JP5057632B2 - Method for producing porphyrin compound - Google Patents
Method for producing porphyrin compound Download PDFInfo
- Publication number
- JP5057632B2 JP5057632B2 JP2003297201A JP2003297201A JP5057632B2 JP 5057632 B2 JP5057632 B2 JP 5057632B2 JP 2003297201 A JP2003297201 A JP 2003297201A JP 2003297201 A JP2003297201 A JP 2003297201A JP 5057632 B2 JP5057632 B2 JP 5057632B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- acid
- porphyrin compound
- represented
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- -1 porphyrin compound Chemical class 0.000 title claims description 47
- 238000004519 manufacturing process Methods 0.000 title claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 59
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 37
- 239000001301 oxygen Substances 0.000 claims description 37
- 229910052760 oxygen Inorganic materials 0.000 claims description 37
- 238000010306 acid treatment Methods 0.000 claims description 29
- KORIJXKQGMTQTO-UHFFFAOYSA-N 1h-pyrrol-2-ylmethanol Chemical class OCC1=CC=CN1 KORIJXKQGMTQTO-UHFFFAOYSA-N 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 18
- 125000000623 heterocyclic group Chemical group 0.000 claims description 12
- 150000004034 porphyrinogens Chemical class 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 10
- 239000007789 gas Substances 0.000 claims description 9
- 125000000962 organic group Chemical group 0.000 claims description 9
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 9
- 230000005587 bubbling Effects 0.000 claims description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 8
- 125000003302 alkenyloxy group Chemical group 0.000 claims description 7
- 125000004414 alkyl thio group Chemical group 0.000 claims description 7
- 125000004122 cyclic group Chemical group 0.000 claims description 7
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- 125000002252 acyl group Chemical group 0.000 claims description 6
- 125000004104 aryloxy group Chemical group 0.000 claims description 6
- 125000000392 cycloalkenyl group Chemical group 0.000 claims description 6
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 claims description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 5
- 125000004423 acyloxy group Chemical group 0.000 claims description 5
- 125000003545 alkoxy group Chemical group 0.000 claims description 5
- 125000004397 aminosulfonyl group Chemical group NS(=O)(=O)* 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 5
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 5
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 claims description 5
- 230000002194 synthesizing effect Effects 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 4
- 125000001931 aliphatic group Chemical group 0.000 claims description 4
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 claims description 4
- 230000001590 oxidative effect Effects 0.000 claims description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 4
- 125000000475 sulfinyl group Chemical group [*:2]S([*:1])=O 0.000 claims description 4
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 claims description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 3
- 125000001651 cyanato group Chemical group [*]OC#N 0.000 claims description 3
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 3
- 229910052731 fluorine Inorganic materials 0.000 claims description 3
- 125000001153 fluoro group Chemical group F* 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims description 3
- 125000001261 isocyanato group Chemical group *N=C=O 0.000 claims description 3
- 125000002462 isocyano group Chemical group *[N+]#[C-] 0.000 claims description 3
- 125000001810 isothiocyanato group Chemical group *N=C=S 0.000 claims description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 3
- 125000000018 nitroso group Chemical group N(=O)* 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 125000005017 substituted alkenyl group Chemical group 0.000 claims description 3
- 125000000547 substituted alkyl group Chemical group 0.000 claims description 3
- 125000005346 substituted cycloalkyl group Chemical group 0.000 claims description 3
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 3
- 125000000858 thiocyanato group Chemical group *SC#N 0.000 claims description 3
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 3
- 239000005711 Benzoic acid Substances 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 235000010233 benzoic acid Nutrition 0.000 claims description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 2
- 125000004185 ester group Chemical group 0.000 claims description 2
- 150000007522 mineralic acids Chemical class 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims description 2
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 claims 1
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 18
- 239000000243 solution Substances 0.000 description 15
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 14
- 238000003756 stirring Methods 0.000 description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 239000007800 oxidant agent Substances 0.000 description 6
- VCRBUDCZLSQJPZ-UHFFFAOYSA-N porphyrinogen Chemical compound C1C(N2)=CC=C2CC(N2)=CC=C2CC(N2)=CC=C2CC2=CC=C1N2 VCRBUDCZLSQJPZ-UHFFFAOYSA-N 0.000 description 6
- 125000003342 alkenyl group Chemical group 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 238000007086 side reaction Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- UGNWTBMOAKPKBL-UHFFFAOYSA-N tetrachloro-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(Cl)=C(Cl)C1=O UGNWTBMOAKPKBL-UHFFFAOYSA-N 0.000 description 5
- HZNVUJQVZSTENZ-UHFFFAOYSA-N 2,3-dichloro-5,6-dicyano-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(C#N)=C(C#N)C1=O HZNVUJQVZSTENZ-UHFFFAOYSA-N 0.000 description 4
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- 230000002411 adverse Effects 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000004128 high performance liquid chromatography Methods 0.000 description 4
- 150000002430 hydrocarbons Chemical group 0.000 description 4
- 239000012280 lithium aluminium hydride Substances 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 150000001408 amides Chemical class 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 3
- 125000003262 carboxylic acid ester group Chemical group [H]C([H])([*:2])OC(=O)C([H])([H])[*:1] 0.000 description 3
- 125000000753 cycloalkyl group Chemical group 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 150000002170 ethers Chemical class 0.000 description 3
- 150000008282 halocarbons Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000012544 monitoring process Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- BKOOMYPCSUNDGP-UHFFFAOYSA-N 2-methylbut-2-ene Chemical group CC=C(C)C BKOOMYPCSUNDGP-UHFFFAOYSA-N 0.000 description 2
- BGBOHYIXUAXBRP-UHFFFAOYSA-N 4,7-dihydro-4,7-ethano-2h-isoindole Chemical compound C1CC2C3=CNC=C3C1C=C2 BGBOHYIXUAXBRP-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- 239000007810 chemical reaction solvent Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- YIJOASXMXJOMPB-UHFFFAOYSA-N ctk0j9514 Chemical compound C1CC2C3=C(C(=O)OCC)NC=C3C1C=C2 YIJOASXMXJOMPB-UHFFFAOYSA-N 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 150000004032 porphyrins Chemical class 0.000 description 2
- 125000000168 pyrrolyl group Chemical group 0.000 description 2
- 238000001226 reprecipitation Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- JPJALAQPGMAKDF-UHFFFAOYSA-N selenium dioxide Chemical compound O=[Se]=O JPJALAQPGMAKDF-UHFFFAOYSA-N 0.000 description 2
- 238000010898 silica gel chromatography Methods 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 125000005415 substituted alkoxy group Chemical group 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- 125000004105 2-pyridyl group Chemical group N1=C([*])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 125000000175 2-thienyl group Chemical group S1C([*])=C([H])C([H])=C1[H] 0.000 description 1
- LPEKGGXMPWTOCB-UHFFFAOYSA-N 8beta-(2,3-epoxy-2-methylbutyryloxy)-14-acetoxytithifolin Natural products COC(=O)C(C)O LPEKGGXMPWTOCB-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- PAEYAKGINDQUCT-UHFFFAOYSA-N Ethyl 2-pyrrolecarboxylate Chemical class CCOC(=O)C1=CC=CN1 PAEYAKGINDQUCT-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 241000287463 Phalacrocorax Species 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 125000005073 adamantyl group Chemical group C12(CC3CC(CC(C1)C3)C2)* 0.000 description 1
- ZIXLDMFVRPABBX-UHFFFAOYSA-N alpha-methylcyclopentanone Natural products CC1CCCC1=O ZIXLDMFVRPABBX-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 244000309464 bull Species 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- WORJEOGGNQDSOE-UHFFFAOYSA-N chloroform;methanol Chemical compound OC.ClC(Cl)Cl WORJEOGGNQDSOE-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 125000006165 cyclic alkyl group Chemical group 0.000 description 1
- 125000000596 cyclohexenyl group Chemical group C1(=CCCCC1)* 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 description 1
- 125000002433 cyclopentenyl group Chemical group C1(=CCCC1)* 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- ODQWQRRAPPTVAG-GZTJUZNOSA-N doxepin Chemical compound C1OC2=CC=CC=C2C(=C/CCN(C)C)/C2=CC=CC=C21 ODQWQRRAPPTVAG-GZTJUZNOSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000004705 ethylthio group Chemical group C(C)S* 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 125000006038 hexenyl group Chemical group 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229940057867 methyl lactate Drugs 0.000 description 1
- 125000002816 methylsulfanyl group Chemical group [H]C([H])([H])S[*] 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 125000004573 morpholin-4-yl group Chemical group N1(CCOCC1)* 0.000 description 1
- 125000006606 n-butoxy group Chemical group 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004708 n-butylthio group Chemical group C(CCC)S* 0.000 description 1
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000003506 n-propoxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 125000004706 n-propylthio group Chemical group C(CC)S* 0.000 description 1
- 125000005186 naphthyloxy group Chemical group C1(=CC=CC2=CC=CC=C12)O* 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- WRHZVMBBRYBTKZ-UHFFFAOYSA-N pyrrole-2-carboxylic acid Chemical class OC(=O)C1=CC=CN1 WRHZVMBBRYBTKZ-UHFFFAOYSA-N 0.000 description 1
- 150000003233 pyrroles Chemical class 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 125000005920 sec-butoxy group Chemical group 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000003107 substituted aryl group Chemical group 0.000 description 1
- 125000002130 sulfonic acid ester group Chemical group 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 125000004213 tert-butoxy group Chemical group [H]C([H])([H])C(O*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Nitrogen Condensed Heterocyclic Rings (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
本発明は、効率良くポルフィリン化合物を製造する方法に関する。 The present invention relates to a method for efficiently producing a porphyrin compound.
