CN104926784B - Functionalisable hexyl thiophene class compound of one class side chain terminal and preparation method thereof - Google Patents

Abstract

The invention discloses functionalisable hexyl thiophene class compound of a class side chain terminal and preparation method thereof, belong to organic photoelectric functional material technical field.This kind of compound has following structure：

Description

Functionalisable hexyl thiophene class compound of one class side chain terminal and preparation method thereof

Technical field

The invention belongs to organic photoelectric functional material technical field, the functionalisable hexyl of a more particularly to class side chain terminal Thiophenes and preparation method thereof.

Background technology

In recent years, because the functionalization of side chain can assign polymer or the excellent performance of macromolecular photoelectric functional material, Synthesis based on the functionalisable organic photoelectric functional material of side chain terminal is attracted attention.This is due to by such The functionalization of material, can both reduce the influence of the introducing and reaction of functional group to material photoelectric properties as far as possible, can assign again Material new function and value.For example：Pass through introducing crosslinked group, it is possible to achieve the preparation (U.S. of multilayer organic electro-optic device Pat. Appl. Publ. 2015, US 20150075622 A1 20150319; ACS Nano, 2015, 9, 371- 377;ACS Applied Materials ＆ Interfaces, 2015,7,452-459) or improve device stability With service life (Macromolecules, 2009,42,1610-1618; J. Mater. Chem. C., 2014, 2, 7163-7167; Adv. Funct. Mater., 2009, 19, 2273-2281)；By introducing, special functional group can be with Realize dangerous material such as explosive (Chemical Communications, 2015,51,7207), heavy metal ion (ACS Applied Material ＆ Interfaces, 2015,7,6882-6888) etc. fast and easy detection or assign material Effect (ACS Applied Materials the ＆ Interfaces, 2015,7,3189-3198 of bioprobe; Chemical Science, 2015, 6, 1825-1831)).Hexyl thiophene class organic photoelectric functional material is wherein important One class, however, being used as the important intermediate of synthesis hexyl thiophene class organic photoelectric functional material, functionalisable oneself of side chain terminal The synthetic method report of base thiophenes is actually rare at present.Only conjunction on the bromo- 3- bromines hexyl thiophenes of 2,5- bis- Report into method has two kinds：One kind under -78 °C of anhydrous and oxygen-free, goes bromine to give birth to by butyl lithium first using 3 bromo thiophene as raw material Into anion, 3- bromine hexyl thiophenes then are directly obtained with the reaction of 1,6- dibromos hexyl, last bromination generates target product.Although This method synthetic route is shorter, but be due to 3- anions stability compared with 2- potential differences, therefore in final reaction product It is difficult to avoid 2-（6- bromine hexyls）The generation of thiophene, and the similar nature of two kinds of products, hardly result in a certain chemical combination of high-purity Thing；Other severe reaction conditions, need to be carried out under strict anhydrous and oxygen-free condition of ultralow temperature, be not suitable for large-scale production.In addition A kind of method is protected with p methoxy phenol to one end of 1,6- dibromo-hexanes first, then anti-with Kumada couplings It should be made to be coupled with 3 bromo thiophene, be then deprotected, bromination obtains target product.This method can obtain high-purity Target product, obtains the polymer or high-purity macromolecular compound of HMW beneficial to further reaction, but synthetic route Longer, protected 1, the 6- dibromo-hexanes in one end need just obtain by multiple recrystallization, the preparation process of grignard reagent The concentration of middle Final Format reagent be difficult determine, and the preparation of grignard reagent and Kumada coupling reactions need also exist for it is more strict Anhydrous and oxygen-free operation, realization be more difficult.

In summary, the limitednumber of the functionalisable hexyl thiophene class compound of existing side chain terminal, only 2,5- bis- Bromo- 3- bromines hexyl thiophene is a kind of, and synthetic method or severe reaction conditions, it is difficult to purify, it is difficult to industrialize.

