Fully deuterated thiophene compounds and preparation methods thereof, organic intermediates, and organic electroluminescent devices

Abstract

The present application discloses a perdeuterated thiophene compound and a preparation method thereof, an organic intermediate, and an organic electroluminescent device. The perdeuterated thiophene compound uses cheap deuterated water as a deuterated raw material, toluene as a solvent, and a silver salt as a catalyst. A hydrogen-deuterium exchange reaction is directly carried out on the structure of the thiophene compound to synthesize the perdeuterated thiophene compound, wherein the average deuteration rate of the perdeuterated thiophene compound can reach more than 90%, and the reaction conditions are mild, the process is simple, the substrate applicability is good, and the yield is high.

Description

Technical Field

[0001] The present application relates to the field of organic chemical synthesis, and in particular to a perdeuterated thiophene compound and a preparation method thereof, an organic intermediate, and an organic electroluminescent device. Background Art

[0002] Deuterium is an isotope of hydrogen. Compared with carbon-hydrogen bonds, carbon-deuterium bonds have shorter bond lengths, higher bond energies, and lower vibrational energies. Therefore, replacing hydrogen atoms in organic molecules with deuterium atoms is an effective means of regulating the physical and chemical properties of molecules, and is widely used in the fields of materials science and medicinal chemistry. For example, studies on deuterated polymer materials have found that when deuterium atoms are used to replace hydrogen atoms in polymers, their crystallization properties and film-forming properties will change, thereby affecting the electronic transport properties of polymer materials and the stability of the formed devices.

[0003] In the field of pharmaceutical chemistry, when deuterium atoms efficiently replace specific hydrogen atoms in drug molecules, it will affect the properties of the drug, such as changing the pharmacokinetic of active drug molecules and the efficiency of drugs, thereby prolonging the drug metabolism cycle, reducing the production of toxic metabolites and drug interactions, thereby reducing the dosage, improving safety and achieving better efficacy. Through deuteration transformation, some drugs that have been abandoned due to metabolic problems may eventually pass clinical trials and be marketed. Therefore, deuterium substitution technology is considered a shortcut to develop new drugs and is favored by major pharmaceutical companies.

[0004] Thiophene compounds are widely found in natural products, bioactive molecules and organic optoelectronic materials. Therefore, thiophene compounds are widely used in medicine, pesticides, dyes, optoelectronic materials and other industries. Therefore, it is very important to develop a method that is compatible with various functional groups and can change the physical and chemical properties of materials or drug molecules.

[0005] As a structural skeleton of chemical drugs, thiophene plays an important role in drug molecules. For example, on the Top 200 drug sales list, Xarelto, which is mainly used as an anticoagulant, clopidogrel for the treatment of atherosclerotic thrombosis, tiotropium bromide for the treatment of chronic obstructive pulmonary disease, and epiridol for the treatment of schizophrenia and major depression all contain thiophene structures. In the field of optoelectronic materials, thiophene structure is the core skeleton of many organic optoelectronic molecules. For example, various types of fused-ring thiophenes are the most commonly used skeleton structures in organic solar cells. Therefore, thiophene compounds have been widely used to construct fluorescent molecular probes, sensors, light-emitting diodes and organic light-emitting electronic devices.

[0006] Since thiophene has multiple hydrogen atoms in its structure, and the carbon-hydrogen bond activity at its α position is significantly higher than that at its β position. Therefore, the methods reported for introducing deuterium atoms into thiophene compounds are all to introduce deuterium atoms into the α position of thiophene, and there are few methods that can be used to synthesize fully deuterated thiophene compounds. However, whether in material molecules or drug molecules, the α position of the thiophene structure is mostly substituted by various functional groups and has an exposed β position carbon-hydrogen bond. Therefore, it is of great application value to develop a method that can introduce deuterium atoms into the β position of thiophene to synthesize fully deuterated thiophene compounds. At present, the reported methods for synthesizing fully deuterated thiophenes are as follows:

[0007] Using thiophene as raw material, direct preparation by hydrogen-deuterium exchange. The currently reported process routes include: using expensive palladium carbon and platinum carbon (dosage: 20%-30% mass fraction) as catalysts, directly preparing perdeuterated thiophene compounds at high temperature (160℃-200℃) and high pressure (20-50psi). Although this method can prepare perdeuterated thiophene compounds, this method has harsh conditions (high temperature and high pressure), high cost (huge amount of precious metal catalyst), cumbersome operation (need to use a closed autoclave), poor substrate applicability, and easy decomposition of the product. Therefore, it has caused difficulties for large-scale industrial production.

[0008] From the perspective of economic cost, the catalysts and reaction conditions used in the current process routes have some problems. Therefore, it is of great significance to develop economical and cheap catalysts to directly carry out the hydrogen-deuterium exchange reaction of thiophene under mild conditions to synthesize deuterated thiophene compounds. Summary of the invention

[0009] The purpose of the present invention is to provide a perdeuterated thiophene compound and a preparation method thereof, an organic intermediate, and an organic electroluminescent device to solve the technical problems of the existing perdeuterated thiophene compounds, such as harsh reaction conditions, poor functional group tolerance, and high production cost.