ポルフィリン化合物は、結晶状態で電気伝導や光起電力等の半導体特性を示すので、トランジスタ、発光ダイオード、太陽電池等の電気、光機能素子に応用することができ、特に有機トランジスタには好適に用いることができる。 Porphyrin compounds exhibit semiconductor properties such as electrical conduction and photovoltaic power in the crystalline state, and therefore can be applied to electrical and optical functional elements such as transistors, light-emitting diodes and solar cells, and are particularly suitable for organic transistors. be able to.
ポルフィリン化合物の製造方法には、種々の検討がなされており、例えば、ピロールとアルデヒドによりポルフィリノーゲンを合成し、それを酸化してポルフィリンに変換する製造方法や、2−ヒドロキシメチルピロールを4量化し環化してポルフィリノーゲンとし、それを酸化してポルフィリンに変換する製造方法が知られている。 Various studies have been made on the method for producing a porphyrin compound, for example, a method for synthesizing porphyrinogen with pyrrole and aldehyde and oxidizing it to convert it into porphyrin, or tetramerization of 2-hydroxymethylpyrrole. A production method is known that cyclizes to porphyrinogen and oxidizes it to convert it to porphyrin.
このうち、後者の方法として、非特許文献1及び2には、テトラビシクロポルフィリン化合物を合成するにあたり、ピロール−2−カルボン酸エチルエステル誘導体を水素化リチウムアルミニウムで還元し、生成した2−ヒドロキシメチル−ピロール誘導体を酸処理により環化し、それを酸化してテトラビシクロベンゾポルフィリンを合成する方法が報告されている。 Among these, as the latter method, Non-Patent Documents 1 and 2 include 2-hydroxymethyl produced by reducing a pyrrole-2-carboxylic acid ethyl ester derivative with lithium aluminum hydride when synthesizing a tetrabicycloporphyrin compound. -A method of cyclizing a pyrrole derivative by acid treatment and oxidizing it to synthesize tetrabicyclobenzoporphyrin has been reported.
しかしながら、本発明者らがここに記載されている方法でスケールアップして0.5g以上の化合物を合成しようとしたところ、大幅に収率が低下してしまうことが見出された。
上述の様に、2−ヒドロキシメチルピロール類の4量化によりポルフィリン化合物を大量合成する際に、高収率の合成法が求められていた。 As described above, when a large amount of a porphyrin compound is synthesized by tetramerization of 2-hydroxymethylpyrroles, a high yield synthesis method has been demanded.
以上の事に鑑み、種々検討を行った結果、2−ヒドロキシメチルピロール類を酸処理するにあたり反応系内に酸素を十分に作用させることにより、生成するポルフィリン化合物の収量が飛躍的に向上することを見出し、本発明に到った。 In view of the above, as a result of various investigations, the yield of the porphyrin compound to be produced is dramatically improved by allowing oxygen to sufficiently act in the reaction system in the acid treatment of 2-hydroxymethylpyrroles. The present invention was found.
即ち、本発明の要旨は、下記一般式(1)で表される2−ヒドロキシメチルピロール類の酸処理により、ポルフィリノーゲン類を生成させ、さらに該ポルフィリノーゲン類を酸化して、ポルフィリン化合物を合成するポルフィリン化合物の製造法において、2−ヒドロキシメチルピロール類の酸処理をするにあたり、反応系内に酸素を十分に作用させることを特徴とするポルフィリン化合物の製造方法に存する。
有機基群: 水素原子;フッ素原子、塩素原子、臭素原子等のハロゲン原子;ニトロ基;ニトロソ基;シアノ基;イソシアノ基;シアナト基;イソシアナト基;チオシアナト基;イソチオシアナト基;メルカプト基;ヒドロキシ基;ホルミル基;スルホン酸基;カルボキシル基;置換されていても良いアルキル基;置換されていても良いシクロアルキル基;置換されていても良いアルケニル基;置換されていても良いシクロアルケニル基;置換されていても良いアリール基;置換されていても良い複素環基;置換されていても良いアルコキシ基;置換されていても良いアルケニルオキシ基;置換されていても良いアリールオキシ基;置換されていても良いアルキルチオ基;−COQ 3 で表されるアシル基;−OCOQ 3 で表されるアシルオキシ基;−NQ 4 Q 5 で表されるアミノ基;−COOQ 3 で表されるカルボン酸エステル基;−CONQ 6 Q 7 で表されるカルバモイル基;−SOQ 3 で表されるスルフィニル基;−SO 2 Q 3 で表されるスルホニル基;−SO 3 Q 3 スルホン酸エステル基;−SO 2 NQ 6 Q 7 で表されるスルファモイル基
That is, the gist of the present invention is to generate porphyrinogens by acid treatment of 2-hydroxymethylpyrroles represented by the following general formula (1), and further oxidize the porphyrinogens to obtain a porphyrin compound. In the method for producing a porphyrin compound for synthesizing the compound, a method for producing a porphyrin compound is characterized in that oxygen is sufficiently allowed to act in the reaction system in the acid treatment of 2-hydroxymethylpyrroles.
Organic group: hydrogen atom; halogen atom such as fluorine atom, chlorine atom, bromine atom; nitro group; nitroso group; cyano group; isocyano group; cyanato group; isocyanato group; thiocyanato group; isothiocyanato group; mercapto group; Formyl group; sulfonic acid group; carboxyl group; optionally substituted alkyl group; optionally substituted cycloalkyl group; optionally substituted alkenyl group; optionally substituted cycloalkenyl group; Aryl group which may be substituted; heterocyclic group which may be substituted; alkoxy group which may be substituted; alkenyloxy group which may be substituted; aryloxy group which may be substituted; acyloxy represented by -OCOQ 3; acyl group represented by -COQ 3; which may alkylthio ; Sulfinyl group represented by -SOQ 3;; carboxylic acid represented by -COOQ 3 ester group;; -NQ 4 Q 5 group represented by -CONQ 6 carbamoyl group represented by Q 7 -SO 2 A sulfonyl group represented by Q 3 ; a —SO 3 Q 3 sulfonate group; a sulfamoyl group represented by —SO 2 NQ 6 Q 7
2−ヒドロキシメチルピロール類の4量化によりポルフィリン化合物を効率的に大量合成する方法を提供する。 A method for efficiently synthesizing a porphyrin compound in large quantities by tetramerization of 2-hydroxymethylpyrroles is provided.
