JPS6227068B2 - - Google Patents
Info
- Publication number
- JPS6227068B2 JPS6227068B2 JP60036705A JP3670585A JPS6227068B2 JP S6227068 B2 JPS6227068 B2 JP S6227068B2 JP 60036705 A JP60036705 A JP 60036705A JP 3670585 A JP3670585 A JP 3670585A JP S6227068 B2 JPS6227068 B2 JP S6227068B2
- Authority
- JP
- Japan
- Prior art keywords
- palladium
- diphenyl
- diphenylpyrazole
- parts
- reference example
- 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
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- 239000003054 catalyst Substances 0.000 claims description 19
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 15
- JXHKUYQCEJILEI-UHFFFAOYSA-N 3,5-diphenyl-1h-pyrazole Chemical compound C=1C(C=2C=CC=CC=2)=NNC=1C1=CC=CC=C1 JXHKUYQCEJILEI-UHFFFAOYSA-N 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 14
- 238000010992 reflux Methods 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 6
- RXQQWLMUBOTBSO-UHFFFAOYSA-N 3,5-diphenyl-2,3-dihydro-1h-pyrazole Chemical compound N1NC(C=2C=CC=CC=2)=CC1C1=CC=CC=C1 RXQQWLMUBOTBSO-UHFFFAOYSA-N 0.000 claims description 5
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 4
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Inorganic materials [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 239000007858 starting material Substances 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims 1
- 239000012442 inert solvent Substances 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- 239000011541 reaction mixture Substances 0.000 description 7
- VJFQJTFADLQQNS-UHFFFAOYSA-N 3,5-diphenyl-4,5-dihydro-1h-pyrazole Chemical compound C1C(C=2C=CC=CC=2)NN=C1C1=CC=CC=C1 VJFQJTFADLQQNS-UHFFFAOYSA-N 0.000 description 6
- 238000002844 melting Methods 0.000 description 6
- 230000008018 melting Effects 0.000 description 6
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 6
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- GODJIHYACPNRIJ-UHFFFAOYSA-N 4-methyl-3,5-diphenyl-1h-pyrazole Chemical compound CC=1C(C=2C=CC=CC=2)=NNC=1C1=CC=CC=C1 GODJIHYACPNRIJ-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- 239000008096 xylene Substances 0.000 description 4
- 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 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 238000006356 dehydrogenation reaction Methods 0.000 description 3
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- DQFBYFPFKXHELB-VAWYXSNFSA-N trans-chalcone Chemical compound C=1C=CC=CC=1C(=O)\C=C\C1=CC=CC=C1 DQFBYFPFKXHELB-VAWYXSNFSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical group CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- XOFYZVNMUHMLCC-ZPOLXVRWSA-N prednisone Chemical compound O=C1C=C[C@]2(C)[C@H]3C(=O)C[C@](C)([C@@](CC4)(O)C(=O)CO)[C@@H]4[C@@H]3CCC2=C1 XOFYZVNMUHMLCC-ZPOLXVRWSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- GIWVQKNTAVVGBQ-UHFFFAOYSA-N 4-methyl-3,5-diphenyl-2,3-dihydro-1h-pyrazole Chemical compound CC1=C(C=2C=CC=CC=2)NNC1C1=CC=CC=C1 GIWVQKNTAVVGBQ-UHFFFAOYSA-N 0.000 description 1
- DQFBYFPFKXHELB-UHFFFAOYSA-N Chalcone Natural products C=1C=CC=CC=1C(=O)C=CC1=CC=CC=C1 DQFBYFPFKXHELB-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- -1 alkyl chalcone Chemical compound 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 238000010533 azeotropic distillation Methods 0.000 description 1
- FFSAXUULYPJSKH-UHFFFAOYSA-N butyrophenone Chemical group CCCC(=O)C1=CC=CC=C1 FFSAXUULYPJSKH-UHFFFAOYSA-N 0.000 description 1
- 235000005513 chalcones Nutrition 0.000 description 1
- 229960004285 fomepizole Drugs 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- KRIOVPPHQSLHCZ-UHFFFAOYSA-N propiophenone Chemical compound CCC(=O)C1=CC=CC=C1 KRIOVPPHQSLHCZ-UHFFFAOYSA-N 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
- C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
- C07D231/06—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
- C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
- C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D231/12—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Description
【発明の詳細な説明】
本発明は特許第1225642号(特願昭49−107068
号、特公昭58−55143号)の主題となる発明の変
形および改良に関する。[Detailed description of the invention] The present invention is disclosed in Japanese Patent No. 1225642 (Japanese Patent Application No. 107068/1989
(Japanese Patent Publication No. 58-55143).
