WO2022071449A1 - 重水素化芳香族化合物の製造方法 - Google Patents
重水素化芳香族化合物の製造方法 Download PDFInfo
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- WO2022071449A1 WO2022071449A1 PCT/JP2021/036009 JP2021036009W WO2022071449A1 WO 2022071449 A1 WO2022071449 A1 WO 2022071449A1 JP 2021036009 W JP2021036009 W JP 2021036009W WO 2022071449 A1 WO2022071449 A1 WO 2022071449A1
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- ring
- aromatic
- aromatic compound
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- 150000001491 aromatic compounds Chemical class 0.000 title claims abstract description 153
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 76
- 125000006413 ring segment Chemical group 0.000 claims abstract description 150
- 125000003118 aryl group Chemical group 0.000 claims abstract description 114
- 229910052805 deuterium Inorganic materials 0.000 claims abstract description 48
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 claims abstract description 37
- 239000002904 solvent Substances 0.000 claims abstract description 27
- -1 Benzocrisen ring Chemical group 0.000 claims description 85
- 125000004429 atom Chemical group 0.000 claims description 26
- XLYOFNOQVPJJNP-ZSJDYOACSA-N Heavy water Chemical compound [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 claims description 24
- 239000003054 catalyst Substances 0.000 claims description 22
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 15
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 10
- 125000005577 anthracene group Chemical group 0.000 claims description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- DXBHBZVCASKNBY-UHFFFAOYSA-N 1,2-Benz(a)anthracene Chemical group C1=CC=C2C3=CC4=CC=CC=C4C=C3C=CC2=C1 DXBHBZVCASKNBY-UHFFFAOYSA-N 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- 229910052763 palladium Inorganic materials 0.000 claims description 5
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- JZOIZKBKSZMVRV-UHFFFAOYSA-N benzo(a)triphenylene Chemical group C1=CC=CC2=C3C4=CC=CC=C4C=CC3=C(C=CC=C3)C3=C21 JZOIZKBKSZMVRV-UHFFFAOYSA-N 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 125000005581 pyrene group Chemical group 0.000 claims description 3
- 125000005578 chrysene group Chemical group 0.000 claims description 2
- 125000003914 fluoranthenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC=C4C1=C23)* 0.000 claims description 2
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical group C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 claims description 2
- SLGBZMMZGDRARJ-UHFFFAOYSA-N triphenylene Chemical group C1=CC=C2C3=CC=CC=C3C3=CC=CC=C3C2=C1 SLGBZMMZGDRARJ-UHFFFAOYSA-N 0.000 claims description 2
- 125000005580 triphenylene group Chemical group 0.000 claims description 2
- 125000003310 benzodiazepinyl group Chemical group N1N=C(C=CC2=C1C=CC=C2)* 0.000 claims 1
- 239000010410 layer Substances 0.000 description 100
- 150000001875 compounds Chemical class 0.000 description 84
- 239000007787 solid Substances 0.000 description 45
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 36
- 230000004888 barrier function Effects 0.000 description 34
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 27
- 239000012044 organic layer Substances 0.000 description 26
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 24
- 229910052739 hydrogen Inorganic materials 0.000 description 24
- 239000001257 hydrogen Substances 0.000 description 24
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 19
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 18
- 238000002347 injection Methods 0.000 description 18
- 239000007924 injection Substances 0.000 description 18
- 230000015572 biosynthetic process Effects 0.000 description 13
- 238000003786 synthesis reaction Methods 0.000 description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 11
- 238000001816 cooling Methods 0.000 description 9
- 238000001914 filtration Methods 0.000 description 9
- 230000005525 hole transport Effects 0.000 description 9
- 238000001819 mass spectrum Methods 0.000 description 9
- 239000012046 mixed solvent Substances 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 238000010898 silica gel chromatography Methods 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 241000209094 Oryza Species 0.000 description 8
- 235000007164 Oryza sativa Nutrition 0.000 description 8
- 239000012300 argon atmosphere Substances 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 235000009566 rice Nutrition 0.000 description 8
- TXCDCPKCNAJMEE-UHFFFAOYSA-N dibenzofuran Chemical group C1=CC=C2C3=CC=CC=C3OC2=C1 TXCDCPKCNAJMEE-UHFFFAOYSA-N 0.000 description 7
- 239000000376 reactant Substances 0.000 description 7
- 238000000034 method Methods 0.000 description 6
- 238000009835 boiling Methods 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000000543 intermediate Substances 0.000 description 4
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 4
- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical group C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 description 4
- 230000002194 synthesizing effect Effects 0.000 description 4
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Natural products C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 238000006356 dehydrogenation reaction Methods 0.000 description 3
- 238000005401 electroluminescence Methods 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical group 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthrene Natural products C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- VJNCRYFTQUKZQM-UHFFFAOYSA-N methane;dihydrobromide Chemical compound C.Br.Br VJNCRYFTQUKZQM-UHFFFAOYSA-N 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 125000003367 polycyclic group Chemical group 0.000 description 2
- UHOVQNZJYSORNB-RHQRLBAQSA-N 1,2,3,4-tetradeuteriobenzene Chemical compound [2H]C1=CC=C([2H])C([2H])=C1[2H] UHOVQNZJYSORNB-RHQRLBAQSA-N 0.000 description 1
- VVZRKVYGKNFTRR-UHFFFAOYSA-N 12h-benzo[a]xanthene Chemical group C1=CC=CC2=C3CC4=CC=CC=C4OC3=CC=C21 VVZRKVYGKNFTRR-UHFFFAOYSA-N 0.000 description 1
- JKTCBAGSMQIFNL-UHFFFAOYSA-N 2,3-dihydrofuran Chemical compound C1CC=CO1 JKTCBAGSMQIFNL-UHFFFAOYSA-N 0.000 description 1
- KHNYNFUTFKJLDD-UHFFFAOYSA-N Benzo[j]fluoranthene Chemical group C1=CC(C=2C3=CC=CC=C3C=CC=22)=C3C2=CC=CC3=C1 KHNYNFUTFKJLDD-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-VVKOMZTBSA-N Dideuterium Chemical compound [2H][2H] UFHFLCQGNIYNRP-VVKOMZTBSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- UHOVQNZJYSORNB-MZWXYZOWSA-N benzene-d6 Chemical compound [2H]C1=C([2H])C([2H])=C([2H])C([2H])=C1[2H] UHOVQNZJYSORNB-MZWXYZOWSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- UAIZDWNSWGTKFZ-UHFFFAOYSA-L ethylaluminum(2+);dichloride Chemical compound CC[Al](Cl)Cl UAIZDWNSWGTKFZ-UHFFFAOYSA-L 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B59/00—Introduction of isotopes of elements into organic compounds ; Labelled organic compounds per se
- C07B59/001—Acyclic or carbocyclic compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B59/00—Introduction of isotopes of elements into organic compounds ; Labelled organic compounds per se
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B61/00—Other general methods
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C15/00—Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts
- C07C15/20—Polycyclic condensed hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/05—Isotopically modified compounds, e.g. labelled
Definitions
- the present invention relates to a method for producing a deuterated aromatic compound.