以下、本発明の実施形態を詳細に説明する。
本発明は、下記反応式で表されるような、2−ヒドロキシメチルピロール類の酸処理、ついでポルフィリノーゲン類の酸化によりポルフィリン化合物を得る製造において、2−ヒドロキシメチルピロール類の酸処理にあたり反応系内に酸素を十分作用させることを特徴とする。
Hereinafter, embodiments of the present invention will be described in detail.
In the production of a porphyrin compound by acid treatment of 2-hydroxymethylpyrroles and then oxidation of porphyrinogens as represented by the following reaction formula, the present invention reacts with acid treatment of 2-hydroxymethylpyrroles. It is characterized by allowing oxygen to sufficiently act in the system.
式中、Q1、Q2は、それぞれ独立して1価の有機基を示し、又、Q1とQ2は互いに結合して環構造を形成していても良い。 In the formula, Q 1 and Q 2 each independently represent a monovalent organic group, and Q 1 and Q 2 may be bonded to each other to form a ring structure.
上記Q1、Q2の1価の有機基としては、反応時に悪影響を与えない基であれば特に限定されないが具体的には、水素原子;フッ素原子、塩素原子、臭素原子等のハロゲン原子;ニトロ基;ニトロソ基;シアノ基;イソシアノ基;シアナト基;イソシアナト基;チオシアナト基;イソチオシアナト基;メルカプト基;ヒドロキシ基;ホルミル基;スルホン酸基;カルボキシル基;置換されていても良いアルキル基;置換されていても良いシクロアルキル基;置換されていても良いアルケニル基;置換されていても良いシクロアルケニル基;置換されていても良いアリール基;置換されていても良い複素環基;置換されていても良いアルコキシ基;置換されていても良いアルケニルオキシ基;置換されていても良いアリールオキシ基;置換されていても良いアルキルチオ基;−COQ3で表されるアシル
基;−OCOQ3で表されるアシルオキシ基;−NQ4Q5で表されるアミノ基;−COO
Q3で表されるカルボン酸エステル基;−CONQ6Q7で表されるカルバモイル基;−S
OQ3で表されるスルフィニル基;−SO2Q3で表されるスルホニル基;−SO3Q3スル
ホン酸エステル基;−SO2NQ6Q7で表されるスルファモイル基が挙げられる。このう
ち、置換されていても良いアルキル基;置換されていても良いシクロアルキル基;置換されていても良いアルケニル基;置換されていても良いシクロアルケニル基;置換されていても良いアリール基;置換されていても良い複素環基;置換されていても良いアルコキシ基;置換されていても良いアルケニルオキシ基;置換されていても良いアリールオキシ基;置換されていても良いアルキルチオ基;−COQ3で表されるアシル基;−OCOQ3で表されるアシルオキシ基;−NQ4Q5で表されるアミノ基;−COOQ3で表されるカル
ボン酸エステル基;−CONQ6Q7で表されるカルバモイル基;−SOQ3で表されるス
ルフィニル基;−SO2Q3で表されるスルホニル基;−SO3Q3スルホン酸エステル基;−SO2NQ6Q7で表されるスルファモイル基としては、炭素数18以下、好ましくは1
2以下ものが挙げられる。
The monovalent organic group of Q 1 and Q 2 is not particularly limited as long as it is a group that does not adversely influence the reaction, and specifically, a hydrogen atom; a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom; Nitro group; nitroso group; cyano group; isocyano group; cyanato group; isocyanato group; thiocyanato group; isothiocyanato group; mercapto group; hydroxy group; formyl group; sulfonic acid group; carboxyl group; Cycloalkyl group which may be substituted; alkenyl group which may be substituted; cycloalkenyl group which may be substituted; aryl group which may be substituted; heterocyclic group which may be substituted; An optionally substituted alkoxy group; an optionally substituted alkenyloxy group; an optionally substituted aryloxy group; a substituted Amino group represented by -NQ 4 Q 5;; acyloxy group represented by -OCOQ 3; acyl group represented by -COQ 3; alkylthio group can have -COO
A carboxylic acid ester group represented by Q 3 ; a carbamoyl group represented by —CONQ 6 Q 7 ;
A sulfinyl group represented by OQ 3 ; a sulfonyl group represented by —SO 2 Q 3 ; a —SO 3 Q 3 sulfonate group; and a sulfamoyl group represented by —SO 2 NQ 6 Q 7 . Among these, an optionally substituted alkyl group; an optionally substituted cycloalkyl group; an optionally substituted alkenyl group; an optionally substituted cycloalkenyl group; an optionally substituted aryl group; An optionally substituted heterocyclic group; an optionally substituted alkoxy group; an optionally substituted alkenyloxy group; an optionally substituted aryloxy group; an optionally substituted alkylthio group; represented by -CONQ 6 Q 7; carboxylic acid ester group represented by -COOQ 3; amino group represented by -NQ 4 Q 5; acyloxy group represented by -OCOQ 3; acyl group represented by 3 A carbamoyl group represented by —SOQ 3 ; a sulfonyl group represented by —SO 2 Q 3 ; a —SO 3 Q 3 sulfonate group; a —SO 2 NQ 6 Q The sulfamoyl group represented by 7 has 18 or less carbon atoms, preferably 1
2 or less are mentioned.
上記アルキル基としては、メチル基、エチル基、プロピル基、イソプロピル基、n−ブチル基、sec−ブチル基、tert−ブチル基、n−へプチル基等の直鎖又は分岐のアルキル基が挙げられる。 Examples of the alkyl group include linear or branched alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, and n-heptyl group. .
上記シクロアルキル基としてはシクロプロピル基、シクロペンチル基、シクロヘキシル基、アダマンチル基等の環状アルキル基が挙げられる。 Examples of the cycloalkyl group include cyclic alkyl groups such as a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, and an adamantyl group.
上記アルケニル基としては、ビニル基、プロペニル基、ヘキセニル基等の直鎖又は分岐のアルケニル基が挙げられる。 Examples of the alkenyl group include linear or branched alkenyl groups such as a vinyl group, a propenyl group, and a hexenyl group.
上記シクロアルケニル基としては、シクロペンテニル基、シクロヘキセニル基等の環状アルケニル基が挙げられる。 Examples of the cycloalkenyl group include cyclic alkenyl groups such as a cyclopentenyl group and a cyclohexenyl group.
上記アリール基としては、フェニル基又はナフチル基が挙げられる。 Examples of the aryl group include a phenyl group and a naphthyl group.
上記複素環基としては、2−チエニル基、2−ピリジル基、4−ピペリジル基、モルホリノ基等の異項原子を1〜3個有する複素環基が挙げられる。 Examples of the heterocyclic group include heterocyclic groups having 1 to 3 hetero atoms such as 2-thienyl group, 2-pyridyl group, 4-piperidyl group, and morpholino group.
上記アルコキシ基としては、メトキシ基、エトキシ基、n−プロポキシ基、イソプロポキシ基、n−ブトキシ基、sec−ブトキシ基、tert−ブトキシ基等の直鎖または分岐のアルコキシ基が挙げられる。 Examples of the alkoxy group include linear or branched alkoxy groups such as a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy group, and a tert-butoxy group.
上記アルケニルオキシ基としてはプロペニルオキシ基、ブテニルオキシ基、ペンテニルオキシ基等の直鎖または分岐のアルケニルオキシ基が挙げられる。 Examples of the alkenyloxy group include linear or branched alkenyloxy groups such as a propenyloxy group, a butenyloxy group, and a pentenyloxy group.
上記アリールオキシ基としては、フェノキシ基又はナフチルオキシ基が挙げられる。 Examples of the aryloxy group include a phenoxy group and a naphthyloxy group.