この先願は相当するピラゾールを得るためにピ
ラゾリン化合物を接触脱水することによつて3・
5−ジフエニルピラゾールを製造する方法を述べ
ると共に特許請求している。該反応に用いられる
触媒は担体上に支持されたパラジウムである。 This earlier application reported that 3.
A method for making 5-diphenylpyrazole is described and claimed. The catalyst used in the reaction is palladium supported on a support.
本発明によつて我々は他の触媒系並に他の溶媒
が本製造方法に使用することの出来ることと、こ
の製造は3・5−ジフエニルピラゾリン化合物で
と同様に3・5−ジフエニル−4−アルキルピラ
ゾリン化合物でも行なうことの出来ることが判明
した。 By virtue of the present invention we have shown that other catalyst systems as well as other solvents can be used in the process and that the preparation can be carried out with 3,5-diphenylpyrazoline compounds as well as with 3,5-diphenylpyrazoline compounds. It has been found that -4-alkylpyrazoline compounds can also be used.
3・5−ジフエニル−4−アルキルピラゾリン
化合物は適当なケトンを選ぶことによつて製造す
ることが出来る。この様なケトンには例えばプロ
ピオフエノンまたはn−ブチロフエノン又はt−
ブチロフエノンがあり、これはβ−低級アルキル
カルコンを製造するのに使用することが出来る。 A 3,5-diphenyl-4-alkylpyrazoline compound can be produced by selecting an appropriate ketone. Such ketones include, for example, propiophenone or n-butylophenone or t-
There is butyrophenone, which can be used to produce β-lower alkyl chalcone.
本発明に従つて使われる触媒系は、パラジウム
黒、パラジウム−炭素、パラジウム−アルミナ、
パラジウム−硫酸バリウムまたは白金−炭素であ
る。ただし、出発物質が3・5−ジフエニルピラ
ゾリンである場合には、担体上に支持されたパラ
ジウム以外の触媒系すなわちパラジウム黒または
白金−炭素が使用される。 Catalyst systems used according to the invention include palladium black, palladium-carbon, palladium-alumina,
Palladium-barium sulfate or platinum-carbon. However, if the starting material is 3,5-diphenylpyrazoline, a catalyst system other than palladium supported on a support, ie palladium black or platinum-carbon, is used.
前記の先願明細書中に記載されている以外の溶
媒としては、ニトロベンゼンがある。 Examples of solvents other than those described in the specification of the earlier application include nitrobenzene.
本発明の次の実施例および参考例(特許第
1225642号の発明)によつて説明する。 The following Examples and Reference Examples of the present invention (Patent No.
1225642).
参考例 1
メタノール中で12.5部のベンザルアセトフエノ
ンと3.1部(容積)のヒドラジン水化物を反応さ
せて3・5−ジフエニル−2−ピラゾリンを製造
する。次にこの後者に5%パラジウム−炭素触媒
(2部)を加え、反応混合物を1時間20分還流加
熱する。生成物、3・5−ジフエニルピラゾール
が97.8%の収率で得られる。Reference Example 1 12.5 parts of benzalacetophenone and 3.1 parts (by volume) of hydrazine hydrate are reacted in methanol to produce 3,5-diphenyl-2-pyrazoline. To this latter is then added 5% palladium-carbon catalyst (2 parts) and the reaction mixture is heated at reflux for 1 hour and 20 minutes. The product, 3,5-diphenylpyrazole, is obtained with a yield of 97.8%.
参考例 2
1.0部の触媒を用い、溶媒がイソプロパノール
である点を除き参考例1の方法を詳細に繰り返
す。4時間30分還流すると、3・5−ジフエニル
ピラゾールが収率90.7%で得られる。Reference Example 2 The method of Reference Example 1 is repeated in detail using 1.0 part of catalyst, except that the solvent is isopropanol. After refluxing for 4 hours and 30 minutes, 3,5-diphenylpyrazole is obtained with a yield of 90.7%.