[0010] To achieve the above object, the present invention provides a perdeuterated thiophene compound, characterized in that the perdeuterated thiophene compound is prepared from a thiophene compound and deuterated water.

[0011] The molecular structural formula of the thiophene compound is:

[0012]

[0013] Among them, the R 1 , R 2 , R 3 , R 4 , R 5Each is independently selected from one of hydrogen, ester, cyano, carbonyl, hydroxyl, alkoxy, alkyl, amide, amine, borate, alkynyl, alkenyl, aryl, heteroaryl and halogen.

[0014] In one embodiment, the R 1 , R 2 , R 3 , R 4 , R 5 Each is independently selected from an alkyl group or alkoxy group having 1 to 6 carbon atoms, and an aryl group or heteroaryl group having 6 to 18 carbon atoms.

[0015] In one embodiment, the thiophene compound is any one of 5-phenylbenzothiophene, 2-iodothiophene, 3-bromothiophene, 2,5-dibromo-3-hexylthiophene, dithiophene, and 4,8-diketobenzodithiophene.

[0016] To achieve the above object, the present invention also provides a method for preparing a perdeuterated thiophene compound, comprising the following steps:

[0017] Adding raw material components into a reactor, the raw material components including the silver salt catalyst, the deuterated water, the thiophene compound and the toluene solvent to obtain a mixed solution, wherein the molar ratio of the raw material components is 1:(0.2-0.6):(20-50):(5-50);

[0018] heating the mixed solution;

[0019] After the mixed solution is completely reacted by the heating treatment, a saturated ammonium chloride solution is added to the reactor to quench the mixture;

[0020] A dichloromethane solvent is added to the reactor, and the perdeuterated thiophene compound is obtained after extraction, combining the organic phases, and concentrating by rotary evaporation.

[0021] In one embodiment, the silver salt catalyst is any one of silver carbonate, silver oxide, silver acetate, and silver trifluoromethanesulfonate.

[0022] In one embodiment, the heating treatment of the mixed solution includes heating the mixed solution at a temperature of 80-120° C. for 12-48 hours to allow the mixed solution to fully react.

[0023] In one embodiment, the adding of saturated ammonium chloride solution into the reactor comprises adding 99-101 ml of saturated ammonium chloride solution into the reactor.

[0024] In one embodiment, adding dichloromethane solvent into the reactor includes adding 99-101 ml of the dichloromethane solvent into the reactor.

[0025] To achieve the above object, the present invention also provides an organic intermediate, including the perdeuterated thiophene compound.

[0026] To achieve the above object, the present invention further provides an organic electroluminescent device, comprising an anode, a cathode, and at least one organic layer disposed between the anode and the cathode, wherein the organic layer contains the organic intermediate.

[0027] The technical effect of the present invention is to provide a fully deuterated thiophene compound and a preparation method thereof, an organic intermediate, and an organic electroluminescent device, wherein cheap deuterated water is used as a deuterated raw material, ordinary toluene is used as a solvent, and a silver salt is used as a catalyst, and a hydrogen-deuterium exchange reaction is directly carried out on the structure of the thiophene compound to synthesize the thiophene compound, wherein the deuteration rate of the fully deuterated thiophene compound can reach more than 90%, and the synthesis is simple and easy to operate, and the raw materials are easily available, which can meet the needs of industrialization.

[0028] The structural formula of perdeuterated thiophene compounds is:

[0029]

[0030] However, the difficulty in preparing perdeuterated thiophene compounds lies in the deuteration of positions 3 and 4, because the carbon-hydrogen bonds at positions 3 and 4 are relatively less active and are not easy to carry out various functionalization reactions. Due to the existence of this difficulty, the current method for synthesizing perdeuterated thiophene compounds is mainly to catalyze hydrogen-deuterium exchange with precious metal reagents under high temperature and high pressure, the reaction conditions are relatively harsh, and the substrate applicability is poor. Therefore, the present application proposes to use silver salt as a catalyst, which first complexes with thiophene substrates in the reaction to reduce the strength of carbon-hydrogen bonds in thiophene, and then cooperates with acid radical ions to achieve the breaking of carbon-hydrogen bonds and the formation of new carbon-deuterium bonds, and deuterated water (the cheapest source of deuterium atoms) is used as a deuterium source to achieve hydrogen-deuterium exchange reactions. In addition, the functional groups at positions 1, 2, 3, 4, and 5 of the present application have a wide range of selection and are also relatively wide in applicability. BRIEF DESCRIPTION OF THE DRAWINGS

[0031] The technical solution and other beneficial effects of the present application will be made apparent by describing in detail the specific implementation methods of the present application in conjunction with the accompanying drawings.