上記アルキルチオ基としては、メチルチオ基、エチルチオ基、n−プロピルチオ基、n−ブチルチオ基、sec−ブチルチオ基、tert−ブチルチオ基等の直鎖または分岐のアルキルチオ基が挙げられる。 Examples of the alkylthio group include linear or branched alkylthio groups such as a methylthio group, an ethylthio group, an n-propylthio group, an n-butylthio group, a sec-butylthio group, and a tert-butylthio group.
上記アシル基、アシルオキシ基、カルボン酸エステル基、スルフィニル基、スルホニル基及びスルホン酸エステル基におけるQ3としては、置換されていても良い炭化水素基又
は置換されていても良い複素環基が挙げられる。
Examples of Q 3 in the acyl group, acyloxy group, carboxylic acid ester group, sulfinyl group, sulfonyl group, and sulfonic acid ester group include an optionally substituted hydrocarbon group or an optionally substituted heterocyclic group. .
上記アミノ基におけるQ4及びQ5としては、それぞれ独立して、水素原子、水酸基、炭化水素基、複素環基、−COQ3で表されるアシル基、−COOQ3で表されるカルボン酸エステル基又は−SO2Q3で表されるスルホニル基が挙げられる。 The Q 4 and Q 5 in the amino group, each independently, a hydrogen atom, a hydroxyl group, a hydrocarbon group, a heterocyclic group, an acyl group represented by -COQ 3, carboxylic acid ester represented by -COOQ 3 And a sulfonyl group represented by —SO 2 Q 3 .
上記カルバモイル基又はスルファモイル基における、Q6及びQ7としては、それぞれ独立して、水素原子、炭化水素基又は複素環基が挙げられる。 Examples of Q 6 and Q 7 in the carbamoyl group or sulfamoyl group independently include a hydrogen atom, a hydrocarbon group, or a heterocyclic group.
上記アルキル基、シクロアルキル基、アルケニル基、シクロアルケニル基、アリール基、複素環基、アルコキシ基、アルケニルオキシ基、アリールオキシ基、アルキルチオ基及び炭化水素基は、反応において悪影響を与えない範囲で任意の置換されていても良く、その具体例としては、上述のQ1,Q2の具体例として記述したような基が挙げられる。 The alkyl group, cycloalkyl group, alkenyl group, cycloalkenyl group, aryl group, heterocyclic group, alkoxy group, alkenyloxy group, aryloxy group, alkylthio group and hydrocarbon group are optional as long as they do not adversely affect the reaction. Specific examples thereof include groups described as specific examples of Q 1 and Q 2 described above.
また、Q1,Q2は、互いに一体となって、プロピレン基、ブチレン基、等となり、それ
ぞれがピロール環と縮合環を形成する脂肪族炭化水素基となっていてもよく、または形成された縮合環がベンゼン環、ナフタレン環等の芳香族炭素環となっていてもよく、さらにヘテロ原子により置換されてピロール環、ピリジン環等の複素環基を形成していてもよく、このうち好ましくは、脂肪族炭素環である。
In addition, Q 1 and Q 2 may be integrated with each other to form a propylene group, a butylene group, or the like, each of which may or may be an aliphatic hydrocarbon group that forms a condensed ring with a pyrrole ring. The condensed ring may be an aromatic carbocyclic ring such as a benzene ring or a naphthalene ring, and further may be substituted with a heteroatom to form a heterocyclic group such as a pyrrole ring or a pyridine ring. An aliphatic carbocycle.
上記Q1,Q2として好ましくは、Q1及びQ2が一体となって下記一般式 As Q 1 and Q 2 , Q 1 and Q 2 are preferably combined to form the following general formula:
で表される基を形成しているのが好ましい。式中、R1〜R8は、それぞれ独立して前記Q1,Q2と同様な一価の有機基であり、互いに結合して前記Q1,Q2で記述したような環状構造を形成していても良い。環状構造を形成する場合、好ましくは隣り合う炭素に結合したR1〜R8が、組になって環状構造を形成するのが好ましい。R1〜R8として好ましいのは、水素原子である。
(ポルフィリノーゲン類の製造法)
本発明における、ポルフィリノーゲン類は、2−ヒドロキシメチルピロール類の酸処理により製造される。
It is preferable that the group represented by these is formed. In the formula, R 1 to R 8 are each independently a monovalent organic group similar to Q 1 and Q 2, and are bonded to each other to form a cyclic structure as described for Q 1 and Q 2. You may do it. When forming a cyclic structure, it is preferable that R 1 to R 8 bonded to adjacent carbons preferably form a set to form a cyclic structure. R 1 to R 8 are preferably a hydrogen atom.
(Method for producing porphyrinogens)
In the present invention, porphyrinogens are produced by acid treatment of 2-hydroxymethylpyrroles.
2−ヒドロキシメチルピロール類は、公知の方法に従って合成すれば特に構わない。例えば、ピロール−2−カルボン酸エステル類を水素化リチウムアルミニウム等の還元剤で還元して製造する事が出来る。 The 2-hydroxymethylpyrroles are not particularly limited as long as they are synthesized according to a known method. For example, it can be produced by reducing pyrrole-2-carboxylic acid esters with a reducing agent such as lithium aluminum hydride.
本発明では、反応系内に酸素を十分作用させて、2−ヒドロキシメチルピロール類の酸処理を行うことを特徴とする。 The present invention is characterized in that oxygen treatment is sufficiently performed in the reaction system to perform acid treatment of 2-hydroxymethylpyrroles.
反応系内に酸素を十分に作用させるとは、特に限定はないが、例えば、反応系に酸素あるいは酸素を含む気体をバブリングする;反応系の表面積を大きし、酸素との接触面積を増やす(反応液の体積Vについて断面積を、体積Vで除した値が0.5cm-1以上となるような反応容器を用いる等);反応系を強攪拌する、又は攪拌して空気との接触面積を増やす又は系中に空気の泡を取り込ませバブリングするのと同様の状態とする;反応系を高圧にし、表面から取り込まれる酸素の量を増やす;反応系内で酸素ガスを発生させる物質や酸素ガスを吸着する物質を系内に共存させる等の方法が挙げられる。このうち好ましくは、反応系に酸素あるいは酸素を含む気体をバブリングする;反応系を強攪拌する、又は攪拌する;もしくは、反応系を高圧にする方法であり、さらに好ましくは、反応系に酸素あるいは酸素を含む気体をバブリングする;もしくは、反応系を強攪拌する、又は攪拌する方法である。 Although there is no particular limitation on causing oxygen to sufficiently act in the reaction system, for example, bubbling oxygen or a gas containing oxygen in the reaction system; increasing the surface area of the reaction system and increasing the contact area with oxygen ( Use a reaction vessel in which the value obtained by dividing the cross-sectional area with respect to volume V of the reaction liquid by volume V is 0.5 cm −1 or more, etc.); Or increase the amount of oxygen taken from the surface by increasing the pressure of the reaction system; substances and oxygen that generate oxygen gas in the reaction system Examples thereof include a method in which a substance that adsorbs gas coexists in the system. Of these, a method of bubbling oxygen or a gas containing oxygen in the reaction system; stirring the reaction system vigorously or stirring; or increasing the pressure of the reaction system, more preferably oxygen or A gas containing oxygen is bubbled; or the reaction system is vigorously stirred or stirred.
反応系に酸素あるいは酸素を含む気体をバブリングする方法としては、特に限定はないが、例えば反応系中にガラス等の不活性な管を入れ、そこから酸素あるいは酸素を含む気体を吹き込みバブリングを行うことが挙げられる。吹き込み口は複数でも構わない。又、細かい気泡でバブリングしても構わない。酸素の流量は反応系の大きさにもよるが、反応系1Lに対して、5mL/分以上が好ましく、さらに好ましくは50mL/分以上、特に好ましくは100mL/分以上である。又、10L/分以下が好ましく、さらに好ましくは5L/分以下、特に好ましくは1L/分以下である。 The method for bubbling oxygen or a gas containing oxygen into the reaction system is not particularly limited. For example, an inert tube such as glass is put into the reaction system, and bubbling is performed by blowing oxygen or a gas containing oxygen from there. Can be mentioned. There may be a plurality of air inlets. Further, fine bubbles may be used for bubbling. Although depending on the size of the reaction system, the flow rate of oxygen is preferably 5 mL / min or more, more preferably 50 mL / min or more, and particularly preferably 100 mL / min or more with respect to 1 L of the reaction system. Moreover, 10 L / min or less is preferable, More preferably, it is 5 L / min or less, Most preferably, it is 1 L / min or less.