- Organic electroluminescence devices (hereinafter, may be referred to as "organic EL devices”) are applied to full-color displays such as mobile phones and televisions.
- organic EL devices When a voltage is applied to the organic EL element, holes are injected into the light emitting layer from the anode, and electrons are injected into the light emitting layer from the cathode. Then, in the light emitting layer, the injected holes and electrons are recombined to form excitons.
- singlet excitons are generated at a rate of 25%, and triplet excitons are generated at a rate of 75%.
- various studies have been conducted on compounds used in organic EL devices.
- the performance of the organic EL element includes, for example, luminance, emission wavelength, chromaticity, luminous efficiency, drive voltage, and life.
- Patent Document 1 and Patent Document 2 describe deuterated compounds and methods for producing them as compounds for organic EL devices.
- Patent Document 1 describes a method for deuterating an aryl-substituted anthracene compound in which an aryl group is bonded to carbon atoms at the 9- and 10-positions of anthracene.
- Patent Document 2 describes a method including a plurality of steps for synthesizing a deuterated intermediate and a step of synthesizing deuterated diarylpyrene using a plurality of deuterated intermediates. Has been done.
- An object of the present invention is to provide a method for producing a deuterated aromatic compound capable of efficiently producing a deuterated aromatic compound having a high deuterated rate.
- a method for producing a dehydrogenated aromatic compound for producing a dehydrogenated aromatic compound which comprises a step of dehydrogenating the aromatic compound in a dehydrogenated solvent.
- the aromatic compound has a structure in which two or more aromatic rings are bonded to each other via a bond in the molecule, and at least one of the two or more aromatic rings of the aromatic compound is a fused aromatic ring.
- at least one of the fused aromatic rings is a first fused ring atom having the bond related to a bond with another aromatic ring, and a second fused ring adjacent to the first fused ring atom on both sides.
- a method for producing a dehydrogenated aromatic compound which is not an atom constituting a 6-membered ring among rings condensed with an aromatic ring containing a third fused ring atom, is provided.
- 6 is a 1 H NMR spectrum of a deuterated aromatic compound produced by the production method according to Example 1. 6 is a 1 H NMR spectrum of an aromatic compound used in the production method according to Example 1.
- the method for producing a deuterated aromatic compound of the present embodiment is a method for producing a deuterated aromatic compound.
- the method for producing a deuterated aromatic compound of the present embodiment includes a step of deuterating the aromatic compound in a deuterium-containing solvent.
- the aromatic compound has a structure in which two or more aromatic rings are bonded via a bond in the molecule. Of the two or more aromatic rings contained in the aromatic compound, at least one is a condensed aromatic ring.
- At least one of the fused aromatic rings is a first fused ring atom having the bond involved in a bond with another aromatic ring, a second fused ring atom adjacent to the first fused ring atom on both sides, and a second fused ring atom adjacent to the first fused ring atom. It has an aromatic ring containing a third fused ring atom. At least one of the second condensed ring atom and the third condensed ring atom is among the rings condensed with the aromatic ring containing the first condensed ring atom, the second condensed ring atom and the third condensed ring atom. , It is not an atom that constitutes a 6-membered ring.
- the aromatic compound used in the method for producing a deuterated aromatic compound of the present embodiment is a non-deuterated aromatic compound (sometimes referred to as a non-deuterated aromatic compound).
- the aromatic ring means a ring in which the number of ⁇ electrons is 4n + 2 (n is a positive integer including 0).
- the aromatic ring is at least one of an aromatic hydrocarbon ring and an aromatic heterocycle.
- the ring condensed with respect to the aromatic ring containing the first fused ring atom, the second fused ring atom and the third fused ring atom is preferably a 5-membered ring, a 6-membered ring, a 7-membered ring or an 8-membered ring. It is more preferably a 5-membered ring or a 6-membered ring.
- At least one of the second condensed ring atom and the third condensed ring atom is a 6-membered ring among the rings fused to the aromatic ring containing the first condensed ring atom, the second condensed ring atom and the third condensed ring atom.
- "Not an atom constituting” means, for example, as shown in (E1), (E2) or (E3) below.
- One of the second fused ring atom and the third fused ring atom constitutes a 6-membered ring that is condensed with an aromatic ring containing the first fused ring atom, the second condensed ring atom and the third fused ring atom. It is an atom, and the other of the second fused ring atom and the third fused ring atom is not an atom constituting a ring other than the aromatic ring containing the first fused ring atom, the second condensed ring atom and the third fused ring atom (). The other of the second fused ring atom and the third fused ring atom is contained only in the aromatic ring containing the first fused ring atom, the second condensed ring atom and the third fused ring atom.)
- One of the second fused ring atom and the third fused ring atom constitutes a 6-membered ring that is condensed with an aromatic ring containing the first fused ring atom, the second condensed ring atom and the third fused ring atom. It is an atom, and the other of the second fused ring atom and the third fused ring atom constitutes a five-membered ring that is condensed with an aromatic ring containing the first fused ring atom, the second condensed ring atom, and the third fused ring atom. It is an atom that does.
- Both the second condensed ring atom and the third condensed ring atom are not atoms constituting a ring that condenses with an aromatic ring containing the first condensed ring atom, the second condensed ring atom, and the third condensed ring atom. ..
