JPH02101077A - Production of pyrazolo(3,2-c)-1,2,4-triazole-based compound - Google Patents
Production of pyrazolo(3,2-c)-1,2,4-triazole-based compoundInfo
- Publication number
- JPH02101077A JPH02101077A JP25552388A JP25552388A JPH02101077A JP H02101077 A JPH02101077 A JP H02101077A JP 25552388 A JP25552388 A JP 25552388A JP 25552388 A JP25552388 A JP 25552388A JP H02101077 A JPH02101077 A JP H02101077A
- Authority
- JP
- Japan
- Prior art keywords
- group
- compound
- general formula
- formula
- pyrazolo
- 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.)
- Pending
Links
- 150000001875 compounds Chemical class 0.000 title claims abstract description 28
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- BRUJXXBWUDEKCK-UHFFFAOYSA-N 3h-pyrazolo[5,1-c][1,2,4]triazole Chemical compound C1=NN2CN=NC2=C1 BRUJXXBWUDEKCK-UHFFFAOYSA-N 0.000 title 1
- -1 decane Chemical class 0.000 claims abstract description 15
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 12
- 125000003118 aryl group Chemical group 0.000 claims abstract description 10
- 125000000753 cycloalkyl group Chemical group 0.000 claims abstract description 7
- 239000000126 substance Substances 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims 1
- 150000008064 anhydrides Chemical class 0.000 claims 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 abstract description 9
- 150000008065 acid anhydrides Chemical class 0.000 abstract description 9
- 125000003342 alkenyl group Chemical group 0.000 abstract description 4
- 150000001555 benzenes Chemical class 0.000 abstract description 4
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 abstract description 4
- 125000000623 heterocyclic group Chemical group 0.000 abstract description 4
- 229930195733 hydrocarbon Natural products 0.000 abstract description 4
- 150000002430 hydrocarbons Chemical class 0.000 abstract description 4
- 125000004093 cyano group Chemical group *C#N 0.000 abstract description 3
- 229910052736 halogen Inorganic materials 0.000 abstract description 3
- 150000002367 halogens Chemical class 0.000 abstract description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 abstract description 3
- 239000002904 solvent Substances 0.000 abstract description 3
- 238000000034 method Methods 0.000 description 16
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 125000006575 electron-withdrawing group Chemical group 0.000 description 6
- SNTWKPAKVQFCCF-UHFFFAOYSA-N 2,3-dihydro-1h-triazole Chemical class N1NC=CN1 SNTWKPAKVQFCCF-UHFFFAOYSA-N 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 125000004397 aminosulfonyl group Chemical group NS(=O)(=O)* 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 2
- 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 2
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 2
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 2
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 125000000565 sulfonamide group Chemical group 0.000 description 2
- 238000005987 sulfurization reaction Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 2
- RELMFMZEBKVZJC-UHFFFAOYSA-N 1,2,3-trichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1Cl RELMFMZEBKVZJC-UHFFFAOYSA-N 0.000 description 1
- 101150065749 Churc1 gene Proteins 0.000 description 1
- 101100295738 Gallus gallus COR3 gene Proteins 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 125000004442 acylamino group Chemical group 0.000 description 1
- 125000004423 acyloxy group Chemical group 0.000 description 1
- 125000003172 aldehyde group Chemical group 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000004453 alkoxycarbonyl group Chemical group 0.000 description 1
- 125000004390 alkyl sulfonyl group Chemical group 0.000 description 1
- 125000005161 aryl oxy carbonyl group Chemical group 0.000 description 1
- 125000004391 aryl sulfonyl group Chemical group 0.000 description 1
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000005392 carboxamide group Chemical group NC(=O)* 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 125000003438 dodecyl 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])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000000434 field desorption mass spectrometry Methods 0.000 description 1
