JPH0468317B2 - - Google Patents
Info
- Publication number
- JPH0468317B2 JPH0468317B2 JP9475185A JP9475185A JPH0468317B2 JP H0468317 B2 JPH0468317 B2 JP H0468317B2 JP 9475185 A JP9475185 A JP 9475185A JP 9475185 A JP9475185 A JP 9475185A JP H0468317 B2 JPH0468317 B2 JP H0468317B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- general formula
- represented
- alkyl group
- examples
- 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
Links
- 125000000217 alkyl group Chemical group 0.000 claims description 32
- -1 keto acid ester Chemical class 0.000 claims description 29
- 125000003118 aryl group Chemical group 0.000 claims description 15
- 150000001875 compounds Chemical class 0.000 claims description 14
- 238000004519 manufacturing process Methods 0.000 claims description 14
- 125000005843 halogen group Chemical group 0.000 claims description 9
- 125000000623 heterocyclic group Chemical group 0.000 claims description 9
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 125000001424 substituent group Chemical group 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 7
- UDFSJHJKINSRFV-UHFFFAOYSA-N N1N=CN2N=CC=C21 Chemical class N1N=CN2N=CC=C21 UDFSJHJKINSRFV-UHFFFAOYSA-N 0.000 description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 4
- 125000003545 alkoxy group Chemical group 0.000 description 4
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000000921 elemental analysis Methods 0.000 description 4
- 239000005457 ice water Substances 0.000 description 4
- 238000001819 mass spectrum Methods 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000006228 supernatant Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-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
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 125000000753 cycloalkyl group Chemical group 0.000 description 3
- ZHNUHDYFZUAESO-UHFFFAOYSA-N formamide Substances NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- WHQSYGRFZMUQGQ-UHFFFAOYSA-N n,n-dimethylformamide;hydrate Chemical compound O.CN(C)C=O WHQSYGRFZMUQGQ-UHFFFAOYSA-N 0.000 description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 2
- 125000004182 2-chlorophenyl group Chemical group [H]C1=C([H])C(Cl)=C(*)C([H])=C1[H] 0.000 description 2
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 description 2
- 239000005711 Benzoic acid Substances 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 235000011054 acetic acid Nutrition 0.000 description 2
- 125000004442 acylamino group Chemical group 0.000 description 2
- 125000004390 alkyl sulfonyl group Chemical group 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 125000001204 arachidyl 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])[H] 0.000 description 2
- 125000004104 aryloxy group Chemical group 0.000 description 2
- 150000001555 benzenes Chemical class 0.000 description 2
- 235000010233 benzoic acid Nutrition 0.000 description 2
- DIKBFYAXUHHXCS-UHFFFAOYSA-N bromoform Chemical compound BrC(Br)Br DIKBFYAXUHHXCS-UHFFFAOYSA-N 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 150000002170 ethers Chemical class 0.000 description 2
- 125000002541 furyl group Chemical group 0.000 description 2
- 150000008282 halocarbons Chemical class 0.000 description 2
- 229940098779 methanesulfonic acid Drugs 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 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 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 125000001544 thienyl group Chemical group 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- SNTWKPAKVQFCCF-UHFFFAOYSA-N 2,3-dihydro-1h-triazole Chemical class N1NC=CN1 SNTWKPAKVQFCCF-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 238000005684 Liebig rearrangement reaction Methods 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- BNOODXBBXFZASF-UHFFFAOYSA-N [Na].[S] Chemical compound [Na].[S] BNOODXBBXFZASF-UHFFFAOYSA-N 0.000 description 1
- WREOTYWODABZMH-DTZQCDIJSA-N [[(2r,3s,4r,5r)-3,4-dihydroxy-5-[2-oxo-4-(2-phenylethoxyamino)pyrimidin-1-yl]oxolan-2-yl]methoxy-hydroxyphosphoryl] phosphono hydrogen phosphate Chemical compound O[C@@H]1[C@H](O)[C@@H](COP(O)(=O)OP(O)(=O)OP(O)(O)=O)O[C@H]1N(C=C\1)C(=O)NC/1=N\OCCC1=CC=CC=C1 WREOTYWODABZMH-DTZQCDIJSA-N 0.000 description 1