- the atom constituting the ring condensed with respect to the aromatic ring including the first condensed ring atom, the second condensed ring atom and the third condensed ring atom is a carbon atom or a hetero atom, and the hetero atom is, for example, an oxygen atom. , Sulfur atom, nitrogen atom, boron atom, phosphorus atom and the like.
- the following compound BH-A corresponds to the aromatic compound used in the method for producing a deuterated aromatic compound of the present embodiment.
- Compound BH-A has four aromatic rings (two benzene rings and two pyrene rings) in the molecule.
- Compound BH-A has a structure in which four aromatic rings are bonded via a bond (single bond). Of the four aromatic rings of compound BH-A, two are fused aromatic rings (pyrene rings).
- the pyrene ring contained in the compound BH-A has a first fused ring atom C1 having a bond related to a bond with another aromatic ring B1 (benzene ring) and a first fused ring atom C as shown in the following structural formula. It has an aromatic ring A1 containing the second fused ring atom C2 and the third fused ring atom C3 adjacent to each other on both sides of 1 .
- the second condensed ring atom C 2 has six members that condense with the aromatic ring A1 containing the first condensed ring atom C 1 , the second condensed ring atom C 2 and the third condensed ring atom C 3 . It is not an atom that constitutes ring A2, which is a ring.
- the third fused ring atom C 3 is an atom constituting the ring A2 that is condensed with the aromatic ring A1.
- the second condensed ring atom C2 and the third condensed ring atom C3 of the aromatic ring A1 in the compound BH-A correspond to the case of (E1) described above.
- the following compound Ref-BH-A does not correspond to the aromatic compound used in the method for producing a deuterated aromatic compound of the present embodiment.
- the compound Ref-BH-A has three aromatic rings (one each of a benzene ring, an anthracene ring and a dibenzofuran ring) in the molecule.
- the compound Ref-BH-A has a structure in which three aromatic rings are bonded via a bond (single bond). Of the three aromatic rings of the compound Ref-BH-A, two are fused aromatic rings (anthracene ring and dibenzofuran ring).
- the anthracene ring of the compound Ref-BH-A has a first fused ring atom C1 having a bond related to a bond with another aromatic ring B1 (benzene ring) and a first fused ring as shown in the following structural formula.
- the aromatic ring A1 has an aromatic ring A1 containing the atom C 1 and the second fused ring atom C 2 and the third fused ring atom C 3 adjacent to each other on both sides.
- the aromatic ring A1 has a first fused ring atom C4 having a bond related to a bond with another aromatic ring (dibenzofuran ring) and a second condensed ring atom C adjacent to the first fused ring atom C4 on both sides. 5 and the third condensed ring atom C6 are included.
- the first fused ring atom C4 is bonded to one aromatic ring D1 constituting the dibenzofuran ring as another aromatic ring via a bond.
- the second fused ring atoms C 2 and C 5 are atoms constituting the ring A2 which is a 6-membered ring condensed with the aromatic ring A1.
- the third fused ring atoms C 3 and C 6 are atoms constituting the ring A3 which is a 6-membered ring condensed with the aromatic ring A1.
- the ring A2 or the ring A3 in which the second fused ring atoms C 2 and C 5 and the third fused ring atoms C 3 and C 6 are all condensed with the aromatic ring A1 is formed.
- the compound Ref-BH-A does not correspond to the aromatic compound used in the method for producing a dehydrided aromatic compound of the present embodiment.
- the second fused ring atom and the third fused ring atom are atoms constituting the ring A2 or the ring A3 to be condensed with the aromatic ring A1, such as the compound Ref-BH-A, the second of the ring A2 or the ring A3.
- the hydrogen atom bonded to the carbon atom in the vicinity of the 2 fused ring atom and the 3rd fused ring atom and the hydrogen atom bonded to the aromatic ring B1 or the aromatic ring D1 are close to each other and are bulky in the molecule. Regions are formed, and hydrogen atoms located in such bulky regions are less likely to be dehydrogenated.
- At least one of the fused aromatic rings is a condensed aromatic ring in which three or more rings are condensed.
- the fused aromatic ring is a condensed aromatic hydrocarbon ring having 10 or more and 30 or less ring-forming carbon atoms or a condensed aromatic ring having 9 or more and 30 or less ring-forming atoms. It is preferably a heterocycle.
- At least one of the fused aromatic rings is a pyrene ring, a fluoranthene ring, a benzofluoranthene ring, a phenanthren ring, a benzophenanthrene ring, a chrysene ring, a benzochrysene ring, and the like.
- At least one of the fused aromatic rings is at least one selected from the group consisting of rings represented by the following formulas (101) to (148). It is preferably a ring.
- the condensed aromatic ring does not contain a ring represented by the following formulas (X1), (X2), (X3) and (X4).
- the second condensed ring atom and the third condensed ring atom of the aromatic ring to which the bond is bonded correspond to the above-mentioned case (E3).
- the aromatic compound has two or more fused aromatic rings, and the two or more fused aromatic rings are all described in (E1) and (E1). It is preferable to have an aromatic ring containing a first fused ring atom, a second fused ring atom and a third fused ring atom corresponding to any of the cases of E2) or (E3), and the above-mentioned (E1) or (E3) It is more preferable to have an aromatic ring containing a first fused ring atom, a second condensed ring atom and a third fused ring atom corresponding to any of the above cases.
- two or more fused aromatic rings have the same structure as each other.
- the two or more fused aromatic rings have different structures from each other. The same structure means that the ring skeletons of the two or more condensed aromatic rings are the same as each other, and the positions of the bonds are the same as each other.
- the aromatic compound when the aromatic compound has a plurality of fused aromatic rings, all of these plurality of condensed aromatic rings are bound to be bonded to other aromatic rings. It has an aromatic ring containing a first fused ring atom having, a second fused ring atom and a third fused ring atom adjacent to each other on both sides of the first condensed ring atom, and has a second condensed ring atom and a third condensed ring atom.
- At least one of the ring atoms is not an atom constituting a 6-membered ring among the rings condensed with the aromatic ring containing the first fused ring atom, the second condensed ring atom and the third fused ring atom.
- the aromatic compound used in the method for producing a deuterated aromatic compound of the present embodiment has two or more rings selected from the group consisting of the rings represented by the formulas (101) to (148). May be. Two or more rings selected from the group consisting of the rings represented by the formulas (101) to (148) are the same as or different from each other.