- 125000002541 furyl group Chemical group 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000006038 hexenyl group Chemical group 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- ZBKFYXZXZJPWNQ-UHFFFAOYSA-N isothiocyanate group Chemical group [N-]=C=S ZBKFYXZXZJPWNQ-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 125000001802 myricyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000000018 nitroso group Chemical group N(=O)* 0.000 description 1
- 239000012434 nucleophilic reagent Substances 0.000 description 1
- 125000005064 octadecenyl group Chemical group C(=CCCCCCCCCCCCCCCCC)* 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 229940086066 potassium hydrogencarbonate Drugs 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
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 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
- 125000001544 thienyl group Chemical group 0.000 description 1
- 125000003866 trichloromethyl group Chemical group ClC(Cl)(Cl)* 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
- G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
- G03C7/32—Colour coupling substances
- G03C7/36—Couplers containing compounds with active methylene groups
- G03C7/38—Couplers containing compounds with active methylene groups in rings
- G03C7/381—Heterocyclic compounds
- G03C7/382—Heterocyclic compounds with two heterocyclic rings
- G03C7/3825—Heterocyclic compounds with two heterocyclic rings the nuclei containing only nitrogen as hetero atoms
- G03C7/3835—Heterocyclic compounds with two heterocyclic rings the nuclei containing only nitrogen as hetero atoms four nitrogen atoms
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Silver Salt Photography Or Processing Solution Therefor (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は、ピラゾロ［３，２−ｃ］−１，２゜４−トリ
アゾール系化合物の製造方法に関し、更に詳しくは、７
位に電子吸引性基を有する１、２゜４−トリアゾロ［３
，４−ｂｌ−１，３，４−チアジアジン系化合物と酸無
水物とを反応させることによりピラゾロ［３，、２−ｃ
］ １．２．４−トリアゾール系化合物を製造する方
法に関するものである。Detailed Description of the Invention [Industrial Application Field] The present invention relates to a method for producing pyrazolo[3,2-c]-1,2°4-triazole compounds, and more specifically,
1,2゜4-triazolo[3
,4-bl-1,3,4-thiadiazine compound and acid anhydride to form pyrazolo[3,,2-c
] 1.2.It relates to a method for producing a 4-triazole compound.
［発明の背景］
７位に置換基あるいは水素原子を有するピラゾロ［３，
２−ｃ］−１，２，４−）リアゾール系化合物は写真用
カプラー、特にマゼンタカプラーあるいはその中間体又
は有機合成における中間体として有用な化合物である。[Background of the invention] Pyrazolo [3,
2-c]-1,2,4-) lyazole compounds are compounds useful as photographic couplers, particularly magenta couplers or intermediates thereof, or intermediates in organic synthesis.
７位にアルコキシカルボニル基を有するＩＨピラゾロ［
３，２−ｃ］−１，２，４−トリアゾール−７−カルボ
キシレート系化合物は例えば英国特許第１，２５２，４
１８号明細書、米国特許第３，７２５゜０６７号明細書
或はジャーナル・オブ・ザ・ケミカル・ソサイアティー
・パーキンＩ （１９７７） ２０４７〜２０５２頁に
記載された方法で合成することができる。IH pyrazolo [
3,2-c]-1,2,4-triazole-7-carboxylate compounds are disclosed in British Patent No. 1,252,4, for example.
No. 18, US Pat. No. 3,725.067, or Journal of the Chemical Society Perkin I (1977) pages 2047-2052.
すなわち、５−アシルヒドラジノ−Ｉ Ｈ−ピラゾール
−４〜力ルボキシレート系化合物をベンゼン中、オキシ
塩化燐とともに長時間還流することによってＩＨ−ピラ
ゾｉｌ［３，２−ｃ］ −１，２゜４−トリアゾール−
７−カルボキシレート系化合物を得ることができる。That is, IH-pyrazoil[3,2-c]-1,2°4-triazole is produced by refluxing a 5-acylhydrazino-IH-pyrazole-4-carboxylate compound in benzene with phosphorus oxychloride for a long time. −
A 7-carboxylate compound can be obtained.
しかし、これ等の方法では反応時間が長時間であること
、およびＬＨ−ピラゾロ［３，２−ｃ］１．２．４−ト
リアゾール−７−カルボキシレート系化合物の３位のア
ルキル基が２級あるいは３級である場合に更に長時間の
反応時間を要し、また収率が低くなる等の問題点を有し
ている。However, in these methods, the reaction time is long and the alkyl group at the 3-position of the LH-pyrazolo[3,2-c]1.2.4-triazole-7-carboxylate compound is secondary. Alternatively, in the case of a tertiary compound, there are problems such as a longer reaction time being required and a lower yield.
これに加えて、反応により生じる燐化合物は環境公害上
問題であるばかりでなく、工業化の際その処理が大きな
負担となるので好ましくない。In addition to this, the phosphorus compounds produced by the reaction not only pose an environmental pollution problem, but also pose a heavy burden in their treatment during industrialization, which is undesirable.