The content of the invention

It is an object of the invention to provide a kind of simple to operate, easy purification, easily high income, industrialization and lower-cost preparation The method of the serial functionalisable hexyl thiophene class compound of side chain terminal；Another object is that one class side chain terminal of offer can function Change hexyl thiophene class compound.

To realize the object of the invention, the present invention with 2,5- dibromo thiophenes and 6- halogen caproyl chloride for raw material, using classical Fu Gram acylation reaction condition, the functionalisable hexyl thiophene class compound 2 of two kinds of side chain terminals, the bromo- 3- of 5- bis- can be obtained simultaneously （6- halogen caproyls）Thiophene and the bromo- 5- of 2-（6- halogen caproyls）Thiophene；Protect end halogen atom respectively with ROH, obtaining two kinds can Functionalization hexyl thiophene class compound, both compounds can be respectively used to before polymer monomer or macromolecular compound synthesis Body, is deprotected again after reaction, the adaptive of intensified response substrate；Then huang-Minlon reaction reducing carbonyl is used, two kinds are obtained newly Have stronger adaptive hexyl thiophene class compound, be equally applicable to Macroscopic single crystal monomer or macromolecular compound synthesis before Body, is deprotected again after reaction；The functionalisable hexyl thiophene class compound 2,5- of two kinds of side chain terminals is can obtain after deprotection again The two bromo- bromo- 5- halos hexyl thiophenes of 3- halos hexyl thiophene and 2-.Reaction equation is as follows：

Wherein, X is Cl, Br, I, and R is p-methoxyphenyl, C1-C6 alkyl silyl.

Specific preparation method is as follows：

（1）The bromo- 3- of 2,5- bis-（6- halogen caproyls）Thiophene（Compound 1）With the bromo- 5- of 2-（6- halogen caproyls）Thiophene（Chemical combination Thing 2）Synthesis

2,5- dibromo thiophenes, organic aprotic solvents and 6- halogen caproyl chlorides are added in reactor, -5~5 are cooled to after stirring DEG C, lewis acid is added portionwise, is warmed to room temperature naturally after adding, reacts at room temperature.Reaction solution is poured slowly into ice dilute hydrochloric acid solution Middle quenching reaction, washes, extracts, dry, and rotary evaporation removes solvent, and silica gel column chromatography separation obtains yellow thick liquid chemical combination Thing 1 and yellow solid compound 2.Organic aprotic solvents are dichloromethane, carbon disulfide or chloroform.The 6- halogen caproyl chloride choosing 6- chlorine caproyl chloride, 6- bromines caproyl chloride or 6- iodine caproyl chlorides；

（2）The bromo- 3- of 2,5- bis-（6-R epoxide caproyls）Thiophene（Compound 3）With the bromo- 5- of 2-（6- is to R epoxide caproyls） Thiophene（Compound 4）Synthesis

By p methoxy phenol or alkylsilanol, potassium carbonate, 18- crown ether -6, acetonitrile, compound 1 or 2 is added to reaction In bottle, back flow reaction is stayed overnight.Add water and reaction is quenched, extract, silica gel column chromatography separation obtains yellow solid product 3 or 4.

（3）The bromo- 3- of 2,5- bis-（6-R epoxide hexyls）Thiophene（Compound 5）With the bromo- 5- of 2-（6- is to R epoxide hexyls）Thiophene （Compound 6）Synthesis

By compound 3 or compound 4, potassium hydroxide, hydrazine hydrate, diethylene glycol is added in reactor, and 190-200 DEG C anti- It should stay overnight, add water and reaction is quenched, extract, column chromatography for separation obtains yellow solid product compound 5 or compound 6.