- the aromatic compound used in the method for producing a dehydrogenated aromatic compound of the present embodiment is the first condensation corresponding to any of the above-mentioned cases (E1), (E2) and (E3) in the condensed aromatic ring. It is also preferable to have a plurality of sets consisting of a ring atom, a second condensed ring atom and a third condensed ring atom, and the first condensed ring corresponding to any of the above-mentioned cases (E1) and (E3). It is also preferable to have a plurality of sets consisting of an atom, a second condensed ring atom and a third condensed ring atom.
- the fused aromatic ring in the aromatic compound used in the method for producing a deuterated aromatic compound of the present embodiment may have a plurality of binding hands to other aromatic rings.
- the first fused ring atom having the bond is adjacent to the second condensed ring atom and the third fused ring atom on both sides, and at least one of the second condensed ring atom and the third fused ring atom is the first. It is preferable that the atom does not constitute a ring that condenses with an aromatic ring containing a 1-condensed ring atom, a 2nd condensed ring atom, and a 3rd condensed ring atom.
- the condensed aromatic ring represented by the above formula (101) further has a bond
- the condensed aromatic ring represented by the following formula (149) can be mentioned.
- the condensed aromatic ring represented by the above formula (149) has a first fused ring atom C 11 having a bond related to a bond with another aromatic ring and a first fused ring atom C 11 adjacent to each other on both sides.
- the aromatic ring A11 including the two fused ring atoms C 12 and the third fused ring atom C 13 , and the first fused ring atom C 14 having a bond related to the bond with another aromatic ring, and the first condensed ring atom. It contains an aromatic ring A13 containing C 14 and adjacent second condensed ring atoms C 15 and third condensed ring atoms C 16 on both sides.
- the second condensed ring atom C 12 is not the atom constituting the ring A12 and the ring A14 condensed with the aromatic ring A11, but the third condensed ring atom C13 .
- the second fused ring atom C 15 is not the atom constituting the ring A12 and the ring A14 condensed with the aromatic ring A13, but the third fused ring atom C16 . Is an atom constituting the ring A14 that is condensed with the aromatic ring A13.
- the aromatic compound used in the method for producing a deuterated aromatic compound of the present embodiment does not have an anthracene ring.
- the deuterium-containing solvent contains deuterium in the solvent molecule.
- Deuterium-containing solvents are heavy benzene (benzene-d6, C 6D 6 ), heavy water (D2 O), benzene-d4 (C 6 D 4 H 2 ) and heavy toluene (toluene -d 8, CD 3 C 6 D ) . It is preferable to contain at least one solvent selected from the group consisting of 5 ), and the deuterium-containing solvent is more preferably heavy benzene (C 6 D 6 ) or heavy water (D 2 O).
- the amount of the deuterium-containing solvent used is 1 (v / w) when 1 mL of the deuterium-containing solvent is used for 1 g of the aromatic compound (light hydrogen compound). ).
- the amount of the deuterium-containing solvent used is, for example, 5 (v / w) or more and 10000 (v / w) or less, preferably 10 (v / w) or more and 1000 (v / w) or less. More preferably, it is 50 (v / w) or more and 500 (v / w) or less.
- At least one catalyst capable of exchanging light hydrogen for deuterium in the step of deuterating the aromatic compound in a deuterium-containing solvent.
- a Lewis acid H / D exchange catalyst it is also preferable to use a Lewis acid H / D exchange catalyst.
- a deuterated aromatic compound of the present embodiment at least selected from the group consisting of an aluminum catalyst, a platinum catalyst, and a palladium catalyst in the step of deuterating the aromatic compound in a deuterium-containing solvent. It is preferable to use one type of catalyst.
- Examples of the aluminum catalyst include aluminum trichloride and ethyl aluminum chloride.
- the amount of the aluminum catalyst used is, for example, 0.1 times molar equivalent or more and 20 times molar equivalent or less with respect to the aromatic compound (light hydrogen compound). Yes, preferably 0.5-fold molar equivalents or more and 10-fold molar equivalents or less, and more preferably 1-fold molar equivalents or more and 5-fold molar equivalents or less.
- the reaction temperature of the step of deuterating the aromatic compound in a deuterium-containing solvent is, for example, 0 ° C. or higher, containing deuterium used in the step. It is below the boiling point of the solvent, preferably 20 ° C. or higher, below the boiling point of the deuterium-containing solvent, more preferably 40 ° C. or higher, at a temperature of -10 ° C. or lower with respect to the boiling point of the deuterium-containing solvent. be.
- the aromatic compound (light hydrogen compound) as a reaction product is used as a deuterium-containing solvent. It is also preferable to include a step of obtaining a solution by dissolving the solution in hydrogen and a step of adding a catalyst to the solution to react.
- the catalyst is a catalyst capable of exchanging light hydrogen for deuterium, and is preferably at least one catalyst selected from the group consisting of an aluminum catalyst, a platinum catalyst, and a palladium catalyst.
- the aromatic compound and a palladium catalyst of 0.01% by mass or more and 200% by mass or less with respect to the total mass of the aromatic compound are used.
- a platinum catalyst (mass ratio 1: 1) total of palladium metal and platinum metal is 0.0005% by mass or more and 20% by mass or less with respect to the total mass of aromatic compound) is dehydrogenated.
- the deuteration rate of the deuterated aromatic compound produced by the method for producing a deuterated aromatic compound of the present embodiment is preferably 70% or more, more preferably 80% or more, and 90%. % Or more is more preferable.
- the deuteration rate of the deuterated aromatic compound can be determined by NMR analysis.
- Specific examples of aromatic compounds include, for example, the following compounds and deuterium (D) of a specific example of the deuterated aromatic compound described later. Can be mentioned as a compound in which deuterium (H) is changed to light hydrogen (H). However, the present invention is not limited to specific examples of these aromatic compounds.
- deuterated aromatic compounds Specific examples of the deuterated aromatic compound produced by the method for producing a deuterated aromatic compound of the present embodiment include the following compounds. However, the present invention is not limited to specific examples of these deuterated aromatic compounds.