- 125000005041 acyloxyalkyl group Chemical group 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 125000005078 alkoxycarbonylalkyl group Chemical group 0.000 description 1
- 125000006350 alkyl thio alkyl group Chemical group 0.000 description 1
- 150000001409 amidines Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 229950005228 bromoform Drugs 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- BAQGNDVEQGZTOL-UHFFFAOYSA-N chloro 3-oxobutanoate Chemical compound CC(=O)CC(=O)OCl BAQGNDVEQGZTOL-UHFFFAOYSA-N 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 229940125758 compound 15 Drugs 0.000 description 1
- 229940125898 compound 5 Drugs 0.000 description 1
- 239000013078 crystal Substances 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
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- VUYNTIDSHCJIKF-UHFFFAOYSA-N ethyl 4,4-dimethyl-3-oxopentanoate Chemical compound CCOC(=O)CC(=O)C(C)(C)C VUYNTIDSHCJIKF-UHFFFAOYSA-N 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- QGSRSTDENBWCJF-UHFFFAOYSA-N heptylhydrazine;hydrochloride Chemical compound Cl.CCCCCCCNN QGSRSTDENBWCJF-UHFFFAOYSA-N 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000013332 literature search Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 125000002958 pentadecyl 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])[H] 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004309 pyranyl group Chemical group O1C(C=CC=C1)* 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Nitrogen Condensed Heterocyclic Rings (AREA)
Description
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Soc.ïŒPerkin ïŒïŒ1977幎ïŒ2047ã2052é ã«å ±
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[Technical field] The present invention relates to 1H-pyrazolo[3,2-C)-1,
Regarding the method for producing 2,4-triazole compounds, in detail, 1H-pyrazolo[3,2-C]- is produced in one step in high yield using hydrazidines as starting materials.
The present invention relates to a method for producing a 1,2,4-triazole compound. [Prior Art] 1H-pyrazolo[3,2-C]-1,2,4-triazole compounds are useful compounds as photographic couplers, particularly magenta couplers and their intermediates, and their importance is explained by, for example, British patents. No. 1252418,
U.S. Patent No. 3725067, Journal of the Chemical Society, edited by Perkin (J.Chem.
Soc., Perkin I), 1977, pp. 2047-2052. Regarding the method for producing 1H-pyrazolo[3,2-C]-1,2,4-triazole compounds, see the aforementioned patents, literature, and Research Disclosure, Vol. 124, 12443 (1974).
etc. are described. Their manufacturing method is represented by the reaction scheme shown below.
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An object of the present invention is to improve the above problems. That is, the first object of the present invention is to provide a method for producing 1H-pyrazolo[3,2-C]-1,2,4-triazole compounds that does not produce by-products such as sulfur or other compounds unsuitable for industrialization. Our goal is to provide the following. The second objective is to eliminate the need for industrially unsuitable reactions and post-treatments such as the use of large amounts of sulfuric acid or the production of sodium sulfur. An object of the present invention is to provide a method for producing a triazole compound. A third object is to provide a method for producing 1H-pyrazolo[3,2-C]-1,2,4-triazole compounds that does not require high temperatures. The fourth object is to provide a method for producing 1H-pyrazolo[3,2-C]-1,2,4-triazole compounds with high yield and low cost. The fifth purpose is to allow the introduction of a wide range of substituents at the 6-position (for example, primary, secondary, and tertiary alkyl groups,
aryl group, etc.) 1H-pyrazolo[3,2-C]-