それらの欠点を改良すべく特開昭６２−３３１７８号公
報に塩化チオニルを用いて閉環反応を行う方法が開示さ
れているがいまだ十分に満足できる結果は得られていな
い。In order to improve these drawbacks, JP-A No. 62-33178 discloses a method of carrying out a ring-closing reaction using thionyl chloride, but satisfactorily results have not yet been obtained.
またＲＤ−１２４４３に７位が水素原子のＩＨ−ピラゾ
ロ［３，２−ｃ］−１，２，４−トリアゾール系化合物
の合成方法が示されている。しかしこの方法は１，２．
４−トリアゾロ［３，４−ｂコ１．３．４−チアジアジ
ン系化合物からＩＨピラゾロ［３，２−ｃ］ −１，２
，４−トリアゾール系化合物を得る脱イオウ工程で２０
０℃以上の温度を必要とし、そのため脱イオウ反応だけ
でなく母核の分解も進行してしまい収率が大きく低下し
てしまうという致命的な欠点を有しいていた。Further, RD-12443 describes a method for synthesizing an IH-pyrazolo[3,2-c]-1,2,4-triazole compound having a hydrogen atom at the 7th position. However, this method requires 1, 2.
4-triazolo[3,4-b-1.3.4-thiadiazine compound to IH pyrazolo[3,2-c] -1,2
, 20 in the de-sulfurization step to obtain a 4-triazole compound.
This method requires a temperature of 0° C. or higher, and therefore has the fatal disadvantage that not only the de-sulfurization reaction but also the decomposition of the mother nucleus progresses, resulting in a significant drop in yield.
それらの欠点を改良すべく特開昭６３−１０１３８θ号
公報に７位に電子吸引性基を有する１、２．４−トリア
ゾロ［３，４−ｂ］−１，３，４−チアジアジン系化合
物を用いて脱イオウ反応を行なう方法が開示されている
が、より収率の高い方法が望まれていた。In order to improve these drawbacks, 1,2,4-triazolo[3,4-b]-1,3,4-thiadiazine compounds having an electron-withdrawing group at the 7-position were proposed in JP-A-63-10138θ. Although a method has been disclosed in which a desulfurization reaction is carried out using the above method, a method with a higher yield has been desired.
そこで本発明者等は、前記問題点乃至欠点に鑑み、鋭意
研究を続けた結果、特定の１．２．４−トリアゾロ［３
，１−ｂ］−１，３，４−チアジアジン系化合物を用い
て酸無水物と反応させることにより、高収率でピラゾロ
［３，２−ｃ］、−，１゜２．４−トリアゾール系化合
物を製造することができることを発見した。Therefore, in view of the above-mentioned problems and drawbacks, the present inventors continued intensive research and found that a specific 1.2.4-triazolo[3
,1-b]-1,3,4-thiadiazine-based compound is reacted with acid anhydride to produce pyrazolo[3,2-c],-,1゜2.4-triazole-based compound in high yield. discovered that it is possible to produce compounds.
また、特開昭６３−２３１３４１号公報に７位無置換の
１．２．４−トリアゾロ［，３，４−ｂ］−１，３゜４
−チアジアジン系イビ合物と無水＃酸を反応させること
によりピラゾロ［３，２−ｃ］−１，２゜４−トリアゾ
ール系化合物を得る方法が記載されている。この方法で
の生成物は、７位に−５ＣＯＣＨｓが置換した化合物で
あるのに対し、本発明の方法での生成物は、一般式［１
１１］に示したように７位に電子吸引性基が残り、−８
ＣＯＲ３が離脱した化合物であることは予想し得なかっ
たことである。In addition, JP-A-63-231341 discloses 1,2,4-triazolo[,3,4-b]-1,3゜4 with no substitution at the 7-position.
A method for obtaining a pyrazolo[3,2-c]-1,2°4-triazole compound by reacting a -thiadiazine compound with an acid anhydride is described. The product of this method is a compound substituted with -5COCHs at the 7-position, whereas the product of the method of the present invention has the general formula [1
11], an electron-withdrawing group remains at the 7-position, and -8
It was unexpected that COR3 was a dissociated compound.
