JPS5911574B2 - Method for producing cyclic compounds - Google Patents
Method for producing cyclic compoundsInfo
- Publication number
- JPS5911574B2 JPS5911574B2 JP10360373A JP10360373A JPS5911574B2 JP S5911574 B2 JPS5911574 B2 JP S5911574B2 JP 10360373 A JP10360373 A JP 10360373A JP 10360373 A JP10360373 A JP 10360373A JP S5911574 B2 JPS5911574 B2 JP S5911574B2
- Authority
- JP
- Japan
- Prior art keywords
- general formula
- reaction
- cyclic compounds
- formula
- producing cyclic
- 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
- 150000001923 cyclic compounds Chemical class 0.000 title 1
- 238000004519 manufacturing process Methods 0.000 title 1
- 150000001875 compounds Chemical class 0.000 claims description 9
- -1 thionyl halide Chemical class 0.000 claims description 8
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 4
- 125000004453 alkoxycarbonyl group Chemical group 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 12
- 239000002904 solvent Substances 0.000 description 9
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 8
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 8
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 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
- 239000000460 chlorine Substances 0.000 description 5
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 150000008282 halocarbons Chemical class 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- HLPYSMVBIRJSBK-UHFFFAOYSA-N 1-chloro-2,3-dihydro-1h-indene-4-carboxylic acid Chemical compound OC(=O)C1=CC=CC2=C1CCC2Cl HLPYSMVBIRJSBK-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 229940035676 analgesics Drugs 0.000 description 1
- 239000002260 anti-inflammatory agent Substances 0.000 description 1
- 229940121363 anti-inflammatory agent Drugs 0.000 description 1
- 230000001754 anti-pyretic effect Effects 0.000 description 1
- 239000002221 antipyretic Substances 0.000 description 1
- 229940125716 antipyretic agent Drugs 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000004744 butyloxycarbonyl group Chemical group 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- OSVXSBDYLRYLIG-UHFFFAOYSA-N chlorine dioxide Inorganic materials O=Cl=O OSVXSBDYLRYLIG-UHFFFAOYSA-N 0.000 description 1
- 235000019398 chlorine dioxide Nutrition 0.000 description 1
- QBWCMBCROVPCKQ-UHFFFAOYSA-N chlorous acid Chemical compound OCl=O QBWCMBCROVPCKQ-UHFFFAOYSA-N 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 125000003754 ethoxycarbonyl group Chemical group C(=O)(OCC)* 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 125000001160 methoxycarbonyl group Chemical group [H]C([H])([H])OC(*)=O 0.000 description 1
- ZMUQZHDSQVARAM-UHFFFAOYSA-N methyl 1-chloro-2,3-dihydro-1h-indene-4-carboxylate Chemical compound COC(=O)C1=CC=CC2=C1CCC2Cl ZMUQZHDSQVARAM-UHFFFAOYSA-N 0.000 description 1
- NLOZTSUVQBIWPJ-UHFFFAOYSA-N methyl 1-hydroxy-2,3-dihydro-1h-indene-4-carboxylate Chemical compound COC(=O)C1=CC=CC2=C1CCC2O NLOZTSUVQBIWPJ-UHFFFAOYSA-N 0.000 description 1
- 239000000041 non-steroidal anti-inflammatory agent Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 125000005930 sec-butyloxycarbonyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(OC(*)=O)C([H])([H])[H] 0.000 description 1
- HFRXJVQOXRXOPP-UHFFFAOYSA-N thionyl bromide Chemical compound BrS(Br)=O HFRXJVQOXRXOPP-UHFFFAOYSA-N 0.000 description 1
- RKIDPTUGNXTOMU-UHFFFAOYSA-N thionyl iodide Chemical compound IS(I)=O RKIDPTUGNXTOMU-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【発明の詳細な説明】
本発明は一般式（Ｉ）
１５□ （Ｉ）
２０（式中、Ａはカルボキシル基あるいは低級アルコキ
シカルボニル基を示す。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a compound of the general formula (I) 15□ (I) 20 (wherein A represents a carboxyl group or a lower alkoxycarbonyl group).
）で表わされる化合物とハロゲン化チオニルとを反応さ
せることを特徴とする一般式（■）
□ （ ■ ）
（式中、Ａは前記と同意義であり、Ｘはハロゲン原子を
示す。General formula (■) □ (■) characterized by reacting a compound represented by ) with thionyl halide (wherein A has the same meaning as above, and X represents a halogen atom).