反応系を攪拌する場合には、反応容器に邪魔板のあるものや効率的に攪拌のできる攪拌翼(アンカー翼、傾斜パドル翼、平パドル翼、ファドラー翼、マックスブレンド翼(住友重機械工業株式会社)、フルゾーン翼(神鋼パンテック株式会社)ヘリカルリボン翼、ブ
ルマージン翼、スーパミックス翼(佐竹化学機械工業製)、A310翼(LIGHTNIN製)、A320翼(LIGHTNIN製)、インターミグ翼(エカート製)等)を用いることができる。
When stirring the reaction system, the reaction vessel has a baffle plate or a stirring blade that can efficiently stir (anchor blade, inclined paddle blade, flat paddle blade, fiddler blade, Max blend blade (Sumitomo Heavy Industries, Ltd.) Company), Full Zone Wing (Shineko Pantech Co., Ltd.) Helical Ribbon Wing, Bull Margin Wing, Supermix Wing (manufactured by Satake Chemical Machinery), A310 Wing (made by LIGHTTNIN), A320 Wing (made by LIGHTTNIN), Intermig Wing (ecart) Etc.) can be used.
反応系を高圧にする場合には、1.1気圧以上にすることが好ましく、より好ましくは2気圧以上に加圧した酸素あるいは空気等の酸素を含む気体を接触させることが望ましい。 When the reaction system is set to a high pressure, it is preferably 1.1 atm or higher, more preferably oxygen or a gas containing oxygen such as air pressurized to 2 atm or higher.
本発明における、反応系内に酸素を十分作用させて、2−ヒドロキシメチルピロール類の酸処理を行うとは、酸処理を行う前の反応系に酸素を作用させても良いし、酸処理中に反応系内に酸素を作用させても構わない。好ましくは、酸処理を行う反応系に酸素を作用させる方法で、より好ましくは、酸処理を行う前の反応系に酸素を作用させ、さらに引き続いて酸処理中にも反応系内に酸素を作用させる方法である。 In the present invention, when oxygen is sufficiently allowed to act in the reaction system and the acid treatment of 2-hydroxymethylpyrroles is performed, oxygen may be allowed to act on the reaction system before the acid treatment or during the acid treatment. Alternatively, oxygen may be allowed to act on the reaction system. Preferably, in the method of reacting the oxygen acid treatment line cormorants reaction system, more preferably, by the action of oxygen prior to the reaction system to carry out the acid treatment, the oxygen further subsequently in the reaction system even during acid treatment It is a method of acting.
又、酸処理の方法としては、酸を含む溶液に酸素を十分作用させ、その後2−ヒドロキシメチルピロール類を添加しても良いし;2−ヒドロキシメチルピロール類を含む溶液に酸素を十分作用させ、その後酸を添加しても良いし;溶媒に酸素を十分作用させた後に、2−ヒドロキシメチルピロール類と酸を添加しても構わない。これらのうち好ましいのは、酸を含む溶液に酸素を十分作用させ、その後2−ヒドロキシメチルピロール類を添加する方法である。 In addition, as a method of acid treatment, oxygen may sufficiently act on a solution containing acid, and then 2-hydroxymethylpyrroles may be added; oxygen may sufficiently act on a solution containing 2-hydroxymethylpyrroles. Then, an acid may be added; after oxygen has sufficiently acted on the solvent, 2-hydroxymethylpyrroles and an acid may be added. Among these, the method in which oxygen sufficiently acts on a solution containing an acid and then adding 2-hydroxymethylpyrroles is preferable.
酸素を作用させる時間は、原料である2−ヒドロキシメチルピロール類及びポルフィリノーゲン類をクロマトグラフィー等でモニターして、十分に原料が消失してポルフィリノーゲンが生成することを確認すれば、最適な作用時間が分かるが、一般には1分以上、3日以内、好ましくは5分以上2日以内、より好ましくは、10分以上、1日以内が望ましい。 The time for which oxygen is allowed to act is optimal if the raw materials 2-hydroxymethylpyrroles and porphyrinogens are monitored by chromatography, etc., and it is confirmed that the raw materials are sufficiently lost and porphyrinogen is produced. However, it is generally 1 minute or longer and within 3 days, preferably 5 minutes or longer and within 2 days, more preferably 10 minutes or longer and within 1 day.
2−ヒドロキシメチルピロール類の酸処理に用いる酸としては、反応に悪影響を与えないものを適宜選択すればよいが、その具体例としては塩酸、硫酸、燐酸、水素化ハロゲン等の無機酸;酢酸、シュウ酸、トリフルオロ酢酸、安息香酸、フタル酸等の脂肪族又は芳香族カルボン酸;メタンスルホン酸、トリフルオロメタンスルホン酸、p−トルエンスルホン酸等の脂肪族又は芳香族スルホン酸等が挙げられる。これらの内好ましくは芳香族スルホン酸、特に好ましくはp−トルエンスルホン酸である。 The acid used for the acid treatment of 2-hydroxymethylpyrroles may be appropriately selected from those that do not adversely affect the reaction. Specific examples thereof include inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, halogenated hydrogen; acetic acid Aliphatic or aromatic carboxylic acids such as oxalic acid, trifluoroacetic acid, benzoic acid and phthalic acid; aliphatic or aromatic sulfonic acids such as methanesulfonic acid, trifluoromethanesulfonic acid and p-toluenesulfonic acid . Of these, aromatic sulfonic acids are preferable, and p-toluenesulfonic acid is particularly preferable.
用いる酸の量は、反応がスムーズに進行する量に調整する事が望ましいが、一般にヒドロキシメチルピロール類1モルに対して0.1モル以上、好ましくは0.2モル以上用いることが望ましい。0.1モルより少ないと、ポルフィリノーゲン類の生成量が少なくなる。 The amount of acid used is desirably adjusted to an amount that allows the reaction to proceed smoothly, but generally 0.1 mol or more, and preferably 0.2 mol or more is used with respect to 1 mol of hydroxymethylpyrroles. When the amount is less than 0.1 mol, the amount of porphyrinogen produced is reduced.
又、酸処理の反応温度は、通常―20℃以上、80℃以下が望ましい。20℃より低いと、反応が進行せず、ビシクロポルフィリノーゲン類の生成量が少なくなり、60℃より高いと副反応がおこり、結果的にビシクロポルフィリノーゲン類の生成量が少なくなる。 In addition, the reaction temperature for the acid treatment is usually preferably -20 ° C or higher and 80 ° C or lower. When the temperature is lower than 20 ° C., the reaction does not proceed and the amount of bicycloporphyrinogens is reduced. When the temperature is higher than 60 ° C., a side reaction occurs, and as a result, the amount of bicycloporphyrinogens is reduced.
2−ヒドロキシメチルピロール類の酸処理工程では、反応進行度をモニターして、2−ヒドロキシメチルピロール類が消失し、ポルフィリノーゲン類が生成するのを確認して反応時間を設定するのが望ましい。通常は30分以上、好ましくは1時間以上反応させる。また、あまり反応が遅いと副反応が進行して収率が低下するので、12時間以内に反応が終了するように酸の添加量や温度等の反応条件を設定するのが望ましい。 In the acid treatment step of 2-hydroxymethylpyrroles, it is desirable to set the reaction time by monitoring the reaction progress and confirming that 2-hydroxymethylpyrroles disappear and porphyrinogens are produced. . The reaction is usually performed for 30 minutes or longer, preferably 1 hour or longer. If the reaction is too slow, the side reaction proceeds and the yield decreases, so it is desirable to set the reaction conditions such as the amount of acid added and the temperature so that the reaction is completed within 12 hours.