（4）The bromo- 3- of 2,5- bis-（6- halogen hexyls）Thiophene（Compound 7）With the bromo- 5- of 2-（6- halogen hexyls）Thiophene（Compound 8） Synthesis

Halogen acids, glacial acetic acid and compound 5 or 6 are added into reaction bulb, gained mixture is anti-in 90-100 DEG C of stirring Should.Add water and reaction is quenched, extract, neutralize, dry, column chromatography for separation obtains product liquid 7 or 8.The halogen acids is HCl, HI Or HBr.

The step（1）Middle 2,5- dibromo thiophenes, the mol ratio of 6- halogen hexanoyl chloride materials are 1:1~1:1.2.

The step（1）In lewis acid for aluminium chloride, iron chloride etc..

The step（1）The middle preferred 6- bromines caproyl chloride of 6- halogen caproyl chloride or 6- iodine caproyl chlorides.

The step（2）Middle compound 1 or compound 2, p methoxy phenol or alkylsilanol, mole of potassium carbonate material Than for 1:2:2.2~1:2.4:4.8 .

The step（3）The volume ratio of the amount of substance and hydrazine hydrate of middle compound 3 or 4 and potassium hydroxide is 1:10:5~1: 50:10。

The step（4）Middle compound 5 or 6, halogen acids, the mol ratio of glacial acetic acid are 1:5:2~1:6:3.

Beneficial effect of the present invention：The present invention devises the functionalisable 3- hexyl thiophenes of the new side chain terminal of a class first Class compound, such compound can be used for constructing for Mobyneb polymer or macromolecular photoelectric functional material, widen material Application.Such as pass through introducing crosslinked group, it is possible to achieve the preparation of multilayer organic electro-optic device or the stability for improving device And service life；By introducing, special functional group can realize the fast and easy inspection of dangerous material such as explosive, heavy metal ion etc. Survey or assign the effect of material bioprobe.In addition, the invention provides a kind of simple to operate, easy purification, easily high income, industry Change the preparation method with the functionalisable 3- hexyl thiophene class compounds of lower-cost side chain terminal, novel high-performance can be promoted The development and application research of organic photoelectric functional material.

Embodiment

Following instance helps to understand the present invention, but is not limited to present disclosure.

Embodiment 1

（1）The bromo- 3- of 2,5- bis-（6- halogen caproyls）Thiophene（Compound 1）With the bromo- 5- of 2-（6- halogen caproyls）Thiophene（Chemical combination Thing 2）Synthesis

0.01 mol 2,5- dibromo thiophenes are added into reactor, then add 80~160mL dichloromethane and - 5 DEG C are cooled to after 0.01 mol 6- bromine caproyl chlorides, 30 min of stirring, 0.01 mol aluminium chloride is added portionwise, adds It is warmed to room temperature, reacts at room temperature 3~6 hours naturally afterwards.Reaction solution is poured slowly into ice dilute hydrochloric acid solution and is quenched reaction, washing, CH₂Cl₂Extraction, anhydrous Na₂SO₄Dry, rotary evaporation removes solvent, silica gel column chromatography separation, eluent：Petroleum ether：Acetic acid second Ester=30:1, obtain yellow thick liquid compound 1 and yellow solid compound 2.Compound 1: EI-MS m/z (%) : 419 (M⁺, 0.68), 284 (Base Peak, 100%); ¹H NMR （CDCl3）: δ 7.11 (s, 1H), 3.45 (t, J = 6.8 Hz, 2H), 3.02 (t, J = 7.2 Hz, 2H), 1.93 (m, 2H), 1.78 (m, 2H), 1.56 (m, 2H); ¹³C NMR: 191.35, 140.87, 135.83, 121.57, 113.06, 41.08, 33.56, 32.55, 27.71, 23.04; FT-IR: (KBr): ν(cm^-1) 3087, 2930, 2850, 1650, 1495, 1408, 1192, 991, 825, 724;Elementary analysis：Calculated value, C₁₀H₁₁Br₃OS: C, 28.67; H, 2.65; Br, 57.21; O, 3.82; S, 7.65;Measured value：C, 28.91; H, 2.75; Br, 57.05;S, 7.65. compound 2：EI-MS m/ z (%) : 340 (M⁺, 4.28), 206 (Base Peak, 100%); ¹H NMR （CDCl3）: δ 7.46 (d, J = 4 Hz, 1H), 7.12 (d, J = 4 Hz, 1H), 3.45 (t, J = 6.8 Hz, 2H), 3.02 (t, J = 6.8 Hz, 2H), 1.95 (m, 2H), 1.74 (m, 2H), 1.54 (m, 2H); ¹³C NMR: 191.86, 145.77, 131.83, 131.24, 122.52, 38.42, 33.53, 32.53, 27.80, 23.58; FT-IR: (KBr): ν (cm^-1) 3084, 2943, 1655, 1405, 1255, 1202, 921, 823, 724;Elementary analysis：Calculated value, C₁₀H₁₁Br₃OS: C, 35.32; H, 3.56; Br, 46.99; O, 4.70; S, 9.43;Measured value：C, 35.29; H, 3.54; Br, 46.76; S, 9.79.