[0032] Figure 1 This is the NMR image of deuterated 5-phenylbenzothiophene described in Example 1 of the present application;

[0033] Figure 2 This is the NMR image of deuterated 2-iodothiophene described in Example 2 of the present application;

[0034] Figure 3 This is the NMR image of deuterated 3-bromothiophene described in Example 3 of the present application;

[0035] Figure 4 This is the NMR image of deuterated 2,5-dibromo-3-hexylthiophene described in Example 4 of the present application;

[0036] Figure 5 This is the NMR image of the deuterated dithiophene described in Example 5 of the present application;

[0037] Figure 6 This is the NMR image of deuterated 4,8-diketobenzodithiophene described in Example 6 of the present application. DETAILED DESCRIPTION

[0038] The technical solutions in the embodiments of the present application will be described clearly and completely below in conjunction with the drawings in the embodiments of the present application. Obviously, the described embodiments are only part of the embodiments of the present application, rather than all of the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative work are within the scope of protection of the present application.

[0039] The embodiments of the present application provide a perdeuterated thiophene compound and a preparation method thereof, an organic intermediate, and an organic electroluminescent device. The following are described in detail. It should be noted that the description order of the following embodiments is not intended to limit the preferred order of the embodiments. In addition, in the description of the present application, various embodiments of the present invention may be in the form of a range; it should be understood that the description in the form of a range is only for convenience and simplicity, and should not be understood as a rigid limitation on the scope of the present invention; therefore, it should be considered that the range description has specifically disclosed all possible sub-ranges and single values ​​within the range. For example, it should be considered that the range description from 1 to 6 has specifically disclosed sub-ranges, such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 5, from 2 to 6, from 3 to 6, etc., as well as single numbers within the numbered range, such as 1, 2, 3, 4, 5 and 6, which are applicable regardless of the range. In addition, whenever a numerical range is indicated in this article, it is meant to include any quoted numbers (fractions or integers) within the indicated range.

[0040] The present application provides a perdeuterated thiophene compound and a preparation method thereof, an organic intermediate, and an organic electroluminescent device;

[0041] Embodiment 1:

[0042] The present embodiment provides a fully deuterated thiophene compound, whose raw material components include a thiophene compound, a silver salt catalyst, deuterated water and a toluene solvent; wherein the molar ratio of the thiophene compound: the silver salt catalyst: the deuterated water: the toluene solvent is 1:(0.2-0.6):(20-50):(5-50).

[0043] Specifically, the molecular structure of the thiophene compound is:

[0044]

[0045] Among them, the R 1 is any one of hydrogen, ester, cyano, carbonyl, hydroxyl, alkoxy, alkyl, amide, amine, borate, alkynyl, alkenyl, (hetero)aryl, and halogen; 2 It is any one of hydrogen, ester, cyano, carbonyl, hydroxyl, alkoxy, alkyl, amide, amine, borate, alkynyl, alkenyl, (hetero)aryl and halogen.

[0046] The deuterium water is highly deuterated water, and the deuterium substitution rate is 99.99%.

[0047] The silver salt catalyst is any one of silver carbonate, silver oxide, silver acetate and silver trifluoromethanesulfonate.

[0048] Therefore, the embodiments of the present application provide a fully deuterated thiophene compound, which uses cheap deuterated water as a deuterated raw material and toluene as a solvent, avoiding the use of expensive deuterated reagents as solvents, and uses relatively low-priced silver salts as catalysts, thereby reducing production costs and being suitable for large-scale production.

[0049] This embodiment also provides an organic intermediate and an organic electroluminescent device, wherein the organic electroluminescent device comprises an anode, a cathode, and at least one organic layer disposed between the anode and the cathode, wherein the organic layer contains the organic intermediate, and the organic intermediate comprises the deuterated 5-phenylbenzothiophene described above. The organic electroluminescent device can be used to construct fluorescent molecular probes, sensors, alkaloids, and biopharmaceutical molecules, etc.

[0050] The embodiment of the present application also provides a method for preparing a perdeuterated thiophene compound, comprising the following steps S11)-S15).

[0051] S11) preparing and obtaining various raw material components, including thiophene compounds, silver salt catalysts, deuterated water and toluene solvent, wherein the molar ratio of thiophene compounds: silver salt catalysts: deuterated water: toluene solvent is 1: (0.2-0.6): (20-50): (5-50).

[0052] The molecular structural formula of the thiophene compound is:

[0053]

[0054] Among them, the R 1 is any one of hydrogen, ester, cyano, carbonyl, hydroxyl, alkoxy, alkyl, amide, amine, borate, alkynyl, alkenyl, (hetero)aryl, and halogen; 2 It is any one of hydrogen, ester, cyano, carbonyl, hydroxyl, alkoxy, alkyl, amide, amine, borate, alkynyl, alkenyl, (hetero)aryl and halogen.

[0055] In the embodiment of the present application, the thiophene compound is benzothiophene.

