JPH0550507B2 - - Google Patents
Info
- Publication number
- JPH0550507B2 JPH0550507B2 JP26624885A JP26624885A JPH0550507B2 JP H0550507 B2 JPH0550507 B2 JP H0550507B2 JP 26624885 A JP26624885 A JP 26624885A JP 26624885 A JP26624885 A JP 26624885A JP H0550507 B2 JPH0550507 B2 JP H0550507B2
- Authority
- JP
- Japan
- Prior art keywords
- pyridyl
- cyclohexanone
- group
- producing
- vinylpyridine
- 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 - Lifetime
Links
- RSDGRRJTGIGGBP-UHFFFAOYSA-N 4-pyridin-4-ylcyclohexan-1-one Chemical compound C1CC(=O)CCC1C1=CC=NC=C1 RSDGRRJTGIGGBP-UHFFFAOYSA-N 0.000 claims description 13
- KFDVPJUYSDEJTH-UHFFFAOYSA-N 4-ethenylpyridine Chemical compound C=CC1=CC=NC=C1 KFDVPJUYSDEJTH-UHFFFAOYSA-N 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 238000005698 Diels-Alder reaction Methods 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- -1 t-butyldimethylsilyl group Chemical group 0.000 claims description 3
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- 239000000203 mixture Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- XQVWYOYUZDUNRW-UHFFFAOYSA-N N-Phenyl-1-naphthylamine Chemical compound C=1C=CC2=CC=CC=C2C=1NC1=CC=CC=C1 XQVWYOYUZDUNRW-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- BMTBAMFIDWUEMA-UHFFFAOYSA-N buta-1,3-dien-2-yloxy-tert-butyl-dimethylsilane Chemical compound CC(C)(C)[Si](C)(C)OC(=C)C=C BMTBAMFIDWUEMA-UHFFFAOYSA-N 0.000 description 3
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000000741 silica gel Substances 0.000 description 3
- 229910002027 silica gel Inorganic materials 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- YVVUSIMLVPJXMY-UHFFFAOYSA-N 4-phenylcyclohexan-1-ol Chemical compound C1CC(O)CCC1C1=CC=CC=C1 YVVUSIMLVPJXMY-UHFFFAOYSA-N 0.000 description 2
- YKAYMASDSHFOGI-UHFFFAOYSA-N 4-phenylcyclohexan-1-one Chemical compound C1CC(=O)CCC1C1=CC=CC=C1 YKAYMASDSHFOGI-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- YXVFYQXJAXKLAK-UHFFFAOYSA-N biphenyl-4-ol Chemical compound C1=CC(O)=CC=C1C1=CC=CC=C1 YXVFYQXJAXKLAK-UHFFFAOYSA-N 0.000 description 2
- FUSUHKVFWTUUBE-UHFFFAOYSA-N buten-2-one Chemical compound CC(=O)C=C FUSUHKVFWTUUBE-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000012450 pharmaceutical intermediate Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- CBHNZTYRFKGUGD-UHFFFAOYSA-N 2-pyridin-2-ylcyclohexan-1-one Chemical compound O=C1CCCCC1C1=CC=CC=N1 CBHNZTYRFKGUGD-UHFFFAOYSA-N 0.000 description 1
- RGEJCUIWCMDOOK-UHFFFAOYSA-N 2-pyridin-4-ylcyclohexan-1-one Chemical compound O=C1CCCCC1C1=CC=NC=C1 RGEJCUIWCMDOOK-UHFFFAOYSA-N 0.000 description 1
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 1
- NAVNEMDRBCCOTJ-UHFFFAOYSA-N 5,6,7,8-tetrahydro-2h-isoquinolin-3-one Chemical compound C1CCCC2=CNC(=O)C=C21 NAVNEMDRBCCOTJ-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- PMOLKBNSJNLKGB-UHFFFAOYSA-N buta-1,3-dien-2-yl acetate Chemical compound CC(=O)OC(=C)C=C PMOLKBNSJNLKGB-UHFFFAOYSA-N 0.000 description 1
- JOAPBVRQZQYKMS-UHFFFAOYSA-N buta-1,3-dien-2-yloxy(trimethyl)silane Chemical compound C[Si](C)(C)OC(=C)C=C JOAPBVRQZQYKMS-UHFFFAOYSA-N 0.000 description 1
- MXOSTENCGSDMRE-UHFFFAOYSA-N butyl-chloro-dimethylsilane Chemical compound CCCC[Si](C)(C)Cl MXOSTENCGSDMRE-UHFFFAOYSA-N 0.000 description 1