（2）The bromo- 3- of 2,5- bis-（6-R epoxide caproyls）Thiophene（Compound 3）With the bromo- 5- of 2-（6- is to R epoxide caproyls） Thiophene（Compound 4）Synthesis

By the mol of p methoxy phenol 0.02, the mol of potassium carbonate 0.024,18- crown ether -6 of catalytic amount, acetonitrile 100 ML, 0.01 mol compound 1 or 2 is added in reaction bulb, and back flow reaction is stayed overnight.Add water and reaction is quenched, dichloromethane extraction, Silica gel column chromatography is separated, eluent：Petroleum ether：Ethyl acetate=30:1, obtain yellow solid product 3 or 4.Compound 3：EI-MS m/z (%) : 462 (M⁺, 10.18), 269 (Base Peak, 100%); ¹H NMR （CDCl3）: δ 7.11 (s, 1H), 6.04 (s, 4H), 3.96 (t, J = 6.4 Hz, 2H), 3.79 (s, 3H), 3.05 (t, J = 7.2 Hz, 2H), 1.85 (m, 4H), 1.58 (m, 2H); ¹³C NMR: 192.16, 153.77, 153.19, 145.87, 131.81, 131.22, 122.44, 115.46, 114.66, 68.30, 55.77, 38.61, 29.20, 24.32, 20.78; FT-IR: (KBr): ν(cm^-1) 3100, 2939, 2864, 1651, 1507, 1421, 1231, 1180, 1030, 817, 737;Elementary analysis：Calculated value, C₁₀H₁₁Br₃OS: C, 44.18; H, 3.93; Br, 34.58; O, 10.38; S, 6.94;Measured value：C, 45.35; H, 4.09; Br, 34.35;S, 6.62. compound 4：EI-MS m/z (%) : 383 (M⁺, 3.63), 191 (Base Peak, 100%); ¹H NMR （CDCl3）: δ 7.46 (d, J = 4 Hz, 1H), 7.12 (d, J = 4 Hz, 1H), 6.84 (s, 4H), 3.94 (t, J = 6.4 Hz, 2H), 3.79 (s, 3H), 2.88 (t, J = 7.6 Hz, 2H), 1.82 (m, 4H), 1.57 (m, 2H); ¹³C NMR: 191.57, 153.77, 153.21, 140.93, 135.84, 121.44, 115.47, 114.66, 113.02, 68.33, 55.77, 41.25, 29.23, 25.74, 23.72; FT-IR: (KBr): ν(cm^-1) 3098, 2936, 2842, 1644, 1512, 1408, 1238, 1048, 906, 794, 742;Elementary analysis：Calculated value, C₁₀H₁₁Br₃OS: C, 53.27; H, 5.00; Br, 20.85; O, 12.52; S, 8.37;Measured value：C, 53.02; H, 4.92; Br, 20.52; S, 8.28.