An object of the present invention is to provide a method for producing a 1,2,4-triazole compound. The sixth purpose is to allow the introduction of a wide range of substituents at the 3-position (for example, alkylthioalkyl groups, acyloxyalkyl groups, alkoxycarbonylalkyl groups, etc.) 1H-pyrazolo[3,2-C]-1,2,4
- To provide a method for producing a triazole compound. [Summary of the Invention] The above object of the present invention is to react a hydrazidine represented by the following general formula [] or an acid addition salt thereof with a keto acid ester represented by the following general formula [], thereby producing the following general formula []. ]
This is achieved by a manufacturing method for obtaining 1H-pyrazolo[3,2-C]-1,2,4-triazole. General formula [] In the formula, R 1 represents an alkyl group or an aryl group. General formula [] In the formula, R 2 and R 3 each represent an alkyl group, an aryl group or a heterocyclic group, and X represents a hydrogen atom or a halogen atom. Y represents an oxygen atom or =NH. General formula [] In the formula, R 1 , R 2 and X are the above-mentioned R 1 , R 2 and X
is synonymous with [Structure of the Invention] The present invention will be specifically described below. The hydrazidines of the general formula [] used as starting materials in the present invention are, for example, Justus Liebig Annaren Hemie
It can be synthesized by the method described in Liebigs Ann. That is, it is obtained by reacting the corresponding amidine with anhydrous hydrazine or hydrazine hydrate under reduced pressure. These hydrazidines can be used as salts of inorganic acids such as hydrochloric acid, sulfuric acid, and perchloric acid, and as salts of organic acids such as oxalic acid, acetic acid, benzoic acid, methanesulfonic acid, and toluenesulfonic acid. R 1 in the general formula [] represents an alkyl group or an aryl group, and the alkyl group represented by R 1 is preferably a straight or branched alkyl group having 1 to 30 carbon atoms, such as a methyl group, ethyl group,
Examples include isopropyl group, t-butyl group, octyl group, dodecyl group, eicosyl group, and triacontyl group. This alkyl group can have a substituent, and examples of the substituent include a halogen atom, an aryloxy group, an alkylsulfonyl group,
Examples of alkyl groups having such substituents include acylamino group, alkoxy group, hydroxy group, etc.
-amylphenoxy)propyl group, β-(dodecylsulfonyl)ethyl group, phenoxymethyl group,
Examples include methoxyethyl group. The above alkyl group also includes a cycloalkyl group. A specific example of the aryl group represented by R 1 is a phenyl group. This phenyl group can have a substituent, and examples of the substituent include an alkoxy group, a halogen atom, an alkyl group, and an amide group. Examples of the phenyl group having such a substituent include p -methoxyphenyl group, dodecyloxyphenyl group, p-{γ-
(2,4-di-t-amylphenoxy)butyrylamino}phenyl group, o-chlorophenyl group, p
-Tolyl group, mesityl (trimethylphenyl) group, etc. can be mentioned. The group is preferably an alkyl group. Typical specific examples of the compound represented by the general formula [] are shown below, but the present invention is not limited thereto. Keto acid esters of general formula [] are described, for example, in Ber., Vol. 44, pp. 2064-2071 (1911), Journal of the American Chemical Society (J.Am.Chem.Soc.) , 56 volumes, 1171~
1173 (1934) and the same magazine, volume 67, pages 2197-2200 (1945). R 2 in the general formula [] represents an alkyl group, an aryl group, or a heterocyclic group, and the alkyl group represented by R 2 is preferably a straight-chain or branched alkyl group having 1 to 30 carbon atoms, e.g. , methyl group, ethyl group, isopropyl group, t-butyl group,
Examples include octyl group, dodecyl group, eicosyl group, and triacontyl group. This alkyl group can have a substituent, and examples of the substituent include a halogen atom, an aryloxy group, an alkylsulfonyl group, an acylamino group, an alkoxy group,
Examples of alkyl groups having such substituents include γ-