［発明の目的］
したがって、本発明は、上記知見に基づいてなされたも
のであって、本発明は、７位に電子吸引性基を有する１
、２．４−トリアゾロ［３，４ｂ］−１，３，４−チア
ジアジン系化合物を酸無水物と反応させることにより、
写真用カプラーまたはその中間体として、あるいは有機
合成の中間体として有用な７位に電子吸引性基を有する
ピラゾロ［：３． ’ ２− ｃ ］”’ ”ｌ”□、
２．４−トリアゾール系化合物を高収率に製造する新規
な方法を提供することである。[Object of the Invention] Therefore, the present invention has been made based on the above-mentioned findings, and the present invention relates to
, by reacting a 2.4-triazolo[3,4b]-1,3,4-thiadiazine compound with an acid anhydride,
Pyrazolo [:3. '2-c]"'"l"□,
An object of the present invention is to provide a novel method for producing 2.4-triazole compounds in high yield.
［発明の構成］
前記目的は、下記一般式［Ｉ］で示される１゜２．４−
トリアゾロ［３，１−ｂ］−１，３，４チアジアジン系
化合物を下記一般式［Ｉ［］で示される酸無水物と反応
させることにより、下記−般式［１１［］で示されるピ
ラゾロ［３，２−ｃ］１．２．４−トリアゾール系化合
物を製造する方法により達成することかできた６
一般式［Ｉ］
〔式中、Ｒ１、Ｒ２は水素原子、アルキル基、アルケニ
ル基、シクロアルキル基、アリール基、ヘテロ環基を表
し、Ｘは電子吸引性基を表す。〕一般式［ＩＩ］
（Ｒ３−Ｃ＋２０
〔式中、Ｒ５はアルキル基、シクロアルキル基、アリー
ル基を表す。〕
一般式［１［［］
〔式中、Ｒ１、Ｒ２、Ｒ３、Ｘは前式のＲ１、Ｒ２、Ｒ
３およびＸと同義である。〕
Ｒ１，Ｒ２で表わされるアルキル基としては、メチル基
、エチル基、イソプロピル基、ｔ−ブチル基、ヘキシル
基、オクチル基、ドデシル基、オクタデシル基、トリア
コンチル基等を挙げることができる。[Structure of the Invention] The object is to provide a 1°2.4-
By reacting a triazolo[3,1-b]-1,3,4thiadiazine compound with an acid anhydride represented by the following general formula [I[], pyrazolo[ 3,2-c]1.2. General formula [I] [In the formula, R1 and R2 are hydrogen atoms, alkyl groups, alkenyl groups, cyclo It represents an alkyl group, an aryl group, or a heterocyclic group, and X represents an electron-withdrawing group. ] General formula [II] (R3-C+20 [In the formula, R5 represents an alkyl group, a cycloalkyl group, or an aryl group.] General formula [1[[] [In the formula, R1, R2, R3, and X represent the preceding formula R1, R2, R
3 and X. ] Examples of the alkyl group represented by R1 and R2 include a methyl group, an ethyl group, an isopropyl group, a t-butyl group, a hexyl group, an octyl group, a dodecyl group, an octadecyl group, and a triacontyl group.
アルケニル基としては、ビニル基、プロペニル基、ブテ
ニル基、ヘキセニル基、ペンタデセニル基、オクタデセ
ニル基等を挙げることができる。Examples of the alkenyl group include a vinyl group, propenyl group, butenyl group, hexenyl group, pentadecenyl group, and octadecenyl group.
シクロアルキル基としては、シクロプロピル基、シクロ
ブチル基、シクロペンチル基、シクロヘキシル基等を挙
げることができる。Examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group.
アリール基としては、フェニル基、ナフチル基等を挙げ
ることができる。Examples of the aryl group include a phenyl group and a naphthyl group.
ヘテロ環基としては、ピリジル基、フリル基、チエニル
基等を挙げることができる。Examples of the heterocyclic group include a pyridyl group, a furyl group, and a thienyl group.
これらのアルキル基、アルケニル基、シクロアルキル基
、アリール基、ヘテロ環基は置換基を有することができ
、置換基としてはハロゲン原子、ヒドロキシル基、ニト
ロ基、シアノ基、アルキル基、アルコキシ基、アリール
オキシ基、アルキルスルホニル基、アリールスルホニル
基、アシルオキシ基、アシルアミノ基、カルバモイル基
、スルホンアミド基、スルファモイル基等を挙げること
ができる。These alkyl groups, alkenyl groups, cycloalkyl groups, aryl groups, and heterocyclic groups can have substituents, and examples of substituents include halogen atoms, hydroxyl groups, nitro groups, cyano groups, alkyl groups, alkoxy groups, and aryl groups. Examples include an oxy group, an alkylsulfonyl group, an arylsulfonyl group, an acyloxy group, an acylamino group, a carbamoyl group, a sulfonamide group, and a sulfamoyl group.