（3）The bromo- 3- of 2,5- bis-（6-R epoxide hexyls）Thiophene（Compound 5）With the bromo- 5- of 2-（6- is to R epoxide hexyls）Thiophene （Compound 6）Synthesis

By 0.01 mol compound 3 or the mol potassium hydroxide of compound 4,0.10,5 mL hydrazine hydrates, 50 mL diethyls two Alcohol is added in reactor, and 190 DEG C of reactions are stayed overnight, and add water and reaction is quenched, and dichloromethane extraction, column chromatography for separation obtains yellow Solid product compound 5 or compound 6.

（4）The bromo- 3- of 2,5- bis-（6- halogen hexyls）Thiophene（Compound 7）With the bromo- 5- of 2-（6- halogen hexyls）Thiophene（Compound 8） Synthesis

0.05 mol halogen acids is added into reaction bulb（Mass percent 48%）, 0.02 mol glacial acetic acid and 0.01 mol Compound 5 or 6, gained mixture was in 100 DEG C of stirring reactions 1-2 days.Add water and reaction is quenched, ether extraction, sodium acid carbonate saturation Solution is neutralized, anhydrous sodium sulfate drying, column chromatography for separation, eluent：N-hexane, obtains product liquid 7 or 8.The halogen acids is HCl, HI or HBr.

Embodiment 2

（1）The bromo- 3- of 2,5- bis-（6- halogen caproyls）Thiophene（Compound 1）With the bromo- 5- of 2-（6- halogen caproyls）Thiophene（Chemical combination Thing 2）Synthesis

0.02 mol 2,5- dibromo thiophenes are added into reactor, 160 mL carbon disulfide and 0.024 is then added 5 DEG C are cooled to after mol 6- iodine caproyl chlorides, 60 min of stirring, 0.012 mol iron chloride is added portionwise, it is natural after adding It is warmed to room temperature, reacts at room temperature 6 hours.Reaction solution is poured slowly into ice dilute hydrochloric acid solution and is quenched reaction, washing, CH₂Cl₂Extraction, Anhydrous Na₂SO₄Dry, rotary evaporation removes solvent, silica gel column chromatography separation, eluent：Petroleum ether：Ethyl acetate=30:1, obtain Yellow thick liquid compound 1 and yellow solid compound 2.

（2）The bromo- 3- of 2,5- bis-（6-R epoxide caproyls）Thiophene（Compound 3）With the bromo- 5- of 2-（6- is to R epoxide caproyls） Thiophene（Compound 4）Synthesis

By the mol of triisopropyl silanol 0.024, the mol of potassium carbonate 0.048,18- crown ether -6 of catalytic amount, acetonitrile 200 ML, 0.01 mol compound 1 or 2 is added in reaction bulb, and back flow reaction is stayed overnight.Add water and reaction is quenched, dichloromethane extraction, Silica gel column chromatography is separated, eluent：Petroleum ether：Ethyl acetate=30:1, obtain yellow solid product 3 or 4.

（3）The bromo- 3- of 2,5- bis-（6-R epoxide hexyls）Thiophene（Compound 5）With the bromo- 5- of 2-（6- is to R epoxide hexyls）Thiophene （Compound 6）Synthesis

By 0.01 mol compound 3 or the mol potassium hydroxide of compound 4,0.50,10 mL hydrazine hydrates, 100 mL diethyls Glycol is added in reactor, and 200 DEG C of reactions are stayed overnight, and add water and reaction is quenched, and dichloromethane extraction, column chromatography for separation obtains Huang Color solid product compound 5 or compound 6.