- 239000000496 cardiotonic agent Substances 0.000 description 1
- 230000003177 cardiotonic effect Effects 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 229940043279 diisopropylamine Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- VDBNYAPERZTOOF-UHFFFAOYSA-N isoquinolin-1(2H)-one Chemical class C1=CC=C2C(=O)NC=CC2=C1 VDBNYAPERZTOOF-UHFFFAOYSA-N 0.000 description 1
- 150000002537 isoquinolines Chemical class 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- MZRVEZGGRBJDDB-UHFFFAOYSA-N n-Butyllithium Substances [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
Landscapes
- Pyridine Compounds (AREA)
Description
【発明の詳細な説明】
産業上の利用分野
本発明は４−（４−ピリジル）シクロヘキサノ
ンの製造方法で４−（４−ピリジル）シクロヘキ
サノンは医薬中間体として有用である。即ち、強
心活性を有するイソキノリン誘導体を例えば次の
反応経路を通じて導くことができ、この場合の４
−シアノ−１−メチル−７−（４−ピリジル）−
５，６，７，８−テトラヒドロ−３（2H）−イソ
キノリノン（）の製造中間体として重要であ
る。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a method for producing 4-(4-pyridyl)cyclohexanone, and 4-(4-pyridyl)cyclohexanone is useful as a pharmaceutical intermediate. That is, isoquinoline derivatives with cardiotonic activity can be derived, for example, through the following reaction pathway, in which 4
-cyano-1-methyl-7-(4-pyridyl)-
It is important as an intermediate in the production of 5,6,7,8-tetrahydro-3(2H)-isoquinolinone ().
従来技術
４位に置換基を有するシクロヘキサノンの製造
法として、例えば４−フエニルシクロヘキサノン
の製造では、４−フエニルフエノールの選択水添
によつて４−フエニルシクロヘキサノールを得た
のち、酸化によつて４−フエニルシクロヘキサノ
ンを得る方法があるが、４−（４−ピリジル）シ
クロヘキサノンの製造方法は全く知られていな
い。 Prior Art As a method for producing cyclohexanone having a substituent at the 4-position, for example, in the production of 4-phenylcyclohexanone, 4-phenylcyclohexanol is obtained by selective hydrogenation of 4-phenylphenol, and then 4-phenylcyclohexanol is obtained by oxidation. Although there is a method for obtaining 4-phenylcyclohexanone, there is no known method for producing 4-(4-pyridyl)cyclohexanone.
発明が解決しようとする問題点
４−（４−ピリジル）シクロヘキサノンの製造
方法として、通常考えられる４−（４−ピリジル）
フエノールの選択水添と酸化反応の組み合わせに
よる方法は、水添部位の選択性を出すことができ
ず、別途合成法が必要であつた。Problems to be Solved by the Invention As a method for producing 4-(4-pyridyl)cyclohexanone, 4-(4-pyridyl), which is usually considered
Methods based on a combination of selective hydrogenation of phenol and oxidation reaction cannot provide selectivity of the hydrogenation site, and a separate synthesis method is required.
問題点を解決するための手段
本発明者は４−（４−ピリジル）シクロヘキサ
ノンの製造方法について鋭意検討を続けた結果、
４−ビニルピリジンとブタジエンから４−（４−
ピリジル）シクロヘキサノンを得る方法を見出し
本発明に到達した。Means for Solving the Problems As a result of intensive study on the method for producing 4-(4-pyridyl)cyclohexanone, the present inventor found that
4-(4-
They discovered a method for obtaining (pyridyl)cyclohexanone and arrived at the present invention.
本発明は詳しくは、一般式（）
（式中、Ｒはメチル基、エチル基、ｎ−ブチル
基、トリメチルシリル基、ｔ−ブチルジメチルシ
リル基またはアセチル基を表わす）で示される２
−アルコキシ、２−アセチルオキシまたは２−ア
ルキルシリロキシブタジエンと４−ビニルピリジ
ンをDiels−Alder反応したのち、環化生成物を酸
処理することにより４−ピリジルシクロヘキサノ
ンを製造する方法に関するものである。 The present invention specifically describes the general formula () (wherein R represents a methyl group, ethyl group, n-butyl group, trimethylsilyl group, t-butyldimethylsilyl group or acetyl group)
The present invention relates to a method for producing 4-pyridylcyclohexanone by carrying out a Diels-Alder reaction between -alkoxy, 2-acetyloxy or 2-alkylsilyloxybutadiene and 4-vinylpyridine, and then treating the cyclized product with an acid.