Ｒ１，Ｒ２としては特にアルキル基、アリール基が好ま
しい。Especially preferred as R1 and R2 are alkyl groups and aryl groups.
一般式［Ｉ［］のＲ１で表わされるアルキル基としては
、メチル基、エチル基、プロピル基、ブチル基、ヘプチ
ル基、ウンデカニル基、トリデカニル基、トリフルオロ
メチル基、モノクロロメチル基、１−エチルヘプチル基
等を挙げることができる。Examples of the alkyl group represented by R1 in the general formula [I[] include methyl group, ethyl group, propyl group, butyl group, heptyl group, undecanyl group, tridecanyl group, trifluoromethyl group, monochloromethyl group, and 1-ethylheptyl group. Examples include groups.
シクロアルキル基としては、シクロプロピル基、シクロ
ブチル基、シクロペンチル基、シクロヘキシル基等を挙
げることができる。Examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group.
アリール基としては、フェニル基等を挙げることができ
る。Examples of the aryl group include a phenyl group.
一般式［Ｉ］及び［１１］で示されるＸの電子吸引性基
は、「薬物の！ｆＪ造活性相関」 （化学の領域増刊１
２２、南江堂）ｐ９６〜１０３、表１に示されるσρ値
が零より大きい置換基を意味するもので、例えばハロゲ
ン原子（塩素、臭素、フッ素、ヨウ素）、含ハロゲン基
（塩素、臭素、フッ素、ヨウ素を含有する基、例えばト
リクロロメチル基、トリフルオロメチル基等）、アルデ
ヒド基、カルボン酸基、アルコキシカルボニル基、アリ
ールオキシカルボニル基、ニトロ基、ニトロソ基、シア
ノ基、カルボアミド基、スルホンアミド基、イソシアナ
ート基、イソチオシアナート基、スルファモイル基、カ
ルバモイル基等を挙げることができる。The electron-withdrawing group of
22, Nankodo) p96-103, means a substituent whose σρ value shown in Table 1 is larger than zero, such as halogen atoms (chlorine, bromine, fluorine, iodine), halogen-containing groups (chlorine, bromine, fluorine, iodine-containing groups (e.g. trichloromethyl group, trifluoromethyl group, etc.), aldehyde groups, carboxylic acid groups, alkoxycarbonyl groups, aryloxycarbonyl groups, nitro groups, nitroso groups, cyano groups, carboxamide groups, sulfonamide groups, Examples include an isocyanate group, an isothiocyanate group, a sulfamoyl group, and a carbamoyl group.
本発明の一般式［ＩＩで示される７位に電子吸引性基の
導入された１、２．４−）リアゾロ［３，４−ｂ］−チ
アジアジン系化合物は種々の方法によって合成できる。The 1,2,4-)riazolo[3,4-b]-thiadiazine compound of the present invention having an electron-withdrawing group introduced at the 7-position represented by the general formula [II] can be synthesized by various methods.
例えば、特開昭６３−１０１３８７号公報に、活性水素
を離脱基で置換しなケトエステルと４−アミノ−１，２
，４−）−リアゾリン−５−チオン系化合物とを反応さ
せる事により、７位にカルボキシル基の導入された１、
２．４トリアゾロ−［３，４−ｂ］−１，３，４−チア
ジアジン−７−カルボキシレート系化合物を得る方法が
開示されている。また、特開昭６３−１０１３８６号公
報に、７位兼置換の１．２．４−）リアゾロ−［３，４
−ｂ］〜チアジアジン系化合物と求核試薬との反応によ
り、電子吸引性基の導入されたチアジアジン系化合物を
得る方法が開示されている。For example, in JP-A-63-101387, a ketoester in which active hydrogen is not substituted with a leaving group and a 4-amino-1,2
, 4-)-Ryazoline-5-thione compound, 1, with a carboxyl group introduced at the 7-position.
A method for obtaining a 2.4-triazolo-[3,4-b]-1,3,4-thiadiazine-7-carboxylate compound is disclosed. In addition, JP-A No. 63-101386 discloses 1.2.4-)riazolo-[3,4
-b] - A method for obtaining a thiadiazine compound into which an electron-withdrawing group has been introduced is disclosed by reacting the thiadiazine compound with a nucleophilic reagent.