参考例 3
メタノール中でベンザルアセトフエノン(12.5
部)をヒドラジン水化物(3.1容量部)と反応さ
せて、3・5−ジフエニル−2−ピラゾリンを製
造する。次に市販の重質芳香族ナフサ[パナゾー
ル(Panasol)AN−2](30ml)、ニトロベンゼン
(7.4部)及び5%パラジウム−炭素触媒(2部)
を加えて混合物を加熱する。反応混合物からメタ
ノールと水を蒸留後、温度を200℃に上げ、24時
間その温度に保つ。次いで混合物を50℃に冷却、
過すると、触媒含有の3・5−ジフエニルピラ
ゾールのケーキが79.5%で得られ融点194℃から
199℃である。Reference example 3 Benzalacetophenone (12.5
part) with hydrazine hydrate (3.1 parts by volume) to produce 3,5-diphenyl-2-pyrazoline. Next, commercially available heavy aromatic naphtha [Panasol AN-2] (30 ml), nitrobenzene (7.4 parts) and 5% palladium-carbon catalyst (2 parts)
and heat the mixture. After distilling methanol and water from the reaction mixture, the temperature is raised to 200°C and kept at that temperature for 24 hours. Then cool the mixture to 50 °C,
Upon filtration, a cake of 3,5-diphenylpyrazole containing catalyst was obtained with a concentration of 79.5% and a melting point of 194°C.
It is 199℃.
実施例 1
5%のパラジウム−炭素触媒(2部)の代りに
白金−炭素触媒を用いる点を除き参考例3の手順
を繰り返す。反応混合物を200℃に20時間保つ。
3・5−ジフエニルピラゾールが70.4%の収率で
得られる。Example 1 The procedure of Reference Example 3 is repeated except that platinum-carbon catalyst is used instead of 5% palladium-carbon catalyst (2 parts). Keep the reaction mixture at 200°C for 20 hours.
3,5-diphenylpyrazole is obtained with a yield of 70.4%.
参考例 4
反応混合物にニトロベンゼンを加えずに5%パ
ラジウム−炭素触媒の量を0.1部に減らす以外は
実施例1の方法をくり返す。6時間15分200℃に
保つと、3・5−ジフエニルピラゾールが78.7%
の収率で得られる。Reference Example 4 The procedure of Example 1 is repeated except that no nitrobenzene is added to the reaction mixture and the amount of 5% palladium-on-carbon catalyst is reduced to 0.1 part. When kept at 200℃ for 6 hours and 15 minutes, 3,5-diphenylpyrazole was reduced to 78.7%.
obtained with a yield of .
参考例 5
脱水素工程に於てパナゾール(Panasol)AN−
2とは別の市販の重質芳香族ナフサ[ハンブル
アロマテイツク(Hamble Aromatic)150]溶媒
を用る点を除き参考例4の方法をくり返す。4時
間、200℃に保つと3・5−ジフエニルピラゾー
ルが41.5%の収率で得られる。Reference example 5 Panasol AN- in the dehydrogenation process
Commercially available heavy aromatic naphtha [Humble
Repeat the method of Reference Example 4, except using Hamble Aromatic 150] solvent. When kept at 200°C for 4 hours, 3,5-diphenylpyrazole is obtained with a yield of 41.5%.
参考例 6
脱水素工程を窒素雰囲気下で行ない、反応中に
生成された垂素を窒素でパージする点を除き参考
例5の方法をくり返す。次に1時間半200℃に保
つと、3・5−ジフエニルピラゾールが89.3%の
収率で得られる。Reference Example 6 The method of Reference Example 5 is repeated except that the dehydrogenation step is carried out under a nitrogen atmosphere and the hydrogen produced during the reaction is purged with nitrogen. The mixture is then kept at 200° C. for one and a half hours to obtain 3,5-diphenylpyrazole in a yield of 89.3%.
参考例 7
脱水素工程で使用する溶媒がトルエンであるこ
とを除いて、参考例6の方法を繰り返す。4時間
30分還流した後3・5−ジフエニルピラゾールが
91.0%の収率で得られる。Reference Example 7 The method of Reference Example 6 is repeated except that the solvent used in the dehydrogenation step is toluene. 4 hours
After refluxing for 30 minutes, 3,5-diphenylpyrazole
Obtained with a yield of 91.0%.
参考例 8
3・5−ジフエニル−2−ピラゾリン(21.9
部)を二塩化エチレン(75容量部)に溶解する。
次に5%パラジウム−炭素触媒(4部、40%の水
を含む)を加え、その混合物を8時間加熱還流す
る。196℃乃至200℃の融点範囲を有する3・5−
ジフエニルピラゾールが79.3%の収率で得られ
る。Reference example 8 3,5-diphenyl-2-pyrazoline (21.9
part) in ethylene dichloride (75 parts by volume).