- the conventional method for dehydrogenating light hydrogen in the molecule of an aromatic compound is a step of synthesizing an intermediate in which the aromatic rings constituting the aromatic compound are individually dehydrogenated, and an intermediate of the dehydrogenation.
- a step of synthesizing a compound in which light hydrogen in the molecule was dehydrogenated using a body was required.
- the method for producing a deuterated aromatic compound of the present embodiment is a step of deuterating an aromatic compound (light hydrogen compound) having the same skeleton as the deuterated compound for production in a deuterium-containing solvent.
- the dehydrogenation rate is low, but according to the method for producing a dehydrogenated aromatic compound of the present embodiment. , A dehydrogenated aromatic compound can be produced with a higher dehydrogenation rate.
- the deuterated aromatic compound produced by the method for producing a deuterated aromatic compound of the present embodiment can be used as a material for various purposes, and can also be used, for example, as a material for an organic electroluminescence element. ..
- the organic electroluminescence device (sometimes referred to as an organic EL device) includes an organic layer between both electrodes of the anode and the cathode. This organic layer contains at least one layer composed of an organic compound. Alternatively, this organic layer is formed by laminating a plurality of layers composed of organic compounds. The organic layer may further contain an inorganic compound. In an organic EL element, at least one of the organic layers is a light emitting layer.
- the organic layer may be composed of, for example, one light emitting layer, or may include a layer that can be adopted in the organic EL element.
- the layer that can be adopted for the organic EL device is not particularly limited, but is selected from the group consisting of, for example, a hole injection layer, a hole transport layer, an electron barrier layer, an electron injection layer, an electron transport layer, and a hole barrier layer. At least one layer can be mentioned.
- the organic layer of the organic EL element preferably has, for example, any of the following layer configurations.
- the deuterated aromatic compound produced by the method for producing a deuterated aromatic compound of the present embodiment is preferably contained in at least one of the organic layers of the organic EL element.
- the deuterated aromatic compound may be contained in a plurality of layers.
- the deuterated aromatic compound may be contained alone in one layer or may be contained together with at least one other compound.
- the other compounds contained in one layer together with the deuterated aromatic compound may be independently non-deuterated compounds (sometimes referred to as non-deuterated compounds). , It may be a deuterated compound.
- the present invention is not limited to the above-described embodiment, and changes, improvements, etc. to the extent that the object of the present invention can be achieved are included in the present invention.
- specific materials, reaction conditions, structures, shapes, etc. in carrying out the present invention may be changed or improved within the range in which the object of the present invention can be achieved.
- Example 1 relates to a method for producing compound BH-1 as a deuterated aromatic compound.
- the synthesis scheme for compound BH-1 is shown below.
- the washed solid was purified by silica gel column chromatography and then recrystallized from a mixed solvent of toluene and hexane to obtain 15.3 g (yield: 77%) of an orange solid.
- FIG. 2 is a 1 H NMR spectrum of the aromatic compound (Compound BH-A) used in the production method according to Example 1.
- 100 was taken as the standard for methane dibromide, the total integral value of the protons in the molecule was 13259.62, and the number of protons in one molecule was 26.
- FIG. 1 is a 1 H NMR spectrum of a deuterated aromatic compound (Compound BH-1) produced by the production method according to Example 1.
- the total integral value of the protons in the molecule was 802.61 when 100 was taken as the standard for methane dibromide.
- Example 2 relates to a method for producing the compound BH-2 as a deuterated aromatic compound.
- the synthetic scheme for compound BH-2 is shown below.
- the washed solid is purified by silica gel column chromatography, recrystallized from a mixed solvent of toluene and hexane, and suspended and washed with ethyl acetate to obtain 7.2 g (yield: 69%) of a pale yellow solid. rice field.
- Example 3 relates to a method for producing compound BH-3 as a deuterated aromatic compound.
- the synthesis scheme for compound BH-3 is shown below.
- the washed solid is purified by silica gel column chromatography, recrystallized from a mixed solvent of toluene and hexane, and suspended and washed with ethyl acetate to obtain 2.9 g (yield: 55%) of a pale yellow solid. rice field.
- Example 4 relates to a method for producing the compound BH-4 as a deuterated aromatic compound.
- the synthesis scheme for compound BH-4 is shown below.
- the washed solid is purified by silica gel column chromatography, recrystallized from a mixed solvent of toluene and hexane, and suspended and washed with ethyl acetate to obtain 6.5 g (yield: 77%) of a pale yellow solid. rice field.
- Example 5 relates to a method for producing the compound BH-5 as a deuterated aromatic compound.
- the synthesis scheme for compound BH-5 is shown below.
- the washed solid is purified by silica gel column chromatography, recrystallized from a mixed solvent of toluene and hexane, and suspended and washed with ethyl acetate to obtain 6.2 g (yield: 78%) of a pale yellow solid. rice field.
- Example 6 relates to a method for producing the compound BH-6 as a deuterated aromatic compound.
- the synthetic scheme for compound BH-6 is shown below.
- the washed solid is purified by silica gel column chromatography, recrystallized from a mixed solvent of toluene and hexane, and suspended and washed with ethyl acetate to obtain 1.8 g (yield: 69%) of a pale yellow solid. rice field.
- Example 7 relates to a method for producing the compound BH-7 as a deuterated aromatic compound.
- the synthetic scheme for compound BH-7 is shown below.
- the washed solid is purified by silica gel column chromatography, recrystallized from a mixed solvent of toluene and hexane, and suspended and washed with ethyl acetate to obtain 3.9 g (yield: 75%) of a pale yellow solid. rice field.
- Example 8 relates to a method for producing the compound BH-8 as a deuterated aromatic compound.
- the synthetic scheme for compound BH-8 is shown below.
- the washed solid is purified by silica gel column chromatography, recrystallized from a mixed solvent of toluene and hexane, and suspended and washed with ethyl acetate to obtain 2.1 g (yield: 67%) of a pale yellow solid. rice field.
- Example 9 relates to a method for producing the compound BH-9 as a deuterated aromatic compound.
- the synthetic scheme for compound BH-9 is shown below.
- the washed solid is purified by silica gel column chromatography, recrystallized from a mixed solvent of toluene and hexane, and suspended and washed with ethyl acetate to obtain 2.4 g (yield: 57%) of a pale yellow solid. rice field.