Examples include (2,4-di-t-amylphenoxy)propyl group, β-(dodecylsulfonyl)ethyl group, phenoxymethyl group, and methoxyethyl group. The above alkyl group also includes a cycloalkyl group. A specific example of the aryl group represented by R 2 is a phenyl group. This phenyl group can have a substituent, and examples of the substituent include an alkoxy group, a halogen atom, an alkyl group, and an amide group. Examples of the phenyl group having such a substituent include p -methoxyphenyl group, dodecyloxyphenyl group, p-{γ-
(2,4-di-t-amylphenoxy)butyrylamino}phenyl group, o-chlorophenyl group, p
-Tolyl group, mesityl (trimethylphenyl) group, etc. can be mentioned. Specific examples of the heterocyclic group represented by R 2 include furyl group, pyranyl group, thienyl group, pyridyl group, and 2H-pyrrolyl group. Among the alkyl group, aryl group, or heterocyclic group represented by R 2 , an alkyl group is particularly preferred. Among alkyl groups, methyl group, ethyl group,
Primary alkyl groups such as pentadecyl groups are particularly preferred. In the general formula [], X represents a hydrogen atom or a halogen atom, and specific examples of the halogen atom represented by X include a chlorine atom, a bromine atom, an iodine atom, and the like. Particularly preferred is a hydrogen atom. Y in the general formula [] represents an oxygen atom or NR 4 , preferably an oxygen atom. R 3 in the general formula [] represents an alkyl group, an aryl group, or a heterocyclic group, and the alkyl group represented by R 3 is a linear or branched alkyl group having 1 to 30 carbon atoms, such as a methyl group. , ethyl group,
Examples include isopropyl group, t-butyl group, methoxyethyl group, and benzyl group. Also included are cycloalkyl groups such as cyclohexyl. A specific example of the aryl group represented by R 3 is a phenyl group. Specific examples of the heterocyclic group represented by R 3 include furyl group and thienyl group. Among the alkyl group, aryl group, or heterocyclic group represented by R 3 , an alkyl group is particularly preferred. Among the alkyl groups, methyl and ethyl groups are particularly preferred. Next, typical examples of the compound represented by the general formula [] are shown below, but the present invention is not limited thereto. -1 CH 3 COCH 2 COOC 2 H 5 -2 C 2 H 5 COCH 2 COOCH 3 -3 (CH 3 ) 2 CHCOCH 2 COOC 2 H 5 -4 (CH 3 ) 3 CCOCH 2 COOC 2 H 5 -5 C 15 H 31 COCH 2 COOCH 3 â16 CH 3 COCHClCOOC 2 H 5 â17 (CH 3 ) 3 CCOCHClCOOC 2 H 5 â19 C 15 H 31 COCHClCOOC 2 H 5 â20 CH 3 COCHBrCOOC 2 H 5The compound of general formula [] and the compound of general formula [] may be reacted without a solvent, but they must be dissolved or dispersed in an appropriate solvent. It is preferable to let Typical solvents include compounds having no carbonyl group or ester bond, such as alcohols, benzenes, ethers, halogenated hydrocarbons, amides, and the like. The carbonyl groups of aldehydes and ketones, and the ester bonds of organic acid esters, react with the amino groups of hydrazidine to form amide bonds, which are not preferable. Examples of alcohols used in the present invention include methanol, ethanol, n-propanol, ethylene glycol, and ethylene glycol monomethyl ether. Examples of benzenes include benzene, nitrobenzene, toluene, xylene, and the like. Ethers include diethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, dioxane, etc., halogenated hydrocarbons include carbon tetrachloride, chloroform, bromoform, etc., and amides include formamide, N,N-dimethylformamide, etc. can be mentioned. In addition, dimethyl sulfoxide, acetonitrile, water, etc. can also be used as a solvent.
These solvents do not necessarily have to be anhydrous;
Moreover, two or more types can also be used in combination. The solvent is 1 to 1000 parts by weight per 1 part by weight of hydrazidine,
It is preferably used in an amount of 5 to 100 parts by weight. The hydrazidine of general formula [] and the keto acid ester of general formula [] are used in a molar ratio of 1:0.5 to 1:1.5, preferably in the range of 1:0.8 to 1:1.2. The reaction temperature is preferably 80-150â, especially 100-150â.