反応溶媒は、2−ヒドロキシメチルピロール類を溶解するものであって、酸処理に悪影
響を与えないものを適宜選択すればよいが、その具体例としてはクロロホルムや塩化メチレン、ジクロロエタン、トリクロロエタン、トリクロロエチレン等のハロゲン化炭化水素類;トルエンやベンゼン、キシレンやクロロベンゼン等の芳香族炭化水素類;アセトン、メチルエチルケトン、シクロペンタノン、シクロヘキサノン等のケトン類;酢酸エチル、酢酸ブチル、乳酸メチル等のエステル類;ピリジン、キノリン等の含窒素有機溶媒類;エチルエーテル、テトラヒドロフラン、ジオキサン等のエーテル類;又はジメチルホルムアミド、ジメチルアセトアミド等のアミド類の溶媒等が挙げられる。
The reaction solvent dissolves 2-hydroxymethylpyrroles and may be appropriately selected from those that do not adversely affect the acid treatment. Specific examples thereof include chloroform, methylene chloride, dichloroethane, trichloroethane, and trichloroethylene. Halogenated hydrocarbons; aromatic hydrocarbons such as toluene, benzene, xylene and chlorobenzene; ketones such as acetone, methyl ethyl ketone, cyclopentanone and cyclohexanone; esters such as ethyl acetate, butyl acetate and methyl lactate; pyridine And nitrogen-containing organic solvents such as quinoline; ethers such as ethyl ether, tetrahydrofuran and dioxane; and solvents of amides such as dimethylformamide and dimethylacetamide.
好ましくは、ハロゲン化炭化水素類、芳香族炭化水素類、ケトン類、エーテル類、アミド類であり、さらに好ましくは、ハロゲン化炭化水素類、芳香族炭化水素類、エーテル類、アミド類である。
(ポルフィリン化合物の製造法)
本発明においては、前述の方法で得られたポルフィリノーゲン類を酸化してポルフィリン化合物を得る。酸化工程は公知の方法に準じて行えばよい。例えば、前述の酸処理工程で、原料2−ヒドロキシメチルピロール類が消失し、ポルフィリノーゲン類が十分に生成したところで、酸化剤を添加してポルフィリノーゲン類をポルフィリン化合物に変換する。
Preferred are halogenated hydrocarbons, aromatic hydrocarbons, ketones, ethers and amides, and more preferred are halogenated hydrocarbons, aromatic hydrocarbons, ethers and amides.
(Method for producing porphyrin compound)
In the present invention, porphyrinogens obtained by the aforementioned method are oxidized to obtain a porphyrin compound. The oxidation step may be performed according to a known method. For example, in the acid treatment step described above, when the raw material 2-hydroxymethylpyrroles disappear and porphyrinogens are sufficiently formed, an oxidizing agent is added to convert the porphyrinogens into a porphyrin compound.
酸化剤としては、クロラニル、ジクロロジシアノベンゾキノン、N−2,4,6−トリニトロフェニル−N’,N’−フェニルジヒドラジン等の有機酸化剤や二酸化マンガン、二酸化セレン等の無機酸化剤、さらには酸素等の酸化性の気体を吹き込むことも利用できる。好ましくは、クロラニル、ジクロロジシアノベンゾキノンである。 Examples of the oxidizing agent include organic oxidizing agents such as chloranil, dichlorodicyanobenzoquinone, N-2,4,6-trinitrophenyl-N ′, N′-phenyldihydrazine, inorganic oxidizing agents such as manganese dioxide and selenium dioxide, Can also be used to blow an oxidizing gas such as oxygen. Of these, chloranil and dichlorodicyanobenzoquinone are preferable.
酸化剤の量は、反応の進行をLC等でモニターしながら酸化剤を調整するのが望ましいが、原料として用いた2−ヒドロキシメチルピロール類の0.3倍当量〜3倍当量を用いる。好ましくは0.3倍当量〜1倍当量である。 The amount of the oxidizing agent is desirably adjusted by monitoring the progress of the reaction with LC or the like, but 0.3 to 3 times equivalent of 2-hydroxymethylpyrrole used as a raw material is used. Preferably it is 0.3 times equivalent-1 time equivalent.
酸化反応は、通常室温で行うが、副反応速度を制御する為に高温あるいは低温で反応を行うことも可能である。望ましい反応温度は、−20℃から80℃である。20℃より低いと、反応が進行せず、ポルフィリン化合物の生成量が少なくなり、80℃より高いと副反応が起こり、結果的にポルフィリン化合物の生成量が少なくなる。 The oxidation reaction is usually carried out at room temperature, but it is also possible to carry out the reaction at a high or low temperature in order to control the side reaction rate. The desired reaction temperature is -20 ° C to 80 ° C. When the temperature is lower than 20 ° C., the reaction does not proceed and the amount of the porphyrin compound generated is reduced. When the temperature is higher than 80 ° C., a side reaction occurs, and as a result, the amount of the porphyrin compound generated decreases.
酸化に要する反応時間は、反応の進行をモニターしながら決めれば良いが、通常30分以上である。あまり長時間酸化反応を行うと、副反応で収率が低下する可能性があるので、12時間以内に反応が終了するように酸化剤の量や反応温度を調整するのが望ましい。 The reaction time required for the oxidation may be determined while monitoring the progress of the reaction, but is usually 30 minutes or longer. If the oxidation reaction is carried out for too long, the yield may decrease due to side reactions. Therefore, it is desirable to adjust the amount of the oxidizing agent and the reaction temperature so that the reaction is completed within 12 hours.
得られたポルフィリン化合物は必要に応じて精製する事ができる。具体的な精製法としては、反応溶媒を濃縮したり、貧溶媒を加えたりして目的物を取り出す。さらに純度を高めるためには、クロマトグラフィー、再結晶、再沈殿等用いて、望ましい純度まで精製することができる。 The obtained porphyrin compound can be purified as necessary. As a specific purification method, the target product is taken out by concentrating the reaction solvent or adding a poor solvent. In order to further increase the purity, it can be purified to a desired purity using chromatography, recrystallization, reprecipitation or the like.
本発明におけるポルフィリン化合物の製造方法では、0.5g以上、好ましくは0.8g以上、さらに好ましくは1g以上のポルフィリン化合物が効率よく製造できる。又、2−ヒドロキシメチルピロール類からポルフィリン化合物への収率は20%以上、さらに好ましくは30%以上である。
(ポルフィリン化合物の応用)
上記で得られるポルフィリン化合物は結晶状態で電気伝導や光起電力等の半導体特性を示すので、トランジスタ、発光ダイオード、太陽電池等の電気、光機能素子に応用することができ、特に有機トランジスタには好適に用いることができる。
In the method for producing a porphyrin compound in the present invention, 0.5 g or more, preferably 0.8 g or more, more preferably 1 g or more of a porphyrin compound can be produced efficiently. The yield from 2-hydroxymethylpyrroles to the porphyrin compound is 20% or more, more preferably 30% or more.
(Application of porphyrin compounds)
Since the porphyrin compound obtained above exhibits semiconductor properties such as electrical conduction and photovoltaic power in the crystalline state, it can be applied to electrical and optical functional elements such as transistors, light emitting diodes, solar cells, etc. It can be used suitably.
上記用途に用いられる好ましいポルフィリン化合物の具体例としては、下記式に示される様なものを挙げることができる。すなわち、塗布時には、ポルフィリン化合物中に平面性の悪い構造が存在することにより、高い溶解性及び製膜性を有しており、一方、製膜後に加熱することにより平面性の高い構造に変換し、半導体特性を有する膜とするのである。 Specific examples of preferred porphyrin compounds used for the above-mentioned applications include those shown by the following formula. That is, at the time of coating, the structure with poor planarity exists in the porphyrin compound, so that it has high solubility and film forming property, while it is converted into a structure with high planarity by heating after film formation. The film has semiconductor characteristics.