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Abstract
Description
有機EL素子の性能向上を図るため、有機EL素子に用いる化合物について様々な検討がなされている。有機EL素子の性能としては、例えば、輝度、発光波長、色度、発光効率、駆動電圧、及び寿命が挙げられる。
特許文献1には、アントラセンの9位及び10位の炭素原子にアリール基が結合しているアリール置換アントラセン化合物を重水素化する方法が記載されている。
特許文献2には、重水素化された中間体を合成するための複数の工程と、重水素化された複数の中間体を用いて重水素化ジアリールピレンを合成する工程とを含む方法が記載されている。
特許文献2に記載の方法で重水素化されたジアリールピレンを製造するためには、複数の工程が必要であり、製造効率が低い。
化合物Ref-BH-Aのように、第2縮合環原子及び第3縮合環原子が芳香環A1に対して縮合する環A2又は環A3を構成する原子であると、環A2又は環A3の第2縮合環原子及び第3縮合環原子の近傍の炭素原子に結合している水素原子と、芳香環B1又は芳香環D1に結合している水素原子とが互いに近接して、分子中にかさ高い部位が生じ、このようなかさ高い部位に位置する水素原子は、重水素化されにくい。
例えば、前記式(101)で表される縮合芳香環がさらに結合手を有する場合の一態様として、下記式(149)で表される縮合芳香環が挙げられる。
前記式(149)で表される縮合芳香環において、第2縮合環原子C12は、芳香環A11に対して縮合する環A12及び環A14を構成する原子ではなく、第3縮合環原子C13は、芳香環A11に対して縮合する環A12を構成する原子である。
前記式(149)で表される縮合芳香環において、第2縮合環原子C15は、芳香環A13に対して縮合する環A12及び環A14を構成する原子ではなく、第3縮合環原子C16は、芳香環A13に対して縮合する環A14を構成する原子である。
重水素化芳香族化合物の重水素化率は、NMR分析によって求めることができる。
本実施形態の重水素化芳香族化合物の製造方法において、使用する芳香族化合物の具体例としては、例えば、以下の化合物、及び後記の重水素化芳香族化合物の具体例の重水素(D)を軽水素(H)に変更した化合物が挙げられる。ただし、本発明は、これら芳香族化合物の具体例に限定されない。
本実施形態の重水素化芳香族化合物の製造方法よって製造される重水素化芳香族化合物の具体例としては、例えば、以下の化合物が挙げられる。ただし、本発明は、これら重水素化芳香族化合物の具体例に限定されない。
芳香族化合物の分子中の軽水素を重水素化するための従来の方法は、芳香族化合物を構成する芳香環を個別に重水素化した中間体を合成する工程と、当該重水素化した中間体を用いて、分子中の軽水素が重水素化された化合物を合成する工程とが必要であった。
本実施形態の重水素化芳香族化合物の製造方法は、製造目的の重水素体と同じ骨格を有する芳香族化合物(軽水素体)を重水素含有溶媒中で重水素化させる工程により、芳香族化合物の分子中の軽水素を重水素化できるため、従来の方法に比べて、製造方法の工程が少なく、効率的な製造が可能である。
また、縮合多環骨格として9,10-アントラセンジイルを有する芳香族化合物を重水素化する方法では、重水素化率が低いが、本実施形態の重水素化芳香族化合物の製造方法によれば、より高い重水素化率で重水素化芳香族化合物を製造できる。
有機エレクトロルミネッセンス素子(有機EL素子と称する場合がある。)は、陽極及び陰極の両電極間に有機層を備える。この有機層は、有機化合物で構成される層を少なくとも一つ含む。あるいは、この有機層は、有機化合物で構成される複数の層が積層されてなる。有機層は、無機化合物をさらに含んでいてもよい。有機EL素子において、有機層のうち少なくとも一層は、発光層である。ゆえに、有機層は、例えば、一つの発光層で構成されていてもよいし、有機EL素子に採用され得る層を含んでいてもよい。有機EL素子に採用され得る層は、特に限定されないが、例えば、正孔注入層、正孔輸送層、電子障壁層、電子注入層、電子輸送層、及び正孔障壁層からなる群から選択される少なくともいずれかの層が挙げられる。
有機EL素子の有機層は、例えば、以下のいずれかの層構成であることが好ましい。
・電子障壁層/発光層/正孔障壁層
・正孔注入層/電子障壁層/発光層/正孔障壁層
・正孔輸送層/電子障壁層/発光層/正孔障壁層
・正孔注入層/正孔輸送層/電子障壁層/発光層/正孔障壁層
・電子障壁層/発光層/正孔障壁層/電子注入層
・電子障壁層/発光層/正孔障壁層/電子輸送層
・電子障壁層/発光層/正孔障壁層/電子輸送層/電子注入層
・正孔注入層/電子障壁層/発光層/正孔障壁層/電子注入層
・正孔注入層/電子障壁層/発光層/正孔障壁層/電子輸送層
・正孔注入層/電子障壁層/発光層/正孔障壁層/電子輸送層/電子注入層
・正孔輸送層/電子障壁層/発光層/正孔障壁層/電子注入層
・正孔輸送層/電子障壁層/発光層/正孔障壁層/電子輸送層
・正孔輸送層/電子障壁層/発光層/正孔障壁層/電子輸送層/電子注入層
・正孔注入層/正孔輸送層/電子障壁層/発光層/正孔障壁層/電子注入層
・正孔注入層/正孔輸送層/電子障壁層/発光層/正孔障壁層/電子輸送層
・正孔注入層/正孔輸送層/電子障壁層/発光層/正孔障壁層/電子輸送層/電子注入層
(実施例1)
実施例1は、重水素化芳香族化合物としての化合物BH-1の製造方法に関する。化合物BH-1の合成スキームが、以下に示される。