Then 5% palladium-carbon catalyst (4 parts, containing 40% water) is added and the mixture is heated to reflux for 8 hours. 3.5- with melting point range from 196℃ to 200℃
Diphenylpyrazole is obtained with a yield of 79.3%.
参考例 9
適当な反応槽に130部(容量)のメタノールと
20部の水でスラリー化されたベンザルアセトフエ
ノン42部を室温で加える。この混合物を次に窒素
でパージし、13部の85%ヒドラジン水化物を急速
に添加して3・5−ジフエニル−2−ピラゾリン
を生成する。この混合物を加熱還流し、105部の
メタノール−水混合物を蒸留し、次に130部のキ
シレンを添加し、水相を除去し、有機層を水で洗
う。次に0.2部の5%pd−アルミナを窒素雰囲気
下で添加し、この混合物を加熱還流する。更に2
時間還流して後混合物を10℃に冷却する。触媒含
有固体3・5−ジフエニルピラゾールを過して
単離し、ヘキサンで洗つて空気乾燥する。190゜
〜201.5℃で溶融する3・5−ジフエニルピラゾ
ールを90.1%の収率で得る。Reference example 9 130 parts (by volume) of methanol and
Add 42 parts of benzalacetophenone slurried with 20 parts of water at room temperature. The mixture is then purged with nitrogen and 13 parts of 85% hydrazine hydrate are added rapidly to form 3,5-diphenyl-2-pyrazoline. The mixture is heated to reflux and 105 parts of the methanol-water mixture are distilled off, then 130 parts of xylene are added, the aqueous phase is removed and the organic layer is washed with water. Then 0.2 part of 5% PD-alumina is added under nitrogen atmosphere and the mixture is heated to reflux. 2 more
After refluxing for an hour, the mixture is cooled to 10°C. The solid 3,5-diphenylpyrazole containing catalyst is isolated by filtration, washed with hexane and air dried. 3,5-diphenylpyrazole melting between 190° and 201.5°C is obtained with a yield of 90.1%.
参考例 10
2部の5%パラジウム−硫酸バリウムをパラジ
ウム−アルミナの代りに用いることを除いて参考
例9の手順を行なう。2時間30分還流後、未反応
3・5−ジフエニル−2−ピラゾリンが2.4%あ
り、198〜201℃で融ける3・5−ジフエニルピラ
ゾールが収率76.4%で得られる。Reference Example 10 The procedure of Reference Example 9 is followed except that 2 parts of 5% palladium-barium sulfate are used in place of the palladium-alumina. After refluxing for 2 hours and 30 minutes, 3,5-diphenylpyrazole, which contains 2.4% of unreacted 3,5-diphenyl-2-pyrazoline and melts at 198-201°C, is obtained in a yield of 76.4%.
実施例 2
0.4部のパラジウム黒(100%pd)を触媒として
用いる点を除き参考例10の手順を行なう。4時間
還流後未反応の3・5−ジフエニル−2−ピラゾ
リンが1.1%の収率で回収され、融点197〜201℃
の3・5−ジフエニルピラゾールが収率88.9%で
得られる。Example 2 The procedure of Reference Example 10 is followed except that 0.4 parts of palladium black (100% pd) is used as catalyst. After refluxing for 4 hours, unreacted 3,5-diphenyl-2-pyrazoline was recovered in a yield of 1.1%, with a melting point of 197-201°C.
3,5-diphenylpyrazole is obtained in a yield of 88.9%.