）で表わされる化合物の製法に関する。３５前記一般式
においてＡで示される低級アルコキシカルボニル基とし
ては、たとえばメトキシカルボニル、エトキシカルボニ
ル、ｎ−プロポキシカルボニル、ｉ−プロポキシカルボ
ニル、ｎ−ブトキシカルボニル、ｉ−ブトキシカルボニ
ル、Ｓｅｃーブトキシカルボニル、ｔ−ブトキシカルボ
ニルなどがあげられる。). 35 Examples of the lower alkoxycarbonyl group represented by A in the above general formula include methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, i-propoxycarbonyl, n-butoxycarbonyl, i-butoxycarbonyl, Sec-butoxycarbonyl, t- Examples include butoxycarbonyl.
また前記一般式（）で表わされる化合物のＸで示される
ハロゲンとしては、たとえば塩素、臭素、ヨウ素などが
あげられる。本発明の方法において用いられるハロゲン
化チオニルとしては、たとえば塩化チオニル・臭化チオ
ニル、ヨウ化チオニルなどがあげられる。また反応は無
溶媒または溶媒の存在下で進行し、溶媒を用いるならば
反応に不活性なものであればいかなるものでもよい。反
応に不居性な溶媒としては、たとえばベンゼン、トルエ
ン、キシレン、クロルベンゼン、ヘキサン、ハロゲン化
炭化水素（例、クロロホルム、メチレンクロリド、エチ
レンクロリド、１・１・２・２−テトラクロルエタン）
があげられる。反応温度は用いる試薬、溶媒により異る
が、一般に冷却下ないし加熱下で進行し、反応時間に特
に限定はない。反応は無触媒でも進行するが触媒が存在
する方が有利である。触媒としては通常塩基性触媒が用
いられ、たとえば、ジメチルホルムアミド、ピリジンな
どのほか先に述べた芳香族アミンおよびアルキルアミン
など力Ｌ般的である。溶媒としては、これら塩基性物質
を溶媒にかねて大過量用いてもよいし、反応に不活性な
ベンゼン、トルエン、キシレン、クロルベンゼン、ヘキ
サン、ハロゲン化炭化水素（例、クロロホルム、メチレ
ンクロリド、エチレンクロリド、１・１・２・２−テト
ラクロルエタン）などを用いてもよい。反応温度、反応
時間に特に限定はない。かくして得られた一般式（）の
化合物は、蒸留、再結晶、クロマトグラフィ一などの通
常の手段により分離、精製することが出来る。Examples of the halogen represented by X in the compound represented by the general formula () include chlorine, bromine, and iodine. Examples of the thionyl halide used in the method of the present invention include thionyl chloride, thionyl bromide, and thionyl iodide. Further, the reaction proceeds without a solvent or in the presence of a solvent, and if a solvent is used, any solvent may be used as long as it is inert to the reaction. Examples of solvents that are inhospitable to the reaction include benzene, toluene, xylene, chlorobenzene, hexane, and halogenated hydrocarbons (e.g., chloroform, methylene chloride, ethylene chloride, 1,1,2,2-tetrachloroethane).
can be given. Although the reaction temperature varies depending on the reagent and solvent used, the reaction generally proceeds under cooling or heating, and the reaction time is not particularly limited. Although the reaction proceeds without a catalyst, it is more advantageous in the presence of a catalyst. As the catalyst, a basic catalyst is usually used, such as dimethylformamide, pyridine, and the above-mentioned aromatic amines and alkyl amines. As a solvent, these basic substances may be used in large excess as solvents, or benzene, toluene, xylene, chlorobenzene, hexane, halogenated hydrocarbons (e.g., chloroform, methylene chloride, ethylene chloride) that are inert to the reaction. , 1,1,2,2-tetrachloroethane), etc. may also be used. There are no particular limitations on the reaction temperature and reaction time. The compound of general formula () thus obtained can be separated and purified by conventional means such as distillation, recrystallization, and chromatography.
なお、一般式中のＡがカルボキシル基である場合は、反
応の前もしくは反応後に、これをたとえばエステル塩、
酸ハライド、酸アミド、酸無水物などの誘導基に変えて
もよく、またＡがこの様な誘導基である場合は、反応の
前もしくは反応後にこれをカルボキシル基に変えてもよ
い。かくして得られる化合物は、青酸塩を反応させてＸ
をシアノ基に変えた後、加水分解することにより下記一
般式（）あるいは（）で示される化合物に導びくことが
でき、これら（）、（）の化合物はすぐれた消炎剤、鎮
痛剤、解熱剤等として有用である。In addition, when A in the general formula is a carboxyl group, it can be converted into an ester salt, for example, before or after the reaction.
It may be changed to a derivative group such as an acid halide, an acid amide, or an acid anhydride, and if A is such a derivative group, it may be changed to a carboxyl group before or after the reaction. The compound thus obtained is obtained by reacting cyanide with X
After converting into a cyano group, it can be hydrolyzed to lead to compounds represented by the following general formula () or (), and these compounds () and () are excellent anti-inflammatory agents, analgesics, and antipyretics. It is useful as such.
