Preparation method of diaryl acetylene compounds

Abstract

The invention relates to preparation of an organic compound, and aims to provide a preparation method of diaryl acetylene compounds. The preparation method includes steps of adding associated tribromomethylarene compound and copper in a reactor to perform deoxidizing treatment; dissolving polyamine in a proper amount of anhydrous and oxygen-free solvent, and then adding to the reactor; performingcoupling reaction at 30-80DEG C for 3-12 hours; separating and purifying to obtain diaryl acetylene compounds. The preparation is gentle in synthesis condition and the reaction has good compatibilityto different functional groups; the raw material associated tribromomethylarene compound is convenient to compound and has different substituent groups and variable structure; by adopting one raw material, high-quality product can be obtained through simple treatment, and the output is high; by adopting two different raw materials, the asymmetrical diaryl acetylene compound can be prepared.

Description

technical field

[0001] The invention relates to the field of preparation methods of organic compounds, in particular to a new method for synthesizing diaryl acetylene compounds. Background technique

[0002] The diarylethyne compound is shown in the following formula. Alkynes containing carbon-carbon triple bond functional groups are widely used in the fields of medicine and optoelectronic materials due to their linear rigid structure and structural characteristics rich in π electrons.

[0003]

[0004] In organic synthesis, there are different methods for the formation of carbon-carbon triple bonds, which can be divided into conversion from existing functional groups to carbon-carbon triple bonds and direct construction of carbon-carbon triple bonds.

[0005] Elimination reactions are an important strategy to obtain carbon-carbon multiple bonds. A carbon-carbon triple bond can be obtained from a carbon-carbon single bond or a carbon-carbon double bond as a precursor th...

Examples

preparation example Construction

[0045] (1) Preparation of raw materials

[0046] All gem-tribromomethyl arene compounds can be prepared by existing common synthesis methods, and the molecular structure of the gem-tribromomethyl arene compounds used in the examples is shown in the following formula.

[0047]

[0048] Raw compound abbreviation

R 1

R 2

R 3

1a

H-

H-

H-

1b

F-

H-

H-

1c

Cl-

H-

H-

1d

Br-

H-

H-

1e

H-

Cl-

H-

1f

H-

Br-

H-

1g

H-

CH 3 O-

H-

1h

H-

CH 3 C(O)-

H-

1i

H-

H-

F-

1j

H-

H-

Cl-

1k

H-

H-

Br-

1l

H-

H-

tert-C 4 h 9 -

1m

H-

H-

-CF 3

1n

H-

H-

-CN

1p

H-

H-

CH 3 C(O)-

1q

H-

H-

CH 3 OC(O)-

1r

H-

H-

-NO 2

[0049] (2) Synthesis method

[0050] Deoxidize a certain stoichiometric ratio of gem-tribromomethyl...

Embodiment 1 3

[0057] The synthesis of embodiment 1 tribromotoluene (1a)

[0058] Add 9.2 grams of toluene (0.1mol), 58.7 grams of NBS (0.33mol), 4.0 grams of BPO (0.017mol) and 300mL of CCl in a 500mL three-necked flask 4 , through nitrogen for 10 minutes. Heated to reflux, and stopped the reaction after 5 hours of reaction. The filtrate obtained after filtration was concentrated to obtain the crude product. The pure product 20.7 g of 1a was obtained by flash chromatography (petroleum ether). Yield 63%. 1 H NMR (400MHz, CDCl 3 ):δ8.03-8.00(m,2H),7.43-7.38(m,2H),7.36-7.32(m,1H). 13 C NMR (101MHz, CDCl 3 ):δ147.07,130.25,128.18,126.61,36.45.GC-MS(EI,m / z):249[M-Br] + .Anal.Calcd.for C 7 h 5 Br 3 : C, 25.57; H, 1.53. Found: C, 25.51; H, 1.51.