本発明の一般式［ＩＩ［］で表わされる化合物は、以下
に示すルートで得ることができる。The compound represented by the general formula [II[] of the present invention can be obtained by the route shown below.
以下余白
［ＩＩ［ＩＩ
一般式［ＩＩで示される化合物は、一般式［Ｉ［］の酸
無水物とニートで反応させてもよいし、また溶媒に分散
させて反応させてもよい。用いることができる溶媒とし
ては炭化水素類、ベンゼン類、エーテル類、ハロゲン化
炭化水素類を代表的に挙げることができる。The following margin [II[II] The compound represented by the general formula [II] may be reacted neat with the acid anhydride of the general formula [I[], or may be reacted after being dispersed in a solvent. Typical solvents that can be used include hydrocarbons, benzenes, ethers, and halogenated hydrocarbons.
このうち好ましいものとしては、炭化水素類、ベンゼン
類である。Among these, hydrocarbons and benzenes are preferred.
本発明に用いられる炭化水素類としては、デカン、ドデ
カン等があり、ベンゼン類としては、ベンゼン、トルエ
ン、キシレン、クロルベンゼン、トリクロルベンゼン、
ニトロベンゼン等が挙げられる。Hydrocarbons used in the present invention include decane and dodecane, and benzenes include benzene, toluene, xylene, chlorobenzene, trichlorobenzene,
Examples include nitrobenzene.
反応温度は、３０〜２００°Ｃが好ましい。さらに反応
速度及び母核の熱安定性の点から４０〜１５０℃が好ま
しい。The reaction temperature is preferably 30 to 200°C. Further, from the viewpoint of reaction rate and thermal stability of the mother core, the temperature is preferably 40 to 150°C.
以下に、前記特開昭６３−１０１３８６号公報及び同６
３１０１３８７号公報の記載に基づいて製造した化合物
の他に、本発明で用いられる一般式［ＩＩで示される化
合物の具体例を示すが、本発明はこれらに限定されるも
のではない。Below, the above-mentioned Japanese Unexamined Patent Publication No. 63-101386 and 63-101386 are disclosed.
In addition to the compound produced based on the description in JP 3101387, specific examples of the compound represented by the general formula [II used in the present invention are shown below, but the present invention is not limited thereto.
以下余白
次に一般式［Ｉ［］で示される具体的化合物例を挙げる
が、これらはその−例であって、この化合物に限定され
るものではない。Specific examples of compounds represented by the general formula [I[] are listed below in the margins, but these are just examples and are not limited to these compounds.
−Ｉ ■−４ ｌ−５ Ｉ［−６ ■−７ ＣＨ３ＣＯ１２０ ＣｈＣＨ＋ＣＯ１ｔａ。-I ■-4 l-5 I[-6 ■-7 CH3CO120 ChCH+CO1ta.
ＣＨ３（ＣＨ２） ２ＣＯ１２０
ＣＨ３（ＣＨ２］ ４ＣＯ１２０
ＣＦ３ＣＯ） ２０
ＣＨｅＣｊ Ｃ０１２０
ＣＨ３（ＣＨ２） ｌ ０ＣＯ１２０
本発明は、前記例示化合物として示した如き、１．２．
４−トリアゾロ［３，４−ｂ］−１，３゜４−チアジア
ジン系化合物を酸無水物と反応させることにより簡単か
つ容易に高収率でピラゾロ［３，２，−ｃ］ １，２
．４−トリアゾール系化合物を製造することができる。1.2.
By reacting a 4-triazolo[3,4-b]-1,3゜4-thiadiazine compound with an acid anhydride, pyrazolo[3,2,-c] 1,2 can be easily and easily produced in high yield.
．． A 4-triazole compound can be produced.
以下、本発明の製造方法によって製造されたピラゾロ［
３，２，−ｃ］−１，２，４−）リアゾール系化合物の
代表的な具体的化合物を挙げるが、これは、その−例で
あって、この化合物に限定されるものではない。Hereinafter, pyrazolo [
3,2,-c]-1,2,4-) Typical specific compounds of lyazole compounds are listed below, but these are just examples, and the present invention is not limited to these compounds.
以下余白
以下に、本発明の具体的実施例を示すが、本発明はこれ
に限定されない。Specific examples of the present invention are shown below in the margins, but the present invention is not limited thereto.