実施例 3
3・5−ジフエニル−4−メチルピラゾリンの
湿つたキシレン溶液に1.0gの5%パラジウム−
炭素触媒を加える。反応混合物をゆつくり加熱還
流し、デイーン−スターク装置を用いて共沸蒸留
により水を除去する(反応槽にキシレンを戻
す)。還流を145℃で4時間続ける。4時間還流
後、反応混合物を25℃に冷却し、5%パラジウム
−木炭/3・5−ジフエニル−4−メチルピラゾ
ール結合物を別する。この固体を熱アセトンで
スラリー化して3・5−ジフエニル−4−メチル
ピラゾールを溶解する。次に触媒を別する。真
空下でアセトンを除去すると1.5gの3・5−ジ
フエニル−4−メチルピラゾールを得る。熱キシ
レンから再結晶すると、融点225〜226℃を有する
純粋な3・5−ジフエニル−4−メチルピラゾー
ルが得られる。Example 3 1.0 g of 5% palladium in a wet xylene solution of 3,5-diphenyl-4-methylpyrazoline
Add carbon catalyst. The reaction mixture is heated to gentle reflux and water is removed by azeotropic distillation using a Dean-Stark apparatus (xylene is returned to the reactor). Reflux is continued for 4 hours at 145°C. After refluxing for 4 hours, the reaction mixture is cooled to 25 DEG C. and the 5% palladium-charcoal/3.5-diphenyl-4-methylpyrazole conjugate is separated off. This solid is slurried with hot acetone to dissolve the 3,5-diphenyl-4-methylpyrazole. Next, separate the catalyst. Removal of the acetone under vacuum yields 1.5 g of 3,5-diphenyl-4-methylpyrazole. Recrystallization from hot xylene gives pure 3,5-diphenyl-4-methylpyrazole with a melting point of 225-226°C.
実施例 4
0.2gの5%pd−Cを触媒として使用する以外
は実施例3の手順をくり返す。反応混合物を窒素
の雰囲気下で加熱、還流する(140℃)。3・5−
ジフエニル−4−メチルピラゾールを熱アセトン
を用いてpb−C触媒から抽出し、アセトンを真
空で除去する。全量で1.1gの3・5−ジフエニ
ル−4−メチルピラゾールが得られる。その融点
は225゜〜226℃である。Example 4 The procedure of Example 3 is repeated except that 0.2 g of 5% PD-C is used as catalyst. The reaction mixture is heated to reflux (140° C.) under nitrogen atmosphere. 3.5-
Diphenyl-4-methylpyrazole is extracted from the pb-C catalyst using hot acetone and the acetone is removed in vacuo. A total of 1.1 g of 3,5-diphenyl-4-methylpyrazole is obtained. Its melting point is 225°-226°C.
Claims (1)
−ジフエニル−4−アルキルピラゾリンを、不活
性溶媒中において、パラジウム黒、パラジウム−
炭素、パラジウム−アルミナ、パラジウム−硫酸
バリウムおよび白金−炭素より成る群から選ばれ
た触媒、ただし出発物質が3・5−ジフエニルピ
ラゾリンである場合には担体上に支持されたパラ
ジウムを除く、と共に加熱処理することを特徴と
する、3・5−ジフエニルピラゾールまたは3・
5−ジフエニル−4−アルキルピラゾールの製造
方法。 2 反応を還流温度で行なう特許請求の範囲第1
項記載の方法。 3 溶媒が低級アルコールまたは二塩化エチレン
である特許請求の範囲第1項または第2項記載の
方法。[Claims] 1 3,5-diphenylpyrazoline or 3,5
-diphenyl-4-alkylpyrazoline in an inert solvent, palladium black, palladium-
a catalyst selected from the group consisting of carbon, palladium-alumina, palladium-barium sulfate and platinum-carbon, except palladium supported on a support when the starting material is 3,5-diphenylpyrazoline; 3,5-diphenylpyrazole or 3.