以下、本発明を実施例により更に具体的に説明するが、本発明はその趣旨を超えない限り、以下の実施例に限定されるものではない。
(実施例)
窒素雰囲気下、水素化アルミニウムリチウム(4.92g、127mmol)をテトラヒドロフラン(THF、172ml)に懸濁させた。0℃に冷却し、4,7−ジヒドロ−4,7−エタノ−2H−イソインドール−1−カルボン酸エチル (6.93g、31.9mmol)のTHF(172ml)溶液を滴下した。その後10℃に昇温し、全体で約3時間程度攪拌した。HPLCにより、4,7−ジヒドロ−4,7−エタノ−2H−イソインドールが生成していることを確認し、飽和塩化アンモニウム水溶液に反応液を加えて反応を停止した。その後、クロロホルム(和光純薬工業製、安定化剤にアミレンを使用)により抽出を行い、抽出したクロロホルム溶液を濃縮した。これとは別に、p−トルエンスルホン酸(739mg、4.28mmol)のクロロホルム懸濁液(700ml)(和光純薬工業製、安定化剤にアミレンを使用)を用意し、攪拌しながら圧縮空気を500mL/分で10分程度バブリングした。酸素流量としては100mL/分であった。この酸性の溶液に、先ほど濃縮しておいた溶液を、攪拌とバブリングを続けながら、室温で滴下した。HPLCにより、4,7−ジヒドロ−4,7−エタノ−2H−イソインドールの環状4量化が進行し、ビシクロポルフィリノーゲンが生成していることを確認した。別の実験のために50mlを取り分けた。滴下開始から3時間程度攪拌した後、一夜放置した。クロラニル(775mg、3.15mmol)を室温で加え、HPLCにより、確認したところ、ポルフィリノーゲンが残存していたので、さらに、クロラニル(237mg、0.96mmol)を室温で加えた。さらにHPLCにより、反応の進行を確認したところ、ポルフィリノーゲンは完全に消失していたので、水に注いで反応を停止し、有機層を分離した。炭酸水素ナトリウム水溶液で洗滌し(2回)、無水硫酸ナトリウムで乾燥した。減圧下濃縮し、クロロホルムを展開溶媒としたシリカゲルカラムクロマトグラフィーにより精製し、クロロホルム−メタノール混合溶媒を用いて再沈殿によりさらに精製することにより、目的のビシクロポルフィリン誘導体を得た(1.14g)。不純物を含むフラクションからさらに同様の精製を繰り返し行うことにより合計で1.75gのビシクロポルフィリン誘導体を得た。収率は35%であった。別の反応のために取り除いた分を考慮して換算すると、収率は38%であった。
(比較例)
窒素雰囲気下、水素化アルミニウムリチウム(2.58g、68.0mmol)をテトラヒドロフラン(THF、92ml)に懸濁させた。0℃に冷却し、4,7−ジヒドロ−4,7−エタノ−2H−イソインドール−1−カルボン酸エチル (4.00g、18.4mmol)のTHF(184ml)溶液を滴下した。その後10℃に昇温し、全体で約3時間程度攪拌した。酢酸エチル(適当量)を加えて反応を停止し、反応液を飽和塩化アンモニウム水溶液に加えた。クロロホルムにより抽出を行い(750mlずつ3回)、抽出したクロロホルム溶液を5分割した後に、さらにクロロホルムを加えてそれぞれを1000mlとした。このそれぞれにパラトルエンスルホン酸を1.58g(9.2mmol)ずつ加えた。24時間攪拌した後、それぞれにクロラニル(0.47g、1.9mmol)を室温で加え、さらに24時間攪拌した。水に注いで反応を停止し、有機層を分離した。炭酸水素ナトリウム水溶液で洗滌し、無水硫酸ナトリウムで乾燥した。減圧下濃縮し、クロロホルムを展開溶媒としたシリカゲルカラムクロマトグラフィーにより精製を行ったが、ビシクロポルフィリン化合物は19mgしか得られなかった。収率は0.7%であった。
EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist.
(Example)
Under a nitrogen atmosphere, lithium aluminum hydride (4.92 g, 127 mmol) was suspended in tetrahydrofuran (THF, 172 ml). After cooling to 0 ° C., a solution of ethyl 4,7-dihydro-4,7-ethano-2H-isoindole-1-carboxylate (6.93 g, 31.9 mmol) in THF (172 ml) was added dropwise. Thereafter, the temperature was raised to 10 ° C., and the whole was stirred for about 3 hours. It was confirmed by HPLC that 4,7-dihydro-4,7-ethano-2H-isoindole was produced, and the reaction solution was added to a saturated aqueous ammonium chloride solution to stop the reaction. Thereafter, extraction was performed with chloroform (manufactured by Wako Pure Chemical Industries, Ltd., using amylene as a stabilizer), and the extracted chloroform solution was concentrated. Separately, a chloroform suspension (700 ml) of p-toluenesulfonic acid (739 mg, 4.28 mmol) (manufactured by Wako Pure Chemical Industries, Ltd., using amylene as a stabilizer) was prepared, and compressed air was added while stirring. Bubbling was performed at 500 mL / min for about 10 minutes. The oxygen flow rate was 100 mL / min. To this acidic solution, the previously concentrated solution was added dropwise at room temperature while continuing stirring and bubbling. It was confirmed by HPLC that cyclic tetramerization of 4,7-dihydro-4,7-ethano-2H-isoindole proceeded and bicycloporphyrinogen was produced. 50 ml was reserved for another experiment. After stirring for about 3 hours from the start of dropping, the mixture was left overnight. Chloranil (775 mg, 3.15 mmol) was added at room temperature, and as confirmed by HPLC, porphyrinogen remained. Further, chloranil (237 mg, 0.96 mmol) was added at room temperature. Furthermore, when the progress of the reaction was confirmed by HPLC, porphyrinogen had completely disappeared, so the reaction was stopped by pouring into water, and the organic layer was separated. The extract was washed with an aqueous sodium hydrogen carbonate solution (twice) and dried over anhydrous sodium sulfate. Concentration under reduced pressure, purification by silica gel column chromatography using chloroform as a developing solvent, and further purification by reprecipitation using a chloroform-methanol mixed solvent gave the desired bicycloporphyrin derivative (1.14 g). By repeating the same purification from the fraction containing impurities, a total of 1.75 g of bicycloporphyrin derivative was obtained. The yield was 35%. When converted in consideration of the amount removed for another reaction, the yield was 38%.
(Comparative example)
Under a nitrogen atmosphere, lithium aluminum hydride (2.58 g, 68.0 mmol) was suspended in tetrahydrofuran (THF, 92 ml). After cooling to 0 ° C., a solution of ethyl 4,7-dihydro-4,7-ethano-2H-isoindole-1-carboxylate (4.00 g, 18.4 mmol) in THF (184 ml) was added dropwise. Thereafter, the temperature was raised to 10 ° C., and the whole was stirred for about 3 hours. Ethyl acetate (appropriate amount) was added to stop the reaction, and the reaction solution was added to a saturated aqueous ammonium chloride solution. Extraction was performed with chloroform (3 times each of 750 ml), and the extracted chloroform solution was divided into 5 parts, and further chloroform was added to make 1000 ml each. To this, 1.58 g (9.2 mmol) of paratoluenesulfonic acid was added. After stirring for 24 hours, chloranil (0.47 g, 1.9 mmol) was added to each at room temperature, and the mixture was further stirred for 24 hours. The reaction was stopped by pouring into water, and the organic layer was separated. It was washed with an aqueous sodium hydrogen carbonate solution and dried over anhydrous sodium sulfate. The solution was concentrated under reduced pressure and purified by silica gel column chromatography using chloroform as a developing solvent, but only 19 mg of a bicycloporphyrin compound was obtained. The yield was 0.7%.