アルゴン雰囲気下、非重水素化芳香族化合物としての軽水素体(化合物BH-A)19.0g、及び重ベンゼンd61140mLをフラスコに加え、45℃に加熱して反応物を溶解させた後、塩化アルミニウム4.6gを加えて、40℃で、29時間、加熱撹拌した。室温まで冷却後、重水300mLを滴下して、有機層を分取した。有機層を濃縮して析出した固体を濾集した。得られた固体を水、及びアセトンで洗浄した。洗浄した固体を、シリカゲルカラムクロマトグラフィーで精製した後、トルエンとヘキサンの混合溶媒で再結晶し、橙色固体15.3g(収率:77%)を得た。この橙色固体は、マススペクトル分析の結果、重水素化芳香族化合物としての化合物BH-1であり、分子量580.85に対し、m/e=581であった。
標品の軽水素体(化合物BH-A,分子量:554.69)10.2mg(0.0184mmol)を重テトラヒドロフラン中でNMR測定を行った。図2は、実施例1に係る製造方法で使用した芳香族化合物(化合物BH-A)の1H NMRスペクトルである。二臭化メタンを基準とし100としたときに、分子中のプロトンの総積分値は、13259.62であり、1分子中のプロトン数は、26であった。
一方、重水素体(化合物BH-1,分子量:580.85)9.9mg(0.0170mmol)も重テトラヒドロフラン中でNMR測定を行った。図1は、実施例1に係る製造方法で製造した重水素化芳香族化合物(化合物BH-1)の1H NMRスペクトルである。二臭化メタンを基準とし100としたときに、分子中のプロトンの総積分値は、802.61であった。軽水素体と重水素体とのモル比を考慮に入れると、重水素体の重水素化しきれなかったプロトンの総積分値は、802.61×(0.0184/0.0170)=868.71であった。重水素体のプロトンの総積分値と軽水素体のプロトンの総積分値とに基づいて計算すると、下記計算式のとおり、重水素化率は、93.4%であった。
{1-(868.71/13259.62)}×100=93.4%
実施例2は、重水素化芳香族化合物としての化合物BH-2の製造方法に関する。化合物BH-2の合成スキームが、以下に示される。
アルゴン雰囲気下、非重水素化芳香族化合物としての軽水素体(化合物BH-B)10.0g、及び重ベンゼンd61200mLをフラスコに加え、50℃に加熱して反応物を溶解させた後、塩化アルミニウム3.5gを加えて、60℃で、40時間、加熱撹拌した。室温まで冷却後、重水500mLを滴下して、有機層を分取した。有機層を濃縮して析出した固体を濾集した。得られた固体を水、及びアセトンで洗浄した。洗浄した固体を、シリカゲルカラムクロマトグラフィーで精製した後、トルエンとヘキサンの混合溶媒で再結晶し、酢酸エチルで懸濁洗浄することにより、淡黄色固体7.2g(収率:69%)を得た。この淡黄色固体は、マススペクトル分析の結果、重水素化芳香族化合物としての化合物BH-2であり、分子量420.61に対し、m/e=421であった。
実施例3は、重水素化芳香族化合物としての化合物BH-3の製造方法に関する。化合物BH-3の合成スキームが、以下に示される。
窒素雰囲気下、非重水素化芳香族化合物としての軽水素体(化合物BH-C)5.0g、及び重ベンゼンd6800mLをフラスコに加え、45℃に加熱して反応物を溶解させた後、塩化アルミニウム2.2gを加えて、40℃で、30時間、加熱撹拌した。室温まで冷却後、重水300mLを滴下して、有機層を分取した。有機層を濃縮して析出した固体を濾集した。得られた固体を水、及びアセトンで洗浄した。洗浄した固体を、シリカゲルカラムクロマトグラフィーで精製した後、トルエンとヘキサンの混合溶媒で再結晶し、酢酸エチルで懸濁洗浄することにより、淡黄色固体2.9g(収率:55%)を得た。この淡黄色固体は、マススペクトル分析の結果、重水素化芳香族化合物としての化合物BH-3であり、分子量648.92に対し、m/e=649であった。
実施例4は、重水素化芳香族化合物としての化合物BH-4の製造方法に関する。化合物BH-4の合成スキームが、以下に示される。
アルゴン雰囲気下、非重水素化芳香族化合物としての軽水素体(化合物BH-D)8.0g、及び重ベンゼンd6900mLをフラスコに加え、45℃に加熱して反応物を溶解させた後、塩化アルミニウム2.7gを加えて、40℃で、50時間、加熱撹拌した。室温まで冷却後、重水300mLを滴下して、有機層を分取した。有機層を濃縮して析出した固体を濾集した。得られた固体を水、及びアセトンで洗浄した。洗浄した固体を、シリカゲルカラムクロマトグラフィーで精製した後、トルエンとヘキサンの混合溶媒で再結晶し、酢酸エチルで懸濁洗浄することにより、淡黄色固体6.5g(収率:77%)を得た。この淡黄色固体は、マススペクトル分析の結果、重水素化芳香族化合物としての化合物BH-4であり、分子量468.72に対し、m/e=469であった。
実施例5は、重水素化芳香族化合物としての化合物BH-5の製造方法に関する。化合物BH-5の合成スキームが、以下に示される。
アルゴン雰囲気下、非重水素化芳香族化合物としての軽水素体(化合物BH-E)7.5g、及び重ベンゼンd61000mLをフラスコに加え、45℃に加熱して反応物を溶解させた後、塩化アルミニウム2.2gを加えて、40℃で、40時間、加熱撹拌した。室温まで冷却後、重水300mLを滴下して、有機層を分取した。有機層を濃縮して析出した固体を濾集した。得られた固体を水、及びアセトンで洗浄した。洗浄した固体を、シリカゲルカラムクロマトグラフィーで精製した後、トルエンとヘキサンの混合溶媒で再結晶し、酢酸エチルで懸濁洗浄することにより、淡黄色固体6.2g(収率:78%)を得た。この淡黄色固体は、マススペクトル分析の結果、重水素化芳香族化合物としての化合物BH-5であり、分子量468.72に対し、m/e=469であった。
実施例6は、重水素化芳香族化合物としての化合物BH-6の製造方法に関する。化合物BH-6の合成スキームが、以下に示される。