[0056] The silver salt catalyst is any one of silver carbonate, silver oxide, silver acetate and silver trifluoromethanesulfonate.

[0057] S12) adding the silver salt catalyst, the deuterated water, the thiophene compound and the toluene solvent into a reactor to obtain a mixed solution.

[0058] Specifically, 0.3 mmol of the silver salt catalyst, 32 mmol of the deuterated water, 1 mmol of the benzothiophene and 5 mmol of the toluene solvent were added to the 10 mL reactor. In the embodiment of the present application, the reactor includes but is not limited to a pressure tube and a reaction bottle.

[0059] S13) heating the mixed solution.

[0060] Specifically, the mixed solution is heated at a temperature of 80° C. to 120° C. for 11 to 13 hours to allow the mixed solution to fully react.

[0061] S14) After the mixed solution reacts completely, a saturated ammonium chloride solution is added to the reactor to quench the mixture.

[0062] Specifically, 99-101 ml of the saturated ammonium chloride solution, preferably 100 ml of the saturated ammonium chloride solution, is added to the reactor to cause a quenching reaction of the mixed solution in the reactor.

[0063] S15) adding dichloromethane solvent to the reactor, extracting, combining the organic phases, and concentrating by rotary evaporation to obtain a deuterated thiophene compound, wherein the deuterated thiophene compound is deuterated 5-phenylbenzothiophene.

[0064] Specifically, 99-101 ml of the dichloromethane solvent, preferably 100 ml of the dichloromethane solvent, is added to the reactor. The dichloromethane solvent can be used for extraction three to four times, and the organic phases extracted several times are combined into a 250 ml eggplant-shaped bottle, and a rotary evaporator is used with a speed of 120 rpm, a temperature of 37 ° C, a vacuum degree of 0.1 MPa, and a treatment time of 3 min to obtain a fully deuterated thiophene compound, i.e., deuterated 5-phenylbenzothiophene. The deuterated 5-phenylbenzothiophene has 185 mg, a yield of 88.0%, a deuterated rate of 98% at the α position, 97% at the β position, and an analytical purity of 99%.

[0065] Figure 1 This is the NMR image of deuterated 5-phenylbenzothiophene described in Example 1 of the present application.

[0066] like Figure 1 As shown, the NMR spectrum shape, signal, noise and other aspects of deuterated 5-phenylbenzothiophene also reflect that the purity of the deuterated 5-phenylbenzothiophene is extremely high, and no other organic impurities are generated during the preparation process, which can effectively simplify the purification steps and effectively reduce the production cost.

[0067] The present embodiment provides a method for preparing a perdeuterated thiophene compound, wherein cheap deuterated water is used as a deuterated raw material, ordinary toluene is used as a solvent, and a silver salt is used as a catalyst. A hydrogen-deuterium exchange reaction is directly performed on the structure of the thiophene compound to synthesize the perdeuterated thiophene compound, wherein the deuteration rate of the perdeuterated thiophene compound can reach more than 90%, and the reaction conditions are mild, the process is simple, the substrate applicability is good, and the yield is high. In the preparation process, the use of expensive deuterated reagents as solvents and toxic metal reagents is avoided, the production cost is low, and it is conducive to industrial production.

[0068] Example 2

[0069] This embodiment provides a fully deuterated thiophene compound and a preparation method and an organic intermediate thereof, which includes most of the technical solutions of Example 1, except that the thiophene compound is 2-iodothiophene.

[0070] The embodiment of the present application also provides a method for preparing a perdeuterated thiophene compound, comprising the following steps S21)-S25).

[0071] S21) obtaining raw material components of a thiophene compound, a silver salt catalyst, deuterated water and a toluene solvent, wherein the molar ratio of the thiophene compound: the silver salt catalyst: the deuterated water: the toluene solvent is 1:(0.2-0.6):(20-50):(5-50).

[0072] The molecular structural formula of the thiophene compound is:

[0073]

[0074] Among them, the R 3 It is any one of hydrogen, ester, cyano, carbonyl, hydroxyl, alkoxy, alkyl, amide, amine, borate, alkynyl, alkenyl, (hetero)aryl and halogen.

[0075] In the embodiment of the present application, the thiophene compound is 2-iodothiophene.

[0076] The silver salt catalyst is any one of silver carbonate, silver oxide, silver acetate and silver trifluoromethanesulfonate.

[0077] S22) adding the silver salt catalyst, the deuterated water, the thiophene compound and the toluene solvent into a reactor to obtain a mixed solution.

[0078] Specifically, 0.40 mmol of the silver salt catalyst, 40 mmol of the deuterated water, 1 mmol of the 2-iodothiophene and 5.2 mmol of the toluene solvent were added to the 10 mL reactor. In the embodiment of the present application, the reaction solution includes but is not limited to a pressure tube and a reaction bottle.

[0079] S23) heating the mixed solution.

[0080] Specifically, the mixed solution is heated at a temperature of 100° C. to 120° C. for 15 to 20 hours to allow the mixed solution to fully react.