Embodiment 2

[0060] Example 2 Synthesis of o-fluorobenzotribromotoluene (1b), using o-fluorotoluene as raw material, yield 76%. 1 H NMR (400MHz, CDCl 3 ,ppm):δ6.85-6.91(m,2H),7.04-7.31(m,2H), 13 C NMR (101MHz, CDCl 3 ): δ30.93,117.31,123.24,128.44,132.73,133.40,159.19.GC-MS(EI,m / z):346[M + ].Anal.Calcd.for C 7 h 4 Br 3 F: C, 24.24; H, 1.16. Found: C, 24.20; H, 1.13.

technical field

[0001] The invention relates to the field of preparation methods of organic compounds, in particular to a new method for synthesizing diaryl acetylene compounds. Background technique

[0002] The diarylethyne compound is shown in the following formula. Alkynes containing carbon-carbon triple bond functional groups are widely used in the fields of medicine and optoelectronic materials due to their linear rigid structure and structural characteristics rich in π electrons.

[0003]

[0004] In organic synthesis, there are different methods for the formation of carbon-carbon triple bonds, which can be divided into conversion from existing functional groups to carbon-carbon triple bonds and direct construction of carbon-carbon triple bonds.

[0005] Elimination reactions are an important strategy to obtain carbon-carbon multiple bonds. A carbon-carbon triple bond can be obtained from a carbon-carbon single bond or a carbon-carbon double bond as a precursor th...

Examples

preparation example Construction

[0045] (1) Preparation of raw materials

[0046] All gem-tribromomethyl arene compounds can be prepared by existing common synthesis methods, and the molecular structure of the gem-tribromomethyl arene compounds used in the examples is shown in the following formula.

[0047]

[0048] Raw compound abbreviation

R 1

R 2

R 3

1a

H-

H-

H-

1b

F-

H-

H-

1c

Cl-

H-

H-

1d

Br-

H-

H-

1e

H-

Cl-

H-

1f

H-

Br-

H-

1g

H-

CH 3 O-

H-

1h

H-

CH 3 C(O)-

H-

1i

H-

H-

F-

1j

H-

H-

Cl-

1k

H-

H-

Br-

1l

H-

H-

tert-C 4 h 9 -

1m

H-

H-

-CF 3

1n

H-

H-

-CN

1p

H-

H-

CH 3 C(O)-

1q

H-

H-

CH 3 OC(O)-

1r

H-

H-

-NO 2

[0049] (2) Synthesis method

[0050] Deoxidize a certain stoichiometric ratio of gem-tribromomethyl...

Embodiment 1 3

[0057] The synthesis of embodiment 1 tribromotoluene (1a)

[0058] Add 9.2 grams of toluene (0.1mol), 58.7 grams of NBS (0.33mol), 4.0 grams of BPO (0.017mol) and 300mL of CCl in a 500mL three-necked flask 4 , through nitrogen for 10 minutes. Heated to reflux, and stopped the reaction after 5 hours of reaction. The filtrate obtained after filtration was concentrated to obtain the crude product. The pure product 20.7 g of 1a was obtained by flash chromatography (petroleum ether). Yield 63%. 1 H NMR (400MHz, CDCl 3 ):δ8.03-8.00(m,2H),7.43-7.38(m,2H),7.36-7.32(m,1H). 13 C NMR (101MHz, CDCl 3 ):δ147.07,130.25,128.18,126.61,36.45.GC-MS(EI,m / z):249[M-Br] + .Anal.Calcd.for C 7 h 5 Br 3 : C, 25.57; H, 1.53. Found: C, 25.51; H, 1.51.

Embodiment 2

[0060] Example 2 Synthesis of o-fluorobenzotribromotoluene (1b), using o-fluorotoluene as raw material, yield 76%. 1 H NMR (400MHz, CDCl 3 ,ppm):δ6.85-6.91(m,2H),7.04-7.31(m,2H), 13 C NMR (101MHz, CDCl 3 ): δ30.93,117.31,123.24,128.44,132.73,133.40,159.19.GC-MS(EI,m / z):346[M + ].Anal.Calcd.for C 7 h 4 Br 3 F: C, 24.24; H, 1.16. Found: C, 24.20; H, 1.13.

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