Claims (8)
有機基群: 水素原子;フッ素原子、塩素原子、臭素原子等のハロゲン原子;ニトロ基;ニトロソ基;シアノ基;イソシアノ基;シアナト基;イソシアナト基;チオシアナト基;イソチオシアナト基;メルカプト基;ヒドロキシ基;ホルミル基;スルホン酸基;カルボキシル基;置換されていても良いアルキル基;置換されていても良いシクロアルキル基;置換されていても良いアルケニル基;置換されていても良いシクロアルケニル基;置換されていても良いアリール基;置換されていても良い複素環基;置換されていても良いアルコキシ基;置換されていても良いアルケニルオキシ基;置換されていても良いアリールオキシ基;置換されていても良いアルキルチオ基;−COQ 3 で表されるアシル基;−OCOQ 3 で表されるアシルオキシ基;−NQ 4 Q 5 で表されるアミノ基;−COOQ 3 で表されるカルボン酸エステル基;−CONQ 6 Q 7 で表されるカルバモイル基;−SOQ 3 で表されるスルフィニル基;−SO 2 Q 3 で表されるスルホニル基;−SO 3 Q 3 スルホン酸エステル基;−SO 2 NQ 6 Q 7 で表されるスルファモイル基 Porphyrin compound production method for synthesizing a porphyrin compound by generating porphyrinogens by acid treatment of 2-hydroxymethylpyrroles represented by the following general formula (1), and further oxidizing the porphyrinogens In claim 2, a method for producing a porphyrin compound, wherein oxygen is sufficiently allowed to act in the reaction system for acid treatment of 2-hydroxymethylpyrroles.
Organic group: hydrogen atom; halogen atom such as fluorine atom, chlorine atom, bromine atom; nitro group; nitroso group; cyano group; isocyano group; cyanato group; isocyanato group; thiocyanato group; isothiocyanato group; mercapto group; Formyl group; sulfonic acid group; carboxyl group; optionally substituted alkyl group; optionally substituted cycloalkyl group; optionally substituted alkenyl group; optionally substituted cycloalkenyl group; Aryl group which may be substituted; heterocyclic group which may be substituted; alkoxy group which may be substituted; alkenyloxy group which may be substituted; aryloxy group which may be substituted; acyloxy represented by -OCOQ 3; acyl group represented by -COQ 3; which may alkylthio ; Sulfinyl group represented by -SOQ 3;; carboxylic acid represented by -COOQ 3 ester group;; -NQ 4 Q 5 group represented by -CONQ 6 carbamoyl group represented by Q 7 -SO 2 A sulfonyl group represented by Q 3 ; a —SO 3 Q 3 sulfonate group; a sulfamoyl group represented by —SO 2 NQ 6 Q 7
請求項1に記載のポルフィリン化合物の製造方法。The manufacturing method of the porphyrin compound of Claim 1.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2003297201A JP5057632B2 (en) | 2003-08-21 | 2003-08-21 | Method for producing porphyrin compound |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2003297201A JP5057632B2 (en) | 2003-08-21 | 2003-08-21 | Method for producing porphyrin compound |
Publications (2)
Publication Number | Publication Date |
---|---|
JP2005068040A JP2005068040A (en) | 2005-03-17 |
JP5057632B2 true JP5057632B2 (en) | 2012-10-24 |
Family
ID=34403134
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2003297201A Expired - Fee Related JP5057632B2 (en) | 2003-08-21 | 2003-08-21 | Method for producing porphyrin compound |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP5057632B2 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR101957934B1 (en) | 2017-09-05 | 2019-03-13 | 연세대학교 산학협력단 | Method for preparing porphyrin derivate |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH02222730A (en) * | 1989-02-23 | 1990-09-05 | Cataler Kogyo Kk | Method for supporting catalytic metal on catalyst carrier |
DE69208136T2 (en) * | 1991-04-17 | 1996-10-17 | Takeda Chemical Industries Ltd | Automatic synthesis device and method for controlling the device |
JP2002148863A (en) * | 2000-11-10 | 2002-05-22 | Canon Inc | Method of manufacturing toner |
-
2003
- 2003-08-21 JP JP2003297201A patent/JP5057632B2/en not_active Expired - Fee Related
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR101957934B1 (en) | 2017-09-05 | 2019-03-13 | 연세대학교 산학협력단 | Method for preparing porphyrin derivate |
Also Published As
Publication number | Publication date |
---|---|
JP2005068040A (en) | 2005-03-17 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5057632B2 (en) | Method for producing porphyrin compound | |
TW200918511A (en) | Method of producing benzoxazinone-based compound | |
JP5147160B2 (en) | Method for producing porphyrin compound | |
WO2007117027A1 (en) | Process for the production of organic oxides | |
CN108586375B (en) | Green method for synthesizing 2-substituted benzoxazole compound through biocatalytic oxidative cyclization | |
JP2005068041A (en) | Method for producing porphyrin compound | |
JP2549555B2 (en) | Method for producing 1,2-disulfone compound | |
WO2002042254A1 (en) | PROCESS OF PRODUCING CARBONYL a-SUBSTITUTED NITROGEN-CONTAINING COMPOUNDS | |
JP2006131574A (en) | Method for producing porphyrin compound | |
JP4531610B2 (en) | Method for producing croconic acid or a salt thereof | |
JP4595299B2 (en) | Method for producing porphyrin compound | |
CN113666945B (en) | Preparation method of 2 beta-azido methyl penicillanic acid diphenylmethyl ester, tazobactam intermediate and tazobactam | |
US10807962B2 (en) | Process for the synthesis of firocoxib | |
KR102242238B1 (en) | Substituted or unsubstituted 4-bromo-2-fluoroquinoline, method of the same and 2,4 substituted quinoline compounds containing them | |
JP3534816B2 (en) | Method for producing methylthiobenzenes | |
ES2283781T3 (en) | PROCEDURE TO PRODUCE A COMPOSITE OF 1,2,3-TRIAZOL. | |
JP4182396B2 (en) | Method for producing aromatic aldehyde | |
US6762303B2 (en) | Method for producing pyridine compounds | |
JP2008037772A (en) | Method for producing 2, 2-bis (4-amino-3-hydroxyphenyl) propane compound | |
JPH0543572A (en) | Production of 1-alkyl-substituted sultones | |
JP2001247501A (en) | Aromatic compound and method of producing the same | |
FR2735468A1 (en) | PROCESS FOR THE PREPARATION OF A DI- OR POLYHYDROXYL AROMATIC COMPOUND | |
JPH07179468A (en) | Production of 1h-pypazolo(3,2-c)-1,2,4-triazole-based compound | |
KR20040025224A (en) | 2-(2-methyl-4-oxo-6,7,8,9-tetrahydro-4H-pyrido[1,2-a]pyrimidin-3-yl)acetaldehyde and preparation process of the same | |
JP2003104989A (en) | Method of producing dioxazine |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20060223 |
|
RD05 | Notification of revocation of power of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: A7425 Effective date: 20090611 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20090901 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20091028 |
|
A02 | Decision of refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A02 Effective date: 20100126 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20100406 |
|
A911 | Transfer to examiner for re-examination before appeal (zenchi) |
Free format text: JAPANESE INTERMEDIATE CODE: A911 Effective date: 20100428 |
|
A912 | Re-examination (zenchi) completed and case transferred to appeal board |
Free format text: JAPANESE INTERMEDIATE CODE: A912 Effective date: 20100618 |
|
A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20120731 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20150810 Year of fee payment: 3 |
|
R150 | Certificate of patent or registration of utility model |
Free format text: JAPANESE INTERMEDIATE CODE: R150 Ref document number: 5057632 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
S111 | Request for change of ownership or part of ownership |
Free format text: JAPANESE INTERMEDIATE CODE: R313111 |
|
R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
LAPS | Cancellation because of no payment of annual fees |