A range of 140°C is preferred. Reduce the reaction temperature to at least 80
The temperature is set at 150°C or higher to speed up the dehydration reaction, and the temperature is set at 150°C or lower to prevent the product from decomposing and reducing the yield. Further, in the present invention, the time required for the reaction is not particularly limited, but within the above temperature range, a maximum of 20 minutes is sufficient, and even if it takes longer than this, no problems will arise. In the above reaction of the present invention, a catalyst can be used in the reaction system in order to smoothly carry out the dehydration reaction. Examples of catalysts that can be used include hydrochloric acid, hydrobromic acid, sulfuric acid, sulfonic acids (methanesulfonic acid, toluenesulfonic acid, etc.), carboxylic acids (acetic acid, formic acid, propionic acid, benzoic acid, etc.). Such a catalyst is preferably added directly to the dispersion medium as such before carrying out the reaction. The amount added varies depending on the strength of the acid, but is preferably about 0.1 mol to 1 mol. Next, 1H-pyrazolo[3,2-C]- of the present invention
A typical reaction route for producing a 1,2,4-triazole compound is shown. According to the method of the present invention, a compound represented by the following formula [] can be obtained. General formula [] In the formula, R 1 represents an alkyl group or an aryl group, and R 2 represents an alkyl group, an aryl group, or a heterocyclic group. X represents a hydrogen atom or a halogen atom. Next, typical examples of the compound represented by the general formula [] are shown below, but the present invention is not limited thereto. The compound represented by the general formula [] obtained by the method of the present invention is in a crystalline form, and is generally a pale yellow plate crystal. This compound can generally be easily separated and purified by recrystallization from alcohols, acetonitrile, or the like. This compound is useful as a photographic coupler, and is described in the aforementioned British Patent No. 1252418 and in the Journal of the Chemical Society, Perkin, ed. I, 1977.
An example of using this compound as a photographic coupler is described on pages 2047-2052. [Examples] Specific examples of the present invention will be described below, but the present invention is not limited thereto. Example 1 (Synthesis of Exemplified Compound-4) 15.3 g of isopropylhydrazidine hydrochloride and 16.0 g of ethyl pivaloylacetate were refluxed for 30 minutes with stirring in 100 ml of a dimethylformamide-water (1:1 weight ratio) mixture. do. Pour the reaction solution into 100 ml of ice water and remove the supernatant by decanting. Recrystallize the gummy substance from 50ml of methanol and air dry to obtain the desired 6-t.
-Butyl-3-isopropyl-1H-pyrazolo[3,2-C)-1,2,4-triazole 6.8g
(33%). Elemental analysis value as melting point 65-68â C 11 H 18 N 4 Calculated value (%) C: 64.04 H: 8.80 N: 27.16 Actual value (%) C: 64.15 H: 8.91 N: 27.05 FD mass spectrum shows 206 and supported the above structure. Example 2 (Synthesis of Exemplified Compound-5) 12.5 g of methylhydrazidine hydrochloride and 32.7 g of ethyl palmitoyl acetate were refluxed for 30 minutes with stirring in 100 ml of a dimethylformamide-water (1:1 weight ratio) mixture. Pour the reaction solution into 100 ml of ice water and remove the supernatant by decanting. Ethanol gum-like substance
Recrystallize from 100ml and air dry to obtain the desired 3-methyl-6-pentadecyl-1H-pyrazolo[3,2
-C]-1,2,4-triazole 17.6g (53%)
I got it. Elemental analysis value as melting point 69-71â C 20 H 36 N 4 Calculated value C: 72.24 H: 10.91 N: 16.85 Actual value (%) C: 72.29 H: 10.85 N: 16.91 FD mass spectrum shows 332 and the above structure supported. Example 3 (Synthesis of Exemplified Compound-6) Phenylhydrazidine hydrochloride 18.7g, ethyl-
36.2 g of palmitoyliminoacetate are refluxed in 100 ml of isopropanol under stirring for 30 minutes. Pour the reaction solution into 150 ml of ice water and remove the supernatant by decanting. The gummy material gradually solidifies. Add this to ethanol
Recrystallize from 200 ml and air dry to obtain the desired 6-pentadecyl-3-phenyl-1H-pyrazolo [3,
19.3g of 2-C]-1,2,4-triazole
(49%) obtained. Melting point 193-195â C 25 H 38 Elemental analysis value as N 4 Calculated value (%) C: 76.09 H: 9.71 N: 14.20 Actual value (%) C: 76.13 H: 9.65 N: 14.30 FD mass spectrum shows 394 and supported the above structure. Example 4 (Synthesis of Exemplified Compound-15) Heptylhydrazine hydrochloride 20.8g, ethyl-2
-20.5 g of chloroacetoacetate are refluxed for 30 minutes with stirring in 100 ml of a dimethylformamide-water (1:1 weight ratio) mixture. Pour the reaction solution into 100 ml of ice water and remove the supernatant by decanting. The gummy substance is recrystallized from ethanol to obtain the desired 7-chloro-3.