[0081] S24) After the mixed solution reacts completely, a saturated ammonium chloride solution is added to the reactor to quench the mixture.

[0082] Specifically, 99-101 ml of the ammonium chloride solution, preferably 100 ml of the ammonium chloride solution, is added to the reactor to cause a quenching reaction of the mixed solution in the reactor.

[0083] S25) adding dichloromethane solvent to the reactor, extracting, combining the organic phases, and concentrating by rotary evaporation to obtain a perdeuterated thiophene compound, wherein the deuterated thiophene compound is deuterated 2-iodothiophene.

[0084] Specifically, 99-101 ml of the dichloromethane solvent, preferably 100 ml of the dichloromethane solvent, is added to the reactor. The dichloromethane solvent can be used for extraction three to four times, and the organic phases extracted several times are combined into a 250 ml eggplant-shaped bottle, and a rotary evaporator is used with a speed of 120 rpm, a temperature of 37 ° C, a vacuum degree of 0.1 MPa, and a treatment time of 3 min to obtain a fully deuterated thiophene compound, i.e., deuterated 2-iodothiophene. Among them, the deuterated 2-iodothiophene is 185 mg, the yield is 89.0%, the deuteration rate is 96% at the α position, 93% and 96% at the β position, and the analytical purity is 99%.

[0085] Figure 2 This is the NMR image of deuterated 2-iodothiophene described in Example 2 of the present application.

[0086] like Figure 2 As shown, the NMR spectrum shape, signal, noise and other aspects of deuterated 2-iodothiophene also reflect that the deuterated thiophene has extremely high purity, and no other organic impurities are produced during the preparation process, which can effectively simplify the purification steps and effectively reduce the production cost.

[0087] Example 3

[0088] This embodiment provides a fully deuterated thiophene compound and a preparation method and an organic intermediate thereof, which includes most of the technical solutions of Example 1, except that the thiophene compound is 3-bromothiophene.

[0089] The embodiment of the present application also provides a method for preparing a perdeuterated thiophene compound, comprising the following steps S31)-S35).

[0090] S31) obtaining raw material components of thiophene compound, silver salt catalyst, deuterated water and toluene solvent, wherein the molar ratio of the thiophene compound: the silver salt catalyst: the deuterated water: the toluene solvent is 1:(0.2-0.6):(20-50):(5-50).

[0091] The molecular structural formula of the thiophene compound is:

[0092]

[0093] Among them, the R 3 It is any one of hydrogen, ester, cyano, carbonyl, hydroxyl, alkoxy, alkyl, amide, amine, borate, alkynyl, alkenyl, (hetero)aryl and halogen.

[0094] In the embodiment of the present application, the thiophene compound is 3-bromothiophene.

[0095] The silver salt catalyst is any one of silver carbonate, silver oxide, silver acetate and silver trifluoromethanesulfonate.

[0096] S32) adding the silver salt catalyst, the deuterated water, the thiophene compound and the toluene solvent into a reactor to obtain a mixed solution.

[0097] Specifically, 0.5 mmol of the silver salt catalyst, 42 mmol of the deuterated water, 1 mmol of the 3-bromothiophene and 5.2 mmol of the toluene solvent were added to the 10 mL reactor. In the embodiment of the present application, the reaction solution includes but is not limited to a reaction bottle.

[0098] S33) heating the mixed solution.

[0099] Specifically, the mixed solution is heated at a temperature of 100-120° C. for 11-13 hours to allow the mixed solution to fully react.

[0100] S34) After the mixed solution reacts completely, a saturated ammonium chloride solution is added to the reactor to quench the mixture.

[0101] Specifically, 99-101 ml of the ammonium chloride solution, preferably 100 ml of the ammonium chloride solution, is added to the reactor to cause a quenching reaction of the mixed solution in the reactor.

[0102] S35) adding dichloromethane solvent to the reactor, extracting, combining the organic phases, and concentrating by rotary evaporation to obtain a perdeuterated thiophene compound, wherein the deuterated thiophene compound is deuterated 3-bromothiophene.

[0103] Specifically, 99-101 ml of the dichloromethane solvent is added to the reactor, preferably 100 ml of the dichloromethane solvent. The dichloromethane solvent can be used for extraction three to four times, and the organic phases extracted several times are combined into a 250 ml eggplant-shaped bottle, and a rotary evaporator is used with a speed of 120 rpm, a temperature of 37 ° C, a vacuum degree of 0.1 MPa, and a treatment time of 3 min to obtain a fully deuterated thiophene compound, i.e., deuterated 3-bromothiophene. The deuterated 3-bromothiophene is 130 mg, with a yield of 80.0%, a deuterated rate of 91% and 96% at the α position, 96% at the β position, and an analytical purity of 99%.

[0104] Figure 3 This is the NMR image of deuterated 3-bromothiophene described in Example 3 of the present application.