本発明の方法についてさらに詳しく述べると、
本発明の製造法は次に示す反応経路によつて実施
される。 To describe the method of the present invention in more detail,
The production method of the present invention is carried out by the reaction route shown below.
（上記の反応経路におけるＲは前記と同じ置換
基を意味する。）
２−アルコキシまたは２−アルキルシリロキシ
ブタジエン（）と４−ビニルピリジン（）と
をベンゼン、クロロホルム、塩化メチレンなどの
溶媒中または無溶媒下でDiels−Alder反応させる
ことにより環化生成物（）を得る。この際反応
を促進する目的でルイス酸を併用してもよい。反
応は０〜250℃、好ましくは150〜200℃で行なう。
また重合を防止するためフエニル−α−ナフチル
アミン、ハイドロキノンなどの重合禁止剤を用い
てもよい。 (R in the above reaction route means the same substituent as above.) 2-Alkoxy or 2-alkylsilyloxybutadiene () and 4-vinylpyridine () are mixed in a solvent such as benzene, chloroform, methylene chloride or The cyclized product () is obtained by carrying out the Diels-Alder reaction in the absence of a solvent. At this time, a Lewis acid may be used in combination for the purpose of promoting the reaction. The reaction is carried out at 0-250°C, preferably 150-200°C.
Further, in order to prevent polymerization, a polymerization inhibitor such as phenyl-α-naphthylamine or hydroquinone may be used.
環化生成物（）を塩酸、酢酸、トリフルオロ
酢酸などの酸を用いて加水分解することにより４
−（４−ピリジル）シクロヘキサノン（）が得
られる。 4 by hydrolyzing the cyclized product () using an acid such as hydrochloric acid, acetic acid, or trifluoroacetic acid.
-(4-pyridyl)cyclohexanone () is obtained.
発明の効果
本発明により医薬中間体として有用であり、特
に強心剤として有用なイソキノリノン誘導体の製
造中間体である４−（４−ピリジル）シクロヘキ
サノンを製造できる。Effects of the Invention According to the present invention, 4-(4-pyridyl)cyclohexanone, which is a production intermediate for isoquinolinone derivatives, which is useful as a pharmaceutical intermediate, and particularly useful as a cardiotonic agent, can be produced.
以下に実施例を示し本発明をさらに詳細に説明
する。 The present invention will be explained in more detail with reference to Examples below.
実施例 １
４−（４−ピリジル）シクロヘキサノン
２−トリメチルシリロキシブタジエン34ｇと４
−ビニルピリジン21ｇを乾燥ベンゼン50mlに溶解
しフエニル−α−ナフチルアミン100mlを添加し
窒素雰囲気下オートクレーブ中に200℃で24時間
加熱した。Example 1 4-(4-pyridyl)cyclohexanone 34 g of 2-trimethylsilyloxybutadiene and 4
- 21 g of vinylpyridine was dissolved in 50 ml of dry benzene, 100 ml of phenyl-α-naphthylamine was added, and the mixture was heated at 200° C. for 24 hours in an autoclave under a nitrogen atmosphere.
冷却後一部を取り減圧蒸溜して精製して４−
（４−ピリジル）−１−トリメチルシロキシ−２−
シクロヘキセンを得た。 After cooling, take a portion and distill it under reduced pressure to purify it.4-
(4-pyridyl)-1-trimethylsiloxy-2-
Cyclohexene was obtained.
bp135〜137℃／0.3mmHg
IR（Neat）νMax2950、2920、1660、1590、1250、
1190、1180、900、880、840
NMR（CCl4）δppm：0.19（ｓ，9H）、1.7〜2.4
（y.6H）、2.7（ｍ，1H）、4.82（ｍ，1H）、7.06
（ｍ，2H）、8.40（ｍ，2H）
上記の粗生成物をクロロホルム50mlに希釈し、
氷冷後トリフルオロ酢酸30mlと水20ml加え、30分
撹拌した。 bp135~137℃/0.3mmHg IR (Neat) ν Max 2950, 2920, 1660, 1590, 1250,
1190, 1180, 900, 880, 840 NMR ( CCl4 ) δppm: 0.19 (s, 9H), 1.7-2.4
(y.6H), 2.7 (m, 1H), 4.82 (m, 1H), 7.06
(m, 2H), 8.40 (m, 2H) The above crude product was diluted in 50 ml of chloroform,
After cooling on ice, 30 ml of trifluoroacetic acid and 20 ml of water were added, and the mixture was stirred for 30 minutes.