本発明によらないピラゾロ［３，２−ｃ］−１゜２．４
−トリアゾール系化合物の合成
［Ｉ−５］ ｎ、ｗ、５４２．７９
（１） ｎ、ｗ、５１０．７３
２００ ｍｌフラスコに［Ｉ −５］ １０ ｇ ＜
０．０１８モル）、メシチレン１００ｍ１を加え加熱還
流を６，０時間行った。反応終了後、メシチレンを減圧
留去し、残渣をカラム分離することにより目的物を得た
。Pyrazolo[3,2-c]-1°2.4 not according to the invention
-Synthesis of triazole compound [I-5] n, w, 542.79 (1) n, w, 510.73 [I-5] 10 g <
0.018 mol) and 100 ml of mesitylene were added and heated under reflux for 6.0 hours. After the reaction was completed, mesitylene was distilled off under reduced pressure, and the residue was separated by column to obtain the desired product.
無色アメ状物 収量５．７ｇ 収率６２．０％元素分
析 Ｃ
測定 ６１．１９
計算 ６１．１４
ＩＲ，ＮＭＲは（Ｉ
ＦＤ−ＭＳ、ｍ／ｅ
〔実施例〕
ＨＮ Ｓ
９．２１ １０゜８８ ６．１２９．０ｇ
１０．９７ ６．２８）の構造を支持した。Colorless candy-like substance Yield 5.7g Yield 62.0% Elemental analysis C Measurement 61.19 Calculation 61.14 IR, NMR are (I FD-MS, m/e [Example] HN S 9.21 10°88 6.129.0g
10.97 6.28) structure was supported.
５１０（Ｍｌ
［Ｉ−５］
ｒｎ、 ｗ、 ５４２．７９
［■−５］
ｍ、ｗ、５５２．７７
ｎ、ｗ、５１０．７３
１００ ｍｌフラスコに［Ｉ−５］ １０ ｇ （０
，０１８モル）、無水酢酸５０ｍ１を加え加熱還流を２
．０時間行った。室温まで冷却した後２００ｍ１の水中
へ反応液を添加した。５％炭酸水素カリウム水溶液で水
層のＰＨを７に調整した後酢酸エチル１００ ｍｌを加
え分液し、酢酸エチル層を無水硫酸マグネシウムで乾燥
した後、酢酸エチルを留去した。残渣をカラム分離し、
アメ状物として目的物を得た。510 (Ml [I-5] rn, w, 542.79 [■-5] m, w, 552.77 n, w, 510.73 10 g of [I-5] in a 100 ml flask (0
, 018 mol), added 50 ml of acetic anhydride, and heated under reflux for 2 hours.
．． I went for 0 hours. After cooling to room temperature, the reaction solution was added to 200 ml of water. After adjusting the pH of the aqueous layer to 7 with a 5% aqueous potassium hydrogen carbonate solution, 100 ml of ethyl acetate was added to separate the layers. The ethyl acetate layer was dried over anhydrous magnesium sulfate, and then the ethyl acetate was distilled off. The residue is separated by column,
The desired product was obtained as a candy-like substance.
収量８．２ｇ 収率８２．４％
元素分析 ＣＨＮ Ｓ
測定 ６０．９２ ８．８０ １０．０７ ５
．８８計算 ６０．８３ ８．７５ １０．１４
５．８０ＩＲ，ＮＭＲは［１−５］の構造を支持し
た。Yield 8.2g Yield 82.4% Elemental analysis CHN S measurement 60.92 8.80 10.07 5
．． 88 calculation 60.83 8.75 10.14
5.80IR, NMR supported the structure of [1-5].
ＦＡＢ ＭＳ ｍ／ｅ＝ ５５３（Ｍ＋ ）
１００ｍｌフラスコに［ＩＩ［５］ ５ｇ （９，０
５ミリモル）、メタノール３０ｍ１、濃塩酸２ｍｌを加
え加熱還流を１．０時間行った。反応終了後メタノール
を留去し、５％炭酸カリウムでＰ Ｈを７に調整し、酢
酸エチル１００ｍ１を加え分液し、酢酸エチル層を飽和
食塩水で水洗、無水硫酸マグネシウムで乾燥した後、減
圧留去し、残渣をカラム分離することにより目的１勿を
得た。FAB MS m/e=553(M+)
In a 100 ml flask, add 5 g of [II[5] (9,0
5 mmol), 30 ml of methanol, and 2 ml of concentrated hydrochloric acid were added, and the mixture was heated under reflux for 1.0 hour. After the reaction was completed, methanol was distilled off, the pH was adjusted to 7 with 5% potassium carbonate, 100 ml of ethyl acetate was added to separate the layers, the ethyl acetate layer was washed with saturated brine, dried over anhydrous magnesium sulfate, and then vacuumed. The desired product was obtained by distilling the residue off and separating the residue through a column.