[0105] like Figure 3 As shown, the NMR spectrum shape, signal, noise and other aspects of deuterated 3-bromothiophene also reflect that the deuterated thiophene has extremely high purity, and no other organic impurities are produced during the preparation process, which can effectively simplify the purification steps and effectively reduce the production cost.

[0106] Example 4

[0107] This embodiment provides a fully deuterated thiophene compound and a preparation method and an organic intermediate thereof, which includes most of the technical solutions of Example 1, except that the thiophene compound is 2,5-dibromo-3-hexylthiophene.

[0108] The embodiment of the present application also provides a method for preparing a perdeuterated thiophene compound, comprising the following steps S41)-S45).

[0109] S41) obtaining raw material components of thiophene compound, silver salt catalyst, deuterated water and toluene solvent, wherein the molar ratio of the thiophene compound: the silver salt catalyst: the deuterated water: the toluene solvent is 1:(0.2-0.6):(20-50):(5-50).

[0110]

[0111] Among them, the R 1 It is any one of hydrogen, ester, cyano, carbonyl, hydroxyl, alkoxy, alkyl, amide, amine, borate, alkynyl, alkenyl, (hetero)aryl and halogen.

[0112] In the examples of the present application, the thiophene compound is 2,5-dibromo-3-hexylthiophene.

[0113] The silver salt catalyst is any one of silver carbonate, silver oxide, silver acetate and silver trifluoromethanesulfonate.

[0114] S42) adding the silver salt catalyst, the deuterated water, the thiophene compound and the toluene solvent into a reactor to obtain a mixed solution.

[0115] Specifically, 0.5 mmol of the silver salt catalyst, 30 mmol of the deuterated water, 1 mmol of the 2,5-dibromo-3-hexylthiophene and 22 mmol of the toluene solvent were added to the 10 mL reactor. In the embodiment of the present application, the reaction solution includes but is not limited to a reaction bottle.

[0116] S43) heating the mixed solution.

[0117] Specifically, the mixed solution is heated at a temperature of 100-120° C. for 30-48 hours to allow the mixed solution to fully react.

[0118] S44) After the mixed solution reacts completely, a saturated ammonium chloride solution is added to the reactor to quench the mixture.

[0119] Specifically, 99-101 ml of the ammonium chloride solution, preferably 100 ml of the ammonium chloride solution, is added to the reactor to cause a quenching reaction of the mixed solution in the reactor.

[0120] S45) adding dichloromethane solvent to the reactor, extracting, combining the organic phases, and concentrating by rotary evaporation to obtain a perdeuterated thiophene compound, wherein the deuterated thiophene compound is deuterated 2,5-dibromo-3-hexylthiophene.

[0121] Specifically, 99-101 ml of the dichloromethane solvent, preferably 100 ml of the dichloromethane solvent, is added to the reactor. The dichloromethane solvent can be used for extraction three to four times, and the organic phases extracted several times are combined into a 250 ml eggplant-shaped bottle, and a rotary evaporator is used with a speed of 120 rpm, a temperature of 37 ° C, a vacuum degree of 0.1 MPa, and a treatment of 3 min to obtain a fully deuterated thiophene compound, i.e., deuterated 2,5-dibromo-3-hexylthiophene. Among them, the deuterated 2,5-dibromo-3-hexylthiophene 261 mg, the yield is 80.5%, the deuteration rate is 95%, and the analytical purity is 99%.

[0122] Figure 4 This is the NMR image of deuterated 2,5-dibromo-3-hexylthiophene described in Example 4 of the present application.

[0123] like Figure 4 As shown, the NMR spectrum shape, signal, noise and other aspects of deuterated 2,5-dibromo-3-hexylthiophene also reflect that the deuterated thiophene has extremely high purity, and no other organic impurities are produced during the preparation process, which can effectively simplify the purification steps and effectively reduce the production cost.

[0124] Example 5

[0125] This embodiment provides a fully deuterated thiophene compound and a preparation method and an organic intermediate thereof, which includes most of the technical solutions of Example 1, except that the thiophene compound is dithiophene.

[0126] The embodiment of the present application also provides a method for preparing a perdeuterated thiophene compound, comprising the following steps S51)-S55).

[0127] S51) obtaining raw material components of thiophene compound, silver salt catalyst, deuterated water and toluene solvent, wherein the molar ratio of the thiophene compound: the silver salt catalyst: the deuterated water: the toluene solvent is 1:(0.2-0.6):(20-50):(5-50).

[0128]

[0129] Among them, the R4 It is any one of hydrogen, ester, cyano, carbonyl, hydroxyl, alkoxy, alkyl, amide, amine, borate, alkynyl, alkenyl, (hetero)aryl and halogen.

[0130] In the embodiments of the present application, the thiophene compound is dithiophene.

[0131] The silver salt catalyst is any one of silver carbonate, silver oxide, silver acetate and silver trifluoromethanesulfonate.