つづいて重曹の飽和水溶液で中和後、クロロホ
ルム抽出、乾燥、濃縮、シリカゲルカラムによる
精製を行なつて４−（４−ピリジル）シクロヘキ
サノン11.9ｇを得た。 Subsequently, the mixture was neutralized with a saturated aqueous solution of sodium bicarbonate, extracted with chloroform, dried, concentrated, and purified using a silica gel column to obtain 11.9 g of 4-(4-pyridyl)cyclohexanone.
mp：35〜37℃
IRνNeat naxcm-1：3010、2920、2860、1700、1600、
1400
NMR（CDCL3）δppm：1.7〜2.6（ｍ，8H）、2.8〜
3.2（ｍ，1H）、7.15（ｍ，2H）、8.51（ｍ，2H）
実施例 ２
４−（４−ピリジル）シクロヘキサノン
２−１ ２−（ｔ−ブチルジメチルシリロキシ）
ブタジエン
1.55N−ｎ−ブチルリチウムヘキサン溶液52ml
を、−50℃に冷却したジイソプロピルアミン12.31
mlの乾燥テトラヒドロフラン40ml溶液に加え、一
旦−20℃戻し20分撹拌後再び−50℃冷却したヘキ
サメチルホスホロアミド13.9mlを加えたあと、メ
チルビニルケトン5.6mlを滴下し30分撹拌後ｔ−
ブチルジメチルクロロシラン12ｇの乾燥テトラヒ
ドロフラン溶液を30分で滴下した。 mp: 35~37℃ IRν Neat nax cm -1 : 3010, 2920, 2860, 1700, 1600,
1400 NMR (CDCL 3 ) δppm: 1.7~2.6 (m, 8H), 2.8~
3.2 (m, 1H), 7.15 (m, 2H), 8.51 (m, 2H) Example 2 4-(4-pyridyl)cyclohexanone 2-1 2-(t-butyldimethylsilyloxy)
Butadiene 1.55N-n-butyllithium hexane solution 52ml
diisopropylamine cooled to −50°C12.31
ml of dry tetrahydrofuran, then returned to -20℃ and stirred for 20 minutes, then added 13.9ml of hexamethylphosphoramide which had been cooled to -50℃ again, and then added dropwise 5.6ml of methyl vinyl ketone and stirred for 30 minutes.
A solution of 12 g of butyldimethylchlorosilane in dry tetrahydrofuran was added dropwise over 30 minutes.
混合液を室温まで戻し3.5時間撹拌後ヘキサ200
mlを加え、水洗および飽和食塩水による洗浄を行
なつた。ヘキサン溶液を濃縮後減圧蒸溜して２−
（ｔ−ブチルジメチルシリロキシ）ブタジエン5.5
ｇをえた。 After returning the mixture to room temperature and stirring for 3.5 hours,
ml and washed with water and saturated saline. After concentrating the hexane solution and distilling it under reduced pressure, 2-
(t-butyldimethylsilyloxy)butadiene 5.5
I got g.
bp：68〜70℃／70mm／Hg
NMR（CDCL3）δppm：0.2（ｓ，6H）、1.0（ｓ，
9H）、4.3（ｓ，2H）、5.4（ｄ，Ｊ＝６Hz，
1H）、5.48（ｄ，Ｊ＝８Hz，1H）、6.16（dd，
Ｊ＝6.8Hz、1H）
２−２ ４−（４−ピリジル）シクロヘキサノン
２−（ｔ−ブチルジメチルシリロキシ）ブタジ
エン1.1ｇと４−ビニルピリジン２ｇの乾燥トル
エン７ml溶液にフエニル−α−ナフチルアミン５
mgを加え、窒素雰囲気下オートクレーブ中、180
℃で15時間加熱した。 bp: 68-70℃/70mm/Hg NMR (CDCL 3 ) δppm: 0.2 (s, 6H), 1.0 (s,
9H), 4.3 (s, 2H), 5.4 (d, J=6Hz,
1H), 5.48 (d, J=8Hz, 1H), 6.16 (dd,
J=6.8Hz, 1H) 2-2 4-(4-pyridyl)cyclohexanone Phenyl-α-naphthylamine 5 was added to a solution of 1.1 g of 2-(t-butyldimethylsilyloxy)butadiene and 2 g of 4-vinylpyridine in 7 ml of dry toluene.