アルゴン雰囲気下、非重水素化芳香族化合物としての軽水素体(化合物BH-F)2.5g、及び重トルエン(CD3C6H5)500mLをフラスコに加え、45℃に加熱して反応物を溶解させた後、塩化アルミニウム2.1gを加えて、70℃で、65時間、加熱撹拌した。室温まで冷却後、重水150mLを滴下して、有機層を分取した。有機層を濃縮して析出した固体を濾集した。得られた固体を水、及びアセトンで洗浄した。洗浄した固体を、シリカゲルカラムクロマトグラフィーで精製した後、トルエンとヘキサンの混合溶媒で再結晶し、酢酸エチルで懸濁洗浄することにより、淡黄色固体1.8g(収率:69%)を得た。この淡黄色固体は、マススペクトル分析の結果、重水素化芳香族化合物としての化合物BH-6であり、分子量500.73に対し、m/e=501であった。
実施例7は、重水素化芳香族化合物としての化合物BH-7の製造方法に関する。化合物BH-7の合成スキームが、以下に示される。
アルゴン雰囲気下、非重水素化芳香族化合物としての軽水素体(化合物BH-G)5.0g、及び重ベンゼンd61200mLをフラスコに加え、45℃に加熱して反応物を溶解させた後、塩化アルミニウム2.4gを加えて、40℃で、35時間、加熱撹拌した。室温まで冷却後、重水500mLを滴下して、有機層を分取した。有機層を濃縮して析出した固体を濾集した。得られた固体を水、及びアセトンで洗浄した。洗浄した固体を、シリカゲルカラムクロマトグラフィーで精製した後、トルエンとヘキサンの混合溶媒で再結晶し、酢酸エチルで懸濁洗浄することにより、淡黄色固体3.9g(収率:75%)を得た。この淡黄色固体は、マススペクトル分析の結果、重水素化芳香族化合物としての化合物BH-7であり、分子量596.85に対し、m/e=597であった。
実施例8は、重水素化芳香族化合物としての化合物BH-8の製造方法に関する。化合物BH-8の合成スキームが、以下に示される。
アルゴン雰囲気下、非重水素化芳香族化合物としての軽水素体(化合物BH-H)5.0g、及び重ベンゼンd61500mLをフラスコに加え、45℃に加熱して反応物を溶解させた後、塩化アルミニウム4.2gを加えて、50℃で、55時間、加熱撹拌した。室温まで冷却後、重水500mLを滴下して、有機層を分取した。有機層を濃縮して析出した固体を濾集した。得られた固体を水、及びアセトンで洗浄した。洗浄した固体を、シリカゲルカラムクロマトグラフィーで精製した後、トルエンとヘキサンの混合溶媒で再結晶し、酢酸エチルで懸濁洗浄することにより、淡黄色固体2.1g(収率:67%)を得た。この淡黄色固体は、マススペクトル分析の結果、重水素化芳香族化合物としての化合物BH-8であり、分子量500.73に対し、m/e=501であった。
実施例9は、重水素化芳香族化合物としての化合物BH-9の製造方法に関する。化合物BH-9の合成スキームが、以下に示される。
アルゴン雰囲気下、非重水素化芳香族化合物としての軽水素体(化合物BH-J)4.0g、及び重ベンゼンd62000mLをフラスコに加え、50℃に加熱して反応物を溶解させた後、塩化アルミニウム2.8gを加えて、60℃で、48時間、加熱撹拌した。室温まで冷却後、重水500mLを滴下して、有機層を分取した。有機層を濃縮して析出した固体を濾集した。得られた固体を水、及びアセトンで洗浄した。洗浄した固体を、シリカゲルカラムクロマトグラフィーで精製した後、トルエンとヘキサンの混合溶媒で再結晶し、酢酸エチルで懸濁洗浄することにより、淡黄色固体2.4g(収率:57%)を得た。この淡黄色固体は、マススペクトル分析の結果、重水素化芳香族化合物としての化合物BH-9であり、分子量604.87に対し、m/e=605であった。
Claims (7)
- 重水素化芳香族化合物を製造する重水素化芳香族化合物の製造方法であって、
芳香族化合物を重水素含有溶媒中で重水素化させる工程を含み、
前記芳香族化合物は、分子内に2つ以上の芳香環が結合手を介して結合する構造を有し、
前記芳香族化合物が有する前記2つ以上の芳香環のうち、少なくとも1つが縮合芳香環であり、
前記縮合芳香環のうち少なくとも1つは、他の芳香環との結合に係る前記結合手を有する第1縮合環原子と、前記第1縮合環原子と両脇で隣接する第2縮合環原子及び第3縮合環原子と、を含む芳香環を有し、
前記第2縮合環原子及び前記第3縮合環原子の少なくとも一方は、前記第1縮合環原子、前記第2縮合環原子及び前記第3縮合環原子を含む芳香環に対して縮合する環のうち、6員環を構成する原子ではない、
重水素化芳香族化合物の製造方法。 - 請求項1に記載の重水素化芳香族化合物の製造方法において、
前記重水素含有溶媒は、重ベンゼン又は重水である、
重水素化芳香族化合物の製造方法。 - 請求項1又は請求項2に記載の重水素化芳香族化合物の製造方法において、
前記縮合芳香環のうち少なくとも1つは、3つ以上の環が縮合した縮合芳香環である、
重水素化芳香族化合物の製造方法。 - 請求項1から請求項3のいずれか一項に記載の重水素化芳香族化合物の製造方法において、
前記縮合芳香環のうち少なくとも1つは、
ピレン環、
フルオランテン環、
ベンゾフルオランテン環、
フェナントレン環、
ベンゾフェナントレン環、
クリセン環、
ベンゾクリセン環、
トリフェニレン環、
ベンゾトリフェニレン環、
ベンゾキサンテン環、
アントラセン環(但し、当該アントラセン環の1位~8位の少なくともいずれかの炭素原子が前記結合手を有する)、及び
ベンゾ[a]アントラセン環(但し、当該ベンゾ[a]アントラセン環の1位~6位及び8位~11位の少なくともいずれかの炭素原子が前記結合手を有する)からなる群から選択される少なくともいずれかの環である、
重水素化芳香族化合物の製造方法。 - 請求項1から請求項6のいずれか一項に記載の重水素化芳香族化合物の製造方法において、
前記芳香族化合物を重水素含有溶媒中で重水素化させる工程で、アルミニウム触媒、白金触媒、及びパラジウム触媒からなる群から選択される少なくとも1種の触媒を使用する、
重水素化芳香族化合物の製造方法。
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