Method for producing 5-diphenyl-4-alkylpyrazole. 2 Claim 1 in which the reaction is carried out at reflux temperature
The method described in section. 3. The method according to claim 1 or 2, wherein the solvent is a lower alcohol or ethylene dichloride.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19853522542 DE3522542A1 (en) | 1985-02-27 | 1985-06-24 | Disposable cutting insert |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US05/549,219 US3952010A (en) | 1973-09-17 | 1975-02-12 | Catalytic dehydrogenation process for the preparation of 3,5-disubstituted pyrazoles |
US549219 | 1975-02-12 |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS60222463A JPS60222463A (en) | 1985-11-07 |
JPS6227068B2 true JPS6227068B2 (en) | 1987-06-12 |
Family
ID=24192112
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP51012890A Pending JPS51101979A (en) | 1975-02-12 | 1976-02-10 | |
JP60036705A Granted JPS60222463A (en) | 1975-02-12 | 1985-02-27 | Manufacture of 3,5-disubstituted pyrazoles |
Family Applications Before (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP51012890A Pending JPS51101979A (en) | 1975-02-12 | 1976-02-10 |
Country Status (19)
Country | Link |
---|---|
JP (2) | JPS51101979A (en) |
AT (1) | AT350549B (en) |
BE (1) | BE838408R (en) |
BR (1) | BR7600847A (en) |
CA (1) | CA1060455A (en) |
CH (1) | CH608004A5 (en) |
CS (1) | CS192554B2 (en) |
DD (1) | DD124249A6 (en) |
DE (1) | DE2602965A1 (en) |
DK (1) | DK55276A (en) |
ES (1) | ES445094A2 (en) |
FR (1) | FR2300763A2 (en) |
GB (1) | GB1537859A (en) |
IL (1) | IL48724A (en) |
IT (1) | IT1053296B (en) |
NL (1) | NL178075C (en) |
SE (1) | SE7601544L (en) |
SU (1) | SU799657A3 (en) |
ZA (1) | ZA757986B (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3029160A1 (en) * | 1980-08-01 | 1982-03-04 | Basf Ag, 6700 Ludwigshafen | METHOD FOR PRODUCING PYRAZOLES |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5855148A (en) * | 1981-09-29 | 1983-04-01 | Hino Motors Ltd | Production of die for molding |
-
1975
- 1975-12-22 CA CA242,256A patent/CA1060455A/en not_active Expired
- 1975-12-23 ZA ZA00757986A patent/ZA757986B/en unknown
- 1975-12-24 IL IL48724A patent/IL48724A/en unknown
-
1976
- 1976-01-09 IT IT47573/76A patent/IT1053296B/en active
- 1976-01-16 NL NLAANVRAGE7600445,A patent/NL178075C/en not_active IP Right Cessation
- 1976-01-27 DE DE19762602965 patent/DE2602965A1/en active Granted
- 1976-02-03 DD DD191069A patent/DD124249A6/xx unknown
- 1976-02-10 FR FR7603642A patent/FR2300763A2/en active Granted
- 1976-02-10 BE BE164196A patent/BE838408R/en not_active IP Right Cessation
- 1976-02-10 JP JP51012890A patent/JPS51101979A/ja active Pending
- 1976-02-11 SU SU762319859A patent/SU799657A3/en active
- 1976-02-11 AT AT96276A patent/AT350549B/en not_active IP Right Cessation
- 1976-02-11 BR BR7600847A patent/BR7600847A/en unknown
- 1976-02-11 CS CS76899A patent/CS192554B2/en unknown
- 1976-02-11 SE SE7601544A patent/SE7601544L/en unknown
- 1976-02-11 CH CH166976A patent/CH608004A5/en not_active IP Right Cessation
- 1976-02-11 DK DK55276*#A patent/DK55276A/en unknown
- 1976-02-12 GB GB5650/76A patent/GB1537859A/en not_active Expired
- 1976-02-12 ES ES445094A patent/ES445094A2/en not_active Expired
-
1985
- 1985-02-27 JP JP60036705A patent/JPS60222463A/en active Granted
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5855148A (en) * | 1981-09-29 | 1983-04-01 | Hino Motors Ltd | Production of die for molding |
Also Published As
Publication number | Publication date |
---|---|
IL48724A (en) | 1979-07-25 |
FR2300763A2 (en) | 1976-09-10 |
DD124249A6 (en) | 1977-02-09 |
CH608004A5 (en) | 1978-12-15 |
IT1053296B (en) | 1981-08-31 |
AT350549B (en) | 1979-06-11 |
CA1060455A (en) | 1979-08-14 |
AU8790475A (en) | 1977-06-30 |
FR2300763B2 (en) | 1982-09-03 |
ATA96276A (en) | 1978-11-15 |
IL48724A0 (en) | 1976-02-29 |
NL178075C (en) | 1986-01-16 |
NL7600445A (en) | 1976-08-16 |
BR7600847A (en) | 1976-09-14 |
DE2602965A1 (en) | 1976-08-26 |
CS192554B2 (en) | 1979-08-31 |
BE838408R (en) | 1976-08-10 |
ES445094A2 (en) | 1977-06-16 |
ZA757986B (en) | 1976-12-29 |
DK55276A (en) | 1976-08-13 |
NL178075B (en) | 1985-08-16 |
GB1537859A (en) | 1979-01-04 |
DE2602965C2 (en) | 1988-11-17 |
SE7601544L (en) | 1976-08-13 |
JPS51101979A (en) | 1976-09-08 |
JPS60222463A (en) | 1985-11-07 |
SU799657A3 (en) | 1981-01-23 |
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