（4）The bromo- 3- of 2,5- bis-（6- halogen hexyls）Thiophene（Compound 7）With the bromo- 5- of 2-（6- halogen hexyls）Thiophene（Compound 8） Synthesis

0.06 mol halogen acids is added into reaction bulb（Mass percent 48%）, 0.03 mol glacial acetic acid and 0.01 mol Compound 5 or 6, gained mixture was in 90 DEG C of stirring reactions 1-2 days.Add water and reaction is quenched, ether extraction, sodium acid carbonate saturation Solution is neutralized, anhydrous sodium sulfate drying, column chromatography for separation, eluent：N-hexane, obtains product liquid 7 or 8.The halogen acids is HCl, HI or HBr.

Claims (2)

1. the preparation method of the functionalisable hexyl thiophene class compound of the following class side chain terminal of formula, it is characterised in that Synthetic method is as follows：

Wherein, X is Cl, Br, I；

（1）The bromo- 3- of 2,5- bis-（6- halogen caproyls）Thiophene（Compound 1）With the bromo- 5- of 2-（6- halogen caproyls）Thiophene（Compound 2） Synthesis

2,5- dibromo thiophenes, organic aprotic solvents and 6- halogen caproyl chlorides are added in reactor, -5~5 DEG C are cooled to after stirring , lewis acid is added portionwise, is warmed to room temperature naturally after adding, reacts at room temperature；Reaction solution is poured slowly into ice dilute hydrochloric acid solution Reaction is quenched, washes, extracts, dries, rotary evaporation removes solvent, silica gel column chromatography separation obtains compound 1 and compound 2；Have Machine aprotic solvent is dichloromethane or chloroform；The 6- halogen caproyl chloride selects 6- chlorine caproyl chloride, 6- bromines caproyl chloride or 6- iodine hexanoyls Chlorine；

（2）The bromo- 3- of 2,5- bis-（6-R epoxide caproyls）Thiophene（Compound 3）With the bromo- 5- of 2-（6-R epoxide caproyls）Thiophene（Change Compound 4）Synthesis

By p methoxy phenol or alkylsilanol, potassium carbonate, 18- crown ether -6, acetonitrile, compound 1 or 2 is added in reaction bulb, Back flow reaction is stayed overnight；Add water and reaction is quenched, extract, silica gel column chromatography separation obtains compound 3 or 4；

（3）The bromo- 3- of 2,5- bis-（6-R epoxide hexyls）Thiophene（Compound 5）With the bromo- 5- of 2-（6-R epoxide hexyls）Thiophene（Compound 6）Synthesis

By compound 3 or compound 4, potassium hydroxide, hydrazine hydrate, diethylene glycol is added in reactor, and 190-200 DEG C was reacted At night, add water and reaction is quenched, extract, column chromatography for separation obtains compound 5 or compound 6；

（4）The bromo- 3- of 2,5- bis-（6- halogen hexyls）Thiophene（Compound 7）With the bromo- 5- of 2-（6- halogen hexyls）Thiophene（Compound 8）Conjunction Into

Halogen acids, glacial acetic acid and compound 5 or 6 are added into reaction bulb, gained mixture is in 90-100 DEG C of stirring reaction；Plus Water quenching is gone out reaction, is extracted, and is neutralized, and is dried, and column chromatography for separation obtains product 7 or 8；

The halogen acids is HCl, HI or HBr；

The step（1）Middle 2,5- dibromo thiophenes, the mol ratio of 6- halogen hexanoyl chloride materials are 1:1~1:1.2；

The step（2）Middle compound 1 or compound 2, p methoxy phenol or alkylsilanol, potassium carbonate mol ratio are 1:2: 2.2~1:2.4:4.8 ；

The step（3）The volume ratio of the amount of substance and hydrazine hydrate of middle compound 3 or 4 and potassium hydroxide is 1:10:5~1:50: 10；

The step（4）Middle compound 5 or 6, halogen acids, the mol ratio of glacial acetic acid are 1:5:2~1:6:3.

2. the preparation method of the functionalisable hexyl thiophene class compound of side chain terminal according to claim 1, its feature It is：The step（1）In lewis acid select aluminium chloride or iron chloride.