[0132] S52) adding the silver salt catalyst, the deuterated water, the thiophene compound and the toluene solvent into a reactor to obtain a mixed solution.

[0133] Specifically, 0.6 mmol of the silver salt catalyst, 50 mmol of the deuterated water, 1 mmol of the dithiophene and 22 mmol of the toluene solvent were added to the 10 mL reactor. In the embodiment of the present application, the reaction solution includes but is not limited to a reaction bottle.

[0134] S53) heating the mixed solution.

[0135] Specifically, the mixed solution is heated at a temperature of 100-120° C. for 30-48 hours to allow the mixed solution to fully react.

[0136] S54) After the mixed solution reacts completely, a saturated ammonium chloride solution is added to the reactor to quench the mixture.

[0137] Specifically, 99-101 ml of the ammonium chloride solution, preferably 100 ml of the ammonium chloride solution, is added to the reactor to cause a quenching reaction of the mixed solution in the reactor.

[0138] S55) adding dichloromethane solvent to the reactor, extracting, combining the organic phases, and concentrating by rotary evaporation to obtain a perdeuterated thiophene compound, wherein the perdeuterated thiophene compound is deuterated dithiophene.

[0139] Specifically, 99-101 ml of the dichloromethane solvent, preferably 100 ml of the dichloromethane solvent, is added to the reactor. The dichloromethane solvent can be used for extraction three to four times, and the organic phases extracted several times are combined into a 250 ml eggplant-shaped bottle, and a rotary evaporator is used with a speed of 120 rpm, a temperature of 37 ° C, a vacuum degree of 0.1 MPa, and a treatment time of 3 min to obtain a fully deuterated thiophene compound, i.e., deuterated dithiophene. The deuterated dithiophene has 133 mg, a yield of 95.5%, a deuteration rate of 95% at the α position, 94% at the β position, and an analytical purity of 99%.

[0140] Figure 5 This is the NMR image of the deuterated dithiophene described in Example 5 of the present application.

[0141] like Figure 5 As shown, the NMR spectrum shape, signal, noise and other aspects of deuterated dithiophene also reflect that the purity of the deuterated thiophene is extremely high, and no other organic impurities are produced during the preparation process, which can effectively simplify the purification steps and effectively reduce the production cost.

[0142] Example 6

[0143] This embodiment provides a fully deuterated thiophene compound and a preparation method and an organic intermediate thereof, which includes most of the technical solutions of Example 1, except that the thiophene compound is 4,8-diketobenzodithiophene.

[0144] The embodiment of the present application also provides a method for preparing a perdeuterated thiophene compound, comprising the following steps S61)-S65).

[0145] S61) obtaining raw material components of thiophene compound, silver salt catalyst, deuterated water and toluene solvent, wherein the molar ratio of the thiophene compound: the silver salt catalyst: the deuterated water: the toluene solvent is 1:(0.2-0.6):(20-50):(5-50).

[0146]

[0147] Among them, the R 5 It is any one of hydrogen, ester, cyano, carbonyl, hydroxyl, alkoxy, alkyl, amide, amine, borate, alkynyl, alkenyl, (hetero)aryl and halogen.

[0148] In the embodiment of the present application, the thiophene compound is 4,8-diketobenzodithiophene.

[0149] The silver salt catalyst is any one of silver carbonate, silver oxide, silver acetate and silver trifluoromethanesulfonate.

[0150] S62) adding the silver salt catalyst, the deuterated water, the thiophene compound and the toluene solvent into a reactor to obtain a mixed solution.

[0151] Specifically, 0.6 mmol of the silver salt catalyst, 50 mmol of the deuterated water, 1 mmol of the dithiophene and 22 mmol of the toluene solvent were added to the 10 mL reactor. In the embodiment of the present application, the reaction solution includes but is not limited to a reaction bottle.

[0152] S63) heating the mixed solution.

[0153] Specifically, the mixed solution is heated at a temperature of 100-120° C. for 30-48 hours to allow the mixed solution to fully react.

[0154] S64) After the mixed solution reacts completely, a saturated ammonium chloride solution is added to the reactor to quench the mixture.

[0155] Specifically, 99-101 ml of the ammonium chloride solution, preferably 100 ml of the ammonium chloride solution, is added to the reactor to cause a quenching reaction of the mixed solution in the reactor.

[0156] S65) adding dichloromethane solvent to the reactor, extracting, combining the organic phases, and concentrating by rotary evaporation to obtain a perdeuterated thiophene compound, wherein the perdeuterated thiophene compound is deuterated 4,8-diketobenzodithiophene.

[0157] Specifically, 99-101 ml of the dichloromethane solvent, preferably 100 ml of the dichloromethane solvent, is added to the reactor. The dichloromethane solvent can be used for extraction three to four times, and the organic phases extracted several times are combined into a 250 ml eggplant-shaped bottle, and a rotary evaporator is used with a speed of 120 rpm, a temperature of 37 ° C, a vacuum degree of 0.1 MPa, and a treatment of 3 min to obtain a fully deuterated thiophene compound, i.e., deuterated 4,8-diketobenzodithiophene. The deuterated 4,8-diketobenzodithiophene is 187 mg, with a yield of 85.5%, a deuterated rate of 99% at the α position, 97% at the β position, and an analytical purity of 99%.