-hexyl-6-methyl-1H-pyrazolo[3,
2-C]-1,2,4-triazole 8.1g (32
%) was obtained. Elemental analysis value as melting point 96-97â C 12 H 19 ClN 4 Calculated value (%) C: 65.72 H: 8.73 N: 25.55 Actual value (%) C: 65.81 H: 8.83 N: 25.44 FD mass spectrum shows 254 and supported the above structure. As can be seen from the above examples, the manufacturing method of the present invention is
This is an excellent method for synthesizing 1H-pyrazolo[3,2-C]-1,2,4-triazole compounds in one step and in high yield.
Claims (1)
ãŸãã¯ãã®é žä»å å¡©ãšäžèšäžè¬åŒããã§ç€ºãã
ãã±ãé žãšã¹ãã«ãšãåå¿ãããããšãç¹åŸŽãšã
ãäžèšäžè¬åŒããã§ç€ºããã1Hâãã©ãŸã
ãïŒïŒïŒâãâïŒïŒïŒïŒïŒâããªã¢ãŸãŒã«ç³»åå
ç©ã®è£œé æ¹æ³ã äžè¬åŒãã ãåŒäžãR1ã¯ã¢ã«ãã«åºãŸãã¯ã¢ãªãŒã«åºã
è¡šããã äžè¬åŒãã ãåŒäžãR2åã³R3ã¯åã ã¢ã«ãã«åºãã¢ãªãŒ
ã«åºãŸãã¯ãããç°åºãè¡šããã¯æ°ŽçŽ ååãŸã
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NHãè¡šããã äžè¬åŒãã ãåŒäžãR1ïŒR2ããã³ïŒžã¯åèšR1ïŒR2ããã³
ãšå矩ã§ãããã[Claims] 1. A compound represented by the following general formula [], which is characterized by reacting a hydrazidine represented by the following general formula [] or an acid addition salt thereof with a keto acid ester represented by the following general formula []. A method for producing a 1H-pyrazolo[3,2-C]-1,2,4-triazole compound. General formula [] [In the formula, R 1 represents an alkyl group or an aryl group. ] General formula [ ] [In the formula, R 2 and R 3 each represent an alkyl group, an aryl group, or a heterocyclic group, and X represents a hydrogen atom or a halogen atom. Y is an oxygen atom or =
Represents NH. ] General formula [ ] [In the formula, R 1 , R 2 and X have the same meanings as R 1 , R 2 and X above. ]
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9475185A JPS61251684A (en) | 1985-04-30 | 1985-04-30 | Production of 1h-pyrazolo(3,2-c)-1,2,4-triazole compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9475185A JPS61251684A (en) | 1985-04-30 | 1985-04-30 | Production of 1h-pyrazolo(3,2-c)-1,2,4-triazole compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61251684A JPS61251684A (en) | 1986-11-08 |
| JPH0468317B2 true JPH0468317B2 (en) | 1992-11-02 |
Family
ID=14118824
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9475185A Granted JPS61251684A (en) | 1985-04-30 | 1985-04-30 | Production of 1h-pyrazolo(3,2-c)-1,2,4-triazole compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61251684A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05222044A (en) * | 1991-10-25 | 1993-08-31 | Eastman Kodak Co | Preparation of 2equivalent pyrazolotriazol magenta coupler |
-
1985
- 1985-04-30 JP JP9475185A patent/JPS61251684A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61251684A (en) | 1986-11-08 |
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