180 mg in an autoclave under nitrogen atmosphere.
Heated at ℃ for 15 hours.
冷却後、50％酢酸水溶液６mlを加え100℃で４
時間加熱した。水10mlを加え、2N−苛性ソーダ
水溶液でPH８としたあと、酢酸エチルで抽出、乾
燥、濃縮、シリカゲルカラムによる精製を行なつ
て４−（４−ピリジル）シクロヘキサノン0.2ｇを
得た。 After cooling, add 6 ml of 50% acetic acid aqueous solution and incubate at 100℃.
heated for an hour. After adding 10 ml of water and adjusting the pH to 8 with a 2N aqueous sodium hydroxide solution, the mixture was extracted with ethyl acetate, dried, concentrated, and purified using a silica gel column to obtain 0.2 g of 4-(4-pyridyl)cyclohexanone.
IR及びNMRの値は実施例１の化合物と一致し
た。 IR and NMR values were consistent with the compound of Example 1.
実施例 ３
４−（４−ピリジル）シクロヘキサノン
２−アセトキシブタジエン0.9ｇと４−ビニル
ピリジン1.7mlの乾燥トルエン３ml溶液にフエニ
ル−α−ナフチルアミン２mgを添加し、窒素雰囲
気下、オートクレーブ中80℃で10時間加熱した。
冷却後50％酢酸水溶液20mlを加え４時間加熱還流
した。Example 3 4-(4-pyridyl)cyclohexanone 2 mg of phenyl-α-naphthylamine was added to a solution of 0.9 g of 2-acetoxybutadiene and 1.7 ml of 4-vinylpyridine in 3 ml of dry toluene, and the mixture was heated at 80°C in an autoclave under a nitrogen atmosphere for 10 heated for an hour.
After cooling, 20 ml of 50% acetic acid aqueous solution was added and the mixture was heated under reflux for 4 hours.
再び冷却後2N−苛性ソーダ水溶液でPH８とし
酢酸エチルで抽出、乾燥、濃縮、シリカゲルカラ
ムによる精製を行なつて４−（４−ピリジル）シ
クロヘキサノン0.1ｇを得た。 After cooling again, the pH was adjusted to 8 with a 2N aqueous sodium hydroxide solution, extracted with ethyl acetate, dried, concentrated, and purified using a silica gel column to obtain 0.1 g of 4-(4-pyridyl)cyclohexanone.
IRおよびNMRの値は実施例１の化合物と一致
した。 IR and NMR values were consistent with the compound of Example 1.
Claims (1)
基、トリメチルシリル基、ｔ−ブチルジメチルシ
リル基またはアセチル基を表わす）で示される２
−アルコキシ、２−アセチルオキシまたは２−ア
ルキルシリロキシブタジエンと４−ビニルピリジ
ンをデイールス−アルダー反応したのち、環化生
成物を酸処理することによつて４−（４−ピリジ
ル）シクロヘキサノンを製造する方法。[Claims] 1 General formula (1) (wherein R represents a methyl group, ethyl group, n-butyl group, trimethylsilyl group, t-butyldimethylsilyl group or acetyl group)
- Producing 4-(4-pyridyl)cyclohexanone by subjecting alkoxy, 2-acetyloxy or 2-alkylsilyloxybutadiene to 4-vinylpyridine in a Diels-Alder reaction and then treating the cyclized product with acid. Method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26624885A JPS62126170A (en) | 1985-11-28 | 1985-11-28 | Production of 4-(4-pyridyl)cyclohexanone |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26624885A JPS62126170A (en) | 1985-11-28 | 1985-11-28 | Production of 4-(4-pyridyl)cyclohexanone |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62126170A JPS62126170A (en) | 1987-06-08 |
| JPH0550507B2 true JPH0550507B2 (en) | 1993-07-29 |
Family
ID=17428329
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP26624885A Granted JPS62126170A (en) | 1985-11-28 | 1985-11-28 | Production of 4-(4-pyridyl)cyclohexanone |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62126170A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2759079B1 (en) * | 1997-02-03 | 2002-06-14 | Girex | PROCESS FOR THE PREPARATION OF SUBSTITUTED ANTHRAQUINONES AND APPLICATION TO THE PREPARATION OF RHEINES |
-
1985
- 1985-11-28 JP JP26624885A patent/JPS62126170A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62126170A (en) | 1987-06-08 |
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