[0158] Figure 6 This is the NMR image of deuterated 4,8-diketobenzodithiophene described in Example 6 of the present application.

[0159] like Figure 6 As shown, the NMR spectrum shape, signal, noise and other aspects of deuterated 4,8-diketobenzodithiophene also reflect that the deuterated thiophene has extremely high purity, and no other organic impurities are produced during the preparation process, which can effectively simplify the purification steps and effectively reduce the production cost.

[0160] The above embodiments provide a perdeuterated thiophene compound and a preparation method thereof, using cheap deuterated water as a deuterated raw material, and directly performing a hydrogen-deuterium exchange reaction on the structure of the thiophene compound. This method can prepare a wide range of substrates. As shown in Table (1), the substrate (thiophene compound) of the perdeuterated thiophene compound can be any one of 5-phenylbenzothiophene, 2-iodothiophene, 3-bromothiophene, 2,5-dibromo-3-hexylthiophene, dithiophene, and 4,8-diketobenzodithiophene.

[0161] Table (1)

[0162]

[0163] It can be seen from Table (1) that when the substrate (thiophene compound) of the perdeuterated thiophene compound is any one of 5-phenylbenzothiophene, 2-iodothiophene, 3-bromothiophene, 2,5-dibromo-3-hexylthiophene, dithiophene, and 4,8-diketobenzodithiophene, the yield of the perdeuterated thiophene compound is greater than or equal to 80%, and the deuteration rate of the perdeuterated thiophene compound is greater than or equal to 90%.

[0164] Therefore, the embodiments of the present application provide a method for preparing a perdeuterated thiophene compound, which solves the technical problems of the existing perdeuterated thiophene compound synthesis process being complex, the production cost being high, and the substrate range being narrow, while also having a high yield and a high deuteration rate.

[0165] In the above embodiments, the description of each embodiment has its own emphasis. For parts that are not described in detail in a certain embodiment, reference can be made to the relevant descriptions of other embodiments.

[0166] The above is a detailed introduction to a perdeuterated thiophene compound and its preparation method, organic intermediate, and organic electroluminescent device provided in the embodiments of the present application. Specific examples are used in this article to illustrate the principles and implementation methods of the present application. The description of the above embodiments is only used to help understand the technical solution and its core idea of ​​the present application; ordinary technicians in this field should understand that they can still modify the technical solutions recorded in the aforementioned embodiments, or replace some of the technical features therein with equivalents; and these modifications or replacements do not make the essence of the corresponding technical solution deviate from the scope of the technical solution of the embodiments of the present application.

Claims

1. A method for preparing a perdeuterated thiophene compound, The fully deuterated thiophene compound is prepared from a thiophene compound and deuterated water. The thiophene compound is 4,8-diketobenzodithiophene; The preparation method comprises the following steps: Adding raw material components into a reactor, the raw material components include a silver salt catalyst, deuterated water, a thiophene compound and a toluene solvent to obtain a mixed solution, wherein: The ratio of the raw material components is that the molar ratio of the thiophene compound: the silver salt catalyst: the deuterated water: the toluene solvent is 1: (0.2-0.6): (20-50): (5-50); heating the mixed solution; After the mixed solution is completely reacted by the heating treatment, a saturated ammonium chloride solution is added to the reactor to quench the mixture; Add dichloromethane solvent to the reactor, extract, combine the organic phases, and concentrate by rotary evaporation. Obtaining the perdeuterated thiophene compound; The silver salt catalyst is any one of silver oxide, silver acetate and silver trifluoromethanesulfonate.

2. The method for preparing a perdeuterated thiophene compound according to claim 1, characterized in that: The heating treatment of the mixed solution includes heating the mixed solution at a temperature of 80-120° C. for 12-48 hours to allow the mixed solution to fully react.

3. The method for preparing a perdeuterated thiophene compound according to claim 1, characterized in that: The adding of saturated ammonium chloride solution into the reactor comprises adding 99-101 ml of saturated ammonium chloride solution into the reactor.

4. The method for preparing a perdeuterated thiophene compound according to claim 1, characterized in that: The adding of dichloromethane solvent into the reactor comprises adding 99-101 ml of the dichloromethane solvent into the reactor.

5. A perdeuterated thiophene compound, characterized in that: Prepared by the method according to claim 1, The thiophene compound is 4,8-diketobenzodithiophene.

6. An organic intermediate, characterized in that Including the perdeuterated thiophene compound as described in claim 5.

7. An organic electroluminescent device, characterized in that: include: An anode, a cathode, and at least one organic layer disposed between the anode and the cathode, wherein the organic layer contains the organic intermediate according to claim 6.

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