本法の原料である一般式（１）の化合物はたとえば以下
の様にして製造することができる。The compound of general formula (1), which is a raw material for this method, can be produced, for example, as follows.
実施例 １１−ヒドロキシインダン一４−カルボン酸５
．３５７をベンゼン３０ｍ１に加える。Example 11-hydroxyindan-4-carboxylic acid 5
．． Add 357 to 30ml of benzene.
これに塩化チオニル１５ｍ１を加えてかきまぜる。３時
間後、減圧乾固して得られる結晶をベンゼンから再結晶
すると１−クロルインダン一４−カルボン酸が得られる
。Add 15 ml of thionyl chloride to this and stir. After 3 hours, the crystals obtained by drying under reduced pressure are recrystallized from benzene to obtain 1-chloroindane-4-carboxylic acid.
融点１３５．５−１３７．５℃ｏ元素分析値 ＣｌＯＨ
，ＣｌＯ２
計算値 Ｃ：６１，０８、Ｈ：４．６１、Ｃｌ ：１８
．０３
実験値 Ｃ：６１．８５、Ｈ：４．４６、Ｃｌ：１７．
９２
実施例 ２
６ｍ１のクロロホルムに５．７７の１−ヒドロキシイン
ダン一４−カルボン酸メチルエステルを溶かし氷冷しな
がら撹拌する。Melting point 135.5-137.5℃ o Elemental analysis value ClOH
, ClO2 calculated value C: 61.08, H: 4.61, Cl: 18
．． 03 Experimental values C: 61.85, H: 4.46, Cl: 17.
92 Example 2 Dissolve 5.77 ml of 1-hydroxyindane-4-carboxylic acid methyl ester in 6 ml of chloroform and stir while cooling with ice.
つぎに３ｍ１の塩化チオニルを滴下し、滴加終了後１時
間氷冷で攪拌を続ける。つぎに減圧下溶媒および過量の
塩化チオニルを留去する。得られた残留物はシリカゲル
のカラムクロマトで精製する（シリカゲル５００ｙ、ク
ロロホルムで溶出する）。１−クロルインダン一４−カ
ルボン酸メチルエステルが油状物質として得られる。Next, 3 ml of thionyl chloride was added dropwise, and after the dropwise addition was completed, stirring was continued under ice cooling for 1 hour. Next, the solvent and excess thionyl chloride are distilled off under reduced pressure. The resulting residue is purified by column chromatography on silica gel (silica gel 500y, eluted with chloroform). 1-Chlorindane-4-carboxylic acid methyl ester is obtained as an oil.
元素分析値 ＣｌｌＨｌ，Ｏ２Ｃｌ
計算値 Ｃ： ６２．７１、Ｈ：５．２６、Ｃｌ：１６
．８３実験値 Ｃ：６２．４７、Ｈ：５．１１、Ｃｌ：
１６．５９Elemental analysis value CllHl, O2Cl calculated value C: 62.71, H: 5.26, Cl: 16
．． 83 Experimental values C: 62.47, H: 5.11, Cl:
16.59
Claims (1)
ルボニル基を示す）で表わされる化合物とハロゲン化チ
オニルとを反応させることを特徴とする一般式▲数式、
化学式、表等があります▼ （式中、Ａは前記と同意義であり、Ｘはハロゲン原子を
示す）で表わされる化合物の製法。[Claims] 1. Characterized by reacting a compound represented by the general formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (in the formula, A represents a carboxyl group or a lower alkoxycarbonyl group) and a thionyl halide. General formula ▲ mathematical formula,
There are chemical formulas, tables, etc. ▼ (In the formula, A has the same meaning as above, and X represents a halogen atom).
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10360373A JPS5911574B2 (en) | 1973-09-13 | 1973-09-13 | Method for producing cyclic compounds |
| US05/496,855 US3953500A (en) | 1973-08-11 | 1974-08-12 | Benzalicyclic carboxylic acid derivative |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10360373A JPS5911574B2 (en) | 1973-09-13 | 1973-09-13 | Method for producing cyclic compounds |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5058046A JPS5058046A (en) | 1975-05-20 |
| JPS5911574B2 true JPS5911574B2 (en) | 1984-03-16 |
Family
ID=14358334
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10360373A Expired JPS5911574B2 (en) | 1973-08-11 | 1973-09-13 | Method for producing cyclic compounds |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5911574B2 (en) |
-
1973
- 1973-09-13 JP JP10360373A patent/JPS5911574B2/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5058046A (en) | 1975-05-20 |
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