然色アメ状 収量４．Ｏｇ 収率８６．６％ＩＲ１’
ＨＮ Ｍ Ｒは比較例の（１）の化合物と一致した。Natural color candy-like yield 4. Og yield 86.6%IR1'
HNMR was consistent with that of the compound (1) of Comparative Example.
［発明の効果］
比較例及び実施例で示したように従来公知の製造方法に
比較して、本発明では、７位に置換基を有する化合物と
酸無水物とを反応させることにより、ピラゾロ［３，２
−ｃ］−１，２，４−）リアゾール系化合物を収率良く
製造することができる。また、該方法を利用して製造し
た化合物を用いれば、通常の合成手法を用いて写真的に
有用な化合物であるマゼンタカプラーに容易に変換させ
ることができる。[Effects of the Invention] As shown in Comparative Examples and Examples, in comparison with conventionally known production methods, the present invention allows pyrazolo[ 3,2
-c]-1,2,4-) riazole compounds can be produced with good yield. Moreover, by using the compound produced using this method, it can be easily converted into a magenta coupler, which is a photographically useful compound, using ordinary synthetic techniques.
Claims (1)
［３，４−ｂ］−１，３，４−チアジアジン系化合物と
下記一般式［II］で示される酸無水物とを反応させるこ
とを特徴とする下記一般式［III］で示されるピラゾロ
［３，２−ｃ］−１，２，４−トリアゾール系化合物の
製造方法。 一般式［ I ］ ▲数式、化学式、表等があります▼ 〔式中、Ｒ＿１、Ｒ＿２は水素原子、アルキル基、アル
ケニル基、シクロアルキル基、アリール基、ヘテロ環基
を表し、Ｘは電子吸引性基を表す。〕一般式［II］ ▲数式、化学式、表等があります▼ 〔式中、Ｒ＿３はアルキル基、シクロアルキル基、アリ
ール基を表す。〕 一般式［III］ ▲数式、化学式、表等があります▼ 〔式中、Ｒ＿１、Ｒ＿２、Ｒ＿３、Ｘは前式のＲ＿１、
Ｒ＿２、Ｒ＿３およびＸと同義である。〕[Scope of Claims] A 1,2,4-triazolo[3,4-b]-1,3,4-thiadiazine compound represented by the following general formula [I] and an acid represented by the following general formula [II] A method for producing a pyrazolo[3,2-c]-1,2,4-triazole compound represented by the following general formula [III], which comprises reacting the compound with an anhydride. General formula [I] ▲ Numerical formulas, chemical formulas, tables, etc. represents a group. ] General formula [II] ▲ Numerical formulas, chemical formulas, tables, etc. are available▼ [In the formula, R_3 represents an alkyl group, a cycloalkyl group, or an aryl group. ] General formula [III] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R_1, R_2, R_3, and X are R_1 in the previous formula,
Synonymous with R_2, R_3 and X. ]
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25552388A JPH02101077A (en) | 1988-10-11 | 1988-10-11 | Production of pyrazolo(3,2-c)-1,2,4-triazole-based compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25552388A JPH02101077A (en) | 1988-10-11 | 1988-10-11 | Production of pyrazolo(3,2-c)-1,2,4-triazole-based compound |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02101077A true JPH02101077A (en) | 1990-04-12 |
Family
ID=17279928
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP25552388A Pending JPH02101077A (en) | 1988-10-11 | 1988-10-11 | Production of pyrazolo(3,2-c)-1,2,4-triazole-based compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02101077A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5461164A (en) * | 1994-03-14 | 1995-10-24 | Eastman Kodak Company | Oxidative desulfurization and halogenation of thioacylated pyrazolotriazole compounds |
-
1988
- 1988-10-11 JP JP25552388A patent/JPH02101077A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5461164A (en) * | 1994-03-14 | 1995-10-24 | Eastman Kodak Company | Oxidative desulfurization and halogenation of thioacylated pyrazolotriazole compounds |
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