0,130.0,129.5,129.0,127.2,127.0,126.9,125.2,123.2,122.4,120.0,115.1,102.6,90.3,84.4,83.1,47.7,28.0,21.3.HRMS (ESI): calculated value C 25h 26n 2o 48[M+Na] +: 473.1505, detected value: 473.1494..
The foregoing is only preferred embodiment of the present invention, be not used for limiting practical range of the present invention.Under any, in technical field, have and conventionally know the knowledgeable, without departing from the spirit and scope of the present invention, when doing various variations and retouching, protection domain of the present invention should be as the criterion with the protection domain that claims were defined.

Claims (6)

1. a preparation method for arylalkyne ene compound, is characterized in that, taking arylalkyne compounds and propargyl alcohol or propargylamine compounds as raw material, with [Rh (COD) Cl] 2the rhodium complex generating with part effect is catalyzer, and in organic solvent, reaction obtains the described arylalkyne ene compound shown in formula (I);
Described preparation method's reaction scheme is as shown in following formula (A):
Wherein, R 1for hydrogen, methoxyl group, carboxaldehyde radicals, nitro, bromine, amino or-NHAc;
R 2for-OH or-NHTs;
Described part is:
2. preparation method as claimed in claim 1, is characterized in that, described arylalkyne compounds: propargyl alcohol or propargylamine compounds: [Rh (COD) Cl] 2: the mol ratio of part is 1:1-1.5:0.05:0.2-0.3.
3. preparation method as claimed in claim 1, is characterized in that, described part is:
4. preparation method as claimed in claim 1, is characterized in that, described organic solvent be methylene dichloride, trichloromethane, tetrahydrofuran (THF) or 1,2 ?ethylene dichloride.
5. preparation method as claimed in claim 1, is characterized in that, the reaction times is 10-12 hour.
6. preparation method as claimed in claim 1, is characterized in that, temperature of reaction is 25 DEG C to 40 DEG C.
CN201210326046.3A 2012-09-05 2012-09-05 Preparation method of aryl eneyne compound Expired - Fee Related CN103102228B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201210326046.3A CN103102228B (en) 2012-09-05 2012-09-05 Preparation method of aryl eneyne compound

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201210326046.3A CN103102228B (en) 2012-09-05 2012-09-05 Preparation method of aryl eneyne compound

Publications (2)

Publication Number Publication Date
CN103102228A CN103102228A (en) 2013-05-15
CN103102228B true CN103102228B (en) 2014-07-16

Family

ID=48310466

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201210326046.3A Expired - Fee Related CN103102228B (en) 2012-09-05 2012-09-05 Preparation method of aryl eneyne compound

Country Status (1)

Country Link
CN (1) CN103102228B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113354511B (en) * 2021-06-09 2022-03-25 湖南第一师范学院 Synthesis method of gem-1, 3-eneyne compound

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TW434205B (en) * 1997-01-06 2001-05-16 American Cyanamid Co Aryne intermediates and a process for the preparation thereof

Also Published As

Publication number Publication date
CN103102228A (en) 2013-05-15

Similar Documents

Publication Publication Date Title
Hajipour et al. Sonogashira reactions catalyzed by a new and efficient copper (I) catalyst incorporating N-benzyl DABCO chloride
CN102584509A (en) Preparation method of amide
CN106349147A (en) Synthetic method of pyrrole derivatives
CN109476588A (en) The method for preparing phenylmalonic acid dintrile
CN103102228B (en) Preparation method of aryl eneyne compound
CN104151214A (en) Method for synthesizing 2-sulfonyl ketone compounds
CN103275027B (en) Synthesis method of alpha-keto amide compound
WO2019153373A1 (en) Method for synthesizing 2-benzylidene tetrahydrothiophene derivative
CN104829465A (en) Method for preparing 4-isopropamide group-1-butanol
CN106892826B (en) A kind of preparation method and application of amine and imines N-methyl
CN102558095B (en) Method for preparing aromatic amine compound
CN113354500B (en) Method for preparing 1,5-diene derivative
CN102367230A (en) Method for synthesizing nitrile from aldoxime
CN102887807B (en) Method for preparing alpha, beta-unsaturated carbonyl compounds
CN104926577A (en) Preparation method of substituted cis-olefin
CN105985279B (en) A kind of method that nitrone analog derivative prepares indole derivatives with symmetrical alkynes reaction
CN103965057B (en) A kind of nitrile prepares the method for primary amine
CN103864548A (en) Method for rapidly and efficiently preparing 1-haloalkyne
Zhang et al. Gold-catalyzed cyclization of 1-alkynyl cyclopropyl tert-butyl carbonate to construct multifunctionalized vinyl cyclopropane derivatives
CN102070383B (en) Method for preparing 1,2-diketone by performing catalytic oxidation on olefin
Wang et al. 2, 2′-Diamino-6, 6′-dimethylbiphenyl as an efficient ligand in the CuI-catalyzed Sonogashira reaction of aryl iodides and bromides with terminal alkynes
Yi et al. Polymer-supported Pd (0) catalyst for copper-and ligand-free Sonogashira reactions in aqueous media
CN104327025A (en) Preparation method of 4-aryltetralin lactone derivatives
CN104529684A (en) Method for iodization of ortho-position of functional group on palladium/carbon catalytic aromatic ring
CN104193567B (en) A kind of simple method for efficiently preparing efavirenz intermediate

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20140716

